Synthetic structural unit for preparing material for organic electroluminescent device
阅读说明：本技术 用于制备有机电致发光器件用材料的合成结构单元 (Synthetic structural unit for preparing material for organic electroluminescent device ) 是由 菲利普·斯托塞尔 埃米尔·侯赛因·帕勒姆 安雅·雅提斯奇 于 2014-02-24 设计创作，主要内容包括：本发明涉及用于制备有机电致发光器件用材料的合成结构单元。具体地,本发明涉及如下化合物,所述化合物适合作为制备用于有机电致发光器件中的电子活性材料的合成前体。<Image he="329" wi="700" file="DDA0002504342580000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The invention relates to a synthetic building block for preparing materials for organic electroluminescent devices. In particular, the present invention relates to compounds suitable as synthesis precursors for the preparation of electronically active materials for use in organic electroluminescent devices.)
1. a compound of formula (1), formula (2) or formula (3),
where the following applies to the symbols and labels used:
l is a single bond or a di, tri, tetra, penta or hexavalent group;
r is identical or different on each occurrenceSelected from: h, D, Cl, I, NAr2，N(R1)2Wherein R is1Not being equal to H, C (═ O) Ar, C (═ O) R1，BR1，P(＝O)Ar2，PAr2，OAr，S(＝O)Ar，S(＝O)2Ar，Si(R1)3A linear alkyl or alkoxy group having 1 to 40C atoms or a branched or cyclic alkyl or alkoxy group having 3 to 40C atoms or an alkenyl or alkynyl group having 2 to 40C atoms, each of which may be substituted by one or more radicals R1Substitution, in which in each case one or more non-adjacent CH2The group can be represented by R1C＝CR1、C≡C、Si(R1)2、C＝NR1、P(＝O)(R1)、NR1O, S or CONR1And in which one or more H atoms may be replaced by D, F, Cl, Br, I or CN, or an aromatic or heteroaromatic ring system having from 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R1Substitution; two or more adjacent substituents R here may optionally form a mono-or polycyclic aliphatic, aromatic or heteroaromatic ring system which may be interrupted by one or more radicals R1Substitution;
ar, identically or differently on each occurrence, is an aromatic or heteroaromatic ring system having from 5 to 30 aromatic ring atoms, which may be interrupted by one or more radicals R1Substitution; the two groups Ar bonded to the same N atom or P atom can also be bonded by a single bond or selected from N (R)1)、C(R1)2O, S or BR1The bridges of (a) are bridged to each other;
R1selected, identically or differently at each occurrence, from: h, D, F, Cl, Br, I, CN, NO2，N(R2)2，P(＝O)(R2)2A linear alkyl, alkoxy or thioalkyl group having 1 to 40C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40C atoms or an alkenyl or alkynyl group having 2 to 40C atoms, each of which may be substituted by one or more radicals R2Substitution of one or more ofNon-adjacent CH2The group can be represented by R2C＝CR2、C≡C、Si(R2)2、C＝NR2、P(＝O)(R2)、SO、SO2、NR2O, S or CONR2And in which one or more H atoms may be replaced by D, F, Cl, Br, I or CN, aromatic or heteroaromatic ring systems having from 5 to 60 aromatic ring atoms which may in each case be replaced by one or more radicals R2Substitution; where two or more adjacent substituents R1May optionally form a mono-or polycyclic aliphatic ring system which may be substituted by one or more radicals R2Substitution;
R2selected, identically or differently at each occurrence, from: h, D, F, CN, an aliphatic hydrocarbon radical having 1 to 20C atoms, an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms in which one or more H atoms may be replaced by D, F, Cl, Br, I or CN, where two or more adjacent substituents R2Aliphatic ring systems which may form a single ring or multiple rings with one another;
n is 0, 1,2,3,4 or 5, with the proviso that L is absent if n ≧ 0, and with the further proviso that L is bonded to the benzene skeleton in each case in place of the group R and thus the corresponding group R is absent;
wherein at least one group R:
selected from aromatic or heteroaromatic ring systems selected from: benzene, biphenyl, terphenyl, quaterphenyl, 1-spirobifluorene, 2-spirobifluorene, 3-spirobifluorene or 4-spirobifluorene, 1-fluorene, 2-fluorene, 3-fluorene or 4-fluorene, 1-naphthyl or 2-naphthyl, pyrrole, furan, thiophene, indole, benzofuran, benzothiophene, carbazole, azacarbazole, dibenzofuran, dibenzothiophene, pyridine, pyrimidine, pyrazine, pyridazine, triazine, imidazole, benzimidazole, pyrazole, thiazole,
or a group selected from formulae (7) to (18):
wherein the symbols used have the meanings given in claim 1, indicating the position to which the group is bonded, and furthermore:
a is, identically or differently on each occurrence, CR1Or N, with the proviso that one, two or three groups A represent N;
Ar1identical or different on each occurrence is a divalent aromatic or heteroaromatic ring system having 5 to 16 aromatic ring atoms which may be interrupted by one or more radicals R1Substitution;
m is 0 or 1;
or a group selected from formulae (19) to (33):
wherein the symbols used have the same meanings as described above, and furthermore
G is selected from NR1The oxygen, the oxygen or the sulfur is selected from the group consisting of O and S,
e is selected from C (R)1)2、NR1、O、S、BR1Or Si (R)1)2，
Wherein in each case one or two radicals CR1May be replaced by N;
provided that the following compounds are excluded from the present invention:
2. a compound according to claim 1, characterized in that n-0, 1,2 or 3.
3. Compounds according to claim 1 or 2, characterized in that L represents a single bond, NR, BR, P (═ O) R, a linear alkylene or alkylidene group having 1 to 10C atoms or a branched or cyclic alkylene or alkylidene group having 3 to 10C atoms, which groups may be substituted in each case by one or more groups R, where one or more non-adjacent CH's are present2The radicals being optionally substituted by-RC ═ CR-, -C ≡ C-, Si (R)2C ═ O, -O-, -S-, or-CONR-and where one or more H atoms may be replaced by D or F, or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which may be substituted by one or more groups R.
4. The compound according to claim 1 or 2, selected from compounds of formulae (1a) to (1h), (2a) to (2l), and (3a) to (3f),
wherein the symbols used have the meanings given in claim 1.
5. A compound according to claim 1 or 2, characterized in that two adjacent radicals R form a ring of formula (4) with each other,
wherein R is1Having the meaning given above, the dashed bond indicates the attachment of the group to the benzene skeleton, and furthermore:
e is selected from C (R)1)2、NR1、O、S、BR1Or Si (R)1)2。
6. The compound according to claim 1 or 2, wherein R, equal or different at each occurrence, is selected from: h, NAr2，C(＝O)Ar，C(＝O)R1，P(＝O)Ar2，PAr2，Si(R1)3Straight-chain alkyl groups having 1 to 10C atoms or branched or cyclic alkyl groups having 3 to 10C atoms or alkenyl groups having 2 to 10C atoms, each of which may be substituted by one or more radicals R1Substitution, in which in each case one or more non-adjacent CH2The group can be represented by R1C＝CR1Or O and in which one or more H atoms may be replaced by F, an aromatic or heteroaromatic ring system having from 5 to 40 aromatic ring atoms which may in each case be replaced by one or more radicals R1Substitution; two or more adjacent substituents R here may optionally form a mono-or polycyclic aliphatic, aromatic or heteroaromatic ring system which may be interrupted by one or more radicals R1And (4) substitution.
7. A compound according to claim 1 or 2, characterised in that the group R, R1Or R2Are free of fused aryl or heteroaryl groups in which six-membered rings are fused directly to one another.
8. A process for the preparation of a compound according to any one of claims 1 to 7, comprising the reaction steps of:
a) oxidizing a fluoro-m-xylene derivative to produce a carboxylic acid; and
b) the carboxylic acid function is converted to a cyano group.
9. Process for the preparation of a compound according to any one of claims 1 to 7 by reacting a fluorom-dihalobenzene derivative with Zn (CN) in the presence of a catalyst2By reaction with ZnThe process is carried out.
10. Use of a compound according to any one of claims 1 to 7 as a starting material in nucleophilic aromatic substitution reactions.
11. A process for preparing a compound of formula (34) or formula (35) or formula (36) by reacting a compound according to any one of claims 1 to 7 with a nucleophile,
wherein Nu denotes a nucleophilic group and the other symbols used have the meanings given in claim 1.
Technical Field
The invention relates to a synthetic building block for preparing materials for organic electroluminescent devices. In particular, the present invention relates to compounds that are useful as synthetic building blocks for the preparation of electronically active materials, in particular for organic electroluminescent devices.
Background
The structure of organic electroluminescent devices (OLEDs) using organic semiconductors as functional materials is described, for example, in US 4539507, US 5151629, EP 0676461 and WO 98/27136. At present, donor-acceptor-substituted benzene derivatives, in particular those in which the acceptor groups are cyano in meta position to one another and the donor group is a carbazole derivative, are also used in particular for this purpose. Examples of such compounds are described in c.adachi et al, Nature 2012, 492, 234-. However, only the synthesis of symmetrically substituted compounds is disclosed herein. Furthermore, chromatographic purification of the product is necessary, which makes purification especially on an industrial scale more difficult. It is therefore desirable to have available compounds from which the desired electronically active compounds can be synthesized in high yield and purity.
Disclosure of Invention
It was therefore an object of the present invention to provide compounds which are suitable as synthesis precursors for the preparation of electronically active components for use in organic electroluminescent devices, in order on the one hand to be able to prepare the materials in good yield and purity and on the other hand to enable the person skilled in the art to have a greater possible choice of materials for the production of OLEDs.
Surprisingly, it was found that specific compounds described in more detail below achieve this object, being highly suitable for the preparation of donor-acceptor-substituted materials for OLEDs. In these compounds, the fluorine substituent can be selectively displaced by a nucleophile under mild reaction conditions and in high yield in nucleophilic aromatic substitution. The invention therefore relates to these compounds.
The invention relates to compounds of formula (1), formula (2) or formula (3),
where the following applies to the symbols and labels used:
l is a single bond or a di, tri, tetra, penta or hexavalent group;
r, equal or different at each occurrence, is selected from: h, D, Cl, Br, I, NAr2，N(R1)2Wherein R is1Not being equal to H, C (═ O) Ar, C (═ O) R1，BR1，P(＝O)Ar2，PAr2，OAr，SAr，S(＝O)Ar，S(＝O)2Ar，Si(R1)3A linear alkyl or alkoxy group having 1 to 40C atoms or a branched or cyclic alkyl or alkoxy group having 3 to 40C atoms or an alkenyl or alkynyl group having 2 to 40C atoms, each of which may be substituted by one or more radicals R1Substitution, in which in each case one or more non-adjacent CH2The group can be represented by R1C＝CR1、C≡C、Si(R1)2、C＝NR1、P(＝O)(R1)、NR1O, S or CONR1And in which one or more H atoms may be replaced by D, F, Cl, Br, I or CN, or an aromatic or heteroaromatic ring system having from 5 to 60 aromatic ring atoms, which may in each case be substituted by one or more radicals R1Substitution; two or more adjacent substituents R here may optionally form a mono-or polycyclic aliphatic, aromatic or heteroaromatic ring system which may be interrupted by one or more radicals R1Substitution;
ar, identically or differently on each occurrence, is an aromatic or heteroaromatic ring system having from 5 to 30 aromatic ring atoms, which may be interrupted by one or more radicals R1Substitution; two groups Ar which are bonded to the same N atom or P atom can also be bonded by a single bondOr is selected from N (R)1)、C(R1)2O, S or BR1The bridges of (a) are bridged to each other;
R1selected, identically or differently at each occurrence, from: h, D, F, Cl, Br, I, CN, NO2，N(R2)2，P(＝O)(R2)2A linear alkyl, alkoxy or thioalkyl group having 1 to 40C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40C atoms or an alkenyl or alkynyl group having 2 to 40C atoms, each of which may be substituted by one or more radicals R2Substitution of one or more non-adjacent CH2The group can be represented by R2C＝CR2、C≡C、Si(R2)2、C＝NR2、P(＝O)(R2)、SO、SO2、NR2O, S or CONR2And in which one or more H atoms may be replaced by D, F, Cl, Br, I or CN, aromatic or heteroaromatic ring systems having from 5 to 60 aromatic ring atoms which may in each case be replaced by one or more radicals R2Substitution; where two or more adjacent substituents R1May optionally form a mono-or polycyclic aliphatic ring system which may be substituted by one or more radicals R2Substitution;
R2selected, identically or differently at each occurrence, from: h, D, F, CN, an aliphatic hydrocarbon radical having 1 to 20C atoms, an aromatic or heteroaromatic ring system having 5 to 30 aromatic ring atoms in which one or more H atoms may be replaced by D, F, Cl, Br, I or CN, where two or more adjacent substituents R2Aliphatic ring systems which may form a single ring or multiple rings with one another;
n is 0, 1,2,3,4 or 5, with the proviso that L is absent if n ≧ 0, and with the further proviso that, for n ≧ 1, L is bonded to the benzene skeleton in each case in place of the group R and thus the corresponding group R is absent;
provided that the following compounds are excluded from the present invention:
Detailed Description
An aryl group in the sense of the present invention contains 6 to 60C atoms; heteroaryl groups in the sense of the present invention contain 2 to 60C atoms and at least one heteroatom, with the proviso that the sum of C atoms and heteroatoms is at least 5. The heteroatom is preferably selected from N, O and/or S. An aryl group or heteroaryl group is herein understood to mean a simple aromatic ring, i.e. benzene, or a simple heteroaromatic ring, such as pyridine, pyrimidine, thiophene, etc., or a fused (condensed) aryl or heteroaryl group, such as naphthalene, anthracene, phenanthrene, quinoline, isoquinoline, etc. Aromatic groups, such as biphenyl, which are connected to one another by single bonds, are, in contrast, not referred to as aryl or heteroaryl groups, but rather as aromatic ring systems.
An aromatic ring system in the sense of the present invention contains 6 to 60C atoms in the ring system. A heteroaromatic ring system in the sense of this invention contains 2 to 60C atoms and at least one heteroatom in the ring system, with the proviso that the sum of C atoms and heteroatoms is at least 5. The heteroatom is preferably selected from N, O and/or S. For the purposes of the present invention, aromatic or heteroaromatic ring systems are intended to be taken to mean systems which do not necessarily contain only aryl or heteroaryl groups, but in which a plurality of aryl or heteroaryl groups may also be linked by non-aromatic units, for example C, N or O atoms. Thus, for example, systems such as fluorene, 9' -spirobifluorene, 9-diarylfluorene, triarylamines, diaryl ethers, stilbene and the like are also intended to be considered aromatic ring systems for the purposes of the present invention, as are systems in which two or more aryl groups are connected by, for example, short alkyl groups.
For the purposes of the present invention, it may contain 1 to 40C atoms and where the individual H atoms or CH2Aliphatic hydrocarbon groups or alkyl groups or alkenyl or alkynyl groups whose groups may also be substituted by the above-mentioned groups are preferably taken to mean the following groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, neopentyl, cyclopentyl, n-hexyl, neohexyl, cyclohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylAn alkyl group, such as an alkyl group, an aryl group, an. Alkoxy radicals having 1 to 40C atoms are to be understood as preferably meaning methoxy, trifluoromethoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, sec-pentoxy, 2-methylbutoxy, n-hexoxy, cyclohexyloxy, n-heptoxy, cycloheptoxy, n-octoxy, cyclooctoxy, 2-ethylhexoxy, pentafluoroethoxy and 2,2, 2-trifluoroethoxy. Thioalkyl radicals having 1 to 40C atoms are to be understood as meaning, in particular, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio, n-pentylthio, sec-pentylthio, n-hexylthio, cyclohexylthio, n-heptylthio, cycloheptylthio, n-octylthio, cyclooctylthio, 2-ethylhexylthio, trifluoromethylthio, pentafluoroethylthio, 2,2, 2-trifluoroethylthio, vinylthio, propenylthio, butenylthio, pentenylthio, cyclopentenylthio, hexenylthio, cyclohexenylthio, heptenylthio, octenylthio, cyclooctenylthio, ethynylthio, propynylthio, butynylthio, pentynylthio, hexynylthio, heptynylthio or octynylthio. In general, the alkyl, alkoxy or thioalkyl groups according to the invention may be straight-chain, branched or cyclic, in which one or more non-adjacent CH's are2The groups may be replaced by the above-mentioned groups; furthermore, one or more H atoms may also be replaced by D, F, Cl, Br, I, CN or NO2Preferably F, Cl or CN, more preferably F or CN, particularly preferably CN.
Aromatic or heteroaromatic ring systems having from 5 to 60 aromatic ring atoms, which may also be substituted in each case by the abovementioned radicals R2Or a hydrocarbon group substituted and may be attached via any desired position on the aromatic or heteroaromatic ring system, is taken to mean in particular a group derived from: benzene, naphthalene, anthracene, benzanthracene, phenanthrene, pyrene,perylene, fluoranthene, tetracene, pentacene, benzopyrene, biphenyl, terphenyl, fluorene, spirobifluorene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis-or trans-indenofluorene, cis-or trans-indenocarbazole, cis-or trans-indolocarbazole, triindene, isotridendene, spirotriindene, spiroisotridendene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5, 6-quinoline, benzo-6, 7-quinoline, benzo-7, 8-quinoline, phenothiazine, thiopheneOxazines, pyrazoles, indazoles, imidazoles, benzimidazoles, naphthoimidazoles, phenanthroimidazoles, pyridoimidazoles, pyrazinoimidazoles, quinoxalines,
In an embodiment of the invention, the following compounds of formulae (1), (2) and (3) are excluded from the invention: wherein R, the same or different, represents a carbazole or a substituted carbazole, each of which is bonded to the backbone through a nitrogen atom.
In a preferred embodiment of the invention, n is 0, 1,2 or 3, particularly preferably 0, 1 or 2, very particularly preferably 0 or 1, and in particular n is 0. And L is a single bond or a divalent group when n ═ 1, and a trivalent group when n ═ 2, and the like.
In a further preferred embodiment of the invention, L represents a single bond, NR, BR, P (═ O) R, a linear alkylene or alkylidene group having 1 to 10C atoms or a branched or cyclic alkylene or alkylidene group having 3 to 10C atoms, which groups may in each case be substituted by one or more radicals R, where one or more non-adjacent CH's are present2The radicals being optionally substituted by-RC ═ CR-, -C ≡ C-, Si (R)2C ═ O, -O-, -S-, or-CONR-, and in which one or more H atoms may be replaced by D or F, or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which may be substituted by one or more groups R. L particularly preferably represents a single bond, NR, a linear alkylene or alkylidene group having 1 to 6C atoms or a branched or cyclic alkylene or alkylidene group having 3 to 6C atoms, in which one or more non-adjacent CH' s2The radicals may be replaced by-O-, or an aromatic or heteroaromatic ring system having from 5 to 18 aromatic ring atoms, which may be substituted by one or more radicals R. As already mentioned, the group L is absent when n ≧ 0, and the group L is bonded in each case to the benzene skeleton instead of to one of the groups R when n ≧ 1. When n ═ 2, the preferred group L can furthermore also be selected from N, B or P ═ O.
Preferred embodiments of the compounds of formula (1) are compounds of the following formulae (1a) to (1e) when n ≧ 0, and compounds of the following formulae (1f) to (1h) when n ≧ 1. Preferred embodiments of the compound of formula (2) are compounds of formulae (2a) to (2g) below when n ≧ 0, and compounds of formulae (2h) to (2l) below when n ≧ 1. A preferred embodiment of the compound of formula (3) is a compound of the following formulae (3a) to (3f) at n.gtoreq.1.
Wherein R and L have the meanings given above. In the monomeric structures, i.e. the structures of formulae (1a) to (1e) and (2a) to (2g), the radical R is preferably not equal to H or D.
As mentioned above, a plurality of adjacent radicals R may also form a ring with one another, so that naphthalene is formed overall, for example by forming fused-on benzo groups. Preference is also given to forming fused-on aliphatic rings, where the ring system preferably has a total of from 5 to 7 ring atoms. Preferred fused-on rings formed by ring formation of adjacent groups R are additionally structures of the following formula (4),
wherein R is1Having the meaning given above, the dashed bond indicates the attachment of the group to the benzene skeleton, and furthermore:
e is selected from C (R)1)2、NR1、O、S、BR1Or Si (R)1)2Preferably NR1O or S.
Preferred embodiments of formula (1) containing a group of formula (4) are compounds of the following formulae (5a) and (5b), and preferred embodiments of formula (2) containing a group of formula (4) are compounds of the following formulae (6a) and (6b),
wherein the symbols used have the meanings given above.
In each case, only the structure when n is 0 is depicted. Accordingly, the structure may also contain units of formula (4) when n.gtoreq.1.
Preferred radicals R, equal or different at each occurrence, are selected from: h, NAr2，C(＝O)Ar，P(＝O)Ar2，PAr2，Si(R1)3Straight-chain alkyl groups having 1 to 10C atoms or branched or cyclic alkyl groups having 3 to 10C atoms or alkenyl groups having 2 to 10C atoms, each of which may be substituted by one or more radicals R1Substitution, in which in each case one or more non-adjacent CH2The group can be represented by R1C＝CR1Or O and in which one or more H atoms may be replaced by F, an aromatic or heteroaromatic ring system having from 5 to 40 aromatic ring atoms which may in each case be replaced by one or more radicals R1Substitution; two or more adjacent substituents R here may optionally form a mono-or polycyclic aliphatic, aromatic or heteroaromatic ring system which may be interrupted by one or more radicals R1And (4) substitution.
Particularly preferred radicals R are identical in each occurrenceOr differently selected from: h, NAr2A linear alkyl radical having 1 to 6C atoms or a branched or cyclic alkyl radical having 3 to 8C atoms, each of which may be substituted by one or more radicals R1Substituted, aromatic or heteroaromatic ring systems having 5 to 24 aromatic ring atoms which may in each case be substituted by one or more radicals R1Substitution; two or more adjacent substituents R here may optionally form a mono-or polycyclic aliphatic, aromatic or heteroaromatic ring system which may be interrupted by one or more radicals R1And (4) substitution.
Preferred radicals Ar are selected from aromatic or heteroaromatic ring systems having from 5 to 24 aromatic ring atoms, particularly preferably from 5 to 18 aromatic ring atoms, which may in each case be substituted by one or more radicals R1And (4) substitution. Ar here preferably contains no fused aryl or heteroaryl groups in which more than two six-membered rings are fused directly to one another. In particular, it is preferred that Ar is free of fused aryl or heteroaryl groups in which two or more six-membered rings are directly fused to each other.
If R represents an alkyl group, it is preferred that the alkyl group has no benzylic proton, i.e., no hydrogen atom bonded to a carbon atom directly bonded to the phenyl ring. This is achieved, for example, by using tertiary alkyl groups, such as tertiary butyl groups.
If R represents Si (R)1)3Or R in the radical1Preferably, identical or different at each occurrence denotes an alkyl radical having 1 to 10C atoms, particularly preferably having 1 to 4C atoms.
In a preferred embodiment of the invention, at least one of the radicals R is an aromatic or heteroaromatic ring system or a diarylamino group NAr2。
If R represents an aromatic or heteroaromatic ring system, it preferably has 5 to 24 aromatic ring atoms as described above and may be substituted by one or more radicals R1And (4) substitution. Preferred aromatic or heteroaromatic radicals R are selected from: benzene, biphenyl, in particular ortho-, meta-or para-biphenyl, terphenyl, in particular ortho-, meta-, para-or branched terphenyl, quaterphenyl, in particular ortho-, meta-quaterphenylBenzene, p-or branched-quaterphenyl, 1-spirobifluorene, 2-spirobifluorene, 3-spirobifluorene or 4-spirobifluorene, 1-fluorene, 2-fluorene, 3-fluorene or 4-fluorene, 1-naphthyl or 2-naphthyl, pyrrole, furan, thiophene, indole, benzofuran, benzothiophene, carbazole, azacarbazole, dibenzofuran, dibenzothiophene, pyridine, pyrimidine, pyrazine, pyridazine, triazine, imidazole, benzimidazole, pyrazole, thiazole,the amount of oxazole,diazoles, triazoles, phenanthrenes, terphenyls, or combinations of two or three of these radicals, each of which may be substituted by one or more radicals R1And (4) substitution.
If the radical R is an aromatic or heteroaromatic ring system, the compounds preferably do not contain fused aryl or heteroaryl groups in which more than two six-membered rings are fused directly to one another. In particular, it is preferred that R does not contain a fused aryl or heteroaryl group in which two or more six-membered rings are directly fused to each other. Compounds of formula (1), formula (2), formula (3) or preferred embodiments are particularly preferred at group R, R1Or R2Are free of fused aryl or heteroaryl groups in which six-membered rings are directly fused to each other.
Suitable and preferred aromatic ring systems R are radicals of the formulae (7) to (14),
wherein the symbols used have the meanings given above and indicate the position at which the radicals of formulae (7) to (14) are bonded.
Suitable electron-deficient radicals R are radicals of the formulae (15) to (18),
wherein R is1Having the meaning given above(15) The position at which the group to (18) is bonded, and further:
a is, identically or differently on each occurrence, CR1Or N, with the proviso that one, two or three groups A represent N;
Ar1identical or different on each occurrence is a divalent aromatic or heteroaromatic ring system having 5 to 16 aromatic ring atoms which may be interrupted by one or more radicals R1Substitution;
m is 0 or 1.
Preferred groups of formula (15) are groups of formulae (15a) to (15g),
wherein the symbols and indices used have the meanings given above.
The group R in formula (15a)1Preferably on each occurrence identically or differently, denotes an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which may be interrupted by one or more radicals R2Substituted, in particular by phenyl, o-biphenyl, m-biphenyl or p-biphenyl, o-terphenyl, m-terphenyl, p-terphenyl or branched terphenyl, or o-quaterphenyl, m-quaterphenyl, p-quaterphenyl or branched quaterphenyl. These preferably have the same structures as shown above in formulae (7) to (14), wherein the bonding group R2Instead of the group R1。
The group R in the formulae (15b) to (15g)1Preferably on each occurrence identically or differently H, D or an aromatic or heteroaromatic ring system having 5 to 24 aromatic ring atoms, which may be substituted by one or more radicals R2Substituted, in particular by H or phenyl, o-biphenyl, m-biphenyl or p-biphenyl, o-terphenyl, m-terphenyl, p-terphenyl or branched terphenyl, or o-quaterphenyl, m-quaterphenyl, p-quaterphenyl or branched quaterphenyl. These preferably have the same structures as shown above in formulae (7) to (14), wherein the bonding group R2Instead of the group R1。
Further preferably, formula (1)At least one group R in the compounds (1), (2) or (3) is selected from triarylamine derivatives, carbazole derivatives, indenocarbazole derivatives, indolocarbazole derivatives, azacarbazole derivatives, indole derivatives, furan derivatives, benzofuran derivatives, dibenzofuran derivatives, thiophene derivatives, benzothiophene derivatives or dibenzothiophene derivatives, each of which may be substituted with one or more groups R1Substituted, or at least one substituent R represents-NAr2Wherein two groups Ar may also be selected from NR1、O、S、C(R1)2、Si(R1)2Or BR1Are bridged to each other. These groups are preferably selected from the following formulae (19) to (33),
wherein the symbols used have the meanings given above, and furthermore
G is selected from NR1O or S.
Furthermore preferably, one or two radicals CR in the above-mentioned structure1May be replaced by N.
Preferred substituents R on the above structure1Is H, CN, an alkyl radical having 1 to 10C atoms, said radical being substituted by one or more radicals R2Substituted, or aromatic or heteroaromatic ring systems having 5 to 24 aromatic ring atoms, said ring systems being substituted by one or more radicals R2And (4) substitution.
If E represents BR1Then R is1Preference is given to aryl or heteroaryl groups having from 5 to 10 aromatic ring atoms, which groups may be substituted by one or more radicals R2And (4) substitution. Particular preference is given to substituents R other than H2Such as alkyl, CN or aryl, bonded to the aryl or heteroaryl group at two positions ortho to the attached boron atom.
If E represents C (R)1)2Or Si (R)1)2Then R is1Preferably on each occurrence, identically or differently, an alkyl, aryl or heteroaryl group, each of which may be substituted by one or more radicals R2Substitution; where two radicals R1Or may form a ring system with each other.
If E represents NR1Then R is1Preferably, identically or differently on each occurrence, are alkyl, aryl or heteroaryl groups, in particular aryl groups, each of which may be substituted by one or more radicals R2Substitution; where two radicals R1Or may form a ring system with each other.
The above-described preferred embodiments may be combined with each other as necessary. In a particularly preferred embodiment of the invention, the above-mentioned preferences occur simultaneously.
Examples of preferred compounds according to the above embodiments are the following compounds of structures 1 to 246.
The compounds according to the invention can be prepared, for example, by the routes outlined in schemes 1 and 2.
Scheme 1:
the synthesis depicted in scheme 1 starts from a 2-fluoro-m-xylene derivative, wherein the group R is as defined above. Depending on the precise structure of the substituents R, protecting groups may also be necessary here. Suitable protecting groups are known to those skilled in the art of organic synthesis. These are oxidized in a first step to produce the corresponding isophthalic acid. Suitable oxidizing agents are, for example, inorganic oxidizing agents, such as permanganates, chromates, peroxodisulfates (oxones), hypochlorites, chlorites, hydrogen peroxide or oxygen, or organic oxidizing agents, such as peroxides or peroxycarboxylic acids. In the next step, the carboxylic acid group is converted into the corresponding carboxylic acid chloride by the action of, for example, an inorganic acid chloride such as thionyl chloride, phosphorus oxychloride or oxalyl chloride, optionally in the presence of an activating agent such as DMF. In the next step, the carboxylic acid chloride is converted into the carboxamide by the action of ammonia. It is dehydrated to give the nitrile by the action of a dehydrating agent such as an inorganic acid chloride, for example thionyl chloride, phosphorus oxychloride or oxalyl chloride, optionally in the presence of an activating agent such as DMF.
A similar reaction sequence can also be carried out starting from 6-fluoro-m-xylene derivatives.
If R represents Cl, Br or iodine, the compounds can be further functionalized by C-C or C-N coupling reactions known to those skilled in the art, for example, the coupling of Suzuki, Negishi, Yamamoto, Grignard-Cross, Heck, Sonogashira, Buchwald, and the like. It is also possible to convert the halogen function first into a boronic acid derivative. These halogen-or boronic acid-substituted compounds are also suitable as starting materials for the corresponding dimeric, trimeric, etc. structures, i.e. structures of the formulae (1), (2) and (3) in which n.gtoreq.1, since these abovementioned coupling reactions can also be carried out with the corresponding disubstituted, trisubstituted, etc. radicals L.
Scheme 2:
the synthesis depicted in scheme 2 starts from a 2-fluoro-1, 3-dihalobenzene derivative, wherein Hal represents Cl, Br or I and the group R is as defined above. Depending on the precise structure of the substituents R, protecting groups may also be necessary here. Suitable protecting groups are known to those skilled in the art of organic synthesis. They are reacted with Zn (in the presence of zinc and a catalyst)CN)2Reaction to produce the corresponding cyano compound. Suitable catalysts are palladium compounds with phosphine ligands, e.g. Pd (OAc) with XPhos2。
A similar reaction sequence can also be carried out starting from 6-fluoro-1, 3-dihalobenzene derivatives.
The present invention therefore also relates to a process for the preparation of a compound of formula (1) or (2) or (3), said process comprising the reaction steps of:
a) oxidizing a fluoro-m-xylene derivative to produce a carboxylic acid; and
b) the carboxylic acid function is converted to a cyano group.
The invention furthermore relates to a process for preparing compounds of the formula (1) or (2) or (3) by reacting fluoro-m-dihalobenzene derivatives with Zn (CN)2And Zn.
The compounds according to the invention are suitable as synthesis precursors for the synthesis of materials which can be used in organic electroluminescent devices. The fluorine substituents of these compounds are nucleophilically aromatic (S)N2 aromatic) is selectively displaced by a nucleophile.
The present invention therefore also relates to the use of the compounds according to the invention as starting materials in nucleophilic aromatic substitution reactions.
The invention furthermore relates again to a process for preparing compounds of the formula (34) or of the formula (35) or of the formula (36) by reacting compounds of the formula (1) or of the formula (2) or of the formula (3) with nucleophiles,
where Nu denotes a nucleophilic group, the other symbols used have the meanings given above.
The reaction is a nucleophilic aromatic substitution. This type of reaction is known to those skilled in the art and those skilled in the art also know which structures are nucleophiles.
A compound of formula (34) or formula (35) or formula (36), which is a reaction product of the process according to the invention, is suitable for use in an electronic device, in particular an organic electroluminescent device. An electronic device in the sense of the present invention is a device comprising at least one layer containing at least one organic compound. The components herein may also comprise inorganic materials or may also comprise layers made entirely of inorganic materials.
The compounds according to the invention are distinguished over the prior art by one or more of the following surprising advantages:
1. the compounds according to the invention can be reacted in nucleophilic aromatic substitution reactions with high selectivity and under mild reaction conditions in high yields. The reaction products are formed in such a high degree of purity that complex purifications, which are also always associated with material losses, are superfluous or are necessary at least only to a slight extent. In particular, chromatographic purification of the material is not necessary.
2. The compounds according to the invention are valuable precursors for the synthesis of materials which can be used in organic electroluminescent devices.
The invention is illustrated in more detail by the following examples, without wishing to be limited thereby. Those skilled in the art will be able to practice the invention using the description throughout the disclosure and be able to prepare other compounds according to the invention and use them in electronic devices or use methods according to the invention without the need for inventive work.