阅读说明：本技术 氟取代多环芳香族化合物 (Fluorine substituted polycyclic aromatic compound ) 是由 畠山琢次 枝连一志 田中裕之 王国防 马场大辅 笹田康幸 于 2019-04-09 设计创作，主要内容包括：通过向利用硼原子与氧原子等将多个芳香族环连结而成的新颖的多环芳香族化合物中导入氟原子,而增加有机EL元件用材料等有机器件用材料的选择项。另外,通过将所述新颖的氟取代多环芳香族化合物用作有机EL元件用材料,而提供例如发光效率或元件寿命优异的有机EL元件。(Fluorine atoms are introduced into a novel polycyclic aromatic compound in which a plurality of aromatic rings are connected by boron atoms, oxygen atoms, or the like, thereby increasing the options for materials for organic devices such as materials for organic EL elements. Further, by using the novel fluorine-substituted polycyclic aromatic compound as a material for an organic EL element, an organic EL element having excellent light-emitting efficiency or element life, for example, can be provided.)

1. A polycyclic aromatic compound represented by the following general formula (1) or a polymer of the polycyclic aromatic compound having a plurality of structures represented by the following general formula (1),

[ solution 1]

(in the above-mentioned formula (1),

ring A, ring B and ring C are each independently an aryl or heteroaryl ring, at least one of which rings may be substituted,

Y¹is B, P, P ═ O, P ═ S, Al, Ga, As, Si-R or Ge-R, R of said Si-R and Ge-R being aryl, alkyl or cycloalkyl,

X¹and X²Each independently O, N-R, S or Se, R of the N-R is an aryl group which may be substituted, a heteroaryl group which may be substituted, an alkyl group which may be substituted or a cycloalkyl group which may be substituted, and further, R of the N-R may be bonded to the A ring, the B ring and/or the C ring by a linking group or a single bond,

at least one hydrogen in the compound or structure represented by formula (1) may be substituted by cyano, chlorine, bromine, iodine or deuterium, and,

at least one hydrogen in the compound or structure represented by formula (1) is substituted by fluorine).

2. The polycyclic aromatic compound or multimer thereof according to claim 1, wherein

The A, B and C rings are each independently an aryl or heteroaryl ring, at least one hydrogen in these rings may be replaced by substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted diarylamino, substituted or unsubstituted diheteroarylamino, substituted or unsubstituted arylheteroarylaminoSubstituted diarylboron groups (two aryl groups may be bonded by a single bond or a linking group), substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkoxy, or substituted or unsubstituted aryloxy, and the rings have and include Y¹、X¹And X²The condensed bicyclic structure at the center of the formula (I) has a bonded 5-or 6-membered ring in common,

Y¹is B, P, P ═ O, P ═ S, Al, Ga, As, Si-R or Ge-R, R of said Si-R and Ge-R being aryl, alkyl or cycloalkyl,

X¹and X²Each independently O, N-R, S or Se, R of the N-R is aryl which can be substituted by alkyl or cycloalkyl, heteroaryl which can be substituted by alkyl or cycloalkyl, and R of the N-R can be replaced by-O-, -S-, -C (-R)₂-or a single bond to the A ring, B ring and/or C ring, the-C (-R)₂R of-is hydrogen, alkyl or cycloalkyl,

at least one hydrogen in the compound or structure represented by formula (1) may be substituted by cyano, chlorine, bromine, iodine or deuterium,

in the case of multimers, dimers or trimers having 2 or 3 structures represented by the general formula (1), and,

at least one hydrogen in the compound or structure represented by formula (1) is substituted by fluorine.

3. The polycyclic aromatic compound or the multimer thereof according to claim 1, represented by the following general formula (2),

[ solution 2]

(in the above-mentioned formula (2),

R¹～R¹¹each independently is hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboron (two aryl groups may be linked via a single bond or a bond)Bonded to a substituent), alkyl, cycloalkyl, alkoxy, or aryloxy, at least one of which may be substituted with aryl, heteroaryl, alkyl, or cycloalkyl, and R¹～R¹¹May be bonded to each other and form, together with the a-ring, the b-ring or the c-ring, an aryl ring or a heteroaryl ring, at least one hydrogen in the formed ring may be substituted by an aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboron group (two aryl groups may be bonded via a single bond or a linking group), an alkyl, cycloalkyl, alkoxy or aryloxy group, at least one hydrogen of these may be substituted by an aryl, heteroaryl, alkyl or cycloalkyl group,

Y¹b, P, P is O, P is S, Al, Ga, As, Si-R or Ge-R, wherein R of the Si-R and Ge-R is aryl with 6-12 carbon atoms, alkyl with 1-6 carbon atoms or cycloalkyl with 3-14 carbon atoms,

X¹and X²O, N-R, S or Se, wherein R of the N-R is aryl with 6-12 carbon atoms, heteroaryl with 2-15 carbon atoms, alkyl with 1-6 carbon atoms or cycloalkyl with 3-14 carbon atoms, and R of the N-R can be selected from-O-, -S-, -C (-R)₂-or a single bond to the a-ring, b-ring and/or C-ring, the-C (-R)₂R is C1-C6 alkyl or C3-C14 cycloalkyl,

at least one hydrogen in the compound represented by formula (2) may be substituted by cyano, chlorine, bromine, iodine or deuterium, and further,

at least one hydrogen in the compound represented by formula (2) is substituted by fluorine).

4. The polycyclic aromatic compound or multimer thereof according to claim 3, wherein

R¹～R¹¹Independently represents hydrogen, an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, a diarylamino group (wherein the aryl group is an aryl group having 6 to 12 carbon atoms), a diarylboron group (wherein the aryl group is an aryl group having 6 to 12 carbon atoms, and the two aryl groups may be bonded by a single bond or a linking group), an alkyl group having 1 to 24 carbon atoms, or a cycloalkyl group having 3 to 24 carbon atoms, and R is¹～R¹¹Adjacent groups of (1) to each otherThe bond and the a, b or c ring form an aryl ring having 9 to 16 carbon atoms or a heteroaryl ring having 6 to 15 carbon atoms, at least one hydrogen in the formed ring is substituted by an aryl group having 6 to 10 carbon atoms, an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 3 to 16 carbon atoms,

Y¹b, P, P is O, P is S or Si-R, wherein R of the Si-R is aryl having 6 to 10 carbon atoms, alkyl having 1 to 4 carbon atoms or cycloalkyl having 5 to 10 carbon atoms,

X¹and X²O, N-R or S, wherein R of N-R is aryl group with 6-10 carbon atoms, alkyl group with 1-4 carbon atoms or cycloalkyl group with 5-10 carbon atoms,

at least one hydrogen in the compound represented by formula (2) may be substituted by cyano, chlorine, bromine, iodine or deuterium, and further,

at least one hydrogen in the compound represented by formula (2) is substituted by fluorine.

5. The polycyclic aromatic compound or multimer thereof according to claim 3, wherein

R¹～R¹¹Independently hydrogen, an aryl group having 6 to 16 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, a diarylamino group (wherein the aryl group is an aryl group having 6 to 10 carbon atoms), a diarylboron group (wherein the aryl group is an aryl group having 6 to 10 carbon atoms, and the two aryl groups may be bonded by a single bond or a linking group), an alkyl group having 1 to 12 carbon atoms, or a cycloalkyl group having 3 to 16 carbon atoms,

Y¹is B, P, P ═ O or P ═ S,

X¹and X²Each independently O or N-R, wherein R in the N-R is aryl having 6 to 10 carbon atoms, alkyl having 1 to 4 carbon atoms or cycloalkyl having 5 to 10 carbon atoms,

at least one hydrogen in the compound represented by formula (2) is substituted by fluorine.

6. The polycyclic aromatic compound or multimer thereof according to claim 3, wherein

R¹～R¹¹Independently represents hydrogen, aryl group having 6 to 16 carbon atoms, diarylamino group (wherein aryl group is aryl group having 6 to 10 carbon atoms), or diarylamino groupAn arylboron group (wherein the aryl group is an aryl group having 6 to 10 carbon atoms, and two aryl groups may be bonded via a single bond or a linking group), an alkyl group having 1 to 12 carbon atoms, or a cycloalkyl group having 3 to 16 carbon atoms,

Y¹in the form of a block B having a structure,

X¹and X²Are all N-R, or X¹Is N-R and X²Is O, R of the N-R is aryl having 6 to 10 carbon atoms, alkyl having 1 to 4 carbon atoms or cycloalkyl having 5 to 10 carbon atoms,

at least one hydrogen in the compound represented by formula (2) is substituted by fluorine.

7. The polycyclic aromatic compound or the multimer thereof according to any one of claims 1 to 6, wherein R of said N-R is fluoro-substituted aryl or heteroaryl.

8. The polycyclic aromatic compound or the multimer thereof according to claim 7, wherein R of said N-R is fluoro-substituted phenyl.

9. The polycyclic aromatic compound or the multimer thereof according to any one of claims 1 to 8, substituted with a fluorine-substituted alkyl or cycloalkyl group, a fluorine-substituted alkoxy group, a fluorine-substituted diarylamino group, a fluorine-substituted diarylboron group (two aryl groups may be bonded via a single bond or a linking group), a fluorine-substituted carbazolyl group, or a fluorine-substituted benzocarbazolyl group.

10. The polycyclic aromatic compound or multimer thereof according to claim 9, substituted with a fluorine-substituted diarylamino group.

11. The polycyclic aromatic compound or the multimer thereof according to claim 10, substituted with a fluoro-substituted diphenylamino group.

12. The polycyclic aromatic compound according to claim 1, represented by any one of the following structural formulae,

[ solution 3]

(in each structural formula, "tBu" represents a t-butyl group).

13. The polycyclic aromatic compound according to claim 1, represented by any one of the following structural formulae,

[ solution 4]

(Me in each of the formulae represents a methyl group).

14. A material for organic devices, comprising the polycyclic aromatic compound according to any one of claims 1 to 13 or a multimer thereof.

15. The material for organic devices according to claim 14, wherein the material for organic devices is a material for organic electroluminescent elements, a material for organic field effect transistors, or a material for organic thin film solar cells.

16. The material for an organic electroluminescent element according to claim 15, which is a material for a light-emitting layer.

17. An organic electroluminescent element comprising: a pair of electrodes including an anode and a cathode; and a light-emitting layer which is arranged between the pair of electrodes and contains the material for a light-emitting layer according to claim 16.

18. The organic electroluminescent element according to claim 17, wherein the light-emitting layer comprises: a main body; and a material for the light-emitting layer as a dopant.

19. The organic electroluminescent element according to claim 18, wherein the host is an anthracene-based compound, a fluorene-based compound, or a dibenzoIs a compound of the formula (I).

20. The organic electroluminescent element according to any one of claims 17 to 19, which has an electron transport layer and/or an electron injection layer disposed between the cathode and the light-emitting layer, and at least one of the electron transport layer and the electron injection layer contains at least one selected from the group consisting of borane derivatives, pyridine derivatives, fluoranthene derivatives, BO-based derivatives, anthracene derivatives, benzofluorene derivatives, phosphine oxide derivatives, pyrimidine derivatives, carbazole derivatives, triazine derivatives, benzimidazole derivatives, phenanthroline derivatives, and hydroxyquinoline-based metal complexes.

21. The organic electroluminescent element according to claim 20, wherein the electron transport layer and/or the electron injection layer further contains at least one selected from the group consisting of alkali metals, alkaline earth metals, rare earth metals, oxides of alkali metals, halides of alkali metals, oxides of alkaline earth metals, halides of alkaline earth metals, oxides of rare earth metals, halides of rare earth metals, organic complexes of alkali metals, organic complexes of alkaline earth metals, and organic complexes of rare earth metals.

22. A display device or a lighting device comprising the organic electroluminescent element according to any one of claims 17 to 21.

Technical Field

The present invention relates to a fluorine-substituted polycyclic aromatic compound, and an organic electroluminescent element, an organic field effect transistor, an organic thin film solar cell, a display device, and a lighting device each using the same. In the present specification, the term "organic electroluminescent element" may be referred to as an "organic el (electroluminescence) element" or simply an "element".

Background

Conventionally, display devices using light-emitting elements that perform electroluminescence have been variously studied because of the realization of reduction in power consumption and thickness, and further, organic electroluminescence elements including organic materials have been actively studied because of their ease of weight reduction and size increase. In particular, active studies have been made so far on the development of an organic material having light-emitting characteristics such as blue, which is one of the three primary colors of light, and on the development of an organic material having charge transport capability (having a possibility of becoming a semiconductor or a superconductor) of holes, electrons, and the like, regardless of a high molecular compound and a low molecular compound.

The organic EL element has a structure including: a pair of electrodes including an anode and a cathode, and one or more layers which are disposed between the pair of electrodes and include an organic compound. The layer containing an organic compound includes a light-emitting layer, a charge transporting/injecting layer for transporting or injecting charges such as holes and electrons, and various organic materials suitable for these layers have been developed.

As a material for the light-emitting layer, for example, a benzofluorene compound has been developed (international publication No. 2004/061047). Further, as the hole transporting material, for example, triphenylamine compounds and the like have been developed (Japanese patent laid-open No. 2001-172232). Further, as an electron transport material, for example, an anthracene compound has been developed (Japanese patent laid-open No. 2005-170911).

In recent years, as a material used for an organic EL device or an organic thin film solar cell, a material in which a triphenylamine derivative is improved has also been reported (international publication No. 2012/118164). The material is characterized by comprising the following components in parts by weight: referring to N, N '-diphenyl-N, N' -bis (3-methylphenyl) -1,1 '-biphenyl-4, 4' -diamine (triphenyldiamine, TPD), which has been put to practical use, aromatic rings constituting triphenylamine are linked to each other, thereby improving planarity thereof. In the above-mentioned document, for example, the charge transport properties of the NO-linked compound (compound 1 on page 63) were evaluated, but there is NO description about the production method of the material other than the NO-linked compound, and the properties obtained from the material other than the NO-linked compound are not known because the electron state of the whole compound differs depending on the element to be linked. Examples of such compounds are also found elsewhere (International publication No. 2011/107186). For example, a compound having a conjugated structure with a large triplet exciton energy (T1) can emit phosphorescence with a shorter wavelength, and is therefore useful as a material for a blue light-emitting layer. Further, a compound having a novel conjugated structure with a large T1 is also required as an electron transporting material or a hole transporting material which sandwiches the light-emitting layer.

The host (host) material of the organic EL device is generally a molecule in which a plurality of conventional aromatic rings such as benzene and carbazole are connected by a single bond, a phosphorus atom, or a silicon atom. The reason for this is that: by linking a plurality of relatively small aromatic rings of a conjugated system, a large Highest Occupied Molecular Orbital (HOMO) to Lowest Unoccupied Molecular Orbital (LUMO) gap (band gap Eg of the film) required for the host material is ensured. Furthermore, high triplet excitation energy (E) is also required for the host material of an organic EL device using a phosphorescent material or a thermally active delayed fluorescence material_T) However, by linking an aromatic ring or a substituent of donor or acceptor to the molecule, Single Occupied Molecular Orbital (SOMO) 1 and SOMO2 in triplet excited state (T1) are localized, and exchange interaction between both orbitals is reduced, whereby triplet excitation energy (E) can be increased_T). However, the redox stability of the aromatic ring having a small conjugated system is not sufficient, and the life of the device using a molecule having a conventional aromatic ring bonded thereto as a host material is not sufficient. On the other hand, a polycyclic aromatic compound having an extended pi-conjugated system is generally excellent in redox stability, but has a HOMO-LUMO gap (band gap Eg of thin film) or triplet excitation energy (E)_T) Low and therefore is considered unsuitable for the host material.

Documents of the prior art

Patent document

Patent document 1: international publication No. 2004/061047

Patent document 2: japanese patent laid-open No. 2001-172232

Patent document 3: japanese patent laid-open No. 2005-170911

Patent document 4: international publication No. 2012/118164

Patent document 5: international publication No. 2011/107186

Patent document 6: international publication No. 2015/102118

Disclosure of Invention

Problems to be solved by the invention

As described above, various materials have been developed as materials for organic EL devices, and in order to increase the options for materials for organic EL devices, it is desired to develop materials containing compounds different from those in the prior art. In particular, the characteristics of organic EL obtained from materials other than the NO-linking compound reported in patent documents 1 to 4 and the production method thereof are not known.

Patent document 6 reports a polycyclic aromatic compound containing boron and an organic EL element using the compound, but in order to further improve element characteristics, a material for a light-emitting layer, particularly a dopant (dopant) material, which can improve light-emitting efficiency and element lifetime is desired.

Means for solving the problems

The present inventors have made extensive studies to solve the above-mentioned problems, and as a result, have found that an excellent organic EL element can be obtained by configuring, for example, an organic EL element by disposing a layer containing a polycyclic aromatic compound having fluorine atoms introduced between a pair of electrodes, and have completed the present invention. That is, the present invention provides a fluorine-substituted polycyclic aromatic compound or a polymer thereof as described below, and further provides a material for an organic device such as a material for an organic EL element containing a fluorine-substituted polycyclic aromatic compound or a polymer thereof as described below.

In the present specification, the chemical structure or the substituent may be represented by carbon number, but the carbon number in the case of substituting the substituent for the chemical structure or the substituent for the substituent means the carbon number of each of the chemical structure or the substituent, and does not mean the total carbon number of the chemical structure and the substituent or the total carbon number of the substituent and the substituent. For example, the "substituent B having a carbon number Y substituted with the substituent a having a carbon number X" means that the "substituent a having a carbon number X" is substituted with the "substituent B having a carbon number Y, and the carbon number Y is not the total carbon number of the substituent a and the substituent B. For example, the "substituent B having a carbon number Y substituted with the substituent a" means that the substituent a "(not limited to a carbon number) is substituted with the" substituent B having a carbon number Y "and the carbon number Y is not the total carbon number of the substituent a and the substituent B.

Item 1.

Disclosed is a polycyclic aromatic compound represented by the general formula (1) below or a polymer of a polycyclic aromatic compound having a plurality of structures represented by the general formula (1) below.

[ solution 5]

(in the above-mentioned formula (1),

ring A, ring B and ring C are each independently an aryl or heteroaryl ring, at least one of which rings may be substituted,

Y¹is B, P, P ═ O, P ═ S, Al, Ga, As, Si-R or Ge-R, R of said Si-R and Ge-R being aryl, alkyl or cycloalkyl,

X¹and X²Each independently O, N-R, S or Se, R of the N-R is an aryl group which may be substituted, a heteroaryl group which may be substituted, an alkyl group which may be substituted or a cycloalkyl group which may be substituted, and further, R of the N-R may be bonded to the A ring, the B ring and/or the C ring by a linking group or a single bond,

at least one hydrogen in the compound or structure represented by formula (1) may be substituted by cyano, chlorine, bromine, iodine or deuterium, and,

at least one hydrogen in the compound or structure represented by the formula (1) is substituted by fluorine)

Item 2.

The polycyclic aromatic compound or multimer thereof according to item 1, wherein

The A, B and C rings are each independently an aryl or heteroaryl ring, at least one hydrogen in these rings may be replaced by a substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted diarylamino, substituted or unsubstituted diheteroarylamino, substituted or unsubstituted arylheteroarylamino, substituted or unsubstituted diarylboryl (two aryl groups may be replaced by an aryl or heteroaryl ring)Bonded by a single bond or a linking group), substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted alkoxy, or substituted or unsubstituted aryloxy, and further wherein the rings have a structure corresponding to that of Y¹、X¹And X²The condensed bicyclic structure at the center of the formula (I) has a bonded 5-or 6-membered ring in common,

Y¹is B, P, P ═ O, P ═ S, Al, Ga, As, Si-R or Ge-R, R of said Si-R and Ge-R being aryl, alkyl or cycloalkyl,

X¹and X²Each independently O, N-R, S or Se, R of the N-R is aryl which can be substituted by alkyl or cycloalkyl, heteroaryl which can be substituted by alkyl or cycloalkyl, and R of the N-R can be replaced by-O-, -S-, -C (-R)₂-or a single bond to the A ring, B ring and/or C ring, the-C (-R)₂R of-is hydrogen, alkyl or cycloalkyl,

at least one hydrogen in the compound or structure represented by formula (1) may be substituted by cyano, chlorine, bromine, iodine or deuterium,

in the case of multimers, dimers or trimers having 2 or 3 structures represented by the general formula (1), and,

at least one hydrogen in the compound or structure represented by formula (1) is substituted by fluorine.

Item 3.

The polycyclic aromatic compound or multimer thereof according to item 1, represented by the following general formula (2).

[ solution 6]

(in the above-mentioned formula (2),

R¹～R¹¹each independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboron (two aryl groups may be bonded via a single bond or a linking group), alkyl, cycloalkyl, alkoxy, or aryloxy,at least one hydrogen of these may be substituted by aryl, heteroaryl, alkyl or cycloalkyl, and further, R is¹～R¹¹May be bonded to each other and form, together with the a-ring, the b-ring or the c-ring, an aryl ring or a heteroaryl ring, at least one hydrogen in the formed ring may be substituted by an aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboron group (two aryl groups may be bonded via a single bond or a linking group), an alkyl, cycloalkyl, alkoxy or aryloxy group, at least one hydrogen of these may be substituted by an aryl, heteroaryl, alkyl or cycloalkyl group,

Y¹b, P, P is O, P is S, Al, Ga, As, Si-R or Ge-R, wherein R of the Si-R and Ge-R is aryl with 6-12 carbon atoms, alkyl with 1-6 carbon atoms or cycloalkyl with 3-14 carbon atoms,

X¹and X²O, N-R, S or Se, wherein R of the N-R is aryl with 6-12 carbon atoms, heteroaryl with 2-15 carbon atoms, alkyl with 1-6 carbon atoms or cycloalkyl with 3-14 carbon atoms, and R of the N-R can be selected from-O-, -S-, -C (-R)₂-or a single bond to the a-ring, b-ring and/or C-ring, the-C (-R)₂R is C1-C6 alkyl or C3-C14 cycloalkyl,

at least one hydrogen in the compound represented by formula (2) may be substituted by cyano, chlorine, bromine, iodine or deuterium, and further,

at least one hydrogen in the compound represented by the formula (2) is substituted by fluorine)

Item 4.

The polycyclic aromatic compound or multimer thereof according to item 3, wherein

R¹～R¹¹Independently represents hydrogen, an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, a diarylamino group (wherein the aryl group is an aryl group having 6 to 12 carbon atoms), a diarylboron group (wherein the aryl group is an aryl group having 6 to 12 carbon atoms, and the two aryl groups may be bonded by a single bond or a linking group), an alkyl group having 1 to 24 carbon atoms, or a cycloalkyl group having 3 to 24 carbon atoms, and R is¹～R¹¹Wherein adjacent groups are bonded to each other and form an aryl ring having 9 to 16 carbon atoms or a carbon atom together with the a-ring, the b-ring or the c-ringA heteroaryl ring having 6 to 15 carbon atoms, wherein at least one hydrogen in the ring is substituted by an aryl group having 6 to 10 carbon atoms, an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 3 to 16 carbon atoms,

Y¹b, P, P is O, P is S or Si-R, wherein R of the Si-R is aryl having 6 to 10 carbon atoms, alkyl having 1 to 4 carbon atoms or cycloalkyl having 5 to 10 carbon atoms,

X¹and X²O, N-R or S, wherein R of N-R is aryl group with 6-10 carbon atoms, alkyl group with 1-4 carbon atoms or cycloalkyl group with 5-10 carbon atoms,

at least one hydrogen in the compound represented by formula (2) may be substituted by cyano, chlorine, bromine, iodine or deuterium, and further,

at least one hydrogen in the compound represented by formula (2) is substituted by fluorine.

Item 5.

The polycyclic aromatic compound or multimer thereof according to item 3, wherein

R¹～R¹¹Independently hydrogen, an aryl group having 6 to 16 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, a diarylamino group (wherein the aryl group is an aryl group having 6 to 10 carbon atoms), a diarylboron group (wherein the aryl group is an aryl group having 6 to 10 carbon atoms, and the two aryl groups may be bonded by a single bond or a linking group), an alkyl group having 1 to 12 carbon atoms, or a cycloalkyl group having 3 to 16 carbon atoms,

Y¹is B, P, P ═ O or P ═ S,

X¹and X²Each independently O or N-R, wherein R in the N-R is aryl having 6 to 10 carbon atoms, alkyl having 1 to 4 carbon atoms or cycloalkyl having 5 to 10 carbon atoms,

at least one hydrogen in the compound represented by formula (2) is substituted by fluorine.

Item 6.

The polycyclic aromatic compound or multimer thereof according to item 3, wherein

R¹～R¹¹Independently represents hydrogen, aryl group having 6 to 16 carbon atoms, diarylamino group (wherein aryl group is aryl group having 6 to 10 carbon atoms), diarylboron group (wherein aryl group is aryl group having 6 to 10 carbon atoms, and two aryl groups may be bonded via single bond or linking groupA bond), an alkyl group having 1 to 12 carbon atoms or a cycloalkyl group having 3 to 16 carbon atoms,

Y¹in the form of a block B having a structure,

X¹and X²Are all N-R, or X¹Is N-R and X²Is O, R of the N-R is aryl having 6 to 10 carbon atoms, alkyl having 1 to 4 carbon atoms or cycloalkyl having 5 to 10 carbon atoms,

at least one hydrogen in the compound represented by formula (2) is substituted by fluorine.

Item 7.

The polycyclic aromatic compound or the multimer thereof according to any one of claims 1 to 6, wherein R of the N-R is a fluorine-substituted aryl or heteroaryl group.

Item 8.

The polycyclic aromatic compound or the multimer thereof according to item 7, wherein R of said N-R is a fluoro-substituted phenyl group.

Item 9.

The polycyclic aromatic compound or the multimer thereof according to any one of items 1 to 8, substituted with a fluorine-substituted alkyl or cycloalkyl group, a fluorine-substituted alkoxy group, a fluorine-substituted diarylamino group, a fluorine-substituted diarylboron group (two aryl groups may be bonded via a single bond or a linking group), a fluorine-substituted carbazolyl group, or a fluorine-substituted benzocarbazolyl group.

Item 10.

The polycyclic aromatic compound or the multimer thereof according to item 9, substituted with a fluorine-substituted diarylamino group.

Item 11.

The polycyclic aromatic compound or the multimer thereof according to item 10, substituted with a fluorine-substituted diphenylamino group.

Item 12.

The polycyclic aromatic compound according to claim 1, represented by any one of the following structural formulae.

[ solution 7]

(in each of the formulae, "tBu" represents a t-butyl group)

Item 13.

The polycyclic aromatic compound according to claim 1, represented by any one of the following structural formulae.

[ solution 8]

(wherein "Me" in each of the formulae represents a methyl group)

Item 14.

A material for organic devices, comprising the polycyclic aromatic compound according to any one of items 1 to 13 or a multimer thereof.

Item 15.

The material for an organic device according to item 14, wherein the material for an organic device is a material for an organic electroluminescent element, a material for an organic field-effect transistor, or a material for an organic thin-film solar cell.

Item 16.

The material for an organic electroluminescent element according to item 15, which is a material for a light-emitting layer.

Item 17.

An organic electroluminescent element comprising: a pair of electrodes including an anode and a cathode; and a light-emitting layer which is arranged between the pair of electrodes and contains the material for a light-emitting layer according to item 16.

Item 18.

The organic electroluminescent element according to item 17, wherein the light-emitting layer comprises: a main body; and a material for the light-emitting layer as a dopant.

Item 19.

The organic electroluminescent element according to item 18, wherein the host is an anthracene-based compound, a fluorene-based compound, or a dibenzoIs a compound of the formula (I).

Item 20.

The organic electroluminescent element according to any one of claims 17 to 19, which has an electron transport layer and/or an electron injection layer disposed between the cathode and the light-emitting layer, and at least one of the electron transport layer and the electron injection layer contains at least one selected from the group consisting of borane derivatives, pyridine derivatives, fluoranthene derivatives, BO-based derivatives, anthracene derivatives, benzofluorene derivatives, phosphine oxide derivatives, pyrimidine derivatives, carbazole derivatives, triazine derivatives, benzimidazole derivatives, phenanthroline derivatives, and quinolinol (quinolinol) -based metal complexes.

Item 21.

The organic electroluminescent element according to item 20, wherein the electron transport layer and/or the electron injection layer further contains at least one selected from the group consisting of alkali metals, alkaline earth metals, rare earth metals, oxides of alkali metals, halides of alkali metals, oxides of alkaline earth metals, halides of alkaline earth metals, oxides of rare earth metals, halides of rare earth metals, organic complexes of alkali metals, organic complexes of alkaline earth metals, and organic complexes of rare earth metals.

Item 22.

A display device or a lighting device, comprising the organic electroluminescent element according to any one of items 17 to 21.

ADVANTAGEOUS EFFECTS OF INVENTION

According to a preferred embodiment of the present invention, a novel fluorine-substituted polycyclic aromatic compound which is useful as a material for an organic device such as a material for an organic EL element can be provided, and by using the fluorine-substituted polycyclic aromatic compound, an excellent organic device such as an organic EL element can be provided.

Specifically, the present inventors have found that a polycyclic aromatic compound (basic skeleton portion) in which aromatic rings are connected by a heterogeneous element such as boron, phosphorus, oxygen, nitrogen, or sulfur has a large HOMO-LUMO gap (band gap Eg of a thin film) and a high triplet excitation energy (E)_T). The reason is considered to be that: since the hetero element-containing 6-membered ring has low aromaticity, the decrease in HOMO-LUMO gap accompanying the expansion of the conjugated system is suppressed, and electron perturbation due to the hetero element causesSOMO1 and SOMO2 in the triplet excited state (T1) are localized. Further, the hetero element-containing polycyclic aromatic compound (basic skeleton portion) of the present invention is useful as a fluorescent material for an organic EL element because the exchange interaction between the two orbitals is small due to localization of SOMO1 and SOMO2 in the triplet excited state (T1), and therefore, the energy difference between the triplet excited state (T1) and the singlet excited state (S1) is small, and thermally active delayed fluorescence is exhibited. In addition, has high triplet excitation energy (E)_T) The material of (3) is also useful as an electron transport layer or a hole transport layer of a phosphorescent organic EL device or an organic EL device using thermally active delayed fluorescence. Further, since the energy of HOMO and LUMO can be arbitrarily changed by introducing a substituent into these polycyclic aromatic compounds (basic skeleton portions), the ionization potential (ionization potential) or the electron affinity can be optimized according to the peripheral materials.

In addition to the characteristics of the basic skeleton portion, the compound of the present invention can be expected to lower the sublimation temperature due to the decrease in molecular polarity by introducing a fluorine atom. In the sublimation purification, which is almost indispensable as a purification method for a material for an organic device such as an organic EL element requiring high purity, the purification can be performed at a relatively low temperature, and thus thermal decomposition of the material and the like can be avoided. In addition, since the vacuum deposition process, which is a powerful means for producing an organic device such as an organic EL element, can be carried out at a relatively low temperature, thermal decomposition of the material can be avoided, and as a result, a high-performance organic device can be obtained.

As the halogen, chlorine, bromine and iodine are included in addition to fluorine, but since a carbon bond at the time of substitution with chlorine, bromine and iodine is active, it is slightly unstable chemically or electrochemically, and when it is used as an organic device material, driving deterioration may be caused. On the other hand, carbon-fluorine bonds are inert, chemically and electrochemically stable, and thus are suitable as organic device materials.

In addition, since there are many compounds having a high sublimation temperature due to high molecular weight, high planarity, or the like, a polymer of a polycyclic aromatic compound is more effective in reducing the sublimation temperature by introducing a fluorine atom.

Further, by introducing an electron-accepting fluorine atom, the emission wavelength can be shortened. This is particularly important in display applications where high color purity blue emission is required.

Drawings

Fig. 1 is a schematic sectional view showing an organic EL element according to the present embodiment.

Detailed Description

1. Fluorine-substituted polycyclic aromatic compound and multimer thereof

The present invention is a polycyclic aromatic compound represented by the following general formula (1) or a polymer of a polycyclic aromatic compound having a plurality of structures represented by the following general formula (1), and preferably a polycyclic aromatic compound represented by the following general formula (2) or a polymer of a polycyclic aromatic compound having a plurality of structures represented by the following general formula (2), wherein at least one hydrogen in these compounds or structures is substituted by fluorine. In the formula (1), "a" and "C" and "B" in the ring are each a symbol representing a ring structure represented by the ring, and other symbols are the same as defined above.

[ solution 9]

The A ring, the B ring and the C ring in the general formula (1) are each independently an aryl ring or a heteroaryl ring, and at least one hydrogen in these rings may be substituted by a substituent. The substituents are preferably substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted diarylamino, substituted or unsubstituted diheteroarylamino, substituted or unsubstituted arylheteroarylamino (amino having aryl and heteroaryl), substituted or unsubstituted diarylboron (two aryl groups may be bonded via a single bond or a linking group), substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heteroaryl, or substituted or unsubstituted heteroarylboronA substituted or unsubstituted alkoxy group or a substituted or unsubstituted aryloxy group. Examples of the substituent in the case where these groups have a substituent include: aryl, heteroaryl, alkyl or cycloalkyl. In addition, the aryl or heteroaryl ring preferably has a ring structure with a ring structure comprising Y¹、X¹And X²The condensed bicyclic structure at the center of the general formula (1) has a bonded 5-or 6-membered ring in common.

Here, the "condensed bicyclic structure" means that Y is contained in the center of the general formula (1)¹、X¹And X²And 2 saturated hydrocarbon rings are condensed. The "6-membered ring bonded in common to the condensed bicyclic structure" means an a-ring (benzene ring (6-membered ring)) condensed in the condensed bicyclic structure, as shown in the general formula (2), for example. The phrase "(a ring) aryl ring or heteroaryl ring having the 6-membered ring" means that the a ring is formed by only the 6-membered ring or by further condensing another ring or the like on the 6-membered ring so as to include the 6-membered ring. In other words, the term "an (a-ring) aryl ring or heteroaryl ring having 6-membered rings" as used herein means that the 6-membered rings constituting all or a part of the a ring are condensed in the condensed bicyclic structure. The same applies to the "B ring (B ring)", "C ring (C ring)", and "5-membered ring".

The A ring (or B ring, C ring) in the general formula (1) corresponds to the a ring and the substituent R thereof in the general formula (2)¹～R³(or b Ring and its substituent R⁸～R¹¹C ring and its substituent R⁴～R⁷). That is, the general formula (2) corresponds to a structure in which "ring A to ring C having 6-membered rings" are selected as ring A to ring C of the general formula (1). In the meaning, each ring of the general formula (2) is represented by a to c of a lower case letter.

In the general formula (2), the substituent R of the ring a, the ring b and the ring c¹～R¹¹May be bonded to each other and together with the a-ring, b-ring or c-ring form an aryl or heteroaryl ring, at least one hydrogen in the formed ring may be replaced by an aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboron (two aryl groups may be bonded via a single bond or a linking group), alkyl, or heteroaryl ringCycloalkyl, alkoxy or aryloxy, at least one hydrogen of which may also be substituted by aryl, heteroaryl, alkyl or cycloalkyl. Therefore, the polycyclic aromatic compound represented by the general formula (2) has a structure of a ring constituting the compound changed as shown in the following formulae (2-1) and (2-2) depending on the bonding form among the substituents in the a-ring, b-ring and c-ring. The A ' ring, B ' ring and C ' ring in the formulae correspond to the A ring, B ring and C ring in the general formula (1), respectively. In addition, R in each formula¹～R¹¹、a、b、c、Y¹、X¹And X²Is the same as defined in the general formula (2).

[ solution 10]

When the general formula (2) is used for illustration, the A ' ring, the B ' ring and the C ' ring in the formula (2-1) and the formula (2-2) represent a substituent R¹～R¹¹An aryl ring or a heteroaryl ring (which may also be referred to as a condensed ring in which other ring structures are condensed in the a-ring, the b-ring, or the c-ring) formed together with the a-ring, the b-ring, and the c-ring, respectively. Although not shown in the formula, there are also compounds in which all of the a, B and C rings are changed to a ' ring, B ' ring and C ' ring. As is clear from the above formulae (2-1) and (2-2), for example, R in the b ring⁸R with ring c⁷R of ring b¹¹R with ring a¹R of ring c⁴R with ring a³Etc. do not correspond to "adjacent groups to each other", these are not bonded. That is, the term "adjacent groups" refers to groups adjacent to each other on the same ring.

The compound represented by the formula (2-1) or the formula (2-2) is, for example, a compound having an a 'ring (or B' ring or C 'ring) formed by condensing a benzene ring as an a ring (or B ring or C ring) with a benzene ring, an indole ring, a pyrrole ring, a benzofuran ring or a benzothiophene ring, and the formed condensed ring a' (or condensed ring B 'or condensed ring C') is a naphthalene ring, a carbazole ring, an indole ring, a dibenzofuran ring or a dibenzothiophene ring, respectively.

Y in the general formula (1)¹Is B, P, P ═ O, P ═ S, Al, Ga, As, Si-R, or Ge-R, where R of the Si-R and Ge-R is aryl, alkyl, or cycloalkyl. When P-O, P-S, Si-R or Ge-R, the atom bonded to the a, B or C ring is P, Si or Ge. Y is¹Preferably B, P, P ═ O, P ═ S or Si — R, particularly preferably B. The same applies to Y in the formula (2)¹。

X in the general formula (1)¹And X²Each independently O, N-R, S or Se, R of the N-R is aryl which may be substituted, heteroaryl which may be substituted, alkyl which may be substituted or cycloalkyl which may be substituted, R of the N-R may be bonded to the B ring and/or the C ring by a linking group or a single bond as a linking group, and is preferably-O-, -S-or-C (-R)₂-. Again, the "-C (-R)₂R of the-is hydrogen, alkyl or cycloalkyl. The same applies to X in the formula (2)¹And X²。

Here, the definition that "R of the N-R is bonded to the A ring, the B ring and/or the C ring through a linking group or a single bond" in the general formula (1) corresponds to the definition that "R of the N-R is bonded through-O-, -S-, -C (-R) in the general formula (2)₂-or a single bond to the a-ring, b-ring and/or c-ring.

The regulation can be represented by a compound represented by the following formula (2-3-1) and having X¹Or X²A ring structure introduced into the condensed rings B 'and C'. I.e. for example with other rings to introduce X¹(or X)²) The compound of (1) is a compound of ring B '(or ring C') (wherein the ring B '(or ring C') (in the general formula (2)) is formed by condensation of benzene rings. The condensed ring B '(or condensed ring C') formed is, for example, a phenoxazine ring, a phenothiazine ring or an acridine ring.

The above-mentioned definition may be expressed by a compound represented by the following formula (2-3-2) or formula (2-3-3) and having X¹And/or X²A ring structure introduced into the condensed ring A'. I.e. for example with other rings to introduce X¹(and/or X)²) The method of (1) is performed on a benzene ring as the a ring in the general formula (2)A compound of ring A' formed by condensation. The condensed ring A' formed is, for example, a phenoxazine ring, a phenothiazine ring or an acridine ring.

[ solution 11]

Examples of the "aryl ring" of the ring A, ring B and ring C of the general formula (1) include aryl rings having 6 to 30 carbon atoms, preferably aryl rings having 6 to 16 carbon atoms, more preferably aryl rings having 6 to 12 carbon atoms, and particularly preferably aryl rings having 6 to 10 carbon atoms. Further, the "aryl ring" corresponds to the "R" defined in the general formula (2)¹～R¹¹The "aryl ring" in which adjacent groups in (a) are bonded to each other and form together with the a-ring, the b-ring, or the c-ring "and the a-ring (or the b-ring, or the c-ring) already contains a benzene ring having 6 carbon atoms, and therefore the total carbon number 9 of the condensed rings in which the 5-membered ring is condensed is the lower limit carbon number.

Specific "aryl ring" may include: a benzene ring as a monocyclic system, a biphenyl ring as a bicyclic system, a naphthalene ring as a condensed bicyclic system, a tribiphenyl ring (m-terphenyl, o-terphenyl, p-terphenyl) as a tricyclic system, an acenaphthene ring, a fluorene ring, a phenalene ring, a phenanthrene ring as a condensed tricyclic system, a triphenylene ring, a pyrene ring, a tetracene ring as a condensed tetracyclic system, a perylene ring, a pentacene ring as a condensed pentacene ring, and the like.

Examples of the "heteroaryl ring" of the a ring, B ring and C ring of the general formula (1) include heteroaryl rings having 2 to 30 carbon atoms, preferably heteroaryl rings having 2 to 25 carbon atoms, more preferably heteroaryl rings having 2 to 20 carbon atoms, still more preferably heteroaryl rings having 2 to 15 carbon atoms, and particularly preferably heteroaryl rings having 2 to 10 carbon atoms. Examples of the "heteroaryl ring" include heterocyclic rings containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen as ring-constituting atoms in addition to carbon. Further, the "heteroaryl ring" corresponds to the "R" defined in the general formula (2)¹～R¹¹The adjacent groups in (1) are bonded to each other and form a heteroaryl ring together with the a-ring, the b-ring or the c-ring ", andsince the a ring (or b ring, c ring) already contains a benzene ring having 6 carbon atoms, the total number of carbon atoms of the condensed rings in which the 5-membered ring is condensed is the lower limit of carbon atoms.

Specific examples of the "heteroaryl ring" include: a pyrrole ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, an imidazole ring, an oxadiazole ring, a thiadiazole ring, a triazole ring, a tetrazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, a triazine ring, an indole ring, an isoindole ring, a 1H-indazole ring, a benzimidazole ring, a benzoxazole ring, a benzothiazole ring, a 1H-benzotriazole ring, a quinoline ring, an isoquinoline ring, a cinnoline (cinnoline) ring, a quinazoline ring, a quinoxaline ring, a phthalazine ring, a naphthyridine ring, a purine ring, a pteridine ring, a carbazole ring, an acridine ring, a phenoxazine ring, a phenothiazine ring, a indolizine ring, a furan ring, a benzofuran ring, an isobenzofuran ring, a dibenzofuran ring, a benzothiophene ring, a dibenzothiophene ring, a furazan ring, an oxadiazole ring, an anthracene ring, and the like.

At least one of the "aryl ring" or "heteroaryl ring" may be substituted with a substituted or unsubstituted "aryl", a substituted or unsubstituted "heteroaryl", a substituted or unsubstituted "diarylamino", a substituted or unsubstituted "diheteroarylamino", a substituted or unsubstituted "arylheteroarylamino", a substituted or unsubstituted "diarylboryl" (two aryl groups may be bonded via a single bond or a linking group), a substituted or unsubstituted "alkyl", a substituted or unsubstituted "cycloalkyl", a substituted or unsubstituted "alkoxy", or a substituted or unsubstituted "aryloxy" as a first substituent, an aryl group or a "heteroaryl", "diarylamino" or a "diheteroarylamino" as a first substituent, The aryl and heteroaryl groups of the "arylheteroarylamino group", the aryl group of the "diarylboryl group", and the aryl group of the "aryloxy group" may be exemplified by the monovalent radicals of the "aryl ring" or the "heteroaryl ring".

The "alkyl group" as the first substituent may be either a straight chain or branched chain, and examples thereof include a straight chain alkyl group having 1 to 24 carbon atoms and a branched chain alkyl group having 3 to 24 carbon atoms. Preferably an alkyl group having 1 to 18 carbon atoms (branched chain alkyl group having 3 to 18 carbon atoms), more preferably an alkyl group having 1 to 12 carbon atoms (branched chain alkyl group having 3 to 12 carbon atoms), still more preferably an alkyl group having 1 to 6 carbon atoms (branched chain alkyl group having 3 to 6 carbon atoms), and particularly preferably an alkyl group having 1 to 4 carbon atoms (branched chain alkyl group having 3 to 4 carbon atoms).

Specific examples of the alkyl group include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, 1-methylpentyl, 4-methyl-2-pentyl, 3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, t-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2-dimethylheptyl, 2, 6-dimethyl-4-heptyl, 3,5, 5-trimethylhexyl, n-decyl, n-undecyl, 1-methyldecyl, n-dodecyl, n-tridecyl, 1-hexylheptyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-eicosyl and the like.

In addition, "cycloalkyl" as the first substituent may be exemplified by: a cycloalkyl group having 3 to 24 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 16 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, a cycloalkyl group having 5 carbon atoms, and the like.

As specific cycloalkyl groups, there may be mentioned: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, and substituents of these groups having 1 to 4 carbon atoms of an alkyl group (particularly methyl), norbornenyl, bicyclo [1.0.1] butyl, bicyclo [1.1.1] pentyl, bicyclo [2.0.1] pentyl, bicyclo [1.2.1] hexyl, bicyclo [3.0.1] hexyl, bicyclo [2.1.2] heptyl, bicyclo [2.2.2] octyl, adamantyl, diamantanyl, decahydronaphthyl (decahydronaphthyl), decahydroazulenyl (decahydroazulenyl), and the like.

Examples of the "alkoxy" as the first substituent include: a linear alkoxy group having 1 to 24 carbon atoms or a branched alkoxy group having 3 to 24 carbon atoms. The alkoxy group is preferably an alkoxy group having 1 to 18 carbon atoms (an alkoxy group having 3 to 18 carbon atoms in a branched chain), more preferably an alkoxy group having 1 to 12 carbon atoms (an alkoxy group having 3 to 12 carbon atoms in a branched chain), yet more preferably an alkoxy group having 1 to 6 carbon atoms (an alkoxy group having 3 to 6 carbon atoms in a branched chain), and particularly preferably an alkoxy group having 1 to 4 carbon atoms (an alkoxy group having 3 to 4 carbon atoms in a branched chain).

Specific examples of the alkoxy group include: methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy and the like.

In addition, as the "aryl group" in the "diarylboron group" of the first substituent, a description of the aryl group can be cited. In addition, the two aryl groups may be linked via a single bond or a linking group (e.g.>C(-R)₂、>O、>S or>N-R) is bonded. Here, the number of the first and second electrodes,>C(-R)₂and>r of N-R is an aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, alkoxy, or aryloxy group (the above is the first substituent), and the first substituent may be further substituted with an aryl, heteroaryl, alkyl, or cycloalkyl group (the above is the second substituent), and as specific examples of these groups, the description of the aryl, heteroaryl, diarylamino, alkyl, cycloalkyl, alkoxy, or aryloxy group as the first substituent may be cited.

Specifically, the emission wavelength can be adjusted by the steric hindrance, electron donating property, and electron withdrawing property of the structure of the first substituent, and is preferably a group represented by any one of the following structural formulae (S-1) to (S-94), more preferably a group represented by any one of the following formulae (S-1), (S-2), (S-5), (S-9) to (S-19), (S-24) to (S-50), and (S-51) to (S-94), and still more preferably any one of the formulae (S-1), (S-2), (S-5), (S-9), (S-10), (S-15), (S-16), (S-24), (S-30), and (S-30), A group represented by any one of the formulae (S-46), (S-48), (S-50), (S-51), (S-56) to (S-58), (S-70), (S-71), (S-73), (S-74), (S-76), (S-79), (S-80), (S-83) and (S-84).

In the following structural formula, "Me" represents a methyl group and "tBu" represents a tert-butyl group.

[ solution 12]

-Me -tBu

(S-1) (S-2)

[ solution 13]

[ solution 14]

[ solution 15]

[ solution 16]

A substituted or unsubstituted "aryl", a substituted or unsubstituted "heteroaryl", a substituted or unsubstituted "diarylamino", a substituted or unsubstituted "diheteroarylamino", a substituted or unsubstituted "arylheteroarylamino", a substituted or unsubstituted "diarylboryl (two aryl groups may be bonded via a single bond or a linking group)", a substituted or unsubstituted "alkyl", a substituted or unsubstituted "cycloalkyl", a substituted or unsubstituted "alkoxy", or a substituted or unsubstituted "aryloxy" as specified as substituted or unsubstituted, at least one of which may be substituted by a second substituent. As the second substituent, for example, an aryl group, a heteroaryl group, an alkyl group or a cycloalkyl group can be cited, and specific substituents thereof can be described with reference to the monovalent group of the "aryl ring" or the "heteroaryl ring" and the "alkyl group" or the "cycloalkyl group" as the first substituent. Among the aryl or heteroaryl groups as the second substituent, those wherein at least one hydrogen is substituted with an aryl group such as a phenyl group (specifically, the above-mentioned group), an alkyl group such as a methyl group (specifically, the above-mentioned group), or a cycloalkyl group such as a cyclohexyl group (specifically, the above-mentioned group) are also included in the aryl or heteroaryl groups as the second substituent. For example, when the second substituent is a carbazolyl group, a carbazolyl group in which at least one hydrogen at the 9-position is substituted with an aryl group such as a phenyl group, an alkyl group such as a methyl group, or a cycloalkyl group such as a cyclohexyl group is also included in the heteroaryl group as the second substituent.

R as formula (2)¹～R¹¹The aryl, heteroaryl, diarylamino aryl, diheteroarylamino heteroaryl, arylheteroarylamino aryl and heteroaryl, diarylboron aryl, or aryloxy aryl in (1) may be exemplified by a monovalent group of the "aryl ring" or "heteroaryl ring" as illustrated in the general formula (1). In addition, as R¹～R¹¹The alkyl group, cycloalkyl group or alkoxy group in (1) can be referred to the description of the "alkyl group", "cycloalkyl group" or "alkoxy group" as the first substituent in the description of the general formula (1). Further, aryl, heteroaryl, alkyl or cycloalkyl groups as substituents for these groups are also the same. In addition, as R¹～R¹¹The heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl, alkyl, cycloalkyl, alkoxy, or aryloxy groups as substituents for the rings when adjacent groups in (a) are bonded to each other and form an aryl ring or heteroaryl ring together with the a-ring, b-ring, or c-ring, and aryl, heteroaryl, alkyl, or cycloalkyl groups as further substituents are also the same.

Y of the formula (1)¹In the above-mentioned examples, the R of Si-R and Ge-R is an aryl group, an alkyl group or a cycloalkyl group, and the aryl group, the alkyl group or the cycloalkyl group may be the same as those mentioned above. Particularly preferably aryl group having 6 to 10 carbon atoms (e.g., phenyl group, naphthyl group, etc.) or aryl group having 1 to 4 carbon atomsAn alkyl group (e.g., methyl group, ethyl group, etc.) or a cycloalkyl group having 5 to 10 carbon atoms (preferably a cyclohexyl group or adamantyl group). The same applies to Y in the formula (2)¹。

X of the general formula (1)¹And X²R of N-R in (a) is aryl, heteroaryl, alkyl or cycloalkyl which may be substituted by said second substituent, at least one hydrogen in aryl or heteroaryl may for example be substituted by alkyl or cycloalkyl. As the aryl, heteroaryl, alkyl and cycloalkyl groups, the groups described above can be exemplified. Particularly preferred is an aryl group having 6 to 10 carbon atoms (e.g., phenyl group, naphthyl group, etc.), a heteroaryl group having 2 to 15 carbon atoms (e.g., carbazolyl group, etc.), an alkyl group having 1 to 4 carbon atoms (e.g., methyl group, ethyl group, etc.), or a cycloalkyl group having 5 to 10 carbon atoms (preferably cyclohexyl group or adamantyl group). The same applies to X in the formula (2)¹And X²。

-C (-R) as a linking group in the general formula (1)₂R of the above-mentioned group is hydrogen, an alkyl group or a cycloalkyl group, and the alkyl group and the cycloalkyl group may be the same groups as those mentioned above. Particularly preferably an alkyl group having 1 to 4 carbon atoms (e.g., methyl group, ethyl group, etc.) or a cycloalkyl group having 5 to 10 carbon atoms (preferably cyclohexyl group or adamantyl group). The same applies to "-C (-R) as the linking group in the general formula (2)₂-”。

The present invention is directed to a polymer of a polycyclic aromatic compound having a plurality of unit structures represented by general formula (1), preferably a polymer of a polycyclic aromatic compound having a plurality of unit structures represented by general formula (2). The multimer is preferably a dimer to a hexamer, more preferably a dimer to a trimer, and particularly preferably a dimer. The polymer may be in the form of a single compound having a plurality of the unit structures, and may be in the form of a single bond, a linkage group such as alkylene having 1 to 3 carbon atoms, phenylene, or naphthylene, or in the form of a plurality of unit structures bonded together (a linked polymer), or in the form of a plurality of unit structures sharing any of rings (a, B, or C, a, B, or C) contained in the unit structures (a ring-shared polymer), or in the form of a plurality of unit structures bonded together such that any of rings (a, B, or C, a, B, or C) contained in the unit structures are condensed together (ring-condensed polymer).

Examples of such multimers include multimer compounds represented by the following formula (2-4), formula (2-4-1), formula (2-4-2), formula (2-5-1) to formula (2-5-4), or formula (2-6). When the general formula (2) is used for explanation, the multimeric compound represented by the following formula (2-4) is a multimeric compound (ring-shared multimer) having a plurality of unit structures represented by the general formula (2) in one compound so as to share a benzene ring as an a-ring. In addition, the general formula (2) is described, the multimeric compound represented by the following formula (2-4-1) is a multimeric compound having two unit structures represented by the general formula (2) in one compound (ring-shared multimeric compound) so that a benzene ring as an a ring is shared. In addition, the polymer compound represented by the following formula (2-4-2) is a polymer compound having three unit structures represented by the general formula (2) in one compound (ring-shared polymer) so that benzene rings as a ring are shared. In addition, the polymer compound represented by the following formula (2-5-1) to formula (2-5-4) is a polymer compound (ring-shared polymer) having a plurality of unit structures represented by the general formula (2) in one compound so as to share a benzene ring as a b-ring (or c-ring). In addition, when the general formula (2) is described, the multimeric compound represented by the following formula (2-6) is, for example, a multimeric compound having a plurality of unit structures represented by the general formula (2) in one compound (ring condensation type multimeric compound) such that a benzene ring of a b-ring (or a-ring, c-ring) as a certain unit structure is condensed with a benzene ring of a b-ring (or a-ring, c-ring) as a certain unit structure.

[ solution 17]

The polymer compound may be a polymer in which the polymerization form expressed by the formula (2-4), the formula (2-4-1) or the formula (2-4-2) is combined with any one of the formulae (2-5-1) to (2-5-4) or the formula (2-6), may be a polymer in which the polymerization form expressed by any one of the formulae (2-5-1) to (2-5-4) is combined with the polymerization form expressed by the formula (2-6), or may be a polymer in which the polymerization form expressed by the formula (2-4), the formula (2-4-1) or the formula (2-4-2) is combined with any one of the formulae (2-5-1) to (2-5-4), and a multimer in which the multimerization patterns represented by the formulae (2-6) are combined.

In addition, all or a part of hydrogen in the chemical structure of the polycyclic aromatic compound represented by the general formula (1) or the general formula (2) and the multimer thereof may be cyano, chlorine, bromine, iodine or deuterium. For example, in formula (1), ring A, ring B, ring C (ring A to ring C are aryl or heteroaryl rings), substituents for ring A to ring C, Y¹R (═ alkyl, cycloalkyl, aryl) when Si-R or Ge-R is used, and X¹And X²In the case of N — R, hydrogen in R (═ alkyl, cycloalkyl, and aryl) may be substituted with cyano, chlorine, bromine, iodine, or deuterium, and among these, there may be mentioned a form in which all or a part of hydrogen in aryl or heteroaryl is substituted with cyano, chlorine, bromine, iodine, or deuterium. Among chlorine, bromine or iodine, chlorine or bromine is preferred, and chlorine is more preferred.

The polycyclic aromatic compound and multimers thereof of the present invention can be used as materials for organic devices. Examples of the organic device include: organic electroluminescent devices, organic field effect transistors, organic thin film solar cells, and the like. In particular, in the organic electroluminescent element, Y is preferable as a dopant material of the light-emitting layer¹Is B, X¹And X²A compound of formula N-R, Y¹Is B, X¹Is O, X²A compound of formula N-R, Y¹Is B, X¹And X²A compound of O, preferably Y as a host material of the light-emitting layer¹Is B, X¹Is O, X²A compound of formula N-R, Y¹Is B, X¹And X²A compound of O, as an electron transport material, Y can be preferably used¹Is B, X¹And X²Is a compound of OSubstance, Y¹Is P O, X¹And X²A compound which is O.

In addition, at least one hydrogen in the chemical structures of the polycyclic aromatic compound represented by the general formula (1) or the general formula (2) and the multimer thereof has been substituted with fluorine, and all or a part of hydrogen may be fluorine.

Examples of the fluorine substitution include a substitution of fluorine directly on the ring A to the ring C of the formula (1), and a substitution of fluorine with R of the formula (2)¹～R¹¹In addition to the form in which hydrogen is substituted with fluorine, at least one of hydrogen of aryl, heteroaryl (particularly carbazolyl or benzocarbazolyl), diarylamino, diheteroarylamino, arylheteroarylamino, diarylboron (two aryl groups may be bonded via a single bond or a linking group), alkyl, cycloalkyl, alkoxy, or aryloxy, or at least one of hydrogen of aryl, heteroaryl, alkyl, or cycloalkyl, which is the second substituent, may be substituted with fluorine as the first substituent. In addition, at least one of hydrogen in an aryl group, a heteroaryl group, an alkyl group, or a cycloalkyl group (the above is the first substituent) as R of N — R, or a substituent (the second substituent) for these groups may be substituted with fluorine. Furthermore, pentafluoromercapto (-SF) group can be also exemplified₅) And the like.

Examples of other fluorine-substituted forms include: examples of the polycyclic aromatic compound represented by the general formula (1) or the general formula (2) and multimers thereof include those substituted with a fluorine-substituted aryl group, a fluorine-substituted alkyl or cycloalkyl group, a fluorine-substituted alkoxy group, a fluorine-substituted diarylamino group, a fluorine-substituted diarylboron group (two aryl groups may be bonded via a single bond or a linking group), a fluorine-substituted carbazolyl group, or a fluorine-substituted benzocarbazolyl group. As the "aryl group", "alkyl group", "cycloalkyl group", "alkoxy group", "diarylamino group", and "diarylboron group", the groups described as the "first substituent" can be cited. Examples of the substitution pattern of fluorine for diarylamino groups, diarylboron groups, carbazolyl groups, and benzocarbazolyl groups include: examples of these groups in which a part or all of the hydrogens of the aryl ring or benzene ring are replaced with fluorine. X in the general formula (1) or the general formula (2) is preferable¹And X²Is N-R, and said R is an aryl group substituted with fluorine (in particular, a phenyl group substituted with fluorine), and further, an aryl group which is preferably a diarylamino group as the first substituent or the second substituent is an aryl group substituted with fluorine (in particular, a phenyl group substituted with fluorine), more preferably X¹And X²Is N-R, and said R is aryl substituted by fluorine (in particular phenyl substituted by fluorine).

The "aryl group substituted with fluorine" includes a group in which at least one of the hydrogens of the aryl group is substituted with fluorine, and specifically includes a group represented by any one of the following structural formulae (S-100) to (S-110). Among these, a group represented by any one of the formulae (S-100) to (S-107) is preferable, and a group represented by any one of the formulae (S-100), (S-103), (S-104) and (S-105) is more preferable. The description also applies to the case where fluorine is substituted at the aryl site of a "diarylamino", "arylheteroarylamino", "diarylboron group", or "aryloxy".

[ solution 18]

The "alkyl group substituted with fluorine" includes a group in which at least one of hydrogen atoms of the alkyl group is substituted with fluorine, and specifically includes a trifluoromethyl group, a difluoromethyl group, a monofluoromethyl group, a pentafluoroethyl group, and the like, and preferably a trifluoromethyl group. The above description applies also to the case where fluorine is substituted at the alkyl portion of "alkoxy (alkyloxy)". In addition, as the "cycloalkyl group" substituted with fluorine, at least one group substituted with fluorine of hydrogen of the cycloalkyl group can be mentioned.

Further, as more specific examples, there are: r of polycyclic aromatic compound represented by general formula (2) and multimer thereof²Examples of the group are a diarylamino group substituted with fluorine, a diarylboron group substituted with fluorine (two aryl groups may be bonded via a single bond or a linking group), or a carbazolyl group substituted with fluorine.

Examples thereof include: a polycyclic aromatic compound represented by the following general formula (2-A), or a polymer of a polycyclic aromatic compound having a plurality of structures represented by the following general formula (2-A). The symbols in the structural formula are as defined as those in the general formula (2).

[ solution 19]

Specific examples of the fluorine-substituted polycyclic aromatic compound and the multimer thereof of the present invention include compounds in which at least one hydrogen in 1 or more aromatic rings in the compound is substituted by 1 or more fluorine, and for example, compounds substituted by 1 to 2 fluorine.

Specifically, compounds represented by the following structural formula are exemplified. N in the following structural formula is 0 to 2, preferably 1, independently. In the following structural formulae, "F" represents fluorine, "OPh" represents phenoxy, and "Me" represents methyl.

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More specific examples of the fluorine-substituted polycyclic aromatic compound of the present invention include compounds represented by the following structural formulae. In the following structural formulae, "F" represents fluorine, "D" represents deuterium, "Me" represents methyl, "Et" represents ethyl, and "tBu" represents tert-butyl.

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2. Method for producing fluorine-substituted polycyclic aromatic compound and multimer thereof

Regarding the polycyclic aromatic compound represented by the general formula (1) or the general formula (2) and the multimer thereof, basically, the bonding group (including X) is first used¹Or X²A group of (B) and (C) rings) to bond the a ring (a ring) with the B ring (B ring) and the C ring (C ring), thereby producing an intermediate (first reaction), after which a bonding group (including Y) is utilized¹Group (B) bonds the a ring (a ring), the B ring (B ring), and the C ring (C ring), thereby producing a final product (second reaction). In the first Reaction, for example, in the case of etherification, a nucleophilic substitution Reaction, Ullmann Reaction (Ullmann Reaction) or the like can be used, and in the case of amination, a Buchwald-Hartwig Reaction (Buchwald-Hartwig Reaction) or the like can be used. In the second Reaction, a Tandem Hetero-Friedel-Crafts Reaction (a successive aromatic electrophilic substitution Reaction, which will be described below) can be used. Further, the compound of the present invention, which is fluorinated at a desired position, can be produced by using a fluorinated starting material or a step of introducing an additional fluorinated or fluorine-containing substituent at some of these reaction steps.

The second reaction is to bond Y to the A ring (ring a), B ring (ring B) and C ring (ring C) as shown in the following scheme (1) or scheme (2)¹The reaction of introduction is, for example, Y shown below¹Is a boron atom, X¹And X²In the case of an oxygen atom. First of all, the first step is to,using n-butyllithium, sec-butyllithium, tert-butyllithium or the like as the X¹And X²The hydrogen atoms in between undergo ortho-metallation. Then, after metal exchange of lithium-boron by adding boron trichloride, boron tribromide or the like, a Bronsted base (e.g., N-diisopropylethylamine) is added to carry out a Tandem borohybrid-quart Reaction (Tandem Bora-Friedel-Crafts Reaction), and the target compound can be obtained. In the second reaction, a Lewis acid (Lewis acid) such as aluminum trichloride may be added to accelerate the reaction. The symbols of the structural formulae in the following schemes (1) and (2), and in the following schemes (3) to (28) are defined as the same as the above.

[ solution 217]

Flow (1)

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Flow (2)

The above-mentioned scheme (1) or scheme (2) mainly represents a method for producing a polycyclic aromatic compound represented by the general formula (1) or general formula (2), but the multimer thereof can be produced by using an intermediate having a plurality of rings a, B and C. More specifically, the following schemes (3) to (5) are explained. In this case, the amount of the reagent such as butyllithium used is 2 times or 3 times the amount of the reagent, whereby the target product can be obtained.

[ solution 219]

Flow (3)

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Flow (4)

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Flow (5)

In the above-mentioned schemes, lithium is introduced to a desired position by ortho-metalation, but it is also possible to introduce lithium to a desired position by halogen-metal exchange by introducing a bromine atom or the like to a position to which lithium is to be introduced as in the following schemes (6) and (7).

[ solution 222]

Flow (6)

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Flow (7)

In addition, as for the scheme (3) described in the method for producing multimers, in the above-mentioned scheme (6) and (7), in order to introduce lithium into the position to be introduced, a halogen such as a bromine atom or a chlorine atom may be introduced, and lithium may also be introduced into a desired position by halogen-metal exchange (the following scheme (8), scheme (9) and scheme (10)).

[ 224]

Flow (8)

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Flow (9)

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Flow (10)

According to the method, the target compound can be synthesized even when ortho-metalation cannot be performed due to the influence of the substituent, and thus the method is useful.

By appropriately selecting the synthesis method and the raw materials used, it is possible to synthesize a compound in which a desired position is fluorinated, a substituent is present at a desired position, and Y¹Is a boron atom, X¹And X²Polycyclic aromatic compounds which are oxygen atoms and polymers thereof.

Then, Y is put¹Is a boron atom, X¹And X²The case of a nitrogen atom is shown as an example in the following schemes (11) and (12). And X¹And X²Similarly in the case of an oxygen atom, first, X is treated with n-butyllithium or the like¹And X²The hydrogen atoms in between undergo ortho-metallation. Subsequently, boron tribromide or the like is added to perform metal exchange of lithium-boron, and then a bransted base such as N, N-diisopropylethylamine or the like is added to perform a tandem borohybrid reed-quart reaction, whereby the target product can be obtained. Here, in order to accelerate the reaction, lewis acid such as aluminum trichloride may be added. Further, as shown in the following scheme (12'), when the reaction is carried out at a high temperature of about 200 ℃, the target compound can be obtained by using only boron tribromide. Further, the compound of the present invention, which is fluorinated at a desired position, can be produced by using a fluorinated starting material or a step of introducing an additional fluorinated or fluorine-containing substituent at some of these reaction steps.

[ formulation 227]

Flow (11)

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Flow (12)

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Flow (12')

In addition, regarding Y¹Is a boron atom, X¹And X²In the case of a nitrogen atom, a halogen such as a bromine atom or a chlorine atom may be introduced into a position to be introduced with lithium as in the above-mentioned schemes (6) and (7), and lithium may be introduced into a desired position by halogen-metal exchange (the following schemes (13), (14) and (15)). Further, as shown in the following scheme (13'), Y can be synthesized using boron triiodide and triphenylborane without using halogen-metal exchange¹Is a boron atom, X¹And X²Multimers in the case of nitrogen atoms.

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Flow (13)

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Flow (14)

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Flow (15)

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Flow (13')

Then, Y is put¹Is phosphorus sulfide, phosphorus oxide or phosphorus atom, X¹And X²The case of oxygen atoms is shown as an example in the following schemes (16) to (19). As in the conventional case, X is first paired with n-butyllithium or the like¹And X²The hydrogen atoms in between undergo ortho-metallation. Then, phosphorus trichloride and sulfur are sequentially added, and finally Lewis acid such as aluminum trichloride and Bronsted base such as N, N-diisopropylethylamine are added to carry out Tandem phosphafloat-quart Reaction (Tandem Phosphas-Friedel-Crafts Reaction), thereby obtaining Y¹Is a compound of phosphorus sulfide. Y can be obtained by treating the obtained phosphorus sulfide compound with m-chloroperbenzoic acid (m-CPBA)¹Y is obtained by treatment with triethylphosphine as a phosphorus oxide compound¹Is a compound of phosphorus atom. Further, the compound of the present invention, which is fluorinated at a desired position, can be produced by using a fluorinated starting material or a step of introducing an additional fluorinated or fluorine-containing substituent at some of these reaction steps.

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Flow (16)

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Flow (17)

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Flow (18)

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Flow path (19)

In addition, regarding Y¹Is phosphorus sulfide, X¹And X²In the case of oxygen atom, a halogen such as bromine atom or chlorine atom may be introduced into a position to be introduced with lithium as in the above-mentioned schemes (6) and (7), and lithium may be introduced into a desired position by halogen-metal exchange (the following schemes (20), (21) and (22)). In addition, Y formed in the manner described¹Is phosphorus sulfide, X¹And X²When the polymer is an oxygen atom, Y can be obtained by treating with m-chloroperbenzoic acid (m-CPBA) as in the above-mentioned schemes (18) and (19)¹Y is obtained by treatment with triethylphosphine as a phosphorus oxide compound¹Is a compound of phosphorus atom.

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Flow (20)

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Flow (21)

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Flow (22)

Here, Y is described¹Is B, P, P ═ O or P ═ S, X¹And X²Examples of O and NR, but Y can also be synthesized by appropriately changing the starting material¹Is Al, Ga, As, Si-R or Ge-R, or X¹And X²A compound which is S.

In the above-mentioned flow, examples of the step for producing the target product using a halogen-metal exchange or coupling reaction are given. The halogen also includes a fluorine atom, but generally a carbon-fluorine bond is extremely inert, and thus in the case of using fluorine as the halogen, a halogen-metal exchange or coupling reaction does not generally occur. Therefore, in most cases, even if fluorine atoms coexist, the reaction proceeds selectively at the positions of chlorine, bromine, or iodine, and therefore, even if a raw material containing fluorine atoms is used, the progress of the reaction is not inhibited, and the compound of the present invention in which a desired position is fluorinated can be produced.

Further, there may be used an alkyl group substituted not only with a fluorine atom but also with a fluorine atom, a fluorine-substituted aryl group, a fluorine-substituted heteroaryl group, a fluorine-substituted aryloxy group or a pentafluoromercapto group (-SF)₅) And the like, or a step of introducing these functional groups, thereby producing the compound of the present invention fluorinated at a desired position.

Specific examples of the solvent used in the above reaction include tert-butyl benzene, xylene, and the like.

In the general formula (2), the substituent R for the ring a, ring b and ring c¹～R¹¹May be bonded to each other and form, together with the a-ring, b-ring or c-ring, an aryl or heteroaryl ring, at least one hydrogen in the formed ring being substitutable by aryl or heteroaryl. Therefore, the polycyclic aromatic compound represented by the general formula (2) has a structure of a ring constituting the compound changed as shown in the following formulae (2-1) and (2-2) in the formulae (23) and (24) depending on the bonding form among the substituents in the a-ring, the b-ring, and the c-ring. These compounds can be synthesized by applying the synthesis methods shown in the above-mentioned schemes (1) to (19) to intermediates shown in the following schemes (23) and (24). In addition, in these reaction stepsThe compound of the present invention fluorinated at a desired position can be produced by using a fluorinated starting material or by adding a step of introducing a fluorinated or fluorine-containing substituent.

[ solution 241]

Flow path (23)

[ solution 242]

Flow (24)

The A ' ring, B ' ring and C ' ring in the formula (2-1) and the formula (2-2) represent a substituent R¹～R¹¹An aryl ring or a heteroaryl ring (which may also be referred to as a condensed ring in which other ring structures are condensed in the a-ring, the b-ring, or the c-ring) formed together with the a-ring, the b-ring, and the c-ring, respectively. Although not shown in the formula, there are also compounds in which all of the a, B and C rings are changed to a ' ring, B ' ring and C ' ring.

In addition, "R of N-R in the general formula (2) is represented by-O-, -S-, -C (-R)₂The definition of-or a single bond to the a-ring, the b-ring and/or the c-ring "may be represented by a compound represented by formula (2-3-1) of the following scheme (25) and having X¹Or X²A ring structure introduced into the condensed rings B 'and C', or a ring structure represented by the formula (2-3-2) or (2-3-3) and having X¹Or X²The ring structure introduced into the condensed ring A'. These compounds can be synthesized by applying the synthesis methods shown in the above-mentioned schemes (1) to (19) to intermediates shown in the following scheme (25). Further, the compound of the present invention, which is fluorinated at a desired position, can be produced by using a fluorinated starting material or a step of introducing an additional fluorinated or fluorine-containing substituent at some of these reaction steps.

[ solution 243]

Flow path (25)

In the synthetic methods of the above-mentioned schemes (1) to (17) and (20) to (25), it is shown that X is treated with butyl lithium or the like before adding boron trichloride, boron tribromide or the like¹And X²While the tandem heterofriedel-quardt reaction is performed by ortho-metalation of the hydrogen atom (or halogen atom) therebetween, the reaction may be performed by adding boron trichloride, boron tribromide or the like without performing ortho-metalation using butyllithium or the like.

In addition, in Y¹In the case of phosphorus-based compounds, X is treated with n-butyllithium, sec-butyllithium, tert-butyllithium or the like as shown in the following scheme (26) or (27)¹And X²The target compound can be obtained by subjecting hydrogen atoms between (O in the following formula) to ortho-metalation, then adding bis-diethylaminochlorophosphine to perform metal exchange of lithium-phosphorus, and then adding a Lewis acid such as aluminum trichloride to perform a tandem phosphafldor-quart reaction. The reaction method is also described in International publication No. 2010/104047 (e.g., page 27). Further, the compound of the present invention, which is fluorinated at a desired position, can be produced by using a fluorinated starting material or a step of introducing an additional fluorinated or fluorine-containing substituent at some of these reaction steps.

[ chemical 244]

Flow path (26)

[ chemical 245]

Flow path (27)

In the above-mentioned scheme (26) or scheme (27), a multimeric compound can also be synthesized by using 2-fold or 3-fold molar amount of an ortho-metallation reagent such as butyllithium relative to the molar amount of intermediate 1. Further, a halogen such as a bromine atom or a chlorine atom is introduced in advance to a position where a metal such as lithium is to be introduced, and halogen-metal exchange is performed, whereby the metal can be introduced to a desired position.

Further, the polycyclic aromatic compound represented by the general formula (2-a) can be synthesized by synthesizing a fluorinated intermediate and cyclizing the intermediate as in the following scheme (28), thereby synthesizing a polycyclic aromatic compound in which a desired position is substituted with a fluorine atom. In the scheme (28), X represents halogen or hydrogen, and the other symbols are as defined in the general formula (2).

[ solution 246]

Flow (28)

Flow (28)

The intermediate before cyclization in the scheme (28) can also be synthesized by the method shown in the scheme (1) and the like. That is, an intermediate having a desired substituent can be synthesized by appropriately combining a buhward-hartwight reaction, a suzuki coupling reaction, an etherification reaction by a nucleophilic substitution reaction, an ullmann reaction, or the like. In these reactions, commercially available raw materials that become fluorinated precursors can also be used.

The compound of the general formula (2-A) having a fluorinated diphenylamino group can also be synthesized, for example, by the following method. That is, fluorinated diphenylamino group is introduced into commercially available bromopentafluorophenyl benzene and trihalogenated aniline by amination such as Buhward-Hartvich reaction, and then X¹、X²In the case of N-R, an amination reaction such as the Buhward-Hartvich reaction is usedShould be derivatized as intermediate (M-3) at X¹、X²In the case of O, the compound of the general formula (2-a) can be synthesized by an intermediate (M-3) derived by etherification with phenol, followed by a tandem boraodel-quardt reaction in which a metallating agent such as butyl lithium is reacted to perform trans-metallation, a boron halide such as boron tribromide is reacted, and a bronsted base such as diethyl isopropylamine is reacted. These reactions can also be applied to other fluorinated compounds.

The ortho-metallation reagent used in the above-mentioned schemes (1) to (28) includes: alkyllithium such as methyllithium, n-butyllithium, sec-butyllithium and tert-butyllithium, and organic basic compounds such as lithium diisopropylamide, lithium tetramethylpiperidide, lithium hexamethyldisilazide and potassium hexamethyldisilazide.

Further, as the metal-Y used in the above-mentioned flows (1) to (28)¹The metal exchange reagent of (2) includes: y is¹Of (b) a trifluoride, Y¹Trichloride of (a) and Y¹Tribromide of (5), Y¹Y being triiodide or the like¹Halide of (4), CIPN (NEt)₂)₂Equal Y¹Of an aminated halide of, Y¹Alkoxylates of (2), Y¹Aryloxy compounds of (a) and the like.

Examples of the bronsted base used in the above-mentioned schemes (1) to (28) include: n, N-diisopropylethylamine, triethylamine, 2,2,6, 6-tetramethylpiperidine, 1,2,2,6, 6-pentamethylpiperidine, N-dimethylaniline, N-dimethyltoluidine, 2, 6-lutidine, sodium tetraphenylborate, potassium tetraphenylborate, triphenylborane, tetraphenylsilane, Ar, N-diisopropylethylamine, N-tetramethylpiperidine, N-dimethyltoluidine, N-dimethylpyridine, N-tetramethylpiperidine, N-dimethylpiperidine, N-dimethylpiperidine₄BNa、Ar₄BK、Ar₃B、Ar₄Si (Ar is an aryl group such as phenyl) and the like.

The lewis acid used in the above-mentioned schemes (1) to (28) includes: AlCl₃、AlBr₃、AlF₃、BF₃·OEt₂、BCl₃、BBr₃、GaCl₃、GaBr₃、InCl₃、InBr₃、In(OTf)₃、SnCl₄、SnBr₄、AgOTf、ScCl₃、Sc(OTf)₃、ZnCl₂、ZnBr₂、Zn(OTf)₂、MgCl₂、MgBr₂、Mg(OTf)₂、LiOTf、NaOTf、KOTf、Me₃SiOTf、Cu(OTf)₂、CuCl₂、YCl₃、Y(OTf)₃、TiCl₄、TiBr₄、ZrCl₄、ZrBr₄、FeCl₃、FeBr₃、CoCl₃、CoBr₃And the like.

In the above-mentioned schemes (1) to (28), in order to promote the tandem type heterolydrol-quart reaction, a bronsted base or a lewis acid may be used. Wherein, Y is used¹Of (b) a trifluoride, Y¹Trichloride of (a) and Y¹Tribromide of (5), Y¹Y being triiodide or the like¹In the case of the halide of (3), an acid such as hydrogen fluoride, hydrogen chloride, hydrogen bromide, or hydrogen iodide is generated as the aromatic electrophilic substitution reaction proceeds, and therefore, it is effective to use a Bronsted base which traps an acid. On the other hand, in the use of Y¹Of an aminated halide of, Y¹In the case of the alkoxylate (b), since an amine or an alcohol is produced as the aromatic electrophilic substitution reaction proceeds, it is not necessary to use a bronsted base in many cases, but since the ability to remove an amino group or an alkoxy group is low, it is effective to use a lewis acid for accelerating the removal thereof.

The polycyclic aromatic compound or multimer thereof of the present invention also includes a structure in which at least a part of hydrogen atoms is substituted with a cyano group, a structure in which at least a part of hydrogen atoms is substituted with a halogen such as chlorine, bromine, or iodine, or a structure in which hydrogen atoms is substituted with deuterium, and such a compound or the like can be synthesized in the same manner as described above by using a raw material in which a desired position is cyanated, chlorinated, brominated, iodinated, or deuterated.

3. Organic device

The fluorine-substituted polycyclic aromatic compound of the present invention is useful as a material for an organic device. Examples of the organic device include: organic electroluminescent devices, organic field effect transistors, organic thin film solar cells, and the like.

3-1. organic electroluminescent element

Hereinafter, the organic EL device of the present embodiment will be described in detail with reference to the drawings. Fig. 1 is a schematic sectional view showing an organic EL element according to the present embodiment.

< Structure of organic electroluminescent element >

The organic EL element 100 shown in fig. 1 includes: the light-emitting device comprises a substrate 101, an anode 102 disposed on the substrate 101, a hole injection layer 103 disposed on the anode 102, a hole transport layer 104 disposed on the hole injection layer 103, a light-emitting layer 105 disposed on the hole transport layer 104, an electron transport layer 106 disposed on the light-emitting layer 105, an electron injection layer 107 disposed on the electron transport layer 106, and a cathode 108 disposed on the electron injection layer 107.

The organic EL element 100 may have a structure in which the order of production is reversed, for example, the structure including: the organic light emitting diode comprises a substrate 101, a cathode 108 arranged on the substrate 101, an electron injection layer 107 arranged on the cathode 108, an electron transport layer 106 arranged on the electron injection layer 107, a light emitting layer 105 arranged on the electron transport layer 106, a hole transport layer 104 arranged on the light emitting layer 105, a hole injection layer 103 arranged on the hole transport layer 104, and an anode 102 arranged on the hole injection layer 103.

The minimum structural unit is a structure including the anode 102, the light-emitting layer 105, and the cathode 108, and the hole injection layer 103, the hole transport layer 104, the electron transport layer 106, and the electron injection layer 107 are arbitrarily provided. In addition, each of the layers may include a single layer, or may include a plurality of layers.

The form of the layer constituting the organic EL element may be, in addition to the form of the "substrate/anode/hole injection layer/hole transport layer/light-emitting layer/electron transport layer/electron injection layer/cathode", substrate/anode/hole injection layer/light-emitting layer/electron transport layer/electron injection layer/cathode "," substrate/anode/hole injection layer/hole transport layer/light-emitting layer/electron transport layer/cathode "), The structural forms of "substrate/anode/light-emitting layer/electron transport layer/electron injection layer/cathode", "substrate/anode/hole transport layer/light-emitting layer/electron transport layer/cathode", "substrate/anode/hole injection layer/light-emitting layer/electron injection layer/cathode", "substrate/anode/hole injection layer/light-emitting layer/electron transport layer/cathode", "substrate/anode/light-emitting layer/electron injection layer/cathode".

< substrate in organic electroluminescent element >

The substrate 101 is a support of the organic EL element 100, and quartz, glass, metal, plastic, or the like is generally used. The substrate 101 is formed in a plate shape, a film shape, or a sheet shape according to the purpose, and for example, a glass plate, a metal foil, a plastic film, a plastic sheet, or the like can be used. Among them, glass plates and plates made of transparent synthetic resins such as polyester, polymethacrylate, polycarbonate, and polysulfone are preferable. In the case of a glass substrate, soda-lime glass, alkali-free glass, or the like can be used, and the thickness is sufficient to maintain the mechanical strength, and therefore, for example, the thickness may be 0.2mm or more. The upper limit of the thickness is, for example, 2mm or less, preferably 1mm or less. As for the material of the glass, the less the ion eluted from the glass, the better, so it is preferably alkali-free glass, because SiO is applied₂Etc. soda lime glass is also commercially available, and therefore the soda lime glass can be used. In addition, in order to improve the gas barrier property, a gas barrier film such as a fine silicon oxide film may be provided on at least one surface of the substrate 101, and in particular, when a synthetic resin plate, film or sheet having low gas barrier property is used as the substrate 101, it is preferable to provide a gas barrier film.

< Anode in organic electroluminescent element >

The anode 102 functions to inject holes into the light-emitting layer 105. In the case where the hole injection layer 103 and/or the hole transport layer 104 are provided between the anode 102 and the light-emitting layer 105, holes are injected into the light-emitting layer 105 through these layers.

Examples of the material for forming the anode 102 include inorganic compounds and organic compounds. Examples of the inorganic compound include: metals (aluminum, gold, silver, nickel, palladium, chromium, etc.), metal oxides (Indium Oxide, Tin Oxide, Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), etc.), metal halides (copper iodide, etc.), copper sulfide, carbon black, ITO glass, or NESA glass, etc. Examples of the organic compound include: polythiophene such as poly (3-methylthiophene), and conductive polymers such as polypyrrole and polyaniline. Further, it can be used by appropriately selecting from substances used as an anode of an organic EL element.

The resistance of the transparent electrode is not limited as long as it can supply a sufficient current for light emission of the light-emitting element, but is preferably low in terms of power consumption of the light-emitting element. For example, an ITO substrate of 300. omega./□ or less functions as an element electrode, but a substrate of about 10. omega./□ can be provided at present, and therefore, a low-resistance product of, for example, 100. omega./□ to 5. omega./□, preferably 50. omega./□ to 5. omega./□, is particularly preferably used. The thickness of ITO can be arbitrarily selected depending on the resistance value, but is usually used in a range of 50nm to 300nm in many cases.

< hole injection layer, hole transport layer in organic electroluminescent element >

The hole injection layer 103 functions to efficiently inject holes transferred from the anode 102 into the light-emitting layer 105 or the hole transport layer 104. The hole transport layer 104 functions to efficiently transport holes injected from the anode 102 or holes injected from the anode 102 through the hole injection layer 103 to the light-emitting layer 105. The hole injection layer 103 and the hole transport layer 104 are formed by laminating and mixing one or more kinds of hole injection/transport materials, or are formed by mixing a hole injection/transport material and a polymer binder. Further, an inorganic salt such as iron (III) chloride may be added to the hole injection/transport material to form a layer.

The hole injecting/transporting substance is required to efficiently inject/transport holes from the positive electrode between electrodes to which an electric field is applied, and it is desirable that the injected holes be efficiently transported with high hole injection efficiency. Therefore, a substance having a small ionization potential, a large hole mobility, and excellent stability, and in which impurities to become traps (traps) are not easily generated during production and use, is preferable.

As materials for forming the hole injection layer 103 and the hole transport layer 104, any compound can be selected from compounds conventionally used as charge transport materials for holes in photoconductive materials, and known compounds used for p-type semiconductors and hole injection layers and hole transport layers in organic EL devices. Specific examples of these materials include carbazole derivatives (e.g., N-phenylcarbazole, polyvinylcarbazole, etc.), biscarbazole derivatives such as bis (N-arylcarbazole) and bis (N-alkylcarbazole), triarylamine derivatives (e.g., polymers having an aromatic tertiary amino group in the main chain or side chain, 1-bis (4-di-p-tolylaminophenyl) cyclohexane, N '-diphenyl-N, N' -di (3-methylphenyl) -4,4 '-diaminobiphenyl, N' -diphenyl-N, N '-dinaphthyl-4, 4' -diaminobiphenyl, N '-diphenyl-N, N' -di (3-methylphenyl) -4,4 '-diphenyl-1, 1' -diamine, and mixtures thereof, N, N '-dinaphthyl-N, N' -diphenyl-4, 4 '-diphenyl-1, 1' -diamine, N⁴,N⁴' -Diphenyl-N⁴,N⁴'-bis (9-phenyl-9H-carbazol-3-yl) - [1,1' -biphenyl]4,4' -diamine, N⁴,N⁴,N⁴',N⁴'-tetrakis [1,1' -biphenyl]-4-yl) - [1,1' -biphenyl]Triphenylamine derivatives such as-4, 4 '-diamine, 4',4 ″ -tris (3-methylphenyl (phenyl) amino) triphenylamine, starburst amine derivatives, and the like), stilbene derivatives, phthalocyanine derivatives (metal-free, copper phthalocyanine, and the like), pyrazoline derivatives, hydrazone-based compounds, benzofuran derivatives or thiophene derivatives, oxadiazole derivatives, quinoxaline derivatives (for example, 1,4,5,8,9, 12-hexaazatriphenylene-2, 3,6,7,10, 11-hexacarbonitrile, and the like), heterocyclic compounds such as porphyrin derivatives, polysilanes, and the like. In the polymer system, polycarbonate or styrene derivative having the monomer in the side chain, polyvinylcarbazole, polysilane, or the like is preferable, but as long as a thin film necessary for manufacturing a light-emitting element is formed, holes can be injected from the anode, and further, holes can be injected, and further, a thin film necessary for manufacturing a light-emitting element can be formedThe compound which transports holes is not particularly limited.

Further, it is also known that the conductivity of an organic semiconductor is strongly affected by doping. Such an organic semiconductor matrix material contains a compound having a good electron donating property or a compound having a good electron accepting property. For the doping of electron-donating substances, strong electron acceptors such as Tetracyanoquinodimethane (TCNQ) or 2,3,5, 6-tetrafluorotetracyanoquinodimethane (2,3,5,6-tetrafluorotetracyano-1, 4-quinodimethane (2,3,5, 6-tetrafluoro-1, 4-benzoquinodimethane, F4TCNQ) are known (see, for example, the documents "m. faffy, a. bayer, t. friez, k. rio (m. pfeiffer, a. beyer, t.fritz, k.leo), the application physics promo (app. phys. lett.),73 (73), (22),3202- -3204 (1998)" and the documents "j. bulohowez, m. faffy, t. friez, k. jeftz, k. bewez, p. phys. lett, p. philis. 731, p. philis.t., t.t., p. peff 72z)", the documents "pp. beweftz, t. These generate so-called holes by an electron transfer process of an electron-donating base substance (hole-transporting substance). The conductivity of the base material varies considerably depending on the number and mobility of holes. As a matrix material having a hole transporting property, for example, a benzidine derivative (TPD or the like), a starburst amine derivative (4,4',4 ″ -tris (N, N-diphenylamino) triphenylamine, TDATA, or the like), or a specific metal phthalocyanine (in particular, zinc phthalocyanine (ZnPc) or the like) is known (japanese unexamined patent application publication No. 2005-167175).

< light-emitting layer in organic electroluminescent element >

The light-emitting layer 105 emits light by recombination of holes injected from the anode 102 and electrons injected from the cathode 108 between electrodes to which an electric field is applied. The material forming the light-emitting layer 105 may be a compound (light-emitting compound) which emits light by being excited by recombination of holes and electrons, and is preferably a compound which can be formed into a stable thin film shape and which exhibits strong light emission (fluorescence) efficiency in a solid state. In the present invention, as a material for the light-emitting layer, a host material and, for example, a polycyclic aromatic compound represented by the above general formula (1) as a dopant material can be used.

The light-emitting layer may be a single layer or may include a plurality of layers, and each of the layers is formed of a material (host material or dopant material) for the light-emitting layer. The host material and the dopant material may be one kind or a combination of two or more kinds, respectively. The dopant material may be contained within the bulk of the host material, or may be contained within a portion of the host material, either. The doping method may be a co-evaporation method with the host material, or may be a method in which the host material is mixed in advance and then evaporated at the same time.

The amount of the host material to be used differs depending on the type of the host material, and may be determined in accordance with the characteristics of the host material. The amount of the host material used is preferably 50 to 99.999 wt%, more preferably 80 to 99.95 wt%, and still more preferably 90 to 99.9 wt% of the total amount of the light-emitting layer material.

The amount of the dopant material used differs depending on the type of the dopant material, and may be determined by matching the characteristics of the dopant material. The amount of the dopant used is preferably 0.001 to 50 wt%, more preferably 0.05 to 20 wt%, and still more preferably 0.1 to 10 wt% of the total amount of the material for the light-emitting layer. In the above range, for example, concentration quenching is preferably prevented.

Examples of the host material include anthracene, pyrene and dibenzo which have been known as a light-emitting bodyOr a condensed ring derivative such as fluorene, a bisstyryl derivative such as a bisstyrylanthracene derivative or a distyrylbenzene derivative, a tetraphenylbutadiene derivative, a cyclopentadiene derivative, and the like. Particularly preferred is an anthracene compound, a fluorene compound or a dibenzoIs a compound of the formula (I).

< Anthracene-based Compound >

The anthracene compound as a main component is, for example, a compound represented by the following general formula (3).

[ formulation 247]

In the general formula (3), X is a group represented by the formula (3-X1), the formula (3-X2) or the formula (3-X3), and the group represented by the formula (3-X1), the formula (3-X2) or the formula (3-X3) is bonded with the anthracene ring of the formula (3) at the position. It is preferable that two X's do not simultaneously form a group represented by the formula (3-X3). More preferably, both X's are not simultaneously a group represented by the formula (3-X2).

In addition, the structure represented by formula (3) can also be used as a unit structure to form a polymer (preferably dimer). In this case, for example, the unit structures represented by formula (3) may be bonded to each other via X, and X may be: a single bond, an arylene group (e.g., phenylene, biphenylene, and naphthylene), and a heteroarylene group (e.g., a group having a divalent valence such as a pyridine ring, a dibenzofuran ring, a dibenzothiophene ring, a carbazole ring, a benzocarbazole ring, and a phenyl-substituted carbazole ring).

The naphthylene moiety in the formulae (3-X1) and (3-X2) may be condensed with a benzene ring. The structure obtained by condensation in the above-described manner is as follows.

[ chemical 248]

Ar¹And Ar²Each independently is hydrogen, phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, phenanthryl, fluorenyl, benzofluorenyl, or,A triphenylene group, a pyrenyl group, or a group represented by the formula (A) (including a carbazolyl group, a benzocarbazolyl group, and a phenyl-substituted carbazolyl group). Further, in Ar¹Or Ar²In the case of the group represented by the formula (A), the group represented by the formula (A) is bonded to the group represented by the formula (3-X) at the position of1) Or a naphthalene ring bond in the formula (3-X2).

Ar³Is phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, phenanthryl, fluorenyl, benzofluorenyl, or the like,A triphenylene group, a pyrenyl group, or a group represented by the formula (A) (including a carbazolyl group, a benzocarbazolyl group, and a phenyl-substituted carbazolyl group). Further, in Ar³In the case of the group represented by formula (a), the group represented by formula (a) is bonded at one site thereof to a single bond represented by a straight line in formula (3-X3). That is, the anthracene ring of the formula (3) is directly bonded to the group represented by the formula (A).

In addition, Ar³May have a substituent, Ar³At least one hydrogen in the above (a) may further be an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a phenanthryl group, a fluorenyl group,A triphenylene group, a pyrenyl group, or a group represented by the formula (A) (including a carbazolyl group and a phenyl-substituted carbazolyl group). Further, in Ar³When the substituent is a group represented by the formula (A), the group represented by the formula (A) is bonded to Ar in the formula (3-X3)³Bonding.

Ar⁴Each independently represents hydrogen, phenyl, biphenyl, terphenyl, naphthyl, or a silyl group substituted with an alkyl group having 1 to 4 carbon atoms (methyl, ethyl, tert-butyl, etc.) and/or a cycloalkyl group having 5 to 10 carbon atoms.

Examples of the alkyl group having 1 to 4 carbon atoms which is substituted in the silyl group include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, cyclobutyl and the like, and three hydrogens in the silyl group are independently substituted with these alkyl groups.

Specific examples of the "silyl group substituted with an alkyl group having 1 to 4 carbon atoms" include: trimethylsilyl group, triethylsilyl group, tripropylsilyl group, triisopropylsilyl group, tributylsilyl group, tri-sec-butylsilyl group, tri-tert-butylsilyl group, ethyldimethylsilyl group, propyldimethylsilyl group, isopropyldimethylsilyl group, butyldimethylsilyl group, sec-butyldimethylsilyl group, tert-butyldimethylsilyl group, methyldiethylsilyl group, propyldiethylsilyl group, isopropyldiethylsilyl group, butyldiethylsilyl group, sec-butyldiethylsilyl group, tert-butyldiethylsilyl group, methyldipropylsilyl group, ethyldipropylsilyl group, sec-butyldipropylsilyl group, tert-butyldipropylsilyl group, methyldiisopropylsilyl group, ethyldiisopropylsilyl group, butyldiisopropylsilyl group, sec-butyldiisopropylsilyl group, and, T-butyldiisopropylsilane, and the like.

Examples of the cycloalkyl group having 5 to 10 carbon atoms substituted in the silyl group include: cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, norbornenyl, bicyclo [1.1.1] pentyl, bicyclo [2.0.1] pentyl, bicyclo [1.2.1] hexyl, bicyclo [3.0.1] hexyl, bicyclo [2.1.2] heptyl, bicyclo [2.2.2] octyl, adamantyl, decahydronaphthyl, decahydroazulenyl and the like, and three hydrogens in the silane group are each independently substituted by these cycloalkyl groups.

Specific examples of the "silyl group substituted with a cycloalkyl group having 5 to 10 carbon atoms" include: tricyclopentylsilyl, tricyclohexylsilyl, and the like.

Examples of the substituted silyl group include a dialkylcycloalkylsilyl group substituted with 2 alkyl groups and 1 cycloalkyl group, and an alkylbicycloalkylsilyl group substituted with 1 alkyl group and 2 cycloalkyl groups.

In addition, hydrogen in the chemical structure of the anthracene compound represented by the general formula (3) may be substituted with a group represented by the formula (a). In the case of substitution by the group represented by formula (a), the group represented by formula (a) is substituted at one site thereof with at least one hydrogen in the compound represented by formula (3).

The group represented by the formula (A) is one of the substituents which the anthracene compound represented by the formula (3) may have.

[ Hua 249]

In the formula (A), Y is-O-, -S-or > N-R²⁹，R²¹～R²⁸Each independently hydrogen, alkyl which may be substituted, cycloalkyl which may be substituted, aryl which may be substituted, heteroaryl which may be substituted, alkoxy which may be substituted, aryloxy which may be substituted, arylthio which may be substituted, trialkylsilyl, tricycloalkylsilyl, dialkylcycloalkylsilyl, alkylbicycloalkylsilyl, amino which may be substituted, halogen, hydroxyl or cyano, R²¹～R²⁸May be bonded to each other to form a hydrocarbon ring, an aryl ring or a heteroaryl ring, R²⁹Is hydrogen or aryl which may be substituted.

As R²¹～R²⁸The "alkyl group" of the "alkyl group which may be substituted" in (1) may be either a straight chain or branched chain, and examples thereof include a straight chain alkyl group having 1 to 24 carbon atoms and a branched chain alkyl group having 3 to 24 carbon atoms. Preferably an alkyl group having 1 to 18 carbon atoms (branched chain alkyl group having 3 to 18 carbon atoms), more preferably an alkyl group having 1 to 12 carbon atoms (branched chain alkyl group having 3 to 12 carbon atoms), still more preferably an alkyl group having 1 to 6 carbon atoms (branched chain alkyl group having 3 to 6 carbon atoms), and particularly preferably an alkyl group having 1 to 4 carbon atoms (branched chain alkyl group having 3 to 4 carbon atoms).

Specific examples of the "alkyl group" include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, 1-methylpentyl, 4-methyl-2-pentyl, 3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, t-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2-dimethylheptyl, 2, 6-dimethyl-4-heptyl, 3,5, 5-trimethylhexyl, n-decyl, n-undecyl, 1-methyldecyl, n-dodecyl, n-tridecyl, 1-hexylheptyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-eicosyl and the like.

As R²¹～R²⁸The "cycloalkyl group" of the "cycloalkyl group which may be substituted" in (1) includes: a cycloalkyl group having 3 to 24 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 16 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, a cycloalkyl group having 5 carbon atoms, and the like.

Specific "cycloalkyl" groups include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, and substituents of these groups having 1 to 4 carbon atoms of alkyl (particularly methyl), norbornenyl, bicyclo [1.0.1] butyl, bicyclo [1.1.1] pentyl, bicyclo [2.0.1] pentyl, bicyclo [1.2.1] hexyl, bicyclo [3.0.1] hexyl, bicyclo [2.1.2] heptyl, bicyclo [2.2.2] octyl, adamantyl, diamantanyl, decahydronaphthyl, decahydroazulenyl, and the like.

As R²¹～R²⁸Examples of the "aryl group" of the "aryl group which may be substituted" in (1) include aryl groups having 6 to 30 carbon atoms, preferably aryl groups having 6 to 16 carbon atoms, more preferably aryl groups having 6 to 12 carbon atoms, and particularly preferably aryl groups having 6 to 10 carbon atoms.

Specific "aryl" groups include: phenyl as a monocyclic system; biphenyl as a bicyclic ring system; naphthyl as the condensed bicyclic system; terphenyl (m-terphenyl, o-terphenyl, p-terphenyl) as a tricyclic system; acenaphthenyl, fluorenyl, phenalkenyl, phenanthrenyl as condensed tricyclic systems; triphenylene, pyrenyl, and tetracenyl groups as condensed quaternary ring systems; perylene groups and pentacene groups as condensed five-ring systems, and the like.

As R²¹～R²⁸Examples of the "heteroaryl group" of the "heteroaryl group which may be substituted" in (1) include a heteroaryl group having 2 to 30 carbon atoms, preferably a heteroaryl group having 2 to 25 carbon atoms, more preferably a heteroaryl group having 2 to 20 carbon atoms, still more preferably a heteroaryl group having 2 to 15 carbon atoms, and particularly preferably a heteroaryl group having 2 to 10 carbon atoms. Examples of the heteroaryl group include heterocyclic rings containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen as ring-constituting atoms in addition to carbon.

Specific examples of the "heteroaryl group" include: pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, indolyl, isoindolyl, 1H-indazolyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, naphthyridinyl, purinyl, pteridinyl, carbazolyl, acridinyl, phenoxathiyl, phenoxazinyl, phenothiazinyl, phenazinyl, indolizinyl, furyl, benzofuryl, isobenzofuryl, dibenzofuryl, thienyl, benzo [ b ] thienyl, dibenzothienyl, furazanyl, oxadiazolyl, thianthrenyl, naphthobenzofuryl, naphthobenzothienyl, and the like.

As R²¹～R²⁸Examples of the "alkoxy group" of the "alkoxy group which may be substituted" in (1) include a linear alkoxy group having 1 to 24 carbon atoms and a branched alkoxy group having 3 to 24 carbon atoms. The alkoxy group is preferably an alkoxy group having 1 to 18 carbon atoms (an alkoxy group having 3 to 18 carbon atoms in a branched chain), more preferably an alkoxy group having 1 to 12 carbon atoms (an alkoxy group having 3 to 12 carbon atoms in a branched chain), yet more preferably an alkoxy group having 1 to 6 carbon atoms (an alkoxy group having 3 to 6 carbon atoms in a branched chain), and particularly preferably an alkoxy group having 1 to 4 carbon atoms (an alkoxy group having 3 to 4 carbon atoms in a branched chain).

Specific "alkoxy" may include: methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy and the like.

As R²¹～R²⁸The "aryloxy group" of the "aryloxy group which may be substituted" in (1) is a group in which hydrogen of an-OH group is substituted by an aryl group which may be cited as said R²¹～R²⁸The "aryl" in (1).

As R²¹～R²⁸The "arylthio group" of the "arylthio group which may be substituted" in (1) is a group in which hydrogen of the-SH group is substituted with an aryl group, which may be cited as the R²¹～R²⁸The "aryl" in (1).

As R²¹～R²⁸As the "trialkylsilyl group" in (1), there can be mentioned groups in which three hydrogens in the silyl group are each independently substituted with an alkyl group, which may be cited as said R²¹～R²⁸The "alkyl" in (1). Preferred alkyl groups for substitution are alkyl groups having 1 to 4 carbon atoms, and specific examples thereof include: methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, cyclobutyl and the like.

Specific examples of the "trialkylsilyl group" include: trimethylsilyl group, triethylsilyl group, tripropylsilyl group, triisopropylsilyl group, tributylsilyl group, tri-sec-butylsilyl group, tri-tert-butylsilyl group, ethyldimethylsilyl group, propyldimethylsilyl group, isopropyldimethylsilyl group, butyldimethylsilyl group, sec-butyldimethylsilyl group, tert-butyldimethylsilyl group, methyldiethylsilyl group, propyldiethylsilyl group, isopropyldiethylsilyl group, butyldiethylsilyl group, sec-butyldiethylsilyl group, tert-butyldiethylsilyl group, methyldipropylsilyl group, ethyldipropylsilyl group, sec-butyldipropylsilyl group, tert-butyldipropylsilyl group, methyldiisopropylsilyl group, ethyldiisopropylsilyl group, butyldiisopropylsilyl group, sec-butyldiisopropylsilyl group, and, T-butyldiisopropylsilane, and the like.

As R²¹～R²⁸As the "tricycloalkylsilyl group" in (1), there can be mentioned groups in which three hydrogens in the silyl group are each independently substituted with a cycloalkyl group, which can be cited as said R²¹～R²⁸The "cycloalkyl group" in (1). Preferred cycloalkyl groups for substitution are those having 5 to 10 carbon atoms, and specific examples thereof include: cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, bicyclo [1.1.1]Pentyl, bicyclo [2.0.1]Pentyl, bicyclo [1.2.1]Hexyl, bicyclo [3.0.1]Hexyl, bicyclo [2.1.2]Heptyl, bicyclo [2.2.2]Octyl, adamantyl, decahydronaphthyl, decahydroazulenyl, and the like.

Specific examples of the "tricycloalkylsilyl group" include: tricyclopentylsilyl, tricyclohexylsilyl, and the like.

Specific examples of the dialkylcycloalkylsilyl group substituted with 2 alkyl groups and 1 cycloalkyl group and the alkylbicycloalkylsilyl group substituted with 1 alkyl group and 2 cycloalkyl groups include: a silyl group substituted with a group selected from the specific alkyl group and cycloalkyl group.

As R²¹～R²⁸The "substituted amino group" of the "amino group which may be substituted" in ((1) includes, for example, an amino group in which two hydrogens are substituted with an aryl group or a heteroaryl group. The amino group with two hydrogens substituted by aryl is diaryl substituted amino, the amino group with two hydrogens substituted by heteroaryl is diheteroaryl substituted amino, and the amino group with two hydrogens substituted by aryl and heteroaryl is aryl heteroaryl substituted amino. Said aryl or heteroaryl may be cited as said R²¹～R²⁸The "aryl" or "heteroaryl" in (1).

Specific "substituted amino group" includes: diphenylamino, dinaphthylamino, phenylnaphthylamino, bipyrylamino, phenylpyridylamino, naphthylpyridylamino and the like.

As R²¹～R²⁸Examples of the "halogen" in (1) include: fluorine, chlorine, bromine, iodine.

As R²¹～R²⁸In the groups described above, some of the groups may be substituted as described above, and as the substituents in the above case, there may be mentioned: alkyl, cycloalkyl, aryl or heteroaryl. The alkyl, cycloalkyl, aryl or heteroaryl group may be cited as the R²¹～R²⁸The "alkyl", "cycloalkyl", "aryl" or "heteroaryl" in (1).

"> N-R as Y²⁹R in `²⁹Is hydrogen or an aryl group which may be substituted, as said aryl group, the R group may be cited²¹～R²⁸The group described for the "aryl" in (1) and the substituent mentioned above may be cited as the group for R²¹～R²⁸The substituents of (1) or (ii).

R²¹～R²⁸May be bonded to each other to form a hydrocarbon ring, an aryl ring or a heteroaryl ring. The case where no ring is formed is a group represented by the following formula (A-1), and examples of the case where a ring is formed include groups represented by the following formulae (A-2) to (A-14). Further, at least one hydrogen in the group represented by any one of the formulae (A-1) to (A-14) may be substituted with an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, an arylthio group, a trialkylsilyl group, a tricycloalkylsilyl group, a dialkylcycloalkylsilyl group, an alkylbicycloalkylsilyl group, a diarylsubstituted amino group, a diheteroarylsubstituted amino group, an arylheteroaryl substituted amino group, a halogen group, a hydroxyl group, or a cyano group.

[ solution 250]

Examples of the hydrocarbon ring as the ring formed by bonding adjacent groups to each other include a cyclohexane ring, and examples of the aryl ring or the heteroaryl ring include the above-mentioned R²¹～R²⁸The ring structure illustrated in the "aryl" or "heteroaryl" in (1), which is formed by condensation with one or two benzene rings in the formula (A-1).

Examples of the group represented by formula (A) include a group represented by any one of formulae (A-1) to (A-14), preferably a group represented by any one of formulae (A-1) to (A-5) and formulae (A-12) to (A-14), more preferably a group represented by any one of formulae (A-1) to (A-4), even more preferably a group represented by any one of formulae (A-1), (A-3) and (A-4), and particularly preferably a group represented by formula (A-1).

The group represented by formula (A) is bonded at a position: (A) to a naphthalene ring of formula (3-X1) or formula (3-X2), a single bond of formula (3-X3), Ar of formula (3-X3)³The bond(s) and, in addition, the substitution with at least one hydrogen in the compound represented by the formula (3) are as described above, but these bond formsAmong them, preferred is a group bonded to a naphthalene ring of the formula (3-X1) or the formula (3-X2), a single bond of the formula (3-X3) and/or Ar of the formula (3-X3)³The form of the bond.

In the structure of the group represented by the formula (A), a naphthalene ring in the formula (3-X1) or the formula (3-X2), a single bond in the formula (3-X3), Ar in the formula (3-X3)³The position of the bond and the position of the group represented by the formula (A) which is substituted with at least one hydrogen in the compound represented by the formula (3) in the structure of the group represented by the formula (A) may be any position in the structure of the formula (A), for example, any one of two benzene rings in the structure of the formula (A) or R in the structure of the formula (A)²¹～R²⁸In the formula (A), or "> N-R as Y in the structure of the formula (A)²⁹"R of²⁹Is bonded at any position in the above.

Examples of the group represented by the formula (a) include the following groups. Wherein Y and x are as defined above.

[ solution 251]

In the chemical structure of the anthracene compound represented by the general formula (3), all or part of hydrogen may be deuterium.

Specific examples of the anthracene compound include compounds represented by the following formulae (3-1) to (3-72). In the following structural formulae, "Me" represents a methyl group, "D" represents deuterium, and "tBu" represents a tert-butyl group.

[ solution 252]

[ solution 253]

[ solution 254]

[ solution 255]

The anthracene compound represented by the formula (3) may be a compound having a reactive group at a desired position of the anthracene skeleton, or a compound having a reactive group at X, Ar⁴And a compound having a reactive group in a partial structure such as the structure of the formula (A) as a starting material, and produced by suzuki coupling, radial and shore coupling, or other known coupling reactions. Examples of the reactive group of these reactive compounds include halogen and boric acid. As specific production methods, for example, reference is made to: paragraph [0089 ] of International publication No. 2014/141725]～[0175]The synthesis method of (1).

< fluorene-based Compound >

The compound represented by the general formula (4) basically functions as a host.

[ solution 256]

In the above-mentioned formula (4),

R¹to R¹⁰Each independently hydrogen, aryl, heteroaryl (the heteroaryl may be bonded to the fluorene skeleton in the formula (4) via a linking group), diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkenyl, alkoxy, or aryloxy, at least one of which may be substituted with aryl, heteroaryl, alkyl, or cycloalkyl,

in addition, R¹And R²、R²And R³、R³And R⁴、R⁵And R⁶、R⁶And R⁷、R⁷And R⁸Or R⁹And R¹⁰May each be independently bonded to form a condensed ring or a spiro ring, at least one hydrogen in the formed ring may be substituted by an aryl, heteroaryl (which may be bonded to the formed ring via a linking group), diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkenyl, alkoxy, or aryloxy, at least one of which may be substituted by an aryl, heteroaryl, alkyl, or cycloalkyl group, and,

at least one hydrogen in the compound represented by formula (4) may be substituted with halogen, cyano, or deuterium.

The detailed description of each group defined by the formula (4) can be referred to the description of the polycyclic aromatic compound of the formula (1) described above.

As R¹To R¹⁰The alkenyl group in (3) includes, for example, an alkenyl group having 2 to 30 carbon atoms, preferably an alkenyl group having 2 to 20 carbon atoms, more preferably an alkenyl group having 2 to 10 carbon atoms, further preferably an alkenyl group having 2 to 6 carbon atoms, and particularly preferably an alkenyl group having 2 to 4 carbon atoms. Preferred alkenyl groups are vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl or 5-hexenyl.

Specific examples of the heteroaryl group include a monovalent group represented by a compound of the following formula (4-Ar1), formula (4-Ar2), formula (4-Ar3), formula (4-Ar4) or formula (4-Ar5) in which any one hydrogen atom is removed.

[ solution 257]

In the formulae (4-Ar1) to (4-Ar5), Y¹Each independently O, S or N-R, R is phenyl, biphenyl, naphthyl, anthryl or hydrogen,

at least one hydrogen in the structures of formulae (4-Ar1) to (4-Ar5) may be substituted with phenyl, biphenyl, naphthyl, anthryl, phenanthryl, methyl, ethyl, propyl, or butyl.

These heteroaryl groups may be bonded to the fluorene skeleton in the formula (4) via a linking group. That is, the fluorene skeleton and the heteroaryl group in the formula (4) may be bonded not only directly but also via a linking group therebetween. Examples of the linking group include: phenylene, biphenylene, naphthylene, anthracenylene, methylene, ethylene, -OCH₂CH₂-、-CH₂CH₂O-or-OCH₂CH₂O-, etc.

R in the formula (4)¹And R²、R²And R³、R³And R⁴、R⁵And R⁶、R⁶And R⁷Or R⁷And R⁸Each of which may be independently bonded to form a condensed ring, R⁹And R¹⁰May be bonded to form a spiro ring. From R¹To R⁸The condensed ring formed is a ring condensed with the benzene ring in formula (4) and is an aliphatic ring or an aromatic ring. An aromatic ring is preferable, and as the structure containing a benzene ring in formula (4), a naphthalene ring, a phenanthrene ring, or the like can be mentioned. From R⁹And R¹⁰The spiro ring formed is a ring spiro-bonded to the 5-membered ring in formula (4) and is an aliphatic ring or an aromatic ring. Preferred is an aromatic ring, and fluorene rings and the like can be mentioned.

The compound represented by the general formula (4) is preferably a compound represented by the following formula (4-1), formula (4-2) or formula (4-3), and is R in the general formula (4)¹And R²A compound formed by condensation of bonded benzene rings, R in the general formula (4)³And R⁴Bonded to form benzene ringA compound obtained by condensation of R in the general formula (4)¹To R⁸Any of which is not bonded.

[ Hua 258]

R in the formula (4-1), the formula (4-2) and the formula (4-3)¹To R¹⁰Is defined as R corresponding to the formula (4)¹To R¹⁰Same, and R in the formula (4-1) and the formula (4-2)¹¹To R¹⁴Is also defined as R in the formula (4)¹To R¹⁰The same is true.

The compound represented by the general formula (4) is more preferably a compound represented by the following formula (4-1A), formula (4-2A) or formula (4-3A), and R is represented by the following formula (4-1), formula (4-1) or formula (4-3)⁹And R¹⁰A compound bonded to form a spiro-fluorene ring.

[ solution 259]

R in the formula (4-1A), the formula (4-2A) and the formula (4-3A)²To R⁷Is defined as R corresponding to the formula (4-1), the formula (4-2) and the formula (4-3)²To R⁷Same, and R in the formula (4-1A) and the formula (4-2A)¹¹To R¹⁴Is also defined as R in the formula (4-1) and the formula (4-2)¹¹To R¹⁴The same is true.

In addition, all or a part of the hydrogens in the compound represented by formula (4) may be substituted with a halogen, a cyano group, or deuterium.

< dibenzo >Series compound >

Dibenzo as hostAre compounds such asA compound represented by the following general formula (5).

[ solution 260]

In the above-mentioned formula (5),

R¹to R¹⁶Each independently is hydrogen, aryl, heteroaryl (the heteroaryl may be bonded to the dibenzo of formula (5) via a linking groupBackbone bond), diarylamino, diheteroarylamino, arylheteroarylamino, alkyl, cycloalkyl, alkenyl, alkoxy, or aryloxy, at least one of which may be substituted with aryl, heteroaryl, alkyl, or cycloalkyl,

in addition, R¹To R¹⁶May be bonded to each other to form a condensed ring, at least one hydrogen in the formed ring may be substituted by an aryl group, a heteroaryl group (the heteroaryl group may be bonded to the formed ring via a linking group), a diarylamino group, a diheteroarylamino group, an arylheteroarylamino group, an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, or an aryloxy group, at least one of which may be substituted by an aryl group, a heteroaryl group, an alkyl group, or a cycloalkyl group, and,

at least one hydrogen in the compound represented by formula (5) may be substituted with halogen, cyano, or deuterium.

The detailed description of each group defined by the formula (5) can be referred to the description of the polycyclic aromatic compound of the formula (1) described above.

Examples of the alkenyl group defined in the formula (5) include alkenyl groups having 2 to 30 carbon atoms, preferably alkenyl groups having 2 to 20 carbon atoms, more preferably alkenyl groups having 2 to 10 carbon atoms, further preferably alkenyl groups having 2 to 6 carbon atoms, and particularly preferably alkenyl groups having 2 to 4 carbon atoms. Preferred alkenyl groups are vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl or 5-hexenyl.

Specific examples of the heteroaryl group include a monovalent group represented by a compound of the following formula (5-Ar1), formula (5-Ar2), formula (5-Ar3), formula (5-Ar4) or formula (5-Ar5) in which any one hydrogen atom is removed.

[ solution 261]

In the formulae (5-Ar1) to (5-Ar5), Y¹Each independently O, S or N-R, R is phenyl, biphenyl, naphthyl, anthryl or hydrogen,

at least one hydrogen in the structures of formulae (5-Ar1) to (5-Ar5) may be substituted with phenyl, biphenyl, naphthyl, anthryl, phenanthryl, methyl, ethyl, propyl, or butyl.

These heteroaryl groups may be bonded to the dibenzo of the formula (5) via a linking groupThe skeleton is bonded. Namely, dibenzo in the formula (5)The backbone and the heteroaryl group may be bonded not only directly but also via a linking group therebetween. Examples of the linking group include: phenylene, biphenylene, naphthylene, anthracenylene, methylene, ethylene, -OCH₂CH₂-、-CH₂CH₂O-or-OCH₂CH₂O-, etc.

The compound represented by the general formula (5) is preferably R¹、R⁴、R⁵、R⁸、R⁹、R¹²、R¹³And R¹⁶Is hydrogen. In the case, R in the formula (5)²、R³、R⁶、R⁷、R¹⁰、R¹¹、R¹⁴And R¹⁵Preferably each independently hydrogen, phenyl, biphenyl, naphthyl, anthryl, phenanthryl, havingThe monovalent group of the structure of the formula (5-Ar1), (5-Ar2), (5-Ar3), (5-Ar4) or (5-Ar5) (the monovalent group of the structure can be formed by phenylene, biphenylene, naphthylene, anthrylene, methylene, ethylene, -OCH₂CH₂-、-CH₂CH₂O-or-OCH₂CH₂O-and dibenzo in said formula (5)Backbone bond), methyl, ethyl, propyl, or butyl.

The compound represented by the general formula (5) is more preferably R¹、R²、R⁴、R⁵、R⁷、R⁸、R⁹、R¹⁰、R¹²、R¹³、R¹⁵And R¹⁶Is hydrogen. In the case, R in the formula (5)³、R⁶、R¹¹And R¹⁴Is a compound having a structure represented by the general formula (I) wherein at least one (preferably one or two, more preferably one) is a compound having a structure represented by the general formula (I) via a single bond, phenylene, biphenylene, naphthylene, anthracenylene, methylene, ethylene, -OCH₂CH₂-、-CH₂CH₂O-or-OCH₂CH₂A monovalent group of the structure of the formula (5-Ar1), formula (5-Ar2), formula (5-Ar3), formula (5-Ar4) or formula (5-Ar5) of O-,

at least one other hydrogen (i.e., other than the position substituted by the monovalent group having the structure) is hydrogen, phenyl, biphenyl, naphthyl, anthryl, methyl, ethyl, propyl, or butyl, and at least one hydrogen of these may be substituted by phenyl, biphenyl, naphthyl, anthryl, methyl, ethyl, propyl, or butyl.

Further, a monovalent group having a structure represented by the above-mentioned formulas (5-Ar1) to (5-Ar5) is selected as R in the formula (5)²、R³、R⁶、R⁷、R¹⁰、R¹¹、R¹⁴And R¹⁵In the case where at least one hydrogen in the structure may react with R in the formula (5)¹To R¹⁶Any of which is bonded to form a single bond.

< Electron injection layer, Electron transport layer in organic electroluminescent element >

The electron injection layer 107 functions to efficiently inject electrons transferred from the cathode 108 into the light-emitting layer 105 or the electron transport layer 106. The electron transport layer 106 functions to efficiently transport electrons injected from the cathode 108 or electrons injected from the cathode 108 through the electron injection layer 107 to the light-emitting layer 105. The electron transporting layer 106 and the electron injecting layer 107 are formed by laminating and mixing one or more kinds of electron transporting/injecting materials, or are formed by mixing an electron transporting/injecting material and a polymer binder.

The electron injection/transport layer is a layer that is responsible for injecting electrons from the cathode and transporting the electrons, and it is desirable that the injected electrons be efficiently transported with high electron injection efficiency. Therefore, a substance having a high electron affinity, a high electron mobility, and excellent stability is preferable, and impurities that become traps are less likely to be generated during production and use. However, when the balance between the transport of holes and electrons is considered, if the function of efficiently preventing holes from the anode from flowing to the cathode side without being recombined is mainly exerted, even if the electron transport ability is not so high, the effect of improving the light emission efficiency is obtained as much as that of a material having a high electron transport ability. Therefore, the electron injection/transport layer in this embodiment mode may also include a function of a layer capable of efficiently preventing hole transfer.

The material (electron transporting material) for forming the electron transporting layer 106 or the electron injecting layer 107 can be selected and used as desired from compounds conventionally used as electron transporting compounds in photoconductive materials and known compounds used for an electron injecting layer and an electron transporting layer of an organic EL element.

The material used for the electron transport layer or the electron injection layer preferably contains at least one compound selected from the following compounds: a compound containing an aromatic ring or a heteroaromatic ring containing at least one atom selected from the group consisting of carbon, hydrogen, oxygen, sulfur, silicon and phosphorus, a pyrrole derivative or a condensed ring derivative thereof, and a metal complex having an electron-accepting nitrogen. Specifically, there may be mentioned: aromatic ring derivatives having condensed ring systems such as naphthalene and anthracene, styrene-based aromatic ring derivatives represented by 4,4' -bis (diphenylvinyl) biphenyl, perinone derivatives, coumarin derivatives, naphthalimide derivatives, quinone derivatives such as anthraquinone and diphenoquinone, phosphorus oxide derivatives, carbazole derivatives, indole derivatives, and the like. Examples of the metal complex having electron-accepting nitrogen include: and hydroxyoxazole complexes such as hydroxyphenyl oxazole complexes, azomethine complexes, tropolone metal complexes, flavonol metal complexes, and benzoquinoline metal complexes. These materials may be used alone or in combination with different materials.

Specific examples of the other electron transport compound include: pyridine derivatives, naphthalene derivatives, anthracene derivatives, phenanthroline derivatives, perinone derivatives, coumarin derivatives, naphthalimide derivatives, anthraquinone derivatives, diphenoquinone derivatives, diphenylquinone derivatives, perylene derivatives, oxadiazole derivatives (1, 3-bis [ (4-tert-butylphenyl) 1,3, 4-oxadiazolyl ] phenylene, etc.), thiophene derivatives, triazole derivatives (N-naphthyl-2, 5-diphenyl-1, 3, 4-triazole, etc.), thiadiazole derivatives, metal complexes of 8-hydroxyquinoline (oxine) derivatives, hydroxyquinoline-based metal complexes, quinoxaline derivatives, polymers of quinoxaline derivatives, indole (benzoxazole) compounds, gallium complexes, pyrazole derivatives, perfluorinated phenylene derivatives, triazine derivatives, coumarin derivatives, perylene derivatives, and derivatives, Pyrazine derivatives, benzoquinoline derivatives (e.g., 2 '-bis (benzo [ h ] quinolin-2-yl) -9,9' -spirobifluorene), imidazopyridine derivatives, borane derivatives, benzimidazole derivatives (e.g., tris (N-phenylbenzimidazol-2-yl) benzene), benzoxazole derivatives, benzothiazole derivatives, quinoline derivatives, terpyridine derivatives, oligopyridine derivatives such as terpyridine, bipyridine derivatives (e.g., 1, 3-bis (4'- (2,2':6 '2' -terpyridyl)) benzene), naphthyridine derivatives (e.g., bis (1-naphthyl) -4- (1, 8-naphthyridin-2-yl) phenylphosphine oxide), aldazine derivatives, carbazole derivatives, indole derivatives, and the like, Phosphorus oxide derivatives, bisstyryl derivatives, and the like.

In addition, a metal complex having electron-accepting nitrogen may also be used, and examples thereof include: hydroxyoxazole complexes such as hydroxyquinoline metal complexes and hydroxyphenyl oxazole complexes, azomethine complexes, tropolone metal complexes, flavonol metal complexes, and benzoquinoline metal complexes.

The materials can be used alone or in admixture with different materials.

Among the above materials, preferred are borane derivatives, pyridine derivatives, fluoranthene derivatives, BO-based derivatives, anthracene derivatives, benzofluorene derivatives, phosphine oxide derivatives, pyrimidine derivatives, carbazole derivatives, triazine derivatives, benzimidazole derivatives, phenanthroline derivatives, and hydroxyquinoline-based metal complexes.

Borane derivatives

Examples of the borane derivatives are compounds represented by the following general formula (ETM-1), and are disclosed in detail in Japanese patent laid-open No. 2007-27587.

[ solution 262]

In the formula (ETM-1), R¹¹And R¹²Each independently is at least one of hydrogen, alkyl, cycloalkyl, aryl which may be substituted, silyl which may be substituted, nitrogen-containing heterocycle which may be substituted, or cyano, R¹³～R¹⁶Each independently represents an alkyl group which may be substituted, a cycloalkyl group which may be substituted, or an aryl group which may be substituted, X represents an arylene group which may be substituted, Y represents an aryl group having 16 or less carbon atoms which may be substituted, a substituted boron group, or a substituted carbazolyl group, and n is an integer of 0 to 3. In addition, as the substituent in the case of "may be substituted" or "substituted", there may be mentioned: aryl, heteroaryl, alkyl or cycloalkyl, and the like.

Among the compounds represented by the general formula (ETM-1), a compound represented by the following general formula (ETM-1-1) or a compound represented by the following general formula (ETM-1-2) is preferable.

[ solution 263]

In the formula (ETM-1-1), R¹¹And R¹²Each independently is at least one of hydrogen, alkyl, cycloalkyl, aryl which may be substituted, silyl which may be substituted, nitrogen-containing heterocycle which may be substituted, or cyano, R¹³～R¹⁶Each independently an alkyl group which may be substituted, a cycloalkyl group which may be substituted, or an aryl group which may be substituted, R²¹And R²²Each independently is at least one of hydrogen, alkyl, cycloalkyl, aryl which may be substituted, silyl which may be substituted, a nitrogen-containing heterocycle which may be substituted, or cyano, X¹Is an arylene group having 20 or less carbon atoms which may be substituted, n is independently an integer of 0 to 3, and m is independently an integer of 0 to 4. In addition, as the substituent in the case of "may be substituted" or "substituted", there may be mentioned: aryl, heteroaryl, alkyl or cycloalkyl, and the like.

[ chemical 264]

In the formula (ETM-1-2), R¹¹And R¹²Each independently is at least one of hydrogen, alkyl, cycloalkyl, aryl which may be substituted, silyl which may be substituted, nitrogen-containing heterocycle which may be substituted, or cyano, R¹³～R¹⁶Each independently an alkyl group which may be substituted, a cycloalkyl group which may be substituted or an aryl group which may be substituted, X¹Is an arylene group having 20 or less carbon atoms which may be substituted, and n is an integer of 0 to 3 independently. In addition, as the substituent in the case of "may be substituted" or "substituted", there may be mentioned: aryl, heteroaryl, alkyl or cycloalkyl, and the like.

As X¹Specific examples of (2) include divalent groups represented by any one of the following formulae (X-1) to (X-9).

[ solution 265]

(in the formulae, R^aEach independently is alkyl, cycloalkyl or phenyl which may be substituted)

Specific examples of the borane derivative include the following compounds.

[ solution 266]

The borane derivative can be produced using a known raw material and a known synthesis method.

< pyridine derivatives >

The pyridine derivative is, for example, a compound represented by the following formula (ETM-2), and preferably a compound represented by the formula (ETM-2-1) or the formula (ETM-2-2).

[ solution 267]

Phi- (pyridine substituent) n (ETM-2)

Phi is an n-valent aryl ring (preferably an n-valent benzene ring, naphthalene ring, anthracene ring, fluorene ring, benzofluorene ring, phenalene ring, phenanthrene ring or triphenylene ring), and n is an integer of 1-4.

In the formula (ETM-2-1), R¹¹～R¹⁸Each independently represents hydrogen, an alkyl group (preferably an alkyl group having 1 to 24 carbon atoms), a cycloalkyl group (preferably a cycloalkyl group having 3 to 12 carbon atoms) or an aryl group (preferably an aryl group having 6 to 30 carbon atoms).

In the formula (ETM-2-2), R¹¹And R¹²Each independently hydrogen, alkyl (preferably C1-C24 alkyl), cycloalkyl (preferably C3-C12 cycloalkyl) or aryl (preferably C6-C30 aryl), R¹¹And R¹²May be bonded to form a ring.

In each formula, the "pyridine substituent" is any one of the following formulas (Py-1) to (Py-15), and the pyridine substituent may be independently substituted with an alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 5 to 10 carbon atoms. In addition, the pyridine substituent may be bonded to the phi, anthracene ring or fluorene ring in each formula via phenylene or naphthylene.

[ solution 268]

The pyridine substituent is any one of the above formulae (Py-1) to (Py-15), and among these, any one of the following formulae (Py-21) to (Py-44) is preferable.

[ 269]

At least one hydrogen of each pyridine derivative may be substituted by deuterium, and in addition, one of the two "pyridine-based substituents" in the formula (ETM-2-1) and the formula (ETM-2-2) may be substituted by an aryl group.

As R¹¹～R¹⁸The "alkyl group" in (1) may be either a straight chain or branched chain, and examples thereof include a straight chain alkyl group having 1 to 24 carbon atoms and a branched chain alkyl group having 3 to 24 carbon atoms. The preferred "alkyl group" is an alkyl group having 1 to 18 carbon atoms (branched chain alkyl group having 3 to 18 carbon atoms). More preferably, the "alkyl group" is an alkyl group having 1 to 12 carbon atoms (branched chain alkyl group having 3 to 12 carbon atoms). Further preferred "alkyl group" is an alkyl group having 1 to 6 carbon atoms (branched chain alkyl group having 3 to 6 carbon atoms). Particularly preferred "alkyl group" is an alkyl group having 1 to 4 carbon atoms (branched chain alkyl group having 3 to 4 carbon atoms).

Specific examples of the "alkyl group" include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, 1-methylpentyl, 4-methyl-2-pentyl, 3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, t-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2-dimethylheptyl, 2, 6-dimethyl-4-heptyl, 3,5, 5-trimethylhexyl, n-decyl, n-undecyl, 1-methyldecyl, n-dodecyl, n-tridecyl, 1-hexylheptyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-eicosyl and the like.

As the alkyl group having 1 to 4 carbon atoms substituted in the pyridine substituent, the description of the alkyl group can be cited.

As R¹¹～R¹⁸Examples of the "cycloalkyl group" in (1) include cycloalkyl groups having 3 to 12 carbon atoms. The preferable "cycloalkyl group" is a cycloalkyl group having 3 to 10 carbon atoms. More preferably, the "cycloalkyl group" is a cycloalkyl group having 3 to 8 carbon atoms. Further preferred "cycloalkyl group" is a cycloalkyl group having 3 to 6 carbon atoms.

Specific "cycloalkyl" groups include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl, dimethylcyclohexyl, or the like.

As the cycloalkyl group having 5 to 10 carbon atoms substituted in the pyridine substituent, the description thereof can be cited.

As R¹¹～R¹⁸The "aryl group" in (1) is preferably an aryl group having 6 to 30 carbon atoms, more preferably an aryl group having 6 to 18 carbon atoms, still more preferably an aryl group having 6 to 14 carbon atoms, and particularly preferably an aryl group having 6 to 12 carbon atoms.

Specific examples of the "aryl group having 6 to 30 carbon atoms" include: phenyl as monocyclic aryl, (1-, 2-) naphthyl as condensed bicyclic aryl, acenaphthene- (1-, 3-, 4-, 5-) as condensed tricyclic aryl, fluorene- (1-, 2-, 3-, 4-, 9-) as condensed tricyclic aryl, phenalene- (1-, 2-) as condensed tricyclic aryl, (1-, 2-, 3-, 4-, 9-) phenanthrene, triphenylene- (1-, 2-) as condensed tetracyclic aryl, pyrene- (1-, 2-, 4-) as condensed tetracene- (1-, 2-, 5-) as condensed pentacyclic aryl, perylene- (1-, 2-, 3-) as condensed tricyclic aryl, perylene- (1-, 2-, 3-) as condensed tetracyclic aryl, perylene, and the like, Pentacene- (1-, 2-, 5-, 6-) radicals and the like.

Preferred examples of the "aryl group having 6 to 30 carbon atoms" include phenyl, naphthyl, phenanthryl,Examples of the group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group and a phenanthryl group, and examples of the group include a phenyl group, a 1-naphthyl group and a 2-naphthyl group.

R in the formula (ETM-2-2)¹¹And R¹²A ring may be bonded to form a ring, and as a result, cyclobutane, cyclopentane, cyclopentene, cyclopentadiene, cyclohexane, fluorene, indene, or the like may be spiro-bonded to the 5-membered ring of the fluorene skeleton.

Specific examples of the pyridine derivative include the following compounds.

[ solution 270]

The pyridine derivative can be produced using a known raw material and a known synthesis method.

< fluoranthene derivative >

Fluoranthene derivatives are, for example, compounds represented by the following general formula (ETM-3), and are disclosed in detail in international publication No. 2010/134352.

[ 271]

In the formula (ETM-3), X¹²～X²¹Represents hydrogen, halogen, linear, branched or cyclic alkyl, linear, branched or cyclic alkoxy, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl. Here, as the substituent in the case of substitution, there may be mentioned: aryl, heteroaryl, alkyl or cycloalkyl, and the like.

Specific examples of the fluoranthene derivative include the following compounds.

[ solution 272]

< BO series derivative >

The BO derivative is, for example, a polycyclic aromatic compound represented by the following formula (ETM-4) or a polymer of a polycyclic aromatic compound having a plurality of structures represented by the following formula (ETM-4).

[ 273]

R¹～R¹¹Each independently hydrogen, aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl (two aryl groups may be bonded via a single bond or a linking group), alkyl, cycloalkyl, alkoxy, or aryloxy, at least one of which may be substituted with aryl, heteroaryl, alkyl, or cycloalkyl.

In addition, R¹～R¹¹May be bonded to each other and form an aryl or heteroaryl ring together with the a, b or c ring, at least one hydrogen in the formed ring may be substituted by an aryl, heteroaryl, diarylamino, diheteroarylamino, arylheteroarylamino, diarylboryl (two aryl groups may be bonded via a single bond or a linking group), an alkyl, cycloalkyl, alkoxy or aryloxy group, at least one of which may be substituted by an aryl, heteroaryl, alkyl or cycloalkyl group.

In addition, at least one hydrogen in the compound or structure represented by formula (ETM-4) may be substituted with halogen or deuterium.

As for the form of the substituent or ring in the formula (ETM-4) and the polymer formed by combining a plurality of structures of the formula (ETM-4), the description of the polycyclic aromatic compound represented by the general formula (1) or (2) or the polymer thereof can be cited.

Specific examples of the BO-based derivative include the following compounds.

[ solution 274]

The BO-based derivative can be produced using a known raw material and a known synthesis method.

< Anthracene derivatives >

One of the anthracene derivatives is, for example, a compound represented by the following formula (ETM-5-1).

[ design 275]

Ar is each independently divalent benzene or naphthalene, R¹～R⁴Each independently hydrogen, alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms or aryl having 6 to 20 carbon atoms.

Ar may be appropriately selected from divalent benzene or naphthalene, and two Ar may be different or the same, and are preferably the same from the viewpoint of ease of synthesis of the anthracene derivative. Ar is bonded to pyridine to form "a site including Ar and pyridine", and the site is bonded to anthracene as a group represented by any one of the following formulae (Py-1) to (Py-12), for example.

[ 276]

Among these groups, those represented by any one of the formulae (Py-1) to (Py-9) are preferred, and those represented by any one of the formulae (Py-1) to (Py-6) are more preferred. The two "sites containing Ar and pyridine" bonded to anthracene may be the same or different in structure, and the same structure is preferable from the viewpoint of ease of synthesis of the anthracene derivative. Among them, from the viewpoint of device characteristics, it is preferable that the two "sites containing Ar and pyridine" have the same or different structures.

With respect to R¹～R⁴The C1-C6 alkyl group in (A) may be a straight chainAny of a chain and a branched chain. Namely, a linear alkyl group having 1 to 6 carbon atoms or a branched chain alkyl group having 3 to 6 carbon atoms. More preferably an alkyl group having 1 to 4 carbon atoms (branched chain alkyl group having 3 to 4 carbon atoms). Specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, 1-methylpentyl, 4-methyl-2-pentyl, 3-dimethylbutyl, and 2-ethylbutyl, and preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl, and more preferably methyl, ethyl, or tert-butyl.

As R¹～R⁴Specific examples of the cycloalkyl group having 3 to 6 carbon atoms in (b) include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl, dimethylcyclohexyl, or the like.

With respect to R¹～R⁴The aryl group having 6 to 20 carbon atoms in (A) is preferably an aryl group having 6 to 16 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms, and particularly preferably an aryl group having 6 to 10 carbon atoms.

Specific examples of the "aryl group having 6 to 20 carbon atoms" include: phenyl group, (o, m, p) tolyl group, (2,3-, 2,4-, 2,5-, 2,6-, 3,4-, 3,5-) xylyl group, mesityl (2,4, 6-trimethylphenyl group), (o, m, p) cumenyl group, (2-, 3-, 4-) biphenyl group as bicyclic aryl group, (1-, 2-) naphthyl group as condensed bicyclic aryl group, terphenyl group (m-terphenyl-2 ' -yl group, m-terphenyl-4 ' -yl group, m-terphenyl-5 ' -yl group, o-terphenyl-3 ' -yl group, o-terphenyl-4 ' -yl group, p-terphenyl-2 ' -yl group, m-terphenyl-2-yl group, p-terphenyl-4 ' -yl group, p-terphenyl-2-yl group, m-terphenyl-3-yl, m-terphenyl-4-yl, o-terphenyl-2-yl, o-terphenyl-3-yl, o-terphenyl-4-yl, p-terphenyl-2-yl, p-terphenyl-3-yl, p-terphenyl-4-yl), anthracene- (1-, 2-, 9-) yl, acenaphthene- (1-, 3-, 4-, 5-) yl, fluorene- (1-, 2-, 3-, 4-, 9-) yl, phenalene- (1-, 2-) yl, (1-, 2-, 3-, 4-, 9-) phenanthryl as condensed tricyclic aryl, triphenylene- (1-, 9-) -as condensed tricyclic aryl, 2-) group, pyrene- (1-, 2-, 4-) group, tetracene- (1-, 2-, 5-) group, perylene- (1-, 2-, 3-) group as condensed pentacyclic aryl group, and the like.

The "aryl group having 6 to 20 carbon atoms" is preferably a phenyl group, a biphenyl group, a terphenyl group or a naphthyl group, more preferably a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group or an m-terphenyl-5' -yl group, further preferably a phenyl group, a biphenyl group, a 1-naphthyl group or a 2-naphthyl group, and most preferably a phenyl group.

One of the anthracene derivatives is, for example, a compound represented by the following formula (ETM-5-2).

[ Hua 277]

Ar¹Each independently a single bond, divalent benzene, naphthalene, anthracene, fluorene, or phenalene.

Ar²As the aryl group having 6 to 20 carbon atoms, the same description as "aryl group having 6 to 20 carbon atoms" in the formula (ETM-5-1) can be cited. Preferably an aryl group having 6 to 16 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms, and particularly preferably an aryl group having 6 to 10 carbon atoms. Specific examples thereof include: phenyl, biphenyl, naphthyl, terphenyl, anthracenyl, acenaphthenyl, fluorenyl, phenalkenyl, phenanthrenyl, triphenylenyl, pyrenyl, tetracenyl, perylenyl, and the like.

R¹～R⁴Each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms or an aryl group having 6 to 20 carbon atoms, as described in the above formula (ETM-5-1).

Specific examples of the anthracene derivative include the following compounds.

[ 278]

These anthracene derivatives can be produced using a known raw material and a known synthesis method.

< benzofluorene derivative >

The benzofluorene derivative is, for example, a compound represented by the following formula (ETM-6).

[ chemical No. 279]

Ar¹As the aryl group having 6 to 20 carbon atoms, the same description as "aryl group having 6 to 20 carbon atoms" in the formula (ETM-5-1) can be cited. Preferably an aryl group having 6 to 16 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms, and particularly preferably an aryl group having 6 to 10 carbon atoms. Specific examples thereof include: phenyl, biphenyl, naphthyl, terphenyl, anthracenyl, acenaphthenyl, fluorenyl, phenalkenyl, phenanthrenyl, triphenylenyl, pyrenyl, tetracenyl, perylenyl, and the like.

Ar²Independently represents hydrogen, alkyl (preferably C1-C24 alkyl), cycloalkyl (preferably C3-C12 cycloalkyl) or aryl (preferably C6-C30 aryl), or two Ar²May be bonded to form a ring.

As Ar²The "alkyl group" in (1) may be either a straight chain or branched chain, and examples thereof include a straight chain alkyl group having 1 to 24 carbon atoms and a branched chain alkyl group having 3 to 24 carbon atoms. The preferred "alkyl group" is an alkyl group having 1 to 18 carbon atoms (branched chain alkyl group having 3 to 18 carbon atoms). More preferably, the "alkyl group" is an alkyl group having 1 to 12 carbon atoms (branched chain alkyl group having 3 to 12 carbon atoms). Further preferred "alkyl group" is an alkyl group having 1 to 6 carbon atoms (branched chain alkyl group having 3 to 6 carbon atoms). Particularly preferred "alkyl group" is an alkyl group having 1 to 4 carbon atoms (branched chain alkyl group having 3 to 4 carbon atoms). Specific examples of the "alkyl group" include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, 1-methylpentyl, 4-methyl-2-pentyl, 3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl and the like.

As Ar²Examples of the "cycloalkyl group" in (1) include cycloalkyl groups having 3 to 12 carbon atoms. The preferable "cycloalkyl group" is a cycloalkyl group having 3 to 10 carbon atoms. More preferred "cycloalkyl" isA cycloalkyl group having 3 to 8 carbon atoms. Further preferred "cycloalkyl group" is a cycloalkyl group having 3 to 6 carbon atoms. Specific "cycloalkyl" groups include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl, dimethylcyclohexyl, or the like.

As Ar²The "aryl group" in (1) is preferably an aryl group having 6 to 30 carbon atoms, more preferably an aryl group having 6 to 18 carbon atoms, still more preferably an aryl group having 6 to 14 carbon atoms, and particularly preferably an aryl group having 6 to 12 carbon atoms.

Specific examples of the "aryl group having 6 to 30 carbon atoms" include: phenyl, naphthyl, acenaphthenyl, fluorenyl, phenalkenyl, phenanthrenyl, triphenylenyl, pyrenyl, tetracenyl, perylenyl, pentacenyl, and the like.

Two Ar²A ring may be bonded to form a ring, and as a result, cyclobutane, cyclopentane, cyclopentene, cyclopentadiene, cyclohexane, fluorene, indene, or the like may be spiro-bonded to the 5-membered ring of the fluorene skeleton.

Specific examples of the benzofluorene derivative include the following compounds.

[ solution 280]

The benzofluorene derivative can be produced using a known raw material and a known synthesis method.

< phosphine oxide derivative >

The phosphine oxide derivative is, for example, a compound represented by the following formula (ETM-7-1). Details are also described in international publication No. 2013/079217.

[ Hua 281]

R⁵Is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aryl group having 5 to 20 carbon atoms(ii) a heteroaryl group, wherein,

R⁶CN, substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, cycloalkyl group having 3 to 20 carbon atoms, heteroalkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, heteroaryl group having 5 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms or aryloxy group having 6 to 20 carbon atoms,

R⁷and R⁸Independently represents a substituted or unsubstituted aryl group having 6 to 20 carbon atoms or a heteroaryl group having 5 to 20 carbon atoms,

R⁹is oxygen or sulfur, and is selected from the group consisting of,

j is 0 or 1, k is 0 or 1, r is an integer of 0 to 4, and q is an integer of 1 to 3.

Here, as the substituent in the case of substitution, there may be mentioned: aryl, heteroaryl, alkyl or cycloalkyl, and the like.

The phosphine oxide derivative may be, for example, a compound represented by the following formula (ETM-7-2).

[ solution 282]

R¹～R³Which may be the same or different, are selected from the group consisting of condensed rings formed with hydrogen, alkyl, cycloalkyl, aralkyl, alkenyl, cycloalkenyl, alkynyl, alkoxy, alkylthio, cycloalkylthio, aryl ether, arylthioether, aryl, heterocyclic, halogen, cyano, aldehyde, carbonyl, carboxyl, amino, nitro, silane and adjacent substituents.

Ar¹Which may be the same or different, is an arylene or heteroarylene group. Ar (Ar)²Which may be the same or different, are aryl or heteroaryl. Wherein Ar is¹And Ar²Has a substituent, or forms a condensed ring with an adjacent substituent. n is an integer of 0 to 3, and when n is 0, no unsaturated moiety is present, and when n is 3, no R is present¹。

Among these substituents, the alkyl group means, for example, a saturated aliphatic hydrocarbon group such as a methyl group, an ethyl group, a propyl group, or a butyl group, and may be unsubstituted or substituted. The substituent in the case of substitution is not particularly limited, and examples thereof include an alkyl group, an aryl group, and a heterocyclic group, and these are also common in the following description. The number of carbons of the alkyl group is not particularly limited, and is usually in the range of 1 to 20 in terms of easiness of obtaining and cost.

The cycloalkyl group means a saturated alicyclic hydrocarbon group such as a cyclopropyl group, a cyclohexyl group, a norbornyl group, an adamantyl group and the like, and may be unsubstituted or substituted. The number of carbon atoms in the alkyl moiety is not particularly limited, and is usually within a range of 3 to 20.

The aralkyl group means an aromatic hydrocarbon group via an aliphatic hydrocarbon such as a benzyl group or a phenylethyl group, and both the aliphatic hydrocarbon and the aromatic hydrocarbon may be unsubstituted or substituted. The number of carbon atoms in the aliphatic moiety is not particularly limited, and is usually in the range of 1 to 20.

The alkenyl group means an unsaturated aliphatic hydrocarbon group containing a double bond such as a vinyl group, an allyl group, or a butadienyl group, and may be unsubstituted or substituted. The number of carbon atoms of the alkenyl group is not particularly limited, and is usually in the range of 2 to 20.

The cycloalkenyl group means an unsaturated alicyclic hydrocarbon group having a double bond, such as cyclopentenyl group, cyclopentadienyl group, cyclohexenyl group, and the like, and may be unsubstituted or substituted.

The alkynyl group means an unsaturated aliphatic hydrocarbon group containing a triple bond such as an ethynyl group, and may be unsubstituted or substituted. The carbon number of the alkynyl group is not particularly limited, and is usually in the range of 2 to 20.

The alkoxy group means, for example, an aliphatic hydrocarbon group having an ether bond such as a methoxy group, and the aliphatic hydrocarbon group may be unsubstituted or substituted. The number of carbon atoms of the alkoxy group is not particularly limited, and is usually in the range of 1 to 20.

The alkylthio group is a group in which an oxygen atom of an ether bond of an alkoxy group is substituted with a sulfur atom.

The cycloalkylthio group is a group in which an oxygen atom of an ether bond of a cycloalkoxy group is substituted with a sulfur atom.

The aryl ether group means an aromatic hydrocarbon group such as a phenoxy group via an ether bond, and the aromatic hydrocarbon group may be unsubstituted or substituted. The number of carbon atoms of the aryl ether group is not particularly limited, and is usually in the range of 6 to 40.

The arylthioether group is a group in which an oxygen atom of an ether bond of an arylether group is substituted with a sulfur atom.

The aryl group represents, for example, an aromatic hydrocarbon group such as a phenyl group, a naphthyl group, a biphenyl group, a phenanthryl group, a terphenyl group, or a pyrenyl group. The aryl group may be unsubstituted or substituted. The number of carbons of the aryl group is not particularly limited, and is usually in the range of 6 to 40.

The heterocyclic group represents a cyclic structural group having an atom other than carbon, such as a furyl group, a thienyl group, an oxazolyl group, a pyridyl group, a quinolyl group, and a carbazolyl group, and may be unsubstituted or substituted. The number of carbon atoms of the heterocyclic group is not particularly limited, and is usually in the range of 2 to 30.

Halogen means fluorine, chlorine, bromine and iodine.

The aldehyde group, carbonyl group, and amino group may include groups substituted with aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, heterocycles, and the like.

Further, the aliphatic hydrocarbon, alicyclic hydrocarbon, aromatic hydrocarbon, and heterocyclic ring may be unsubstituted or substituted.

The silyl group means, for example, a silicon compound group such as a trimethylsilyl group, which may be unsubstituted or substituted. The number of carbon atoms of the silyl group is not particularly limited, and is usually in the range of 3 to 20. The number of silicon is usually 1 to 6.

The condensed ring formed between the ring and an adjacent substituent is, for example, Ar¹And R²、Ar¹And R³、Ar²And R²、Ar²And R³、R²And R³、Ar¹And Ar²Etc. to form conjugated or non-conjugated condensed rings therebetween. Here, in the case where n is 1, two R' s¹May form conjugated or non-conjugated condensed rings with each other. These condensed rings may contain a nitrogen atom, an oxygen atom, a sulfur atom in the ring inner structure, and may further be condensed with other rings.

Specific examples of the phosphine oxide derivative include the following compounds.

[ 283] chemical reaction

The phosphine oxide derivatives can be produced using known starting materials and known synthesis methods.

[ pyrimidine derivative ]

The pyrimidine derivative is, for example, a compound represented by the following formula (ETM-8), and preferably a compound represented by the following formula (ETM-8-1). Details are also described in international publication No. 2011/021689.

[ CHEMICAL 284]

Ar is independently aryl which may be substituted or heteroaryl which may be substituted. n is an integer of 1 to 4, preferably an integer of 1 to 3, more preferably 2 or 3.

Examples of the "aryl group" of the "aryl group which may be substituted" include aryl groups having 6 to 30 carbon atoms, preferably aryl groups having 6 to 24 carbon atoms, more preferably aryl groups having 6 to 20 carbon atoms, and still more preferably aryl groups having 6 to 12 carbon atoms.

Specific "aryl" groups include: phenyl as monocyclic aryl group, (2-, 3-, 4-) biphenyl as bicyclic aryl group, (1-, 2-) naphthyl as condensed bicyclic aryl group, (m-terphenyl-2 '-yl, m-terphenyl-4' -yl, m-terphenyl-5 '-yl, o-terphenyl-3' -yl, o-terphenyl-4 '-yl, p-terphenyl-2' -yl, m-terphenyl-2-yl, m-terphenyl-3-yl, m-terphenyl-4-yl, o-terphenyl-2-yl, o-terphenyl-3-yl, o-terphenyl-4-yl, p-terphenyl-2-yl, p-terphenyl-3-yl, P-terphenyl-4-yl), acenaphthylene- (1-, 3-, 4-, 5-) as condensed tricyclic aryl, fluorene- (1-, 2-, 3-, 4-, 9-) yl, phenalene- (1-, 2-) yl, (1-, 2-, 3-, 4-, 9-) phenanthryl, tetrabiphenyl (5' -phenyl-m-terphenyl-2-yl, 5' -phenyl-m-terphenyl-3-yl, 5' -phenyl-m-terphenyl-4-yl, m-quaterphenyl) as tetracyclic aryl, triphenylene- (1-, 2-) as condensed tetracyclic aryl, pyrene- (1-, 2-, 4-) group, tetracene- (1-, 2-, 5-) group, perylene- (1-, 2-, 3-) group as condensed pentacyclic aryl group, pentacene- (1-, 2-, 5-, 6-) group, and the like.

Examples of the "heteroaryl group" of the "heteroaryl group which may be substituted" include a heteroaryl group having 2 to 30 carbon atoms, preferably a heteroaryl group having 2 to 25 carbon atoms, more preferably a heteroaryl group having 2 to 20 carbon atoms, still more preferably a heteroaryl group having 2 to 15 carbon atoms, and particularly preferably a heteroaryl group having 2 to 10 carbon atoms. Examples of the heteroaryl group include heterocyclic rings containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen as ring-constituting atoms in addition to carbon.

Specific examples of the heteroaryl group include: furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxadiazolyl, furazanyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, benzofuranyl, isobenzofuranyl, benzo [ b ] thienyl, indolyl, isoindolyl, 1H-indazolyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, naphthyridine ring, purinyl, pteridinyl, carbazolyl, acridinyl, phenoxazinyl, phenothiazinyl, phenazinyl, phenoxathiin, thianthrenyl, indolizinyl and the like.

In addition, the aryl and heteroaryl groups may be substituted, for example by the aryl or heteroaryl groups, respectively.

Specific examples of the pyrimidine derivative include the following compounds.

[ solution 285]

The pyrimidine derivative can be produced using a known raw material and a known synthesis method.

< carbazole derivative >

The carbazole derivative is, for example, a compound represented by the following formula (ETM-9) or a polymer in which a plurality of carbazole derivatives are bonded to each other by a single bond or the like. The details are described in U.S. patent application publication No. 2014/0197386.

[ solution 286]

Ar is independently aryl which may be substituted or heteroaryl which may be substituted. n is an integer of 0 to 4, preferably an integer of 0 to 3, and more preferably 0 or 1.

Examples of the "aryl group" of the "aryl group which may be substituted" include aryl groups having 6 to 30 carbon atoms, preferably aryl groups having 6 to 24 carbon atoms, more preferably aryl groups having 6 to 20 carbon atoms, and still more preferably aryl groups having 6 to 12 carbon atoms.

Specific "aryl" groups include: phenyl as monocyclic aryl group, (2-, 3-, 4-) biphenyl as bicyclic aryl group, (1-, 2-) naphthyl as condensed bicyclic aryl group, (m-terphenyl-2 '-yl, m-terphenyl-4' -yl, m-terphenyl-5 '-yl, o-terphenyl-3' -yl, o-terphenyl-4 '-yl, p-terphenyl-2' -yl, m-terphenyl-2-yl, m-terphenyl-3-yl, m-terphenyl-4-yl, o-terphenyl-2-yl, o-terphenyl-3-yl, o-terphenyl-4-yl, p-terphenyl-2-yl, p-terphenyl-3-yl, P-terphenyl-4-yl), acenaphthylene- (1-, 3-, 4-, 5-) as condensed tricyclic aryl, fluorene- (1-, 2-, 3-, 4-, 9-) yl, phenalene- (1-, 2-) yl, (1-, 2-, 3-, 4-, 9-) phenanthryl, tetrabiphenyl (5' -phenyl-m-terphenyl-2-yl, 5' -phenyl-m-terphenyl-3-yl, 5' -phenyl-m-terphenyl-4-yl, m-quaterphenyl) as tetracyclic aryl, triphenylene- (1-, 2-) as condensed tetracyclic aryl, pyrene- (1-, 2-, 4-) group, tetracene- (1-, 2-, 5-) group, perylene- (1-, 2-, 3-) group as condensed pentacyclic aryl group, pentacene- (1-, 2-, 5-, 6-) group, and the like.

Examples of the "heteroaryl group" of the "heteroaryl group which may be substituted" include a heteroaryl group having 2 to 30 carbon atoms, preferably a heteroaryl group having 2 to 25 carbon atoms, more preferably a heteroaryl group having 2 to 20 carbon atoms, still more preferably a heteroaryl group having 2 to 15 carbon atoms, and particularly preferably a heteroaryl group having 2 to 10 carbon atoms. Examples of the heteroaryl group include heterocyclic rings containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen as ring-constituting atoms in addition to carbon.

Specific examples of the heteroaryl group include: furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxadiazolyl, furazanyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, benzofuranyl, isobenzofuranyl, benzo [ b ] thienyl, indolyl, isoindolyl, 1H-indazolyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, naphthyridine ring, purinyl, pteridinyl, carbazolyl, acridinyl, phenoxazinyl, phenothiazinyl, phenazinyl, phenoxathiin, thianthrenyl, indolizinyl and the like.

In addition, the aryl and heteroaryl groups may be substituted, for example by the aryl or heteroaryl groups, respectively.

The carbazole derivative may be a polymer in which a plurality of compounds represented by the formula (ETM-9) are bonded by a single bond or the like. In this case, the bond may be an aryl ring (preferably a polyvalent benzene ring, naphthalene ring, anthracene ring, fluorene ring, benzofluorene ring, phenalene ring, phenanthrene ring, or triphenylene ring) other than a single bond.

Specific examples of the carbazole derivative include the following compounds.

[ CHEMICAL 287]

The carbazole derivative can be produced using a known raw material and a known synthesis method.

< triazine derivative >

The triazine derivative is, for example, a compound represented by the following formula (ETM-10), and preferably a compound represented by the following formula (ETM-10-1). The details are described in U.S. patent application publication No. 2011/0156013.

[ solution 288]

Ar is independently aryl which may be substituted or heteroaryl which may be substituted. n is an integer of 1 to 3, preferably 2 or 3.

Examples of the "aryl group" of the "aryl group which may be substituted" include aryl groups having 6 to 30 carbon atoms, preferably aryl groups having 6 to 24 carbon atoms, more preferably aryl groups having 6 to 20 carbon atoms, and still more preferably aryl groups having 6 to 12 carbon atoms.

Specific "aryl" groups include: phenyl as monocyclic aryl group, (2-, 3-, 4-) biphenyl as bicyclic aryl group, (1-, 2-) naphthyl as condensed bicyclic aryl group, (m-terphenyl-2 '-yl, m-terphenyl-4' -yl, m-terphenyl-5 '-yl, o-terphenyl-3' -yl, o-terphenyl-4 '-yl, p-terphenyl-2' -yl, m-terphenyl-2-yl, m-terphenyl-3-yl, m-terphenyl-4-yl, o-terphenyl-2-yl, o-terphenyl-3-yl, o-terphenyl-4-yl, p-terphenyl-2-yl, p-terphenyl-3-yl, P-terphenyl-4-yl), acenaphthylene- (1-, 3-, 4-, 5-) as condensed tricyclic aryl, fluorene- (1-, 2-, 3-, 4-, 9-) yl, phenalene- (1-, 2-) yl, (1-, 2-, 3-, 4-, 9-) phenanthryl, tetrabiphenyl (5' -phenyl-m-terphenyl-2-yl, 5' -phenyl-m-terphenyl-3-yl, 5' -phenyl-m-terphenyl-4-yl, m-quaterphenyl) as tetracyclic aryl, triphenylene- (1-, 2-) as condensed tetracyclic aryl, pyrene- (1-, 2-, 4-) group, tetracene- (1-, 2-, 5-) group, perylene- (1-, 2-, 3-) group as condensed pentacyclic aryl group, pentacene- (1-, 2-, 5-, 6-) group, and the like.

Examples of the "heteroaryl group" of the "heteroaryl group which may be substituted" include a heteroaryl group having 2 to 30 carbon atoms, preferably a heteroaryl group having 2 to 25 carbon atoms, more preferably a heteroaryl group having 2 to 20 carbon atoms, still more preferably a heteroaryl group having 2 to 15 carbon atoms, and particularly preferably a heteroaryl group having 2 to 10 carbon atoms. Examples of the heteroaryl group include heterocyclic rings containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen as ring-constituting atoms in addition to carbon.

Specific examples of the heteroaryl group include: furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxadiazolyl, furazanyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, benzofuranyl, isobenzofuranyl, benzo [ b ] thienyl, indolyl, isoindolyl, 1H-indazolyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, naphthyridine ring, purinyl, pteridinyl, carbazolyl, acridinyl, phenoxazinyl, phenothiazinyl, phenazinyl, phenoxathiin, thianthrenyl, indolizinyl and the like.

In addition, the aryl and heteroaryl groups may be substituted, for example by the aryl or heteroaryl groups, respectively.

Specific examples of the triazine derivative include the following compounds.

[ 289]

The triazine derivative can be produced using a known raw material and a known synthesis method.

< benzimidazole derivative >

The benzimidazole derivative is, for example, a compound represented by the following formula (ETM-11).

[ solution 290]

Phi- (benzimidazole substituent) n (ETM-11)

Phi is an n-valent aryl ring (preferably an n-valent benzene ring, naphthalene ring, anthracene ring, fluorene ring, benzofluorene ring, phenalene ring, phenanthrene ring or triphenylene ring), n is an integer of 1 to 4, the "benzimidazole substituent" is a substituent in which a pyridyl group in the "pyridine substituent" of the formulae (ETM-2), (ETM-2-1) and (ETM-2-2) is substituted with a benzimidazole group, and at least one hydrogen in the benzimidazole derivative may be substituted with deuterium.

[ formulation 291]

R in said benzimidazolyl group¹¹Hydrogen, an alkyl group having 1 to 24 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms or an aryl group having 6 to 30 carbon atoms, and R in the above formulae (ETM-2-1) and (ETM-2-2)¹¹And (4) description.

φ is further preferably an anthracycline or fluorene ring, and the structure in this case can be referred to the description in said formula (ETM-2-1) or formula (ETM-2-2), R in each formula¹¹～R¹⁸Reference may be made to the description in said formula (ETM-2-1) or formula (ETM-2-2). In addition, although the formula (ETM-2-1) or the formula (ETM-2-2) has been described as the form in which two pyridine substituents are bonded, when these are substituted with benzimidazole substituents, two pyridine substituents may be substituted with benzimidazole substituents (that is, n ═ 2), or any one pyridine substituent may be substituted with benzimidazole substituents and R may be substituted with benzimidazole substituents¹¹～R¹⁸Substituted with another pyridine substituent (i.e., n ═ 1). Further, R in the formula (ETM-2-1) may be substituted with a benzimidazole-based substituent¹¹～R¹⁸At least one of R and¹¹～R¹⁸substituted "pyridine-based substituents".

Specific examples of the benzimidazole derivative include: 1-phenyl-2- (4- (10-phenylanthren-9-yl) phenyl) -1H-benzo [ d ] imidazole, 2- (4- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl) -1-phenyl-1H-benzo [ d ] imidazole, 2- (3- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl) -1-phenyl-1H-benzo [ d ] imidazole, 5- (10- (naphthalen-2-yl) anthracen-9-yl) -1, 2-diphenyl-1H-benzo [ d ] imidazole, 1- (4- (10- (naphthalen-2-yl) anthracen-9-yl) phenyl) -2-phenyl-1H-imidazole H-benzo [ d ] imidazole, 2- (4- (9, 10-di (naphthalen-2-yl) anthracen-2-yl) phenyl) -1-phenyl-1H-benzo [ d ] imidazole, 1- (4- (9, 10-di (naphthalen-2-yl) anthracen-2-yl) phenyl) -2-phenyl-1H-benzo [ d ] imidazole, 5- (9, 10-di (naphthalen-2-yl) anthracen-2-yl) -1, 2-diphenyl-1H-benzo [ d ] imidazole, and the like.

[ solution 292]

The benzimidazole derivative can be produced using a known raw material and a known synthesis method.

[ phenanthroline derivative ]

The phenanthroline derivative is, for example, a compound represented by the following formula (ETM-12) or formula (ETM-12-1). The details are described in international publication No. 2006/021982.

[ Hua 293]

Phi is an n-valent aryl ring (preferably an n-valent benzene ring, naphthalene ring, anthracene ring, fluorene ring, benzofluorene ring, phenalene ring, phenanthrene ring or triphenylene ring), and n is an integer of 1-4.

Of the formulae R¹¹～R¹⁸Each independently hydrogen, alkyl (preferably C1-C24 alkyl), cycloalkyl (preferably C3-C12 cycloalkyl) or aryl (preferably C6-C30 aryl). Further, in the formula (ETM-12-1), R¹¹～R¹⁸Is bonded to phi as the aryl ring.

At least one hydrogen in each phenanthroline derivative may be substituted by deuterium.

As R¹¹～R¹⁸Alkyl, cycloalkyl and aryl in (1), R in said formula (ETM-2) can be cited¹¹～R¹⁸And (4) description. Further, regarding φ, for example, other than the examples described aboveThe following structural formulae are exemplified. In the following structural formulae, R is independently hydrogen, methyl, ethyl, isopropyl, cyclohexyl, phenyl, 1-naphthyl, 2-naphthyl, biphenyl or terphenyl.

[ solution 294]

Specific examples of the phenanthroline derivative include: 4, 7-diphenyl-1, 10-phenanthroline, 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline, 9, 10-bis (1, 10-phenanthroline-2-yl) anthracene, 2, 6-bis (1, 10-phenanthroline-5-yl) pyridine, 1,3, 5-tris (1, 10-phenanthrolin-5-yl) benzene, 9' -difluoro-bis (1, 10-phenanthrolin-5-yl), 2, 9-dimethyl-4, 7-biphenyl-1, 10-phenanthroline (bathocuproine), 1, 3-bis (2-phenyl-1, 10-phenanthrolin-9-yl) benzene, a compound represented by the following structural formula, or the like.

[ solution 295]

The phenanthroline derivative can be produced using a known raw material and a known synthesis method.

< hydroxyquinoline-based metal complex >

The hydroxyquinoline metal complex is, for example, a compound represented by the following general formula (ETM-13).

[ solution 296]

In the formula, R¹～R⁶Each independently is hydrogen, fluoro, alkyl, cycloalkyl, aralkyl, alkenyl, cyano, alkoxy or aryl, MIs Li, Al, Ga, Be or Zn, and n is an integer of 1-3.

Specific examples of the hydroxyquinoline metal complex include: lithium 8-quinolinolate, aluminum tris (8-quinolinolate), aluminum tris (4-methyl-8-quinolinolate), aluminum tris (5-methyl-8-quinolinolate), aluminum tris (3, 4-dimethyl-8-quinolinolate), aluminum tris (4, 5-dimethyl-8-quinolinolate), aluminum tris (4, 6-dimethyl-8-quinolinolate), aluminum bis (2-methyl-8-quinolinolate) (phenoxide), aluminum bis (2-methyl-8-quinolinolate) (2-methylphenol), aluminum bis (2-methyl-8-quinolinolate) (3-methylphenol), aluminum bis (2-methyl-8-quinolinolate) (4-methylphenol), aluminum tris (4-methyl-8-quinolinolate), Bis (2-methyl-8-quinolinolato) (2-phenylphenol) aluminum, bis (2-methyl-8-quinolinolato) (3-phenylphenol) aluminum, bis (2-methyl-8-quinolinolato) (4-phenylphenol) aluminum, bis (2-methyl-8-quinolinolato) (2, 3-dimethylphenol) aluminum, bis (2-methyl-8-quinolinolato) (2, 6-dimethylphenol) aluminum, bis (2-methyl-8-quinolinolato) (3, 4-dimethylphenol) aluminum, bis (2-methyl-8-quinolinolato) (3, 5-dimethylphenol) aluminum, bis (2-methyl-8-quinolinolato) (3, 5-di-tert-butylphenol) aluminum, bis (2-methyl-8-quinolinolato) (2, 6-diphenylphenol) aluminum, bis (2-methyl-8-quinolinolato) (2,4, 6-triphenylpheno) aluminum, bis (2-methyl-8-quinolinolato) (2,4, 6-trimethylphenol) aluminum, bis (2-methyl-8-quinolinolato) (2,4, 5, 6-tetramethylphenol) aluminum, bis (2-methyl-8-quinolinolato) (1-naphthol) aluminum, bis (2-methyl-8-quinolinolato) (2-naphthol) aluminum, bis (2, 4-dimethyl-8-quinolinolato) (2-phenylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2-naphthol) aluminum, bis (2, 4-dimethyl-8-quinolinolato) (3-phenylphenol) aluminum, bis (2, 4-dimethyl-8-quinolinolato) (4-phenylphenol) aluminum, bis (2, 4-dimethyl-8-quinolinolato) (3, 5-dimethylphenol) aluminum, bis (2, 4-dimethyl-8-quinolinolato) (3, 5-di-tert-butylphenol) aluminum, bis (2-methyl-8-quinolinolato) aluminum- μ -oxo-bis (2-methyl-8-quinolinolato) aluminum, bis (2, 4-dimethyl-8-quinolinolato) aluminum- μ -oxo-bis (2, 4-dimethyl-8-quinolinolato) aluminum, aluminum, Bis (2-methyl-4-ethyl-8-quinolinolato) aluminum- μ -oxo-bis (2-methyl-4-ethyl-8-quinolinolato) aluminum, bis (2-methyl-4-methoxy-8-quinolinolato) aluminum- μ -oxo-bis (2-methyl-4-methoxy-8-quinolinolato) aluminum, bis (2-methyl-5-cyano-8-quinolinolato) aluminum- μ -oxo-bis (2-methyl-5-cyano-8-quinolinolato) aluminum, bis (2-methyl-5-trifluoromethyl-8-quinolinolato) aluminum- μ -oxo-bis (2-methyl-5-trifluoromethyl-8-quinolinolato) aluminum -hydroxyquinoline) aluminum, bis (10-hydroxybenzo [ h ] quinoline) beryllium, and the like.

The hydroxyquinoline metal complex can be produced using a known raw material and a known synthesis method.

< thiazole derivatives and benzothiazole derivatives >

Examples of the thiazole derivative include compounds represented by the following formula (ETM-14-1).

[ Hua 297]

Phi- (thiazole substituent) n (ETM-14-1)

The benzothiazole derivative is, for example, a compound represented by the following formula (ETM-14-2).

[ 298]

Phi- (benzothiazole substituent) n (ETM-14-2)

Phi is an n-valent aryl ring (preferably an n-valent benzene ring, naphthalene ring, anthracene ring, fluorene ring, benzofluorene ring, phenalene ring, phenanthrene ring or triphenylene ring), n is an integer of 1 to 4, and a "thiazole substituent" or a "benzothiadiazole substituent" is a substituent in which a pyridyl group in the "pyridine substituent" of the formula (ETM-2), the formula (ETM-2-1) or the formula (ETM-2-2) is substituted with a thiazolyl group or a benzothiazolyl group, and at least one of the thiazole derivative and the benzothiazole derivative may be substituted with deuterium.

[ 299]

φ is further preferably an anthracycline or fluorene ring, and the structure in this case can be referred to the description in said formula (ETM-2-1) or formula (ETM-2-2), R in each formula¹¹～R¹⁸Reference may be made to the description in said formula (ETM-2-1) or formula (ETM-2-2). In addition, the formula (ETM-2-1) or (ETM-2-2) is described in the form of a bond with two pyridine substituents, but these substituents can be substituted with thiazole substituents (or benzothiazole substituents)Two pyridine substituents (i.e., n ═ 2) are substituted with a group (or a benzothiazole substituent), and either one of the pyridine substituents may be substituted with a thiazole substituent (or a benzothiazole substituent) and R may be substituted with a group (or a benzothiazole substituent)¹¹～R¹⁸Substituted with another pyridine substituent (i.e., n ═ 1). Further, R in the formula (ETM-2-1) may be substituted with a thiazole-based substituent (or a benzothiazole-based substituent), for example¹¹～R¹⁸At least one of R and¹¹～R¹⁸substituted "pyridine-based substituents".

These thiazole derivatives and benzothiazole derivatives can be produced using known starting materials and known synthetic methods.

In the electron transport layer or the electron injection layer, a substance capable of reducing a material forming the electron transport layer or the electron injection layer may be further contained. As the reducing substance, various substances can be used as long as they have a certain reducing property, and for example, at least one selected from the group consisting of alkali metals, alkaline earth metals, rare earth metals, oxides of alkali metals, halides of alkali metals, oxides of alkaline earth metals, halides of alkaline earth metals, oxides of rare earth metals, halides of rare earth metals, organic complexes of alkali metals, organic complexes of alkaline earth metals, and organic complexes of rare earth metals can be used as appropriate.

Preferred reducing substances include: alkali metals such as Na (work function of 2.36eV), K (work function of 2.28eV), Rb (work function of 2.16eV), and Cs (work function of 1.95eV), alkaline earth metals such as Ca (work function of 2.9eV), Sr (work function of 2.0 to 2.5eV), and Ba (work function of 2.52eV), and particularly preferred is a substance having a work function of 2.9eV or less. Among these reducing substances, K, Rb or Cs is a more preferable alkali metal, Rb or Cs is more preferable, and Cs is most preferable. These alkali metals have particularly high reducing power, and the addition of a relatively small amount of these alkali metals to the material forming the electron transporting layer or the electron injecting layer can improve the emission luminance and prolong the life of the organic EL element. In addition, as the reducing substance having a work function of 2.9eV or less, a combination of two or more kinds of the alkali metals is also preferable, and a combination including Cs, for example, a combination of Cs and Na, a combination of Cs and K, Cs and Rb, or a combination of Cs and Na and K is particularly preferable. By containing Cs, the reducing ability can be efficiently exhibited, and by adding Cs to a material for forming an electron transporting layer or an electron injecting layer, the emission luminance of an organic EL element can be improved or the lifetime thereof can be prolonged.

< cathode in organic electroluminescent element >

The cathode 108 functions to inject electrons into the light-emitting layer 105 through the electron injection layer 107 and the electron transport layer 106.

The material forming the cathode 108 is not particularly limited as long as it can efficiently inject electrons into the organic layer, and the same material as the material forming the anode 102 can be used. Among them, metals such as tin, indium, calcium, aluminum, silver, copper, nickel, chromium, gold, platinum, iron, zinc, lithium, sodium, potassium, cesium, and magnesium, and alloys thereof (e.g., magnesium-silver alloys, magnesium-indium alloys, and aluminum-lithium alloys such as lithium fluoride and aluminum) are preferable. In order to improve the electron injection efficiency to improve the element characteristics, lithium, sodium, potassium, cesium, calcium, magnesium, or an alloy containing these low work function metals is effective. However, these low work function metals are generally unstable in the atmosphere in many cases. In order to improve this, for example, a method of doping a minute amount of lithium, cesium, or magnesium into an organic layer and using an electrode having high stability is known. As other dopants, inorganic salts such as lithium fluoride, cesium fluoride, lithium oxide, and cesium oxide can also be used. However, the present invention is not limited to these examples.

Further, the following preferable examples are listed: metals such as platinum, gold, silver, copper, iron, tin, aluminum, and indium, alloys using these metals, and inorganic substances such as silicon dioxide, titanium dioxide, and silicon nitride, polyvinyl alcohol, vinyl chloride, hydrocarbon-based polymer compounds, and the like are laminated to protect the electrodes. The method of manufacturing these electrodes is not particularly limited as long as conduction can be achieved by resistance heating, electron beam evaporation, sputtering, ion plating, coating, or the like.

< Binders applicable to the respective layers >

The materials for the hole injection layer, the hole transport layer, the light emitting layer, the electron transport layer, and the electron injection layer may be individually formed into each layer, or may be dispersed in a solvent-soluble resin such as polyvinyl chloride, polycarbonate, polystyrene, poly (N-vinylcarbazole), polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, polyphenylene oxide (polyphenylene oxide), polybutadiene, a hydrocarbon resin, a ketone resin, a phenoxy resin, polyamide, ethyl cellulose, a vinyl acetate resin, an Acrylonitrile-Butadiene-Styrene (ABS) resin, or a polyurethane resin as a polymer binder, or a curable resin such as phenol resin, xylene resin, petroleum resin, urea resin, melamine resin, unsaturated polyester resin, alkyd resin, epoxy resin, or silicone resin.

< method for manufacturing organic electroluminescent element >

Each layer constituting the organic EL element can be formed by forming a material to be each layer into a thin film by a method such as vapor deposition, resistance heating vapor deposition, electron beam vapor deposition, sputtering, molecular lamination, printing, spin coating, casting, or coating. The film thickness of each layer formed in the above-described manner is not particularly limited, and may be appropriately set according to the properties of the material, but is usually in the range of 2nm to 5000 nm. The film thickness can be measured by a crystal oscillation type film thickness measuring apparatus or the like. When a thin film is formed by a vapor deposition method, the vapor deposition conditions vary depending on the type of material, the target crystal structure and the association structure of the film, and the like. The deposition conditions are preferably set to +50 ℃ to +400 ℃ in the boat heating temperature and 10 degrees of vacuum^-6Pa～10^-3Pa, a deposition rate of 0.01nm/sec to 50nm/sec, a substrate temperature of-150 ℃ to +300 ℃, and a film thickness of 2nm to 5 μm.

Next, as an example of a method for manufacturing an organic EL element, a method for manufacturing an organic EL element including an anode, a hole injection layer, a hole transport layer, a light-emitting layer including a host material and a dopant material, an electron transport layer, an electron injection layer, and a cathode will be described. An anode is formed by forming a thin film of an anode material on an appropriate substrate by vapor deposition or the like, and then a thin film of a hole injection layer and a hole transport layer is formed on the anode. A thin film is formed thereon by co-evaporation of a host material and a dopant material to form a light-emitting layer, an electron-transporting layer and an electron-injecting layer are formed on the light-emitting layer, and a thin film containing a substance for a cathode is formed thereon by an evaporation method or the like to form a cathode, thereby obtaining a target organic EL element. In the production of the organic EL element, the order of production may be reversed, and the organic EL element may be produced by using a cathode, an electron injection layer, an electron transport layer, a light-emitting layer, a hole transport layer, a hole injection layer, and an anode in this order.

When a dc voltage is applied to the organic EL element obtained as described above, the anode may be applied with a + polarity and the cathode may be applied with a-polarity, and when a voltage of about 2V to 40V is applied, light emission can be observed from the transparent or translucent electrode side (anode or cathode, or both). In addition, the organic EL element emits light even when a pulse current or an alternating current is applied thereto. Further, the waveform of the applied alternating current may be arbitrary.

< example of application of organic electroluminescent element >

The present invention is also applicable to a display device including an organic EL element, an illumination device including an organic EL element, and the like.

The display device or the lighting device including the organic EL element can be manufactured by a known method such as connecting the organic EL element of this embodiment to a known driving device, and can be driven by a known driving method such as direct current driving, pulse driving, or alternating current driving.

Examples of the display device include: a panel display such as a color flat panel display, a flexible display such as a flexible color organic Electroluminescence (EL) display, and the like (for example, refer to japanese patent laid-open No. 10-335066, japanese patent laid-open No. 2003-321546, and japanese patent laid-open No. 2004-281086). Examples of the display mode of the display include a matrix mode and a segment mode. Further, the matrix display and the segment display may coexist in the same panel.

The matrix is a matrix in which pixels for display are two-dimensionally arranged in a lattice shape, a mosaic shape, or the like, and characters or images are displayed by a set of pixels. The shape or size of the pixel is determined according to the application. For example, in image and character display of a personal computer, a monitor, and a television, a rectangular pixel having a side of 300 μm or less is generally used, and in the case of a large-sized display such as a display panel, a pixel having a side of mm level is used. In the case of monochrome display, pixels of the same color may be arranged, and in the case of color display, pixels of red, green, and blue are arranged in parallel to perform display. In this case, a triangular shape and a striped shape are typical. Also, as a driving method of the matrix, any one of a line-sequential (line-sequential) driving method or an active matrix may be used. The line sequential driving has an advantage of a simple structure, but when the operation characteristics are taken into consideration, the active matrix is sometimes more excellent, and therefore the driving method needs to be used separately depending on the application.

In the segment method (type), a pattern is formed so as to display information determined in advance, and the determined region is caused to emit light. Examples thereof include: time and temperature display in a digital clock or a thermometer, operation state display of an audio device or an induction cooker, panel display of an automobile, and the like.

Examples of the lighting device include: for example, a lighting device for indoor lighting, a backlight for a liquid crystal display device, and the like (see, for example, japanese patent laid-open nos. 2003-257621, 2003-277741, and 2004-119211). Backlights are used mainly for improving visibility of display devices that do not emit light, and are used for liquid crystal display devices, clocks, audio devices, automobile panels, display panels, signs, and the like. In particular, as a backlight for personal computer applications in which thinning is an issue in liquid crystal display devices, considering that thinning is difficult in the conventional method because of including a fluorescent lamp or a light guide plate, the backlight using the light emitting element of the present embodiment has features of being thin and lightweight.

3-2. other organic devices

The polycyclic aromatic compound of the present invention can be used for the production of an organic field effect transistor, an organic thin film solar cell, or the like, in addition to the organic electroluminescent element.

An organic field effect transistor is a transistor that controls current by an electric field generated by voltage input, and includes a gate electrode in addition to a source electrode and a drain electrode. A transistor in which an electric field is generated when a voltage is applied to a gate electrode, and a flow of electrons (or holes) flowing between a source electrode and a drain electrode is arbitrarily blocked to control a current. A field effect transistor is easy to be miniaturized compared with a single transistor (bipolar transistor), and is often used as an element constituting an integrated circuit or the like.

In general, the organic field effect transistor may be configured such that a source electrode and a drain electrode are provided in contact with an organic semiconductor active layer formed using the polycyclic aromatic compound of the present invention, and a gate electrode is provided through an insulating layer (dielectric layer) in contact with the organic semiconductor active layer. Examples of the element structure include the following structures.

(1) Substrate/gate electrode/insulator layer/source and drain electrodes/organic semiconductor active layer

(2) Substrate, gate electrode, insulator layer, organic semiconductor active layer, source electrode and drain electrode

(3) Substrate/organic semiconductor active layer/source electrode and drain electrode/insulator layer/gate electrode

(4) Substrate/source and drain electrodes/organic semiconductor active layer/insulator layer/gate electrode

The organic field effect transistor thus configured can be used as a pixel driving switching element of an active matrix driving type liquid crystal display, an organic electroluminescence display, or the like.

An organic thin-film solar cell has a structure in which an anode such as ITO, a hole transport layer, a photoelectric conversion layer, an electron transport layer, and a cathode are stacked on a transparent substrate such as glass. The photoelectric conversion layer has a p-type semiconductor layer on the anode side and an n-type semiconductor layer on the cathode side. The polycyclic aromatic compound of the present invention can be used as a material for a hole transport layer, a p-type semiconductor layer, an n-type semiconductor layer, and an electron transport layer, depending on the physical properties thereof. In an organic thin film solar cell, the polycyclic aromatic compound of the present invention can function as a hole transport material or an electron transport material. The organic thin-film solar cell may also be provided with a hole blocking layer, an electron injection layer, a hole injection layer, a smoothing layer, and the like as appropriate, in addition to the above. In the organic thin film solar cell, known materials for the organic thin film solar cell may be appropriately selected for use in combination.

Examples

The present invention will be further specifically described below with reference to examples, but the present invention is not limited to these examples. First, an example of synthesis of a polycyclic aromatic compound will be described below.

Synthesis example (1)

Synthesis of Compound (1-1)

[ equation 300]

Under a nitrogen atmosphere, 1,2, 3-trichloro-5-trifluoromethylbenzene (10.0g), bis (4- (tert-butyl) phenyl) amine (24.8g), bis (dibenzylideneacetone) palladium (0) (Pd (dba)₂A flask of 0.46g), 2-dicyclohexylphosphino-2 ',6' -dimethoxybiphenyl (SPhos, 0.82g), sodium tert-butoxide (NaOtBu, 9.6g) and xylene (130ml) was heated and stirred at 110 ℃ for 1 hour. After the reaction solution was cooled to room temperature, water and ethyl acetate were added to separate the reaction solution. After the organic layer was washed with water, the solvent was distilled off under reduced pressure. Thereafter, purification was carried out using a silica gel short column (eluent: toluene), and reprecipitation was carried out using heptane, whereby intermediate A (17.1g) was obtained.

[ solution 301]

A tert-butyllithium/pentane solution (1.62M, 28.4ml) was charged into a flask containing intermediate A (17.0g) and tert-butylbenzene (120ml) while cooling with an ice bath under a nitrogen atmosphere. After the completion of the dropwise addition, the temperature was raised to 60 ℃ and the mixture was stirred for 1 hour, and the components having a boiling point lower than that of tert-butylbenzene were distilled off under reduced pressure. Cooled to-50 ℃ and boron tribromide (11.5g) was added, warmed to room temperature and stirred for 0.5 h. Thereafter, it was cooled again by means of an ice bath, and N, N-diisopropylethylamine (5.9g) was added. After stirring at room temperature until the heat generation was completed, the temperature was raised to 100 ℃ and the mixture was stirred for 1 hour. The reaction solution was cooled to room temperature, and then an aqueous sodium acetate solution cooled by an ice bath and ethyl acetate were sequentially added thereto to separate the reaction solution, and then the solvent was distilled off under reduced pressure and washed with heptane. Then, the mixture was purified by a silica gel short column (eluent: toluene), reprecipitated with heptane, and finally purified by sublimation to obtain a compound (3.2g) of the formula (1-1).

[ solution 302]

The structure of the obtained compound was confirmed by Nuclear Magnetic Resonance (NMR) measurement.

¹H-NMR(400MHz,CDCl₃)：δ＝1.5(s,18H),1.5(s,18H),6.4(s,2H),7.8(d,2H),7.3(m,4H),7.6(dd,2H),7.7(m,4H),9.0(d,2H).

Synthesis example (2)

Synthesis of Compound (1-82)

[ solution 303]

Under nitrogen atmosphere, 1,3, 5-tribromobenzene (1.57g), 4' -difluorodiphenylamine (3.28g), and tris (dibenzylideneacetone) dipalladium (0) (Pd) were placed₂(dba)₃0.229g), tri-tert-butylphosphine (0.101g), calcium tert-butoxide (KOtBu, 2.24g) and toluene (40ml) were heated and stirred at 100 ℃ for 20 hours. The reaction solution was cooled to room temperature, and then filtered through a magnesium silicate (Florisil) (registered trademark) pad, thereby allowing dichloromethane to flow. Concentrating the filtrate, and removing the crude product with methanolWashed, thereby obtaining intermediate B (2.84 g).

[ solution 304]

Boron tribromide (19.0. mu.l, 0.20mmol) was added to intermediate B (0.137g, 0.20mmol) and 2, 4-dichlorobenzene (2.0ml) under a nitrogen atmosphere at room temperature, and the mixture was stirred at 200 ℃ for 20 hours. Thereafter, the mixture was cooled to room temperature, N-diisopropylethylamine (0.10ml, 0.6mmol) was added thereto, and the solvent was distilled off under reduced pressure. The crude product was washed with acetonitrile, whereby the compound of formula (1-82) was obtained as a yellow solid (0.128g, yield 92%).

[ solution 305]

The structure of the obtained compound was confirmed by NMR measurement and mass analysis.

¹H NMR(CDCl₃Delta ppm of (delta ppm in CDCl)₃))：5.44(s,2H),6.67(dd,2H),6.82-6.93(m,8H),7.12(ddd,2H),7.16-7.23(m,8H),8.42(dd,2H).

¹³C NMR(CDCl₃δ ppm of (d): 96.9(2C),116.0(4C),118.0(4C),118.4-118.8(7C),125.2(2C),127.7(4C),132.0(4C),138.0(2C),142.2(2C),144.2(2C),148.2(2C),151.9(1C),157.2(2C),159.7(2C),162.3(2C).

High Resolution Mass Spectrometry (HRMS) (direct analysis in real time, DART)) M/z [ M + H]⁺Calculated value (calcd for) C₄₂H₂₄BF₆N₃696.2046 observed (observed)696.2097.

Synthesis example (3)

Synthesis of Compound (1-701)

[ solution 306]

Boron triiodide (0.391g, 0.10mmol) and triphenylborane (96.7mg, 0.40mmol) were added to intermediate B (0.138g, 0.20mmol) and 1, 2-dichlorobenzene (5ml) at room temperature under a nitrogen atmosphere, and stirred at 200 ℃ for 20 hours. Thereafter, the mixture was cooled to room temperature, N-diisopropylethylamine (0.52ml, 3mmol) was added thereto, and the solvent was distilled off under reduced pressure. The crude product was washed with acetonitrile, whereby the compound of formula (1-701) was obtained as a yellow solid (81.9mg, yield 58%).

[ solution 307]

The structure of the obtained compound was confirmed by NMR measurement and mass analysis.

¹H NMR(500MHz,(CDCl₂)₂)δ＝5.10(s,1H,a),6.87(dd,J＝4.5,9.0Hz,2H),7.14-7.35(m,12H),8.23(dd,J＝4.5,9.5Hz,2H),8.38(dd,J＝3.0,9.0Hz,2H),8.46(dd,J＝3.0,9.0Hz,2H).

¹³C NMR(101MHz,(CDCl₂)₂)δ＝92.6(2C),93.2(1C),93.7(2C),99.5(1C),110.4(2C),116.3-119.2(m,6C),124.6(2C),125.7(dd,J_C-F＝7.2,20.4Hz,2C),131.2(2C),131.7(2C),132.1(2C),137.4(2C),142.9(2C),143.7(2C),146.8(2C),149.9(4C),157.5(d,J_C-F＝242.3Hz,2C),158.9(d,J_C-F＝245.9Hz,2C),162.4(d,J_C-F＝254.3Hz,2C).

¹¹B NMR(128MHz,(CDCl₂)₂)δ＝37.2.

¹⁹F NMR(376MHz,(CDCl₂)₂)δ＝-123.0,-119.0,-112.3.

HRMS(DART)m/z[M+H]⁺Calculated value C₄₂H₂₁B₂F₆N₃704.1888, respectively; observed value 704.1918.

Synthesis example (4)

Compound (1-883): synthesis of 5, 9-bis (2, 6-difluorophenyl) -2,7, 12-tris (2, 6-dimethylphenyl) -5, 9-dihydro-5, 9-diaza-13 b-boranonaphtho [3,2,1-de ] anthracene

[ chemical 308]

Under a nitrogen atmosphere, 1-bromo-4-iodobenzene (14.2g, 50.0mmol), 2, 6-dimethylphenylboronic acid (7.50g, 50.0mmol), tetrakis (triphenylphosphine) palladium (Pd (PPh) were placed₃)₄A flask of 1.16g, 1.00mmol, potassium carbonate (20.7g, 150mmol), toluene (175ml), and methanol (75.0ml) was heated to 80 ℃ and stirred for 36 hours. The reaction solution was cooled to room temperature, poured into water, and the aqueous layer was extracted with toluene. The obtained organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by means of a silica gel column (eluent: hexane), whereby 4 '-bromo-2, 6-dimethyl-1, 1' -biphenyl (9.71g, yield 74%) was obtained as a white solid.

[ solution 309]

The structure of the obtained compound was confirmed by NMR measurement.

¹H-NMR(500MHz,CDCl₃)：δ＝2.02(s,6H),7.00-7.04(m,2H),7.10(d,J＝7.5Hz,2H),7.17(t,J＝8.0Hz,1H),7.53-7.56(m,2H).

Under a nitrogen atmosphere, 4 '-bromo-2, 6-dimethyl-1, 1' -biphenyl (9.14g, 35.0mmol), 2, 6-difluoroaniline (5.31ml, 52.5mmol), Pd were placed in the flask₂(dba)₃A flask of (0.481g, 0.525mmol), 2 '-bis (diphenylphosphino) -1,1' -binaphthyl (BINAP, 0.654g, 1.05mmol), NaOtBu (5.05g, 52.5mmol), and toluene (175ml) was heated to 110 ℃ and stirred for 12 hours. After the reaction solution was cooled to room temperature, it was poured into water, and the aqueous layer was extracted with toluene. The obtained organic layer was subjected to waterWashed and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by a silica gel short path column (eluent: hexane/toluene 3/1 (volume ratio)), and further washed with hexane, thereby obtaining N- (2, 6-difluorophenyl) -2',6' -dimethyl- [1,1' -biphenyl ] as a white solid]-4-amine (9.93g, 92% yield).

[ chemical 310]

The structure of the obtained compound was confirmed by NMR measurement.

¹H-NMR(500MHz,CDCl₃)：δ＝2.06(s,6H),5.53(s,1H),6.87(d,J＝8.6Hz,2H),6.94-7.06(m,5H),7.07-7.17(m,3H).

Under nitrogen atmosphere, 1-bromo-3, 5-dichlorobenzene (11.3g, 50.0mmol), 2, 6-dimethylphenylboronic acid (9.00g, 60.0mmol), Pd (PPh) were placed in the flask₃)₄A flask of (1.16g, 1.00mmol), potassium carbonate (20.7g, 150mmol), toluene (175ml), and methanol (75.0ml) was heated to 65 ℃ and stirred for 16 hours. After the reaction solution was cooled to room temperature, it was poured into water, and the aqueous layer was extracted with toluene. The obtained organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by means of a silica gel column (eluent: hexane), whereby 3',5' -dichloro-2, 6-dimethyl-1, 1' -biphenyl (11.8g, yield 94%) was obtained as a colorless liquid.

[ solution 311]

The structure of the obtained compound was confirmed by NMR measurement.

¹H-NMR(500MHz,CDCl₃)：δ＝2.03(s,6H),7.05(d,J＝1.7Hz,2H),7.09(d,J＝7.5Hz,2H),7.17(t,J＝7.5Hz,1H),7.35(t,J＝1.7Hz,1H).

Under a nitrogen atmosphere, 3',5' -dichloro-2, 6-dimethyl-1, 1 '-biphenyl (3.01g, 12.0mmol), N- (2, 6-difluorophenyl) -2',6 '-dimethyl- [1,1' -biphenyl were placed]-4-amine (8.17g, 26.4mmol), Pd₂(dba)₃A flask of (0.275g, 0.300mmol), SPhos (0.246g, 0.600mmol), NaOtBu (2.54g, 26.4mmol), and toluene (60.0ml) was heated to 110 ℃ and stirred for 16 hours. After the reaction solution was cooled to room temperature, it was poured into water, and the aqueous layer was extracted with toluene. The obtained organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by a silica gel short path column (eluent: hexane/toluene 3/1 (volume ratio)), and further washed successively with methanol and hexane, thereby obtaining N in the form of a white solid³,N⁵-bis (2, 6-difluorophenyl) -N³,N⁵-bis (2',6' -dimethyl- [1,1' -biphenyl)]-4-yl) -2',6' -dimethyl- [1,1' -biphenyl]3, 5-diamine (8.08g, 85% yield).

[ solution 312]

The structure of the obtained compound was confirmed by NMR measurement.

¹H-NMR(500MHz,CDCl₃)：δ＝2.01(s,12H),2.10(s,6H),6.46(d,J＝2.0Hz,2H),6.83(t,J＝2.4Hz,1H),6.89-6.98(m,8H),7.03-7.17(m,15H).

Under nitrogen atmosphere, putting N³,N⁵-bis (2, 6-difluorophenyl) -N³,N⁵-bis (2',6' -dimethyl- [1,1' -biphenyl)]-4-yl) -2',6' -dimethyl- [1,1' -biphenyl]A flask of (E) -3, 5-diamine (1.59g, 2.00mmol), boron triiodide (6.26g, 16.0mmol), and 1,2, 4-trichlorobenzene (20.0ml) was heated to 150 ℃ and stirred for 12 hours. After the reaction solution was cooled to room temperature, hydrogen iodide in the reaction solution was distilled off under reduced pressure. After the reaction solution was diluted by adding dichloromethane (150ml), a phosphate buffer solution (pH 7,200ml) was added at 0 ℃, and water was extracted with dichloromethaneAnd (3) a layer. The obtained organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, the obtained solid was dissolved in toluene (35.0ml), acetic acid (7.00ml, 122mmol) was added, and the mixture was stirred under heating at 80 ℃ for 12 hours. The reaction solution was cooled to room temperature, and a saturated aqueous solution (100ml) of sodium hydrogencarbonate was added at room temperature to extract an aqueous layer with toluene. The obtained organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by a silica gel column (eluent: hexane/dichloromethane 2/1 (volume ratio)) and washed with acetonitrile at 80 ℃ under heating, whereby the compound of formula (1-883) was obtained as a yellow solid (1.09g, yield 68%).

[ solution 313]

The structure of the obtained compound was confirmed by NMR measurement.

¹H-NMR(500MHz,CDCl₃)：δ＝1.99(s,6H),2.11(s,12H),6.18(s,2H),6.83(d,J＝8.6Hz,2H),7.04(d,J＝7.5Hz,2H),7.09-7.18(m,7H),7.18-7.31(m,6H),7.50-7.58(m,2H),8.60(d,J＝1.4Hz,2H).

¹³C-NMR(126MHz,CDCl₃)：20.8(2C),21.3(4C),105.6(2C),113.5(d,J_C-F＝22.8Hz,4C),115.2(2C),116.3(1C),118.6(t,J_C-F＝18.0Hz,2C),124.4(2C),127.0(2C),127.2(1C),127.4(2C),127.6(4C),130.9(t,J_C-F＝9.6Hz,2C),133.2(2C),133.5(2C),135.8(2C),136.3(2C),136.7(4C),141.6(2C),142.5(1C),145.3(2C),145.9(2C),146.1(1C),160.6(dd,J_C-F＝3.7,250.7Hz,4C).

Synthesis example (5)

Compound (1-1674): n is a radical of⁷,N¹³5, 15-tetrakis (2, 6-difluorophenyl) -N⁷,N¹³9, 11-tetraphenyl-5, 9,11, 15-tetrahydro-5, 9,11, 15-tetraaza-19 b,20 b-diborono [3,2,1-de:1',2',3' -jk]Synthesis of pentacene-7, 13-diamine

[ chemical 314]

Under nitrogen atmosphere, bromobenzene (5.25ml, 50.0mmol), 2, 6-difluoroaniline (7.59ml, 75.0mmol) and Pd were placed₂(dba)₃A flask of (0.687mg, 0.750mmol), BINAP (0.934g, 1.50mmol), NaOtBu (7.21g, 75.0mmol), and toluene (150ml) was heated to 110 ℃ and stirred for 4 hours. The reaction solution was cooled to room temperature, poured into water, and the aqueous layer was extracted with toluene. The obtained organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by a silica gel short path column (eluent: hexane/toluene-5/1 (volume ratio)), whereby 2, 6-difluoro-N-phenylaniline was obtained as a colorless liquid (10.1g, yield 98%).

[ solution 315]

The structure of the obtained compound was confirmed by NMR measurement.

¹H-NMR(500MHz,CDCl₃)：δ＝5.48(s,1H),6.81(dd,J＝1.2,7.5Hz,2H),6.89-7.06(m,4H),7.21-7.27(m,2H).

Under a nitrogen atmosphere, 1, 3-dibromo-5-chlorobenzene (4.87g, 18.0mmol), 2, 6-difluoro-N-phenylaniline (7.39g, 36.0mmol), Pd were placed₂(dba)₃A flask of (0.330g, 0.360mmol), SPhos (0.296g, 0.720mmol), NaOtBu (5.19g, 54.0mmol), and toluene (90.0ml) was heated to 100 ℃ and stirred for 3 hours. The reaction solution was cooled to room temperature, poured into water, and the aqueous layer was extracted with toluene. The obtained organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by a silica gel column (eluent: hexane/toluene 3/1 (volume ratio)), and further purified by methanolWashing, thereby obtaining 5-chloro-N in the form of a white solid¹,N³-bis (2, 6-difluorophenyl) -N¹,N³Diphenylbenzene-1, 3-diamine (7.17g, 77% yield).

[ chemical 316]

The structure of the obtained compound was confirmed by NMR measurement.

¹H-NMR(500MHz,CDCl₃)：δ＝6.40(t,J＝1.7Hz,1H),6.45(d,J＝1.7Hz,2H),6.89-6.96(m,4H),6.98-7.07(m,6H),7.14-7.25(m,6H).

Under a nitrogen atmosphere, N synthesized according to the method described in International publication No. 2018/212169 is put in¹,N³Diphenylbenzene-1, 3-diamine (0.521g, 2.00mmol), 5-chloro-N¹,N³-bis (2, 6-difluorophenyl) -N¹,N³Diphenylbenzene-1, 3-diamine (2.28g, 4.40mmol), Pd₂(dba)₃A flask of (0.0916g, 0.100mmol), SPhos (0.0821g, 0.200mmol), NaOtBu (0.577g, 6.00mmol), and toluene (10.0ml) was heated to 110 ℃ and stirred for 8 hours. The reaction solution was cooled to room temperature, poured into water, and the aqueous layer was extracted with toluene. The obtained organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by a silica gel column (eluent: hexane/ethyl acetate 3/1 (volume ratio)), and further washed with hexane, thereby obtaining N as a white solid¹,N¹' - (1, 3-phenylene) bis (N)³,N⁵-bis (2, 6-difluorophenyl) -N¹,N³,N⁵Triphenylbenzene-1, 3, 5-triamine) (1.96g, yield 80%).

[ chemical 317]

The structure of the obtained compound was confirmed by NMR measurement.

¹H-NMR(500MHz,CDCl₃)：δ＝6.28-6.31(m,6H),6.60(dd,J＝2.3,8.0Hz,2H),6.74(t,J＝2.2Hz,1H),6.79-6.98(m,27H),7.02-7.14(m,16H).

Under nitrogen atmosphere, and at room temperature, putting N¹,N¹' - (1, 3-phenylene) bis (N)³,N⁵-bis (2, 6-difluorophenyl) -N¹,N³,N⁵Boron tribromide (0.990ml, 10.4mmol) was charged into a flask of (1.59g, 1.30mmol) of (E) -triphenylbenzene-1, 3, 5-triamine and (19.5ml) 1,2, 4-trichlorobenzene, and the mixture was stirred at 180 ℃ for 20 hours. After the reaction solution was cooled to room temperature, the residual boron tribromide and hydrogen bromide in the reaction solution were distilled off under reduced pressure. After the reaction solution was diluted by adding dichloromethane (150ml), a phosphoric acid buffer solution (pH 7,300ml) was added at 0 ℃, and the aqueous layer was extracted with dichloromethane. The obtained organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the obtained solid was subjected to heat washing at 80 ℃ with acetonitrile, whereby the compound of formula (1-1674) was obtained as a yellow solid (0.886g, yield 55%).

[ solution 318]

The structure of the obtained compound was confirmed by NMR measurement.

¹H-NMR(500MHz,CDCl₃)：δ＝5.49(d,J＝2.3Hz,2H),5.59(s,2H),5.73(s,1H),6.70-6.82(m,6H),6.91-7.00(m,6H),7.00-7.14(m,16H),7.14-7.19(m,4H),7.32-7.40(m,4H),7.46-7.51(m,2H),9.22(dd,J＝1.7,7.5Hz,2H),10.5(s,1H).

¹³C-NMR(126MHz,CDCl₃)：93.7(2C),96.6(2C),103.4(1C),112.1(d,J_C-F＝24.0Hz,4C),112.4(2C),112.9(d,J_C-F＝22.8Hz,4C),115.1(2C),118.4(2C),118.7(t,J_C-F＝17.3Hz,2C),120.9(2C),122.1(t,J_C-F＝14.5Hz,2C),124.0(2C),124.1(4C),125.1(2C),127.3(t,J＝11.1Hz,2C),127.5(2C),128.8(4C),129.8(4C),130.1(4C+2C),131.1(2C),135.7(2C),141.8(2C),143.7(1C),144.6(2C),146.6(2C),146.8(2C),148.5(2C),150.0(2C),150.4(2C),160.4(dd,J_C-F＝4.2,254.7Hz,4C),160.5(dd,J_C-F＝4.2,253.6Hz,4C).

Synthesis example (6)

Compound (1-1668): 9, 11-bis (2, 4-difluorophenyl) -N⁷,N⁷,N¹³,N¹³5, 15-Hexaphenyl-5, 9,11, 15-tetrahydro-5, 9,11, 15-tetraaza-19 b,20 b-diborono [3,2,1-de:1',2',3' -jk]Synthesis of pentacene-7, 13-diamine

[ formulation 319]

Under nitrogen atmosphere, 1, 3-dibromobenzene (1.22ml, 10.0mmol), 2, 4-difluoroaniline (2.54ml, 25.0mmol), Pd₂(dba)₃A flask of (0.183g, 0.200mmol), SPhos (0.164g, 0.400mmol), NaOtBu (2.88g, 30.0mmol), and toluene (100ml) was heated to 40 ℃ and stirred for 6 hours. The reaction solution was cooled to room temperature, poured into water, and the aqueous layer was extracted with toluene. The obtained organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by a silica gel short path column (eluent: toluene) and further washed with hexane, whereby N was obtained as a white solid¹,N³Bis (2, 4-difluorophenyl) benzene-1, 3-diamine (1.94g, 58% yield).

[ solution 320]

The structure of the obtained compound was confirmed by NMR measurement.

¹H-NMR(500MHz,CDCl₃)：δ＝5.54(s,2H),6.55-6.62(m,3H),6.76-6.83(m,2H),6.86(ddd,J＝2.9,8.6,10.9Hz,2H),7.15(t,J＝8.0Hz,1H),7.26(ddd,J＝5.7,9.2,9.2Hz).

Under nitrogen atmosphere, putting N¹,N³Bis (2, 4-difluorophenyl) benzene-1, 3-diamine (0.997mg, 3.00mmol), 5-chloro-N synthesized according to the method described in International publication No. 2018/212169¹,N¹,N³,N³Tetraphenylphenyl-1, 3-diamine (2.95g, 6.60mmol), Pd₂(dba)₃A flask of (0.137g, 0.150mmol), SPhos (0.123g, 0.300mmol), NaOtBu (0.865g, 9.00mmol), and toluene (15.0ml) was heated to 110 ℃ and stirred for 24 hours. The reaction solution was cooled to room temperature, poured into water, and the aqueous layer was extracted with toluene. The obtained organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by a silica gel column (eluent: hexane/dichloromethane 3/2 (volume ratio)), and further washed with ethyl acetate, thereby obtaining N as a white solid¹,N¹' - (1, 3-phenylene) bis (N)¹- (2, 4-difluorophenyl) -N³,N³,N⁵,N⁵Tetraphenylbenzene-1, 3, 5-triamine) (2.76g, yield 80%).

[ solution 321]

The structure of the obtained compound was confirmed by NMR measurement.

¹H-NMR(500MHz,CDCl₃)：δ＝6.25(d,J＝2.3Hz,4H),6.38(t,J＝2.3Hz,2H),6.41-6.46(m,3H),6.65-6.74(m,4H),6.85-7.02(m,27H),7.09-7.16(m,16H).

Under nitrogen atmosphere, and at room temperature, putting N¹,N¹' - (1, 3-phenylene) bis (N)¹- (2, 4-difluorophenyl) -N³,N³,N⁵,N⁵Boron tribromide (0.114ml, 1.20mmol) was charged into a flask of (0.173g, 0.150mmol) tetraphenylbenzene-1, 3, 5-triamine and (3.00ml) 1,2, 4-trichlorobenzene, and stirred at 180 ℃ for 20 hours. Will be reversedAfter the solution was cooled to room temperature, the residual boron tribromide and hydrogen bromide in the reaction solution were distilled off under reduced pressure. After the reaction solution was diluted by adding dichloromethane (30.0ml), a phosphoric acid buffer solution (pH 7,100ml) was added at 0 ℃, and the aqueous layer was extracted with dichloromethane. The obtained organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the obtained solid was washed with heating at 80 ℃ with acetonitrile. Then, heat washing was performed by toluene at 110 ℃ to obtain the compound of formula (1-1668) as a yellow solid (0.121g, yield 69%).

[ solution 322]

The structure of the obtained compound was confirmed by NMR measurement.

¹H-NMR(500MHz,(CDCl₂)₂)：δ＝5.61(d,J＝5.7Hz,1H),5.66(s,2H),5.66(d,J＝1.7Hz,2H),6.71-6.83(m,6H),6.90-6.99(m,12H),7.02-7.13(m,10H),7.21-7.26(m,4H),7.29-7.38(m,4H),7.38-7.49(m,6H),9.20(dd,J＝1.7,8.0Hz,2H),10.5(s,1H).

¹³C-NMR(126MHz,CDCl₃)：93.7(2C),96.6(2C),103.4(1C),112.1(d,J_C-F＝24.0Hz,4C),112.4(2C),112.9(d,J_C-F＝22.8Hz,4C),115.1(2C),118.4(2C),118.7(t,J_C-F＝17.3Hz,2C),120.9(2C),122.1(t,J_C-F＝14.5Hz,2C),124.0(2C),124.1(4C),125.1(2C),127.3(t,J＝11.1Hz,2C),127.5(2C),128.8(4C),129.8(4C),130.1(4C+2C),131.1(2C),135.7(2C),141.8(2C),143.7(1C),144.6(2C),146.6(2C),146.8(2C),148.5(2C),150.0(2C),150.4(2C),160.4(dd,J_C-F＝4.2,254.7Hz,4C),160.5(dd,J_C-F＝4.2,253.6Hz,4C).

Synthesis example (7)

Compound (1-1666): 9, 11-bis (2, 6-difluorophenyl) -N⁷,N⁷,N¹³,N¹³5, 15-hexaphenyl-5, 9,11, 15-tetrahydro-5, 9,11, 15-tetraaza-19 b,20 b-diborodinaphthaleneAnd [3,2,1-de:1',2',3' -jk]Synthesis of pentacene-7, 13-diamine

[ solution 323]

Under nitrogen atmosphere, 1, 3-dibromobenzene (1.22ml, 10.0mmol), 2, 6-difluoroaniline (3.04ml, 30.0mmol), Pd₂(dba)₃A flask of (0.183g, 0.200mmol), SPhos (0.164g, 0.400mmol), NaOtBu (2.88g, 30.0mmol), and toluene (50.0ml) was heated to 60 ℃ and stirred for 2 hours. After the reaction solution was cooled to room temperature, it was poured into water, and the aqueous layer was extracted with toluene. The obtained organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by a silica gel short path column (eluent: toluene) and further washed with hexane, whereby N was obtained as a white solid¹,N³Bis (2, 6-difluorophenyl) benzene-1, 3-diamine (3.20g, 96% yield).

[ solution 324]

The structure of the obtained compound was confirmed by NMR measurement.

¹H-NMR(500MHz,CDCl₃)：δ＝5.43(s,2H),6.26(s,1H),6.36(d,J＝8.0Hz,2H),6.90-6.98(m,4H),6.98-7.05(m,2H),7.09(t,J＝8.0Hz,1H).

Under nitrogen atmosphere, putting N¹,N³Bis (2, 6-difluorophenyl) benzene-1, 3-diamine (1.16g, 3.50mmol), 5-chloro-N-diamine synthesized according to the method described in International publication No. 2018/212169¹,N¹,N³,N³Tetraphenylphenyl-1, 3-diamine (3.44g, 7.70mmol), Pd₂(dba)₃A flask of (0.160g, 0.180mmol), SPhos (0.144g, 0.350mmol), NaOtBu (1.01g, 10.5mmol), and toluene (17.5ml) was heated to 110 ℃ with stirringStirring for 40 hours. The reaction solution was cooled to room temperature, poured into water, and the aqueous layer was extracted with toluene. The obtained organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by a silica gel column (eluent: hexane/ethyl acetate 5/1 (volume ratio)), and further washed with ethyl acetate, thereby obtaining N as a white solid¹,N¹' - (1, 3-phenylene) bis (N)¹- (2, 6-difluorophenyl) -N³,N³,N⁵,N⁵Tetraphenylbenzene-1, 3, 5-triamine) (3.03g, yield 75%).

[ solution 325]

The structure of the obtained compound was confirmed by NMR measurement.

¹H-NMR(500MHz,CDCl₃)：δ＝6.29(d,J＝1.7Hz,4H),6.38(t,J＝2.3Hz,2H),6.41(t,J＝2.3Hz,1H),6.51(dd,J＝2.3,8.0Hz,2H),6.73-6.80(m,4H),6.85-6.91(m,9H),6.96-7.03(m,18H),7.09-7.16(m,16H).

Under nitrogen atmosphere, and at room temperature, putting N¹,N¹' - (1, 3-phenylene) bis (N)¹- (2, 6-difluorophenyl) -N³,N³,N⁵,N⁵Boron tribromide (1.75ml, 18.4mmol) was added to a flask of (2.65g, 2.30mmol) tetraphenylbenzene-1, 3, 5-triamine and (50.0ml) 1,2, 4-trichlorobenzene, and the mixture was stirred at 200 ℃ for 20 hours. After the reaction solution was cooled to room temperature, the residual boron tribromide and hydrogen bromide in the reaction solution were distilled off under reduced pressure. After the reaction solution was diluted by adding dichloromethane (500ml), a phosphate buffer solution (pH 7,400ml) was added at 0 ℃, and the aqueous layer was extracted with dichloromethane. The obtained organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the obtained solid was washed with heating at 80 ℃ with acetonitrile. Then, the column was heated and washed with toluene at 110 ℃ and then a silica gel short-path column was used(eluent: toluene) and further heated and washed with toluene at 110 ℃ to obtain the compound of formula (1-1666) (1.617g, yield 60%) as a yellow solid.

[ chemical 326]

The structure of the obtained compound was confirmed by NMR measurement.

¹H-NMR(500MHz,(CDCl₂)₂)：δ＝5.80(s,4H),5.91(s,1H),6.81-6.88(m,6H),6.99(t,J＝7.5Hz,4H),7.03(d,J＝8.0Hz,8H),7.15(t,J＝8.0Hz,8H),7.18-7.26(m,2H),7.33(d,J＝8.0Hz,4H),7.37-7.45(m,4H),7.45-7.50(m,2H),7.53(t,J＝8.0Hz,4H),9.30(d,J＝7.5Hz,2H),10.5(s,1H).

¹³C-NMR(126MHz,CDCl₃)：93.7(2C),96.6(2C),103.4(1C),112.1(d,J_C-F＝24.0Hz,4C),112.4(2C),112.9(d,J_C-F＝22.8Hz,4C),115.1(2C),118.4(2C),118.7(t,J_C-F＝17.3Hz,2C),120.9(2C),122.1(t,J_C-F＝14.5Hz,2C),124.0(2C),124.1(4C),125.1(2C),127.3(t,J＝11.1Hz,2C),127.5(2C),128.8(4C),129.8(4C),130.1(4C+2C),131.1(2C),135.7(2C),141.8(2C),143.7(1C),144.6(2C),146.6(2C),146.8(2C),148.5(2C),150.0(2C),150.4(2C),160.4(dd,J_C-F＝4.2,254.7Hz,4C),160.5(dd,J_C-F＝4.2,253.6Hz,4C).

Comparative Synthesis example (1)

Compound (C-1): synthesis of N, N,5, 9-tetraphenyl-5, 9-dihydro-5, 9-diaza-13 b-bora-naphtho [3,2,1-de ] anthracen-7-amine

[ solution 327]

Under nitrogen atmosphere and at room temperature to N¹,N¹,N³,N³,N⁵,N⁵Hexaphenyl-1, 3, 5-benzenetriamine (11.6g, 20 mm)ol) and o-dichlorobenzene (ODCB, 120ml), followed by addition of boron tribromide (3.78ml, 40mmol), was stirred at 170 ℃ for 48 hours. Thereafter, the reaction solution was distilled off at 60 ℃ under reduced pressure. The crude product was obtained by filtration using a magnesium silicate short path column (Florisil short path column) and distilling off the solvent under reduced pressure. The crude product was washed with hexane, whereby the compound of formula (C-1) (11.0g, yield 94%) was obtained as a yellow solid.

[ solution 328]

The structure of the obtained compound was confirmed by NMR measurement.

¹H-NMR(400MHz,CDCl₃)：δ＝5.62(brs,2H),6.71(d,2H),6.90-6.93(m,6H),7.05-7.09(m,4H),7.20-7.27(m,6H),7.33-7.38(m,4H),7.44-7.48(m,4H),8.90(dd,2H).

¹³C-NMR(101MHz,CDCl₃)：δ＝98.4(2C),116.8(2C),119.7(2C),123.5(2C),125.6(4C),128.1(2C),128.8(4C),130.2(4C),130.4(2C),130.7(4C),134.8(2C),142.1(2C),146.6(2C),147.7(2C),147.8(2C),151.1(4H).

Comparative Synthesis example (2)

Compound (C-2): n is a radical of⁷,N⁷,N¹³,N¹³5,9,11, 15-octaphenyl-5, 9,11, 15-tetrahydro-5, 9,11, 15-tetraaza-19 b,20 b-diborono [3,2,1-de:1',2',3' -jk]Synthesis of pentacene-7, 13-diamine

[ solution 329]

Under nitrogen atmosphere, 1, 3-dibromobenzene (25.0g, 106mmol), aniline (20.3ml, 223mmol), Pd₂(dba)₃A flask of (971mg, 1.06mmol), BINAP (1.98g, 3.18mmol), NaOtBu (25.5g, 265mmol) and toluene (400ml) was heated to 110 ℃ and stirred for 18 hours. Cooling the reaction liquidAfter the reaction mixture was cooled to room temperature, the mixture was filtered through silica gel (eluent: toluene), and the solvent was distilled off under reduced pressure to obtain a crude product. The crude product obtained was dissolved in toluene, an appropriate amount was distilled off under reduced pressure, hexane was added and reprecipitated, thereby obtaining N in the form of a white solid¹,N³Diphenylbenzene-1, 3-diamine (16.5g, 60% yield).

[ solution 330]

The structure of the obtained compound was confirmed by NMR spectrum.

¹H-NMR(400MHz,CDCl₃)：δ＝5.63(s,2H),6.60(dd,2H),6.74(t,1H),6.90(t,2H),7.06(d,4H),7.12(t,1H),7.24(dt,4H).

Under a nitrogen atmosphere, 1, 3-dibromo-5-chlorobenzene (8.11g, 30mmol), diphenylamine (10.1g, 60mmol), Pd were placed₂(dba)₃A flask of (550mg, 0.6mmol), SPhos (0.493g, 1.2mmol), NaOtBu (8.60g, 90mmol) and toluene (300ml) was heated to 80 ℃ and stirred for 15 hours. The reaction solution was cooled to room temperature, and filtered with silica gel (eluent: toluene), and the solvent was left under reduced pressure to obtain a crude product. The obtained crude product was dissolved in toluene and then distilled off under reduced pressure, thereby preparing a saturated solution, and hexane was added to reprecipitate it, thereby obtaining 5-chloro-N in the form of a white solid¹,N¹,N³,N³Tetraphenylbenzene-1, 3-diamine (5.66g, 43% yield).

[ solution 331]

The structure of the obtained compound was confirmed by NMR spectrum.

¹H-NMR(400MHz,CDCl₃)：δ＝6.56(d,2H),6.64(t,1H),7.00(t,4H),7.05(d,8H),7.21(dd,8H).

Under the nitrogen environment, the nitrogen gas is added,will be put in with N¹,N³Diphenylbenzene-1, 3-diamine (1.34g, 5.1mmol), 5-chloro-N¹,N¹,N³,N³Tetraphenylphenyl-1, 3-diamine (4.80g, 11mmol), Pd₂(dba)₃A flask of (0.140g, 0.15mmol), tri-tert-butylphosphine (60.7mg, 0.30mmol), NaOtBu (1.47g, 15mmol) and toluene (200ml) was heated to 110 ℃ and stirred for 8 hours. The reaction solution was cooled to room temperature, filtered through silica gel (eluent: toluene), and the solvent was distilled off under reduced pressure to obtain a crude product. The obtained crude product was washed with hexane, methanol successively, thereby obtaining N in the form of a white solid¹,N¹' - (1, 3-phenylene) bis (N)¹,N³,N³,N⁵,N⁵Pentaphenyl-1, 3, 5-triamine) (4.80g, yield 87%).

[ chemical 332]

The structure of the obtained compound was confirmed by NMR spectrum.

¹H-NMR(400MHz,CDCl₃)：δ＝6.38(d,4H),6.41(t,2H),6.58(dd,2H),6.70(t,1H),6.88-6.90(m,14H),6.85(t,1H),6.99(d,16H),7.08-7.15(m,20H).

Under nitrogen atmosphere and at room temperature, N is put into¹,N¹' - (1, 3-phenylene) bis (N)¹,N³,N³,N⁵,N⁵A flask of (E) -pentaphenylbenzene-1, 3, 5-triamine) (3.24g, 3.0mmol) and o-dichlorobenzene (400ml) was charged with boron tribromide (1.13ml, 12 mmol). After the end of the dropwise addition, the temperature was raised to 180 ℃ and stirred for 20 hours. Thereafter, the mixture was cooled again to room temperature, N-diisopropylethylamine (7.70ml, 45mmol) was added thereto, and the mixture was stirred until the completion of the generation of heat. Thereafter, the reaction solution was distilled off at 60 ℃ and under reduced pressure, thereby obtaining a crude product. The crude product obtained was washed with acetonitrile, methanol and toluene in this order, purified with a silica gel column (eluent: toluene), recrystallized twice with o-dichlorobenzene, and then purified at 1X 10^{- 4}Sublimation purification was carried out at 440 ℃ under reduced pressure of mmHg, whereby the compound of formula (C-2) (1.17g) was obtained.

[ 333]

The structure of the obtained compound was confirmed by NMR spectrum.

¹H-NMR(400MHz,CDCl₃)：δ＝5.72(s,2H),5.74(s,2H),5.86(s,1H),6.83(d,2H),6.88-6.93(m,12H),7.05(t,8H),7.12-7.19(m,6H),7.24-7.26(m,4H),7.05(d,4H),7.12(dd,8H),7.12-7.19(m,6H),7.32(d,4H),7.38(dd,2H),7.42(t,2H),7.46(dd,2H),7.47(dd,4H),9.30(d,2H),10.5(s,1H).

¹³C-NMR(101MHz,CDCl₃)：99.5(2C+2C),103.4(1C),116.8(2C),120.0(2C),123.1(4C),125.3(8C),127.1(2C),127.6(2C),128.5(8C),129.6(4C),129.8(4C),130.2(4C+2C),130.3(4C),135.0(2C),142.1(2C),142.5(2C),143.3(1C),146.8(4C),147.9(2C+2C),148.0(2C),150.1(2C),151.1(2C).

By appropriately changing the compounds as raw materials, other polycyclic aromatic compounds of the present invention can be synthesized by the method according to the above synthesis example.

Next, examples of the organic EL element using the compound of the present invention are shown in order to explain the present invention in more detail, but the present invention is not limited to these examples.

< evaluation of organic EL element >

An organic EL element of example 1 was produced and measured as 1000cd/m²Voltage (V) of characteristics at the time of light emission, light emission wavelength (nm), external quantum efficiency (%), and then the following times were measured: at 10mA/cm²The current density of (3) is constant current-driven, and the luminance of 98% or more of the initial luminance is maintained.

The quantum efficiency of a light-emitting element includes an internal quantum efficiency and an external quantum efficiency, and the internal quantum efficiency indicates a ratio of external energy injected as electrons (or holes) into a light-emitting layer of the light-emitting element to be converted into photons. On the other hand, the external quantum efficiency is calculated based on the amount of photons emitted to the outside of the light-emitting element, and since a part of the photons generated in the light-emitting layer is absorbed or continuously reflected by the inside of the light-emitting element without being emitted to the outside of the light-emitting element, the external quantum efficiency is lower than the internal quantum efficiency.

The external quantum efficiency was measured as follows. The luminance of the applied element reached 1000cd/m using a voltage/current generator R6144 manufactured by Edwardten test (Advantest)²The element emits light by the voltage of (3). The spectral radiance in the visible light region was measured from the vertical direction of the light emitting surface using a spectral radiance meter SR-3AR manufactured by Topycon (TOPCON). Assuming that the light-emitting surface is a perfect diffusion surface, the number obtained by dividing the measured value of the spectral emission luminance of each wavelength component by the wavelength energy and multiplying by pi is the number of photons at each wavelength. Then, the number of photons is integrated in the observed full wavelength region, and the total number of photons released from the element is set. A value obtained by dividing an applied current value by an element charge (elementary charge) is set as a carrier number injected into the element, and a value obtained by dividing a total photon number released from the element by a carrier number injected into the element is an external quantum efficiency.

The material composition and EL characteristic data of each layer of the organic EL device of example 1 thus produced are shown in tables 1A and 1B below.

[ Table 1A ]

[ Table 1B ]

In Table 1A, "HI" is N⁴,N^4'-diphenyl-N⁴,N^4'-bis (9-phenyl-9H-carbazol-3-yl) - [1,1' -biphenyl]-4,4' -diamine, "HAT-CN" is 1,4,5,8,9, 12-hexaazatriphenyleneHexacarbonitrile, "HT-1", is N- ([1,1' -biphenyl)]-4-yl) -9, 9-dimethyl-N- (4- (9-phenyl-9H-carbazol-3-yl) phenyl) -9H-fluoren-2-amine, "HT-2" is N, N-bis (4- (dibenzo [ b, d ] s)]Furan-4-yl) phenyl) - [1, 1': 4', 1' -terphenyl]-4-amine, "BH-1" is 2- (10-phenylanthracen-9-yl) naphtho [2,3-b]Benzofuran and "ET-1" is 4,6,8, 10-tetraphenyl [1, 4]]Benzoxaborole heterocyclohexeno [2,3,4-k1]Phenoxyboranyl heterocycle hexene, "ET-2," is 3,3' - ((2-phenylanthracene-9, 10-diyl) bis (4, 1-phenylene)) bis (4-methylpyridine). The chemical structure is shown below together with "Liq".

[ chemical formula 334]

< example 1 >

A glass substrate (manufactured by Opto Science) having a thickness of 180nm and a thickness of 26mm × 28mm × 0.7mm prepared by polishing ITO to 150nm was used as a transparent support substrate. The transparent support substrate was fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Showa vacuum deposition apparatus), and a molybdenum vapor deposition boat to which HI, HAT-CN, HT-1, HT-2, BH-1, compounds (1-1), ET-1, and ET-2 were added and an aluminum nitride vapor deposition boat to which Liq, LiF, and aluminum were added were attached.

The following layers are sequentially formed on the ITO film of the transparent support substrate. The vacuum vessel was depressurized to 5X 10^-4Pa, HI was heated and vapor deposition was performed so that the film thickness became 40nm, HAT-CN was heated and vapor deposition was performed so that the film thickness became 5nm, HT-1 was heated and vapor deposition was performed so that the film thickness became 45nm, HT-2 was heated and vapor deposition was performed so that the film thickness became 10nm, and thus a hole layer including four layers was formed. Then, BH-1 and the compound (1-1) were heated simultaneously, and vapor deposition was performed so that the film thickness became 25nm to form a light-emitting layer. The deposition rate was adjusted so that the weight ratio of BH-1 to the compound (1-1) became approximately 98 to 2. Then, ET-1 was heated to be deposited so that the film thickness became 5nm,then, ET-2 and Liq were simultaneously heated and vapor-deposited so that the film thickness became 25nm, thereby forming an electron layer including two layers. The deposition rate was adjusted so that the weight ratio of ET-2 to Liq became approximately 50 to 50. The deposition rate of each layer is 0.01nm/sec to 1 nm/sec. Then, LiF was heated and vapor deposition was performed at a vapor deposition rate of 0.01nm/sec to 0.1nm/sec so that the film thickness became 1nm, and then aluminum was heated and vapor deposition was performed so that the film thickness became 100nm to form a cathode, thereby obtaining an organic EL element.

An ITO electrode as an anode and a LiF/aluminum electrode as a cathode were applied with a DC voltage to measure 1000cd/m²As a result of the characteristics in light emission, blue light emission having a wavelength of 458nm was obtained, the driving voltage was 3.90V, and the external quantum efficiency was 7.89%.

The material composition and EL characteristic data of each layer of the organic EL devices of examples 2 to 8 and comparative examples 1 to 2 thus produced are shown in tables 2A and 2B below.

[ Table 2A ]

[ Table 2B ]

In Table 2A, "BH-2" is 2- (10-phenylanthracen-9-yl) dibenzo [ b, d ] furan. The chemical structures of the compound (C-1) and the compound (C-2) are shown below.

[ solution 335]

< example 2 >

A glass substrate (manufactured by Opto Science) having a thickness of 180nm and a thickness of 26mm × 28mm × 0.7mm prepared by polishing ITO to 150nm was used as a transparent support substrate. The transparent support substrate was fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Showa vacuum deposition apparatus), and a molybdenum vapor deposition boat to which HI, HAT-CN, HT-1, HT-2, BH-2, compounds (1-1), ET-1, and ET-2 were added and an aluminum nitride vapor deposition boat to which Liq, LiF, and aluminum were added were attached.

The following layers are sequentially formed on the ITO film of the transparent support substrate. The vacuum vessel was depressurized to 5X 10^-4Pa, HI was heated and vapor deposition was performed so that the film thickness became 40nm, HAT-CN was heated and vapor deposition was performed so that the film thickness became 5nm, HT-1 was heated and vapor deposition was performed so that the film thickness became 45nm, HT-2 was heated and vapor deposition was performed so that the film thickness became 10nm, and thus a hole layer including four layers was formed. Then, BH-2 and the compound (1-1) were heated simultaneously, and vapor deposition was performed so that the film thickness became 25nm to form a light-emitting layer. The deposition rate was adjusted so that the weight ratio of BH-2 to the compound (1-1) became approximately 98 to 2. Then, ET-1 was heated to form a film having a thickness of 5nm, and then evaporation was performed, and ET-2 was simultaneously heated with Liq to form a film having a thickness of 25nm, thereby forming an electron layer including two layers. The deposition rate was adjusted so that the weight ratio of ET-2 to Liq became approximately 50 to 50. The deposition rate of each layer is 0.01nm/sec to 1 nm/sec. Then, LiF was heated and vapor deposition was performed at a vapor deposition rate of 0.01nm/sec to 0.1nm/sec so that the film thickness became 1nm, and then aluminum was heated and vapor deposition was performed so that the film thickness became 100nm to form a cathode, thereby obtaining an organic EL element.

An ITO electrode as an anode and a LiF/aluminum electrode as a cathode were applied with a DC voltage to measure 1000cd/m²As a result of the characteristics in light emission, the driving voltage was 3.80V, and the external quantum efficiency was 7.50%. In addition, the following times were measured: at 10mA/cm²The current density of (2) was 53 hours as a result of maintaining the luminance of 98% or more of the initial luminance when the constant current driving was performed.

< example 3 to example 8 and comparative example 1 to comparative example 2 >

Organic EL elements (table 2A) were produced by the method according to example 2, and EL characteristics (table 2B) were measured.

< example 9 >

Then, in the compound represented by the formula (1), the effect of reducing the wavelength of the light emission wavelength by introducing an electron-accepting fluorine atom was verified by measuring the fluorescence spectrum.

For the measurement of fluorescence spectrum, a compound of formula (1-1666), formula (1-1674) or formula (1-1668) is allowed to stand at 2X 10^-5The measurement solution was prepared by dissolving the concentration of M in toluene, and then placed in a quartz optical cell (cell), and excited at an excitation wavelength of 380nm to measure a fluorescence spectrum. The results are shown in table 3A below.

[ Table 3A ]

Compounds of the invention	Peak wavelength (nm) of fluorescence spectrum
		Compound (1-1666)	456
Compound (1-1674)	456
		Compound (1-1668)	462

In addition, the compound of formula (C-2) as a comparative compound was made to be 2X 10^-5The concentration of M was dissolved in toluene to prepare a measurement solution, which was then placed in an optical cell made of quartz to exciteExcitation was performed at a wavelength of 380nm and the fluorescence spectrum was measured. The results are shown in table 3B below.

[ Table 3B ]

Comparative Compounds	Peak wavelength (nm) of fluorescence spectrum
		Compound (C-2)	468

From the above results, it was confirmed that the effect of shortening the wavelength of the fluorescence spectrum by introducing the fluorine atom was obtained. The results show that blue light emission with a shorter wavelength is obtained by introducing fluorine atoms.

Industrial applicability

In the present invention, by providing a novel fluorine-substituted polycyclic aromatic compound, the selection of materials for organic devices such as materials for organic EL elements can be increased. Further, by using a novel fluorine-substituted polycyclic aromatic compound as a material for an organic EL element, for example, an organic EL element having excellent light-emitting efficiency and element life, a display device provided with the same, and a lighting device provided with the same can be provided.

Description of the symbols

100: organic electroluminescent element

101: substrate

102: anode

103: hole injection layer

104: hole transport layer

105: luminescent layer

106: electron transport layer

107: electron injection layer

108: cathode electrode