阅读说明：本技术 化合物及其有机电子装置 (Compound and its organic electronic device ) 是由 吴蕙玲 曾柏宸 谢淑珠 陈济中 于 2018-05-23 设计创作，主要内容包括：本发明提供一种新颖化合物及包含其的有机电子装置,该化合物是以下式(I)表示：<Image he="171" wi="700" file="DDA0001670347580000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>其中n1、n2、m1、m2和m3皆为整数,且n1和n2的总和为2或3；L<Sup>1</Sup>、L<Sup>2</Sup>和L<Sup>3</Sup>各自独立为芳撑基；G是选自于下列所构成的群组：氢原子、氘原子、-N(Z<Sup>3</Sup>)(Z<Sup>4</Sup>)基团、烷基、烯基、炔基、环烷基、杂环烷基、芳香基和杂芳基；R<Sup>1</Sup>和R<Sup>2</Sup>各自独立选自于氢原子、氘原子、烷基或芳香基；以及Z<Sup>1</Sup>至Z<Sup>4</Sup>各自独立选自于下列所构成的群组：烷基、烯基、炔基、环烷基、杂环烷基、芳香基和杂芳基。(The present invention provides a kind of compounds and the organic electronic device comprising it, which is that following formula (I) indicates: Wherein n1, n2, m1, m2 and m3 are all integer, and the summation of n1 and n2 is 2 or 3；L 1 、L 2 And L 3 Respectively stand alone as arylene base；G is selected from following constituted group: hydrogen atom, D-atom ,-N (Z 3 )(Z 4 ) group, alkyl, alkenyl, alkynyl, naphthenic base, Heterocyclylalkyl, aromatic radical and heteroaryl；R 1 And R 2 It is each independently selected from hydrogen atom, D-atom, alkyl or aromatic radical；And Z 1 To Z 4 It is each independently selected from following constituted group: alkyl, alkenyl, alkynyl, naphthenic base, Heterocyclylalkyl, aromatic radical and heteroaryl.)

1. a kind of compound, as shown in following formula (I):

Wherein, n1 and n2 respectively stands alone as 0 to 3 integer, and the summation of n1 and n2 is 2 or 3；

M1, m2 and m3 respectively stand alone as 0 or 1 integer, and m1, m2 and m3 are same or different to each other；

R¹And R²It is each independently selected from by following constituted group: hydrogen atom, D-atom, the alkyl and ring that carbon number is 1 to 12 The aromatic radical that upper carbon number is 6 to 30, R¹And R²It is same or different to each other；

L¹、L²And L³Respectively stand alone as the arylene base that carbon number is 6 to 60 on ring, and L¹、L²And L³It is same or different to each other；

G is selected from following constituted group: hydrogen atom, D-atom ,-N (Z³)(Z⁴) group, carbon number be 1 to 40 alkyl, Carbon number is 3 to 60 in carbon number is 3 to 60 on alkynyl that alkenyl that carbon number is 2 to 40, carbon number are 2 to 40, ring naphthenic base, ring The heteroaryl that carbon number is 3 to 60 on the aromatic radical and ring that carbon number is 6 to 60 on Heterocyclylalkyl, ring；And

Z¹To Z⁴It is each independently selected from following constituted group: alkenyl that alkyl that carbon number is 1 to 40, carbon number are 2 to 40, Carbon number on carbon number is 3 to 60 in carbon number is 3 to 60 on alkynyl that carbon number is 2 to 40, ring naphthenic base, ring Heterocyclylalkyl, ring The heteroaryl for being 3 to 60 for carbon number on 6 to 60 aromatic radical and ring.

2. compound as described in claim 1, wherein shown in the compound such as following formula (I '):

* 1 is connected to * a, * 2 is connected to * b and two * 3 is connected to two * 4；

Group in formula (I ')For

3. compound as claimed in claim 2, wherein the group in the formula (I ')

For

4. compound as claimed in claim 2, wherein the group

It is expressed as any one in following:

Wherein, R¹¹To R¹³It is each independently selected from by following constituted group: hydrogen atom, D-atom, the alkane that carbon number is 1 to 12 The aromatic radical that carbon number is 6 to 30 on base and ring, R¹¹To R¹³It is same or different to each other.

5. compound as claimed in claim 3, wherein the group

It is expressed as any one in following:

Wherein, R²¹To R²³It is each independently selected from by following constituted group: hydrogen atom, D-atom, the alkane that carbon number is 1 to 12 The aromatic radical that carbon number is 6 to 30 on base and ring, R²¹To R²³It is same or different to each other.

6. the compound as described in any one of claims 1 to 5, wherein carbon number is 3 to 60 on the ring that G is indicated in formula (I) Heteroaryl be it is following in any one:

Wherein, R³¹To R³³It is each independently selected from by following constituted group: hydrogen atom, D-atom, the alkane that carbon number is 1 to 12 The aromatic radical that carbon number is 6 to 30 on base and ring, R³¹To R³³It is same or different to each other.

7. the compound as described in any one of claims 1 to 5, wherein shown in the compound such as following formula (I "):

R¹And R²It is each independently selected from by following constituted group: hydrogen atom, D-atom, the alkyl and ring that carbon number is 1 to 12 The aromatic radical that upper carbon number is 6 to 30, R¹And R²It is same or different to each other；And

G is selected from by following constituted group: alkenyl that alkyl that carbon number is 1 to 40, carbon number are 2 to 40, carbon number be 2 to The aromatic radical that carbon number is 6 to 60 on 40 alkynyl and ring.

8. the compound as described in any one of claims 1 to 5, wherein Z¹And Z²Respectively standing alone as carbon number on ring is 6 to 60 Aromatic radical.

9. the compound as described in any one of claims 1 to 5, wherein with G, Z¹To Z⁴Carbon number is 6 to 60 on the ring of expression Aromatic radical be each independently selected from following constituted group: phenyl, xenyl, terphenyl, tetrad phenyl, quinquephenyl Base, naphthalene, acenaphthenyl, anthryl, benzo anthryl, ethylene close anthryl, phenanthryl, benzophenanthrene base, Fu base, fluorenyl, benzo fluorenyl, dibenzo Fluorenyl, Pi base, thick five phenyl, pyrenyl, benzo pyrenyl,Base, benzoBase, fluoranthene base, benzofluoranthrene base, aphthacene base, Base, guan base, dibenzo anthryl, naphthylphenyl, bicyclopentadiene and phenyl, triphenylene, benzo triphenylene and its isomeric compound.

10. the compound as described in any one of claims 1 to 5, wherein with G, Z¹To Z⁴Carbon number is 6 to 60 on the ring of expression Aromatic radical be each independently selected from by following constituted group:

Wherein, m is 1 to 4 integer, and n is integer of 1 to 3, and o is an integer of 1 or 2, and p is 1 to 5 integer；And

X¹To X⁴Be each independently selected from by following constituted group: hydrogen atom, D-atom, halogen, cyano, nitro, carbon number are Carbon number on alkoxy that alkynyl that alkenyl that 1 to 12 alkyl, carbon number are 2 to 12, carbon number are 2 to 12, carbon number are 1 to 12, ring Aromatic radical, the aryloxy group that carbon number is 6 to 30 on the heteroaryl and ring that carbon number is 3 to 30 on ring for 6 to 30.

11. the compound as described in any one of claims 1 to 5, wherein with L¹、L²And L³On the ring of expression carbon number be 6 to 60 aromatic radical is each independently selected from by following constituted group:

Wherein, m is 1 to 4 integer, and n is integer of 1 to 3, and o is an integer of 1 or 2；And

X¹To X⁴Be each independently selected from by following constituted group: hydrogen atom, D-atom, halogen, cyano, nitro, carbon number are Carbon number on alkoxy that alkynyl that alkenyl that 1 to 12 alkyl, carbon number are 2 to 12, carbon number are 2 to 12, carbon number are 1 to 12, ring Aromatic radical, the aryloxy group that carbon number is 6 to 30 on the heteroaryl and ring that carbon number is 3 to 30 on ring for 6 to 30.

12. the compound as described in any one of claims 1 to 5, wherein the group-N (Z¹)(Z²) selected from by following The group constituted:

13. the compound as described in any one of claims 1 to 5, wherein Z¹And Z²It is interconnected to form a hetero-aromatic ring.

14. the compound as described in any one of claims 1 to 5, wherein G is-N (Z³)(Z⁴) group when, Z³And Z⁴Mutually interconnect It connects to form a hetero-aromatic ring.

15. compound as described in claim 1, wherein the compound is selected from by following constituted group:

16. a kind of organic electronic device comprising a first electrode, a second electrode and be set to the first electrode and this second An interelectrode organic layer, the organic layer include the compound as described in any one of claims 1 to 15.

17. organic electronic device as claimed in claim 16, wherein the organic electronic device is an Organic Light Emitting Diode.

18. organic electronic device as claimed in claim 17, wherein the Organic Light Emitting Diode is injected including an electric hole Layer, an electric hole transport layer, a luminescent layer, an electron transfer layer and an electron injecting layer；The electric hole implanted layer is formed in described In first electrode；The electric hole transport layer is formed in the electric hole implanted layer, and the electric hole transport layer is transmitted including an electric hole Material, the electric hole transmission material are the compound as described in any one of claims 1 to 15；The luminescent layer is formed in described In electric hole transport layer；The electron transfer layer is formed on the luminescent layer；The electron injecting layer is formed in the electronics and passes Between defeated layer and the second electrode.

19. organic electronic device as claimed in claim 17, wherein the Organic Light Emitting Diode is injected including an electric hole Layer, an electric hole transport layer, a luminescent layer, an electron transfer layer and an electron injecting layer；The electric hole implanted layer is formed in described In first electrode, the electric hole implanted layer includes an electric hole injection material, which is as in claim 1 to 15 Described in any item compounds；The electric hole transport layer is formed in the electric hole implanted layer；The luminescent layer is formed in described In electric hole transport layer；The electron transfer layer is formed on the luminescent layer；The electron injecting layer is formed in the electronics and passes Between defeated layer and the second electrode.

Technical field

It is espespecially a kind of as electricity the present invention relates to a kind of compounds and a kind of organic electronic device using it The compounds of the material of hole transport layer or electric hole implanted layer and the organic electronic device for using it.

Background technique

With the development of science and technology various flourished using organic electronic device made of organic material, machine common are Electronic device such as Organic Light Emitting Diode (organic light emitting device, OLED), organic phototransistors (organic phototransistor), solar battery (organic photovoltaic cell) and organic light are detectd It surveys device (organic photodetector).

OLED is invented and is proposed, Eastman Kodak by Eastman Kodak (Eastman Kodak) Doctor Deng Qingyun and Steven Van Slyke with vacuum vapour deposition (vacuum evaporation method) in being formed with One electronics of transparent indium tin oxide (indium tin oxide, ITO) deposition on glass of organic aromatic diamine electric hole transport layer Transmission material such as three (8-hydroxyquinoline) aluminium [tris (8-hydroxyquinoline) aluminum (III), referred to as Alq₃]}；A metal electrode is deposited on electron transfer layer, and the production of OLED can be completed.OLED is because having both reaction rate Fastly, the advantages of light, thin type, wide viewing angle, brightness is high, comparison is high, no setting is required backlight and low power consuming, therefore by pass Note, but OLED still has inefficient and short service life problem.

In order to overcome the problems, such as that poor efficiency, one of improvement mode are that middle layer is arranged between cathode and anode, please join It reads shown in Fig. 1, the OLED of improvement is sequentially provided with a substrate 11, an anode 12,13 (hole injection of an electric hole implanted layer Layer, HIL), an electric hole transport layer 14 (hole transport layer, HTL), 15 (an emission of a luminescent layer Layer, EL), an electron transfer layer 16 (electron transport layer, ETL), an electron injecting layer 17 (electron injection layer, EIL) and a cathode 18.When applying a voltage in anode 12 and cathode 18, by sun The electric hole that pole 12 is projected can pass through HIL and HTL and be moved to EL, and it is mobile to pass through EIL and ETL by the electrons that cathode 18 projects To EL, electric hole and electronics is made to reassemble into exciton (exciton) at EL layers, can be produced when exciton is failed by excitation state and returned to ground state Third contact of a total solar or lunar eclipse line.

Another improvement mode is using the amine derivative (amine derivative) with carbazyl (carbazolyl) Electric hole transmission material as electric hole transport layer.However, even with aforementioned electric hole transmission material, the current efficiency of OLED and Luminous efficiency is still to be improved, therefore, uses the present invention provides a kind of compounds and overcomes existing in the prior art ask Topic.

Another improvement mode is the electric hole using diamine derivative (diamine derivative) as electric hole implanted layer Injection material.However, the current efficiency and luminous efficiency of OLED is still to be improved even with aforementioned electric hole injection material, Therefore, the present invention provides a kind of compounds by so as to overcome the problems existing in the prior art.

Summary of the invention

It is an object of the present invention to provide a kind of compounds, can be used for organic electronic device.

The present invention separately provides a kind of organic electronic device using the compounds, promotes organic electronic device whereby Efficiency.

In order to achieve the above object, the compound of the present invention can be indicated by lower formula (I):

In formula (I), n1 and n2 respectively stand alone as 0 to 3 integer, and the summation of n1 and n2 is 2 or 3.

In formula (I), m1, m2 and m3 respectively stand alone as 0 or 1 integer, that is to say, that m1, m2 and m3 can be each other It is identical or different.

In formula (I), R¹And R²It is each independently selected from by following constituted group: hydrogen atom, D-atom, carbon number 1 The aromatic radical that carbon number is 6 to 30 on to 12 alkyl and ring, R¹And R²It is same or different to each other.

In formula (I), L¹、L²And L³The arylene base (arylene group) that carbon number is 6 to 60 on ring is respectively stood alone as, L¹、L²And L³It is same or different to each other.

In formula (I), G is selected from following constituted group: hydrogen atom, D-atom ,-N (Z³)(Z⁴) group, carbon number For 1 to 40 alkyl, carbon number be 2 to 40 alkenyl, carbon number be 2 to 40 alkynyl, the naphthenic base that carbon number is 3 to 60 on ring, ring The heteroaryl that carbon number is 3 to 60 on the aromatic radical and ring that carbon number is 6 to 60 on Heterocyclylalkyl that upper carbon number is 3 to 60, ring.

In formula (I), Z¹To Z⁴It is each independently selected from by following constituted group: alkyl, carbon of the carbon number for 1 to 40 In carbon number is 3 to 60 on alkynyl that alkenyl that number is 2 to 40, carbon number are 2 to 40, ring naphthenic base, ring carbon number be 3 to 60 it is miscellaneous The heteroaryl that carbon number is 3 to 60 on the aromatic radical and ring that carbon number is 6 to 60 in naphthenic base, ring, Z¹、Z²、Z³And Z⁴It is mutually the same or It is different.

According to the present invention, the compound of the present invention can be indicated by following formula (I '):

Wherein, it * 1 is connected to * a, * 2 is connected to * b and two * 3 is connected to two * 4.

When two linkers on dibenzofuran group are located on the same phenyl ring, for example, the group in formula (I ')It is expressed asAlternatively, the group in formula (I ') It is expressed as

Preferably, the group in formula (I ')It is represented by following any group:

Wherein, the R in formula (I)¹It is represented by R¹¹To R¹³, wherein R¹¹To R¹³It is each independently selected from and is constituted in by following Group: the aromatic radical that carbon number is 6 to 30 on the alkyl and ring that hydrogen atom, D-atom, carbon number are 1 to 12, R¹¹To R¹³Phase each other It is same or different.

Preferably, the group in formula (I ')It is represented by following any group:

Wherein, the R in formula (I)²It is represented by R²¹To R²³, wherein R²¹To R²³It is each independently selected from and is constituted in by following Group: the aromatic radical that carbon number is 6 to 30 on the alkyl and ring that hydrogen atom, D-atom, carbon number are 1 to 12, R²¹To R²³Phase each other It is same or different.

More specifically, the group in formula (I ')And groupThat This is identical or different.

When n1 is 1, i.e. group in formula (I ')For

N2 is integer 1 or 2.

It is similar, when n2 is 1, i.e. group in formula (I ')For

N1 is integer 1 or 2.

Preferably, the compound can be indicated by following formula (I "):

In formula (I "), R¹And R²Be each independently selected from by following constituted group: hydrogen atom, D-atom, carbon number are The aromatic radical that carbon number is 6 to 30 on 1 to 12 alkyl and ring, R¹And R²It is same or different to each other；And

G is selected from by following constituted group: alkenyl that alkyl that carbon number is 1 to 40, carbon number are 2 to 40, carbon number The aromatic radical for being 6 to 60 for carbon number on 2 to 40 alkynyl and ring.

Preferably, in formula (I "), R¹And R²Be each independently selected from by following constituted group: hydrogen atom, deuterium are former The aromatic radical that carbon number is 6 to 12 on the alkyl and ring that son, carbon number are 1 to 6.

Preferably, n1 and n2 respectively stand alone as integer 1 or 2 in formula (I ").

Preferably, m2 is integer 0 or 1, L in formula (I ")²For aforementioned arylene base, such as penylene base (phenylene group)；When m2 is integer 0, (L²)_m2For singly-bound.

Preferably, the heteroaryl that carbon number is 3 to 60 on the ring that G is indicated is selected from by following in formula (I) and formula (I ') The group constituted: furyl (furyl group), pyrrole radicals (pyrrolyl group), thienyl (thiophenyl Group), imidazole radicals (imidazolyl group), pyrazolyl (pyrazolyl group), triazolyl (triazolyl Group), tetrazole radical (tetrazolyl group), oxazolyl (oxazolyl group), isoxazolyl (isoxazolyl Group), thiazolyl (thiazolyl group), isothiazolyl (isothiazolyl group), oxadiazoles base (oxadiazolyl group), thiadiazolyl group (thiadiazolyl group), pyridyl group (pyridyl group), pyridazinyl (pyridazinyl group), pyrimidine radicals (pyrimidinyl group), pyrazinyl (pyrazinyl group), triazine radical (triazinyl group), indyl (indolyl group), isoindolyl (isoindolyl group), benzofuranyl (benzofuranyl group), isobenzofuran-base (isobenzofuranyl group), benzothienyl (benzothiophenyl group), isobenzo-thienyl (isobenzothiophenyl group), indolizine base (indolizinyl group), quinazinyl (quinolizinyl group), quinolyl (quinolyl group), isoquinolin Base (isoquinolyl group), cinnoline base (cinnolyl group), phthalazinyl (phthalazinyl group), quinoline azoles Quinoline base (quinazolinyl group), quinoxalinyl (quinoxalinyl group), benzimidazole (benzimidazolyl Group), benzoxazolyl (benzoxazolyl group), benzothiazolyl (benzothiazolyl group), indazolyl (indazolyl group), benzo isoxazolyl (benzisoxazolyl group), benzisothia oxazolyl (benzisothiazolyl group), dibenzofuran group (dibenzofuranyl group), dibenzothiophene (dibenzothiophenyl group), carbazyl (carbazolyl group), two carbazyl (biscarbazolyl Group), cumarin base (coumarinyl group), chromene base (chromenyl group), phenanthryl (phenanthridinyl group), acridinyl (acridinyl group), coffee quinoline base (phenanthrolinyl Group), phenazinyl (phenazinyl group), phenothiazinyl (phenothiazinyl group), phenoxazine base (phenoxazinyl group), azepine dibenzothiophene (azatriphenylenyl group), diaza dibenzo thiophene Pheno base (diazatriphenylenyl group), xanthyl (xanthenyl group), azepine carbazyl (azacarbazolyl group), aza-benzofuranyl (azadibenzofuranyl group), aza-benzothiophenyl (azadibenzothiophenyl group), benzofuran benzothienyl (benzofuranobenzothiophenyl Group), benzothiophene benzothienyl (benzothienobenzothiophenyl group), dibenzofurans naphthalene (dibenzofuranonaphthyl group), dibenzothiophenes naphthalene (dibenzothienonaphthyl group), two Naphthalene thiophene thiophenyl (dinaphthothienothiophenyl group), dinaphthyl carbazyl (dinaphtho [2', 3':2, 3:2', 3':6,7] carbazolyl group), dibenzazepine base (dibenzo [b, f] azepin group), three benzo nitrogen Miscellaneous base (tribenzo [b, d, f] azepin group), dibenzo oxa- base (dibenzo [b, f] oxepin group) and three Benzo oxa- base (tribenzo [b, d, f] oxepin group).

Specifically, in formula (I) and formula (I '), the heteroaryl that carbon number is 3 to 60 on the ring that G is indicated is any in following Person:

Wherein, R³¹To R³³Be each independently selected from by following constituted group: hydrogen atom, D-atom, carbon number be 1 to The aromatic radical that carbon number is 6 to 30 on 12 alkyl and ring, R³¹To R³³It is same or different to each other.

Preferably, in formula (I) to formula (I "), Z¹And Z⁴Respectively stand alone as the aromatic radical for being 6 to 60 for carbon number on ring.

Preferably, in formula (I) to formula (I "), with G, Z¹To Z⁴The aromatic radical that carbon number is 6 to 60 on the ring of expression is respectively only It is vertical to be selected from following constituted group: phenyl (phenyl group), xenyl (biphenylyl group), terphenyl (terphenylyl group), tetrad phenyl (quaterphenylyl group), 5-linked phenyl (quinquephenylyl Group), naphthalene (naphthyl group), acenaphthenyl (acenaphthelenyl group), anthryl (anthryl group), Benzo anthryl (benzanthryl group), ethylene close anthryl (aceanthryl group), phenanthryl (phenanthryl Group), benzo phenanthryl (benzophenanthryl group), Fu base (phenalenyl group), fluorenyl (fluorenyl Group), benzo fluorenyl (benzofluorenyl group), dibenzo fluorenyl (dibenzofluorenyl group), Pi base (picenyl group), thick five phenyl (pentacenyl group), pyrenyl (pyrenyl group), benzo pyrenyl (benzopyrenyl group)、Base (chrysenyl group), benzoIt is base (benzochrysenyl group), glimmering Anthryl (fluoranthenyl group), benzofluoranthrene base (benzofluoranthenyl group), aphthacene base (tetracenyl group), base (perylenyl group), guan base (coronyl group), dibenzo anthryl (dibenzanthryl group), naphthylphenyl (naphthylphenyl group), bicyclopentadiene and phenyl (indacenyl group), triphenylene (triphenylenyl group), benzo triphenylene (benzotriphenylenyl group) and its isomeric compound.

More specifically, formula (I) is into formula (I "), with G, Z¹To Z⁴The aromatic radical that carbon number is 6 to 60 on the ring of expression is respectively only It is vertical to be selected from following constituted group:

Wherein, m is 1 to 4 integer, and n is integer of 1 to 3, and o is an integer of 1 or 2, and p is 1 to 5 integer；And

X¹To X⁴Be each independently selected from by following constituted group: hydrogen atom, D-atom, halogen are (such as: fluorine-based, chlorine Base, bromo), cyano, nitro, carbon number be 1 to 12 alkyl, carbon number be 2 to 12 alkenyl, carbon number be 2 to 12 alkynyl, carbon number Carbon number is 6 on the heteroaryl and ring for being 3 to 30 for carbon number on 1 to 12 alkoxy, the aromatic radical that carbon number is 6 to 30 on ring, ring To 30 aryloxy group.

Preferably, in formula (I) to formula (I "), L¹、L²And L³The aromatic radical that carbon number is 6 to 60 on the ring of expression is respectively only It is vertical to be selected from by following constituted group:

Wherein, m is 1 to 4 integer, and n is integer of 1 to 3, and o is an integer of 1 or 2；And

X¹To X⁴It is each independently selected from by following constituted group: hydrogen atom, D-atom, halogen, cyano, nitro, carbon On alkoxy that alkynyl that alkenyl that alkyl that number is 1 to 12, carbon number are 2 to 12, carbon number are 2 to 12, carbon number are 1 to 12, ring The aryloxy group that carbon number is 6 to 30 on the heteroaryl and ring that carbon number is 3 to 30 on aromatic radical that carbon number is 6 to 30, ring.

Preferably, the group-N (Z of the formula (I) into formula (I ")¹)(Z²) and formula (I) and formula (I ') in G indicate- N(Z³)(Z⁴) group, it is each independently selected from by following constituted group:

Preferably, Z of the formula (I) into formula (I ")¹And Z²It is interconnected to form a hetero-aromatic ring.For example, which can ForBut not limited to this.

Preferably, G is-N (Z in formula (I) and formula (I ')³)(Z⁴) group when, Z³And Z⁴It is interconnected to form a heteroaryl Ring.For example, which can beBut not limited to this.

In the description, L¹、L²Or L³" the arylene base that carbon number is 6 to 60 on ring " is censured, can be carbon number on ring is 6 Carbon number is 6 to 60 and the arylene base that replaces through an at least substituent group on to 60 and the arylene base or ring that are unsubstituted；The arylene Substituent group on base can be aforementioned X¹To X⁴In any one.

In the description, described " aromatic radical " can be the aromatic radical being unsubstituted or through the substitution of an at least substituent group Aromatic radical；The heteroaryl that " heteroaryl " can be the heteroaryl being unsubstituted or replace through an at least substituent group.The virtue Substituent group on perfume base can be aforementioned X¹To X⁴In any one；Substituent group on the heteroaryl can be with aforementioned X¹To X⁴In it is any Person is similar.

In the description, the alkane that described " alkyl " can be the alkyl being unsubstituted or replace through an at least substituent group Base；The alkenyl that " alkenyl " can be the alkenyl being unsubstituted or replace through an at least substituent group；" alkynyl " can be with The alkynyl for being the alkynyl being unsubstituted or replacing through an at least substituent group；Substituent group on aforesaid alkyl, alkenyl and alkynyl can To be but not limited to D-atom.

In the description, described " naphthenic base " can be the naphthenic base being unsubstituted or through the substitution of an at least substituent group Naphthenic base；The heterocycle alkane that " Heterocyclylalkyl " can be the Heterocyclylalkyl being unsubstituted or replace through an at least substituent group Base；Substituent group in aforementioned naphthenic base and Heterocyclylalkyl can be but not limited to alkyl, the carbon number of D-atom, carbon number for 1 to 12 The alkynyl that alkenyl or carbon number for 2 to 12 are 2 to 12.

For example, which can be selected from by following constituted group:

The present invention separately provides a kind of organic electronic device comprising a first electrode, a second electrode and be set to this An organic layer between one electrode and the second electrode, the organic layer include novel compound.

Preferably, the organic electronic device be Organic Light Emitting Diode (organic light emitting device, OLED)。

Specifically, the Organic Light Emitting Diode include one be formed in the first electrode electric hole implanted layer, one formed In in the electric hole implanted layer electric hole transport layer, one be formed in the electric hole transport layer luminescent layer, one be formed in the luminescent layer On electron transfer layer and an electron injecting layer between the electron transfer layer and the second electrode.

More preferably, compounds of the invention can be used as the electric hole injection material (hole in electric hole implanted layer Injection material) or electric hole transport layer in electric hole transmission material (hole transport material).

In a wherein embodiment, which is electric hole implanted layer, i.e., the electric hole implanted layer includes an electric hole injection material, The electric hole injection material includes novel compound.

For example, which can be single layer structure or is set between first electrode and electric hole transport layer Multilayered structure；When the electric hole implanted layer be multilayered structure when (such as the electric hole implanted layer include one first electric hole implanted layer and One second electric hole implanted layer), the first electric hole injection material in first electric hole implanted layer may include a Noval compounds above-mentioned Object, the second electric hole injection material in second electric hole implanted layer may include another novel compound or a traditional electricity Hole injection material compound.Alternatively, the first electric hole injection material in first electric hole implanted layer may include a novel The combination of compound and another novel compound or a novel compound and a traditional electric hole injection material The combination of object is closed, the second electric hole injection material is also such in second electric hole implanted layer.

Preferably, first and/or second electric hole implanted layer is made by the compounds (such as compound 1 to 54) At；Compared to existing electric hole injection material such as polyaniline (polyaniline), polyethylenedioxythiophene (polyethylenedioxythiophene), 4,4 ', 4 "-three (3- methylphenyl-N-phenyl amino) triphenylamines (4,4 ', 4 "- Tris [(3-methylphenyl) phenylamino] triphenylamine) (m-MTDATA) or N¹,N^1′(biphenyl -4,4 ' - Diyl) connection (N¹(1- naphthalene))-N⁴,N^4′Diphenyl benzene -1,4- diamines (N¹,N^1′-(biphenyl-4,4'-diyl)bis(N¹- (naphthalen-1-yl)-N⁴,N^4′- diphenylbenzene-1,4-diamine)), using the compounds as electric hole OLED made of electric hole injection material in implanted layer is preferable compared to having with OLED made of existing electric hole injection material Efficiency.

In another embodiment, which is electric hole transport layer, i.e., the electric hole transport layer includes an electric hole transmission material, should Electric hole transmission material includes novel compound.

For example, the electric hole transport layer can be single layer structure or be set to the double-deck electric hole implanted layer and luminescent layer it Between multilayered structure；When the electric hole transport layer is multilayered structure (such as the electric hole transport layer includes one first electric hole transport layer With one second electric hole transport layer), the first electric hole transmission material in the first electric hole transport layer may include a noveltyization above-mentioned Object is closed, the second electric hole transmission material in the second electric hole transport layer may include that another novel compound or one are existing Electric hole transmission material compound.Alternatively, the first electric hole transmission material in the first electric hole transport layer may include one aforementioned new The combination of clever compound and another novel compound or a novel compound and existing electric hole transmission material The combination of object is closed, the second electric hole transmission material is also such in the second electric hole transport layer.

Preferably, the first and/or second electric hole transport layer is made by the compounds (such as compound 1 to 54) At；[4- (N, N- bis- (p-methylphenyl) amino) phenyl] hexamethylene (1,1-s bis- compared to existing electric hole transmission material such as 1,1- Bis [(di-4-tolylamino) phenylcyclohexane], TPAC), the carbazole derivates or N of such as N- phenyl carbazole⁴, N^4′- two (naphthalene -1- base)-N⁴,N^4′Hexichol xenyl -4,4 '-diamines (N⁴,N^4′-di(naphthalen-1-yl)-N⁴,N^4′- Diphenylbiphenyl-4,4 '-diamine, NPB), using the compounds as electric hole transport layer in electric hole transmit material OLED made of expecting has preferable efficiency compared to OLED made of existing electric hole transmission material.

Preferably, the luminescent layer is made by dopant (dopant) and material of main part (host material).The master Body material can be phenyl anthracene derivant, such as 9- (4- (1- naphthalene) phenyl) -10- (2- naphthalene) anthracene) (9- (4- (naphthalen-1-yl) phenyl) -10- (naphthalen-2-yl) anthracene), it is not limited to this.

For feux rouges OLED, the dopant in emitting layer material can be but not limited to match with quinoline (quinoline) Position base or the divalent iridium organometallic compound of isoquinilone derivatives (isoquinoline derivative) dentate, osmium are wrong Close object or platinum misfit object.For green light OLED, the dopant in luminescent layer can be but be not limited to diamino-fluorene (diaminoflourenes), anthradiamine (diaminoanthracenes) or have phenylpyridine (phenylpyridine) match The divalent iridium organometallic compound of position base.For Nan dian Yao, the dopant in luminescent layer can be but be not limited to tool amido Substituted derivative (aminoperylene derivative),Diamines (diaminochrysene), pyrene diamines (diaminopyrene) or with pyridinecarboxylic dentate (pyridinato picolinate) divalent iridium organometallic Close object.By different host emitter materials, OLED can produce the light of feux rouges, green light or blue light.

Preferably, the electron transfer layer is by [5 '-[3- (3- pyridyl group) benzene of traditional electron transport material such as 3,3 '- Base] [1,1 ': 3 ', 1 "-terphenyl] -3,3 "-diyl] bipyridyl ((3,3 '-(5 '-(3- (3-Pyridinyl) phenyl) (1, 1 ': 3 ', 1 "-terphenyl) -3,3 "-diyl) bispyridine, TmPyPb), 3- (4- xenyl) -5- (4- tert-butyl benzene Base) -4- phenyl -4H-1,2,4- triazine (3- (Biphenyl-4-yl) -5- (4-tert-butylphenyl) -4-phenyl- 4H-1,2,4-triazole, TAZ), 1,3,5- tri- (1- phenyl -1H- benzimidazolyl-2 radicals-yl) benzene (1,3,5-tris (1- Phenyl-1H-benzimidazol-2-yl) benzene, TPBi), three (2,4,6- trimethyl -3- (3- pyridyl group) phenyl) boron Alkane (tris (2,4,6-trimethyl-3- (pyridin-3-yl) phenyl) borane, 3TPYMB), 1,3- join (3,5- bis- pyrroles Pyridine -3- base-phenyl) benzene (1,3-bis (3,5-dipyrid-3-yl-phenyl) benzene, BmPyPb) and 9, bis- (3- of 10- (3- pyridyl group) phenyl) anthracene (9,10-bis (3- (pyridin-3-yl) phenyl) anthracene, DPyPA) formed, but It is without being limited thereto.

Preferably, the OLED includes an electric hole barrier layer, the electric hole barrier layer be formed in electron transfer layer and luminescent layer it Between, electric hole can be prevented to be moved to electron transfer layer by luminescent layer, the electric hole barrier layer can be by 2,9- dimethyl -4,7- hexichol Base -1,10- phenanthrolene (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, BCP) or 2,3,5, 6- tetramethylphenyl -1,4- phthalimide (2,3,5,6-tetramethyl-phenyl-1,4- (bis- Phthalimide), TMPP) it is formed, it is not limited to this.

Preferably, the OLED includes an electronic barrier layer, the electronic barrier layer be formed in electric hole transport layer and luminescent layer it Between, electronics can be prevented to be moved to electric hole transport layer by luminescent layer, the electronic barrier layer can by 9,9'- (1,1'- xenyl) -4, Two -9H- carbazole of 4'- diyl (9,9'- (1,1'-biphenyl) -4,4'-diylbis-9H-carbazole, CBP) or 4,4', 4 "-three (N- carbazyl) triphenylamines (4,4', 4 "-tri (N-carbazolyl)-triphenylamine, TCTA) are formed, but It is not limited to that.

When OLED is provided with electric hole barrier layer and/or electronic barrier layer, aforementioned OLED has compared to traditional OLED Higher luminous efficiency.

The electron injecting layer can be made of an electron injection material, such as 8- oxo naphthalene -1- base lithium ((8- Oxidonaphthalen-1-yl) lithium (II)), but not limited to this.

The first electrode can be indium-tin oxide electrode (indium-doped tin oxide electrode), but simultaneously It is not limited only to this.

The work function (work function) of the second electrode is lower than the work function of first electrode.Therefore, second electrode Aluminium electrode, indium electrode or magnesium electrode can be, but not limited to,.

Other objects of the present invention, effect and technical characteristic can be carried out in more detail with schema, embodiment and comparative example It is bright.

Detailed description of the invention

Fig. 1 is the lateral sectional view of OLED.

Fig. 2 to Figure 10 is respectively the hydrogen nuclear magnetic resonance spectrogram (H of compound 1 to 9¹-NMR)。

Main Reference label declaration:

11 substrate, 12 anode, 13 electric hole implanted layer, 14 electric hole transport layer, 15 luminescent layer

16 electron transfer layer, 17 electron injecting layer, 18 cathode

Specific embodiment

Connection with several embodiments is exemplified below as illustrating the embodiment party of the compound of the present invention and its organic electronic device Formula, to highlight the difference of the present invention compared to the prior art；Those skilled in the art can be by the content of this specification easily Solution present invention the advantages of capable of reaching and effect, and in it is without departing from the spirit it is lower carry out various modifications and change, with Implement or apply the contents of the present invention.

The synthesis of intermediary An

Intermediary An is to be used to prepare a kind of compounds, and can synthesize intermediary An by following step.

The synthesis of intermediary An-2

In step 1, intermediary An-2 can be synthesized by following synthesis mechanism A1.

Wherein, B ' can be B (OH)₂OrGroup, L is one to be substituted or be unsubstituted and carbon number is 6 on ring To 60 arylene base, m is integer 0 or 1, and n is integer 1 or 2.

The synthesis of intermediary A1-2

Using intermediary A1-2 as the example of synthesis intermediary An-2, intermediary A1-2 can pass through following synthesis mechanism A1-1 It is synthesized.

By the bromo- 4- acetylamino dibenzofurans (1-bromo-4-acetamidodibenzofuran) of 1- (30.0g, 1.0 equivalents (eq)), 4- dibenzofurans boric acid (4-dibenzofuranboronic acid) (1.25eq), palladium acetate (palladium(II)acetate)(Pd(OAc)₂), 2- (dicyclohexyl phosphino-) biphenyl (2- (dicyclohexylphosphino)biphenyl)(PCy₂(2-biPh)) (0.04eq) and potassium carbonate (2.0eq) makes an addition to first A mixed solution is formed in benzene (165 milliliters), ethyl alcohol (16.5 milliliters) and water (60.0 milliliters), the mixed solution is in the ring of nitrogen It is heated at 80 DEG C and being persistently stirred at reflux 16 hours under border, to cool down to room temperature after the reaction was completed, is extracted and collected Crude product in organic layer, then it is dry with magnesium sulfate, be separated by filtration and be concentrated and dried, and with the column purified acquisition of silica gel 34.5 grams of white product, the yield of the white product are 90.25%.

The white product is through field desorption mass spectrum (field desorption mass spectroscopy, FD-MS) analysis It determines, white solid product is intermediary A1-2.FD-MS analyzes result: C₂₆H₁₇NO₃, theoretical molecular weight 391.42, detection Molecular weight is 391.42.

The synthesis of intermediary A2-2 to A6-2

Intermediary A2-2 to A6-2 is to be used to prepare a kind of compounds, and can pass through the conjunction similar to intermediary A1-2 Synthesized at step 1, difference is to have used different starting materials in the synthesis step of intermediary A2-2 to A6-2, respectively with Reactant B 2 is to B6 surrogate response object B1 as starting material, and the results are shown in Table 1 for the analysis of each intermediary.

Table 1: the chemistry knot of reactant B n and intermediary A1-2 to A6-2 used in synthesis intermediary A1-2 to A6-2 Structure formula, yield, molecular formula and quality obtained by being analyzed with FD-MS.

In table 1, following resulting intermediary A1-B of synthesis can be used as reactant B 6, and intermediary A1-B is with reactant B1 is synthesized as starting material according to following step 1 to 4.

The modification of intermediary A1-2 to A6-2

Other than intermediary A1-2 to A6-2, the those skilled in the art of technical field can substitute synthesis mechanism A1-1 In starting material, and to synthesize other intermediaries similar to the synthesis path of synthesis mechanism A1-1.If selecting dibenzofurans Base and-B (OH)₂Reactant B 5 between group with a penylene base is used as starting material, when starting material and acetyl bromide amido dibenzo Furans reacts to form intermediary after, can synthesize among two dibenzofuran groups with a penylene base intermediary；If Select there are two the reactant Bs 6 of connected dibenzofuran group as starting material, when starting material and acetyl bromide amido dibenzo furan After reaction of muttering forms intermediary, can synthesizing tool, there are three the intermediaries that dibenzofurans is connected.

The synthesis of intermediary An-3

In step 2, intermediary An-3 can be synthesized by synthesis mechanism A2.

In synthesis mechanism A2, L, m and n are defined with aforementioned synthesis mechanism A1.

The synthesis of intermediary A1-3

Using intermediary A1-3 as the example of synthesis intermediary An-3, intermediary A1-3 can pass through following synthesis mechanism A2-1 It is synthesized.

It will flow back dissolved with the 12N hydrochloric acid (100 milliliters) of intermediary A1-2 (55g, 1.0eq) with the ethyl alcohol in 275 milliliters At a temperature of continue magnetic and be stirred 8 hours, after mixed solution is cooled to room temperature, is isolated by filtration and collects crude product and with pure Water washing, after drying weighing calculate step 2 yield be 98.5%.

The product is determined as intermediary A1-3 through FD-MS analysis, analyzes result through FD-MS are as follows: C₂₄H₁₆ClNO₂, theory point Son amount is 385.84, and measurement molecular weight is 385.84.

The synthesis of intermediary A2-3 to A6-3

Intermediary A2-3 to A6-3 is to be used to prepare a kind of compounds, and can pass through the conjunction similar to intermediary A1-3 Synthesized at step 2, difference is to have used different starting materials in the synthesis step of intermediary A2-3 to A6-3, respectively with Intermediary A2-2 to A6-2 replaces intermediary A1-2 as starting material, and the results are shown in Table 2 for the analysis of each intermediary.

Table 2: the chemical structural formula of intermediary A1-3 to A6-3, yield, molecular formula and quality obtained by being analyzed with FD-MS.

The modification of intermediary A1-3 to A6-3

Other than intermediary A1-3 to A6-3, the those skilled in the art of technical field can substitute synthesis mechanism A2-1 In starting material, and to synthesize other intermediaries similar to the synthesis path of synthesis mechanism A2-1.

The synthesis of intermediary An

In step 3, intermediary An can be synthesized by following synthesis mechanism A3.

In synthesis mechanism A3, with defined in aforementioned synthesis mechanism A1, X is chlorine, bromine or iodine by L, m and n.

The synthesis of intermediary A1

Using intermediary A1 as the example of synthesis intermediary An, intermediary A1 can be closed by following synthesis mechanism A3-1 At.

Intermediary A1-3 (10.0g, 1.0eq) is made an addition into 12N hydrochloric acid (40 milliliters) and acetonitrile (CH₃CN) (130 milliliters) Mixed solution in, and maintain the temperature of mixed solution lower than 5 DEG C；By 15.0 milliliters dissolved with sodium nitrite (2.0eq) and iodate The aqueous solution of potassium (2.5eq) is slowly added in the mixed solution of aforementioned low temperature, and lasting stirring after ten minutes, makes the temperature of mixed solution Degree is warming up to 20 DEG C and continued stirring overnight；Then, molten with the sodium bicarbonate of saturation and sodium thiosulfate (2.5eq) adjustment mixing The pH value of liquid is extremely between 9 to 10, then obtains sediment, and in a manner of filtering or in a manner of ethyl acetate extraction with body The hexane and methylene chloride that product ratio is 5:1 are pure with flash column chromatography (flash chromatography) as elutriant Change and obtain gray solid product, the yield of step 3 is 85.7%.

The gray solid product is determined as intermediary A1 through FD-MS analysis, analyzes result through FD-MS are as follows: C₂₄H₁₃IO₂, reason It is 460.26 by molecular weight, measurement molecular weight is 460.26.

The synthesis of intermediary A2 to A6

Intermediary A2 to A6 is to be used to prepare a kind of compounds, and can pass through the synthesis step similar to intermediary A1 3 synthesize, and difference is to have used different starting materials in the synthesis step of intermediary A2 to A6, respectively with intermediary A2-3 Replace intermediary A1-3 as starting material to A6-3, the results are shown in Table 3 for the analysis of each intermediary.

Table 3: the chemical structural formula of intermediary A1 to A6, yield, molecular formula and quality obtained by being analyzed with FD-MS.

The modification of intermediary A1 to A6

Other than intermediary A1 to A6, the those skilled in the art of technical field can substitute in synthesis mechanism A3-1 Starting material, and other intermediaries are synthesized with the synthesis path similar to synthesis mechanism A3-1.

The synthesis of intermediary An-B

In step 4, intermediary An-B can be synthesized by following synthesis mechanism A4.

In synthesis mechanism A4, L, m and n are with defined in aforementioned synthesis mechanism A1, and X in aforementioned synthesis mechanism A3 the same as determining Justice.

The synthesis of intermediary A1-B

Using intermediary A1-B as the example of synthesis intermediary An-B, intermediary A1-B can pass through following synthesis mechanism A4-1 It is synthesized.

Intermediary A1 (30.0g, 1.0eq), duplex pinacol borate (bis (pinacolato) diboron) (1.20eq), 1,1 '-two (Diphenyl phosphino ferrocene palladium chloride (II) (1,1 '-bis (diphenylphosphino)- ferrocene dichloropalladium(II))(PdCl₂(dppf)) (0.02eq) and potassium acetate (KOAc) (2.0eq) are mixed Together in Isosorbide-5-Nitrae-dioxanes (Isosorbide-5-Nitrae-dioxane) (165 milliliters), and stirred 16 hours under 95 DEG C of nitrogen environment, it is to be cooled To room temperature, the crude product in organic layer is extracted and collected with water and organic phase, then, filtering point dry with magnesium sulfate From and be concentrated to dryness, and 34.5 grams of white product is obtained with silica gel column chromatography purifying, the yield of step 4 is 91.35%.

The white product is determined as intermediary A1-B through FD-MS analysis, analyzes result through FD-MS are as follows: C₃₀H₂₅BO₄, theoretical Molecular weight is 460.33, and measurement molecular weight is 460.33.

The modification of intermediary A1-B

Other than intermediary A1-B, the those skilled in the art of technical field can substitute rising in synthesis mechanism A4-1 Beginning object, and other intermediaries An-B is synthesized with the synthesis path similar to synthesis mechanism A4-1, it can example intermediary described as follows A2-B to A6-B, but not limited to this:

The intermediary An for being used to prepare compounds can separately be synthesized through the following steps.

The synthesis of intermediary A ' n-3

Intermediary A ' n-3 is to be used to prepare a kind of compounds, intermediary A ' n-3 can by following synthesis mechanism A5 into Row synthesis.

Step 1: the synthesis of intermediary A ' 7-2

Using intermediary A ' 7-2 as the example of synthesis intermediary A ' n-2, intermediary A ' 7-2 can pass through above-mentioned synthesis mechanism A5 is synthesized, and as X ' is the situation of bromine.

It will be dissolved with the 12N hydrochloric acid (100 milliliters) of the bromo- 4- acetamido dibenzofurans (55g, 1.0eq) of 1- and 275 milliliters Ethyl alcohol in continue magnetic and be stirred, and be heated to reflux 8 hours, solution to be mixed is cooled to room temperature, and filtering obtains crude product again With pure water and drying, the yield of step 1 is 97%.

The product is determined as intermediary A ' 7-2 through FD-MS analysis, analyzes result through FD-MS are as follows: C₁₂H₉BrClNO, it is theoretical Molecular weight is 298.56, and measurement molecular weight is 298.56.

Step 2: the synthesis of intermediary A ' 7-3

Keep the mixing of intermediary A ' 7-2 (60.0g, 1.0eq) addition 12N hydrochloric acid (50 milliliters) and acetonitrile (240 milliliters) molten In liquid, maintain the temperature of mixed solution lower than 5 DEG C；By 400 milliliters dissolved with sodium nitrite (2.0eq) and potassium iodide (2.5eq) Aqueous solution is slowly added in the mixed solution of aforementioned low temperature, and lasting stirring after ten minutes, makes the temperature of mixed solution be warming up to 20 DEG C and continued stirring overnight；Then, extremely with the pH value of the sodium bicarbonate of saturation and sodium thiosulfate (2.5eq) adjustment mixed solution Between 9 to 10, then sediment is obtained in a manner of filtering or in a manner of ethyl acetate extraction, and be 5:1 with volume ratio Hexane and methylene chloride purified as elutriant with flash column chromatography and obtain gray solid product, the yield of step 2 is 83.2%.

The gray solid product is determined as intermediary A ' 7-3 through FD-MS analysis, analyzes result through FD-MS are as follows: C₁₂H₆BrIO, theoretical molecular weight 372.98, measurement molecular weight are 372.98.

The synthesis of intermediary An

Intermediary An is to be used to prepare a kind of compounds, and intermediary An can be closed by following synthesis mechanism A6 At.

In synthesis mechanism A6, B ', L, m and n are with defined in aforementioned synthesis mechanism A1, and X ' is the same as aforementioned synthesis mechanism A5 Defined in.

Step 3: the synthesis of intermediary A7

Using intermediary A7 as the example of synthesis intermediary An, intermediary A7 can be closed by following synthesis mechanism A6-1 At.

Intermediary A ' 7-3 (the bromo- 4- iodine dibenzofurans of 1-) (30.0g, 1.0eq), 4- dibenzofurans boric acid (4- Dibenzofuranboronic acid) (1.25eq), palladium acetate (0.01eq), triphenylphosphine (triphenylphosphine) (PPh₃) (0.04eq) and potassium carbonate (2.0eq) is mixed in by toluene (260 milliliters), ethyl alcohol (26 milliliters) and water (55 milliliters) group At mixed solution in, which is stirred at reflux 16 hours under 80 DEG C of nitrogen environment, reaction complete and mixed solution Be cooled to room temperature, extract the mixed solution and collect crude product in organic layer, then it is dry with magnesium sulfate, be separated by filtration and be concentrated The crude product, and with 29.3 grams of acquisition of silica gel column chromatography purifying of white solid product, the yield of step 3 is 88.15%.

The white product is determined as intermediary A7 through FD-MS analysis.FD-MS analyzes result: C₂₄H₁₃BrO₂, theoretical molecular weight It is 413.26, detection molecules amount is 413.26.

The synthesis of intermediary A8

Intermediary A8 be used to prepare a kind of compounds, and can by similar to intermediary A7 synthesis step 3 come Synthesis, difference is to have used different starting materials in the synthesis step of intermediary A8, with 2 surrogate response object B1 of reactant B As starting material, the results are shown in Table 4 for the analysis of each intermediary.

Table 4: the chemical structural formula of reactant B n used in synthesis intermediary A7 and A8 and intermediary A7 and A8 produce Rate, molecular formula and quality obtained by being analyzed with FD-MS.

The modification of intermediary A7 and A8

Other than intermediary A7 and A8, the those skilled in the art of technical field can substitute in synthesis mechanism A6-1 Starting material, and other intermediaries An, example intermediary A9 described as follows are synthesized with the synthesis path similar to synthesis mechanism A6-1 To A12, but not limited to this:

The synthesis of intermediary An-L

Intermediary An above-mentioned (such as intermediary A1 to A12) further can be inserted into a penylene base, synthesis with step 4'-1 Intermediary An-L out.

Intermediary An-L be to prepare a kind of compounds, intermediary An-L can by following synthesis mechanism A4-L into Row synthesis.

In synthesis mechanism A4-L, with defined in aforementioned synthesis mechanism A1, X is chlorine, bromine or iodine and X' by L, m and n For chlorine or bromine.

Step 4'-1: the synthesis of intermediary A1-L

Using intermediary A1-L as the example of synthesis intermediary An-L, intermediary A1-L can pass through following synthesis mechanism A4- 1-L is synthesized.

Intermediary A1 (1- (4- dibenzofurans) -4- iodine dibenzofurans) (1- (dibenzofuran-4-yl) -4- Iododibenzofuran) (50.0g, 1.0eq), 4- chlorophenylboronic acid (1.05eq, CAS No.1679-18-1), Pd (OAc)₂ (0.01eq)、PCy₂(2-biPh) (0.04eq) and potassium carbonate (2.0eq) are mixed in by toluene (340 milliliters), ethyl alcohol (34 millis Rise) and water (72 milliliters) composed by mixed solution, mixed solution return stirring 16 hours under 80 DEG C of nitrogen environment, It completes and is cooled to room temperature in reaction, which collects crude product, dried over magnesium sulfate, mistake through extraction and from organic layer After filter separation and concentrate drying, then with 43 grams of acquisition of silica gel column chromatography purifying of white solid product, the yield of step 4'-1 It is 89%.

The white product is determined as intermediary A1-L through FD-MS analysis.FD-MS analyzes result: C₃₀H₁₇ClO₂, Theoretical molecular Amount is 444.91, and detection molecules amount is 444.91.

The modification of intermediary A1-L

Other than intermediary A1-L, the those skilled in the art of technical field can substitute in synthesis mechanism A4-1-L Any one of starting material, such as intermediary A2 to A12 or chlorine substituent connect the chlorophenylboronic acid in different location, and with Synthesize other intermediaries An-L, example intermediary A2-L to A19- described as follows similar to the synthesis path of synthesis mechanism A4-1-L L, but not limited to this:

The synthesis of compounds

Aforementioned each intermediary (i.e. intermediary An and intermediary An-L) can synthesize compounds by synthesis mechanism I, In synthesis mechanism I, the reactant A 1 of " reactant A n " (Reactant An) in table 5 to A10；" intermediary A " (Intermediate A) includes previous intermediate An, intermediary An-L or its homologue, and each compounds are with following steps It is rapid synthesized.

Table 5: chemical structural formula and the CAS number of reactant A 1 to A10.

Synthesis mechanism I: the synthesis of compound 1 to 9

In synthesis mechanism I, intermediary A (1.0eq), reactant A n (1.05eq), Pd (OAc)₂(0.005eq), tetrafluoro Boric acid tri-tert-butylphosphine (tri-tert-butylphosphonium tetrafluoroborate) (P (t-Bu)₃HBF₄) (0.02eq), sodium tert-butoxide (sodium tert-butoxide) (NaOtBu) (1.5eq) are dissolved in toluene (40 milliliters)；It connects , which is heated to 90 DEG C and continues 12 hours, completes and is cooled to room temperature wait react, extracted and received in organic layer Collect crude product, then after being dried and filtered with magnesium sulfate separation and being concentrated and dried, it is solid to can get white after purification with silica gel column chromatography Body product, compounds as of the invention.Intermediary A and reactant A n used in synthesis compound 1 to 9 is listed in the table below In 6.

Compound 1 to 9 is with H¹- NMR and FD-MS are analyzed, and the chemical structural formula of compound 1 to 9, yield, molecule Formula and quality are listed in Table 6 below, as the NMR spectra of Fig. 2 to 10 recognized as a result, the following institute of the chemical structural formula of compound 1 to 9 Show.

Table 6: the yield of reactant and intermediary and compound 1 to 9 used in synthesis compound 1 to 9, molecular formula and The result analyzed with FD-MS.

The modification of compound 1 to 9

Other than compound 1 to 9, the those skilled in the art of technical field can substitute used in synthesis mechanism I Intermediary A (i.e. previous intermediate An or intermediary An-L) and reactant A n, and to be closed similar to the synthesis path of synthesis mechanism I At other compounds out.

The preparation of OLED device

It is coated withThe glass substrate (hereinafter referred to as ito substrate) of thick ito layer is placed in containing abluent (factory Board: Fischer Co.) distilled water (with the filtering of the filter of Millipore Co. company it is secondary obtained by distilled water) in, and with Ultrasonic vibrating 30 minutes；Again with ultrasonic vibrating 10 minutes to clean ito substrate after replacement distilled water, and repeat above-mentioned clean Step is primary；After cleaning, foregoing glass substrate is cleaned with isopropanol, acetone and methanol with ultrasonic vibrating, and be allowed to drying； Then, glass substrate is placed in plasma-based surface cleaner, and with oxygen plasma-based cleaning glass substrate 5 minutes, then will be after cleaning Glass substrate is placed in vacuum evaporation plating machine.

Later, the vacuum degree of vacuum evaporation plating machine is maintained into 1x10^-6Torr to 3x10^-7Torr, and on ito substrate according to Sequence deposits various organic materials and metal material, and obtains the OLED device of embodiment 1 to 29 and comparative example 1 to 10.In this, Deposited in sequential has the first electric hole implanted layer (HIL-1), the second electric hole implanted layer (HIL-2), the transmission of the first electric hole on the ito substrate Layer (HTL-1), the second electric hole transport layer (HTL-2), blue green/red light luminescent layer (BEL/GEL/REL), electron transfer layer (ETL), electron injecting layer (EIL) and cathode (Cthd).

In each layer of above-mentioned OLED device, HAT is used to form HIL-1 and HIL-2；HI-D is used to form HIL-1；HI-A It is for respectively forming HIL-1, HIL-2 and HTL-1；Business HI material (m-MTDATA) is used to form HIL-2；HT-A and HT-B points HTL-1 and HTL-2 are not used to form it；Compounds of the invention are to be for respectively forming HTL-1, HTL-2 or HIL-2；Quotient Industry HT material (such as NPB and HT-C) is for respectively forming HTL-1 or HTL-2；Liq is to be used to form ETL and EIL；RH/GH/BH Respectively form the main material of REL/GEL/BEL；RD/GD/BD can be used as the dopant of REL/GEL/BEL.