Indane derivatives and their use in organic electronic devices

文档序号：1580606 发布日期：2020-01-31 浏览：28次中文

阅读说明：本技术 茚满衍生物及其在有机电子器件的用途 (Indane derivatives and their use in organic electronic devices ) 是由 S·多洛克 M·帕梅耶 C·弗莱克于 2018-05-11 设计创作，主要内容包括：本发明涉及式(I)的茚满衍生物及其混合物,其中X选自式-A-(NAr2)的基团,其中A为化学键或未取代或被1、2或3个选自C1-C6烷基和C1-C6烷氧基的取代基取代的亚苯基；Ar为未取代或取代的芳基,其中键接至同一氮原子的两个基团Ar可与氮原子一起也形成具有3个或超过3个未取代或取代的环的稠环体系；且变量Y、n、m、k和l如权利要求书和说明书中所定义。本发明进一步涉及一种制备该化合物的方法及其在有机电子器件中的用途,尤其是作为空穴传输材料或电子阻挡材料。<Image he="376" wi="700" file="DDA0002265324010000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The present invention relates to indane derivatives of formula (I) wherein X is selected from the group consisting of formula-A- (NAr) and mixtures thereof 2 ) Wherein A is a bond or is unsubstituted or substituted by 1,2 or 3 groups selected from C 1 ‑C 6 Alkyl and C 1 ‑C 6 Ar is an unsubstituted or substituted aryl radical, bonded to the same nitrogen atom as The two groups Ar may form together with the nitrogen atom a fused ring system also having 3 or more than 3 unsubstituted or substituted rings, and the variables Y, n, m, k and l are as defined in the claims and the description the invention further relates to a process for the preparation of the compound and its use in organic electronic devices, especially as a hole transporting material or an electron blocking material.)

1, Compounds of formula (I) and mixtures thereof,

wherein:

x is independently at each occurrence selected from the formula-A- (NAr)₂) Wherein:

a in each occurrence is independently a bond or is unsubstituted or substituted with 1,2 or 3 groups independently selected from C₁-C₆Alkyl and C₁-C₆Phenylene substituted with a substituent of alkoxy;

ar is independently at each occurrence selected in each instance from unsubstituted or substituted aryl groups, wherein two groups Ar bonded to the same nitrogen atom may also form, together with the nitrogen atom , a fused ring system having 3 or more than 3 unsubstituted or substituted rings;

y is independently at each occurrence selected from hydrogen, C₁-C₆Alkyl radical, C₁-C₆Alkoxy radical, C₃-C₈Cycloalkyl radical, C₃-C₈Cycloalkoxy, phenyl and phenoxy, wherein the cyclic rings in the last-mentioned four groups are each unsubstituted or substituted by 1,2 or 3C₁-C₆An alkyl group and wherein the phenyl ring bonded to the phenyl indane moiety by a single bond carries at least Y groups in as hydrogen ortho-positions relative to the phenyl ring of the phenyl indane moiety;

k is 1 or 2;

l is 1 or 2;

m is 2 or 3, wherein 0, 1,2 or 3 of the m Y groups are different from hydrogen;

n is 3 or 4, wherein 0, 1,2 or 3 of the n Y groups are different from hydrogen;

the sum of k and m is 4 and the sum of l and n is 5.

2. A compound of formula (I) according to claim 1, selected from compounds (i.a), (I.B), (i.c), (i.d) and (i.e):

wherein Y, A and Ar are as defined in claim 1;

wherein in formulae (I.A), (I.B), (I.C) and (I.D):

m is 3, wherein 0, 1,2 or 3 of the m Y groups are different from hydrogen; and is

n is 4, wherein 0, 1,2 or 3 of the n Y groups are different from hydrogen;

wherein in formula (i.e):

m is 2, wherein 0, 1 or 2 of the m Y groups are different from hydrogen; and is

n is 3, wherein 0, 1 or 2 of the n Y groups are different from hydrogen.

3. A compound of formula I according to claim 1 or a compound of formulae (i.a), (I.B), (i.c), (i.d) and (i.e) according to claim 2, wherein each of the groups a are chemical bonds.

4. The compound according to any of the preceding claims , wherein the group Ar is independently at each occurrence selected from the group consisting of phenyl, biphenyl, terphenyl, tetraphenyl, wherein phenyl, biphenyl, terphenyl and tetraphenyl are unsubstituted or substituted with or more substituents R^Ar1Substitution;

naphthyl, anthryl, phenanthryl, fluorenyl, spirofluorenyl, C-bonded carbazolyl, dibenzofuranyl and dibenzothienyl, wherein the naphthyl, phenanthryl, fluorenyl, spirofluorenyl, C-bonded carbazolyl, dibenzofuranyl and dibenzothienyl are unsubstituted or substituted with or more substituents R^Ar2Substitution; or

2 groups Ar with the nitrogen atom to which they are attached may form N-bonded carbazolyl which is unsubstituted or substituted by or more substituents R^Ar3Substitution;

wherein each R^Ar1Independently selected from:

C₁-C₆alkyl radical, C₁-C₆Alkoxy, carbazol-9-yl, wherein carbazol-9-yl may be substituted by 1,2, 3 or 4 groups selected from C₁-C₄Alkyl radical, C₁-C₄Alkoxy and phenyl, wherein the phenyl group may be substituted with 1,2, 3 or 4 substituents selected from C₁-C₄Alkyl and C₁-C₄By different or identical substituents of alkoxy, diphenylamino, C₅-C₈Cycloalkyl and naphthyl, wherein the cyclic rings of the last-mentioned three radicals are each unsubstituted or substituted by 1,2, 3 or 4 radicals selected from C₁-C₄Alkyl radical, C₁-C₄Alkoxy and carbazol-9-yl, wherein the carbazol-9-yl group may be substituted with 1,2, 3 or 4 substituents selected from C₁-C₄Alkyl radical, C₁-C₄Alkoxy and phenyl, wherein the phenyl group may be substituted with 1,2, 3 or 4 substituents selected from C₁-C₄Alkyl and C₁-C₄Different or the same substituent of alkoxy;

each R^Ar2Independently selected from:

C₁-C₆alkyl radical, C₁-C₆Alkoxy, carbazol-9-yl, wherein carbazol-9-yl may be substituted by 1,2, 3 or 4 groups selected from C₁-C₄Alkyl radical, C₁-C₄Alkoxy and phenyl, wherein the phenyl group may be substituted with 1,2, 3 or 4 substituents selected from C₁-C₄Alkyl and C₁-C₄By different or identical substituents of alkoxy, diphenylamino, C₅-C₈Cycloalkyl and phenyl, wherein the cyclic rings of the last-mentioned three radicals are each unsubstituted or substituted by 1,2, 3 or 4 radicals selected from C₁-C₄Alkyl radical, C₁-C₄Alkoxy and carbazol-9-yl, wherein the carbazol-9-yl group may be substituted with 1,2, 3 or 4 substituents selected from C₁-C₄Alkyl radical, C₁-C₄Alkoxy and phenyl, wherein the phenyl group may be substituted with 1,2, 3 or 4 substituents selected from C₁-C₄Alkyl and C₁-C₄Different or identical substituents of the alkoxy radical and, furthermore, in the case of the fluorenyl radical, two geminal radicals R^Ar2May form alkylene (CH)₂)_rWherein r is 4,5,6 or 7, wherein 1 or 2 hydrogen atoms in the group may be replaced by methyl or methoxy; and is

Each R^Ar3Independently selected from:

C₁-C₆alkyl radical, C₁-C₆Alkoxy, diphenylamino and phenyl, wherein the cyclic rings in the last two radicals are each unsubstituted or substituted by 1,2, 3 or 4 substituents selected from C₁-C₄Alkyl and C₁-C₄Different or the same substituent of the alkoxy group.

5. The compound of any of the preceding claim, wherein the group Ar at each occurrence is independently selected from groups of formulae (AR-I) to (AR-XLIV)

Wherein:

# denotes in each case the bonding site to the nitrogen atom;

in the formulae AR-I, AR-II, AR-III, AR-IV, AR-V, AR-VI, AR-VII, AR-VIII, AR-IX, AR-X, AR-XI, AR-XII, AR-XIII, AR-XIV, AR-XV, AR-XVI, AR-XVII, AR-XVIII, AR-XIX, AR-XX, AR-XXI, AR-XXII, and AR-XXIII:

R¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶、R¹⁷、R¹⁸and R¹⁹If present, independently of one another, from hydrogen, straight-chain or branched C₁-C₄Alkyl, straight-chain or branched C₁-C₄Alkoxy and carbazol-9-yl, wherein carbazol-9-yl may be substituted by 1,2, 3 or 4 groups selected from C₁-C₄Alkyl radical, C₁-C₄Alkoxy, phenyl, tolyl, xylyl,Different or the same substituents of the group and the anisyl group;

R¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R^9a、R^9b、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵and R¹⁶If present, independently of one another, from hydrogen, straight-chain or branched C₁-C₄Alkyl, straight-chain or branched C₁-C₄Alkoxy, carbazol-9-yl and phenyl, wherein carbazol-9-yl and phenyl are unsubstituted or substituted by 1,2 or 3 substituents selected from C₁-C₄Alkyl radical, C₁-C₄Alkoxy, phenyl, tolyl, xylyl and

6. The compound according to any of the preceding claims , wherein the group (NAr)₂) Independently at each occurrence, selected from formulas (1) to (38):

wherein # represents the bonding site to the rest of the compound.

7. The compound of formula (I) as claimed in any of claims 1 to 6, wherein all radicals (NAr)₂) The two groups Ar having the same meaning and bonded to the same nitrogen atom of have different meanings.

8. A compound of formula (I) as claimed in any of claims 1-6 wherein all groups Ar have the same meaning.

A mixture of compounds of formula (I) comprising compounds of formulae (i.a.a.) and (i.b.a):

wherein:

each Y is independently as defined in claim 1; and is

Each Ar is independently as defined in any one of claims 1 and 4 to 8 at ;

m is 3, wherein 0, 1,2 or 3 of the m Y groups are different from hydrogen; and is

n is 4, wherein 0, 1,2 or 3 of the n Y groups are different from hydrogen.

10, A mixture of compounds of formula (I) comprising compounds of formulae (I.C.a) and (I.D.a):

wherein:

each Y is independently as defined in claim 1;

each Ar is independently as defined in any one of claims 1 and 4 to 8 at ;

m is 3, wherein 0, 1 or 2 of the m Y groups are different from hydrogen; and is

n is 4, wherein 0, 1 or 2 of the n Y groups are different from hydrogen.

11. A process for the preparation of a compound of formula (I.A.a),

wherein:

each Ar is independently as defined in any one of claims 1 and 4 to 8 at ;

each Y is independently as defined in claim 1;

m is 3, wherein 0, 1,2 or 3 of the m Y groups are different from hydrogen; and is

n is 4, wherein 0, 1,2 or 3 of the n Y groups are different from hydrogen;

wherein:

a1) there is provided an isopropenylbenzene compound of the formula (II),

wherein:

X^2aselected from F, Cl, Br, I, O-benzyl, CH₃SO₃And CF₃SO₃；

Each Y is independently selected from hydrogen and C₁-C₆Alkyl radical, C₁-C₆Alkoxy radical, C₃-C₈Cycloalkyl radical, C₃-C₈Cycloalkoxy, phenyl and phenoxy, wherein the cyclic rings in the last-mentioned four groups are each unsubstituted or substituted by 1,2 or 3C₁-C₆Alkyl substitution; and is

z is 3, wherein 0, 1,2 or 3 of the z Y groups are different from hydrogen;

b1) dimerizing an isopropenylbenzene compound of formula (II) in the presence of an acidic catalyst to produce a compound of formula (III)

c1) Aminating the compound of formula (III) with at least aromatic amines of formula (IV) in the presence of a palladium complex catalyst and a base,

Ar₂NH (IV)

thereby obtaining the compound of formula (i.a.a.).

12, A process for the preparation of a compound of formula (I.A.a),

wherein:

each Ar is independently as defined in any one of claims 1 and 4 to 8 at ;

each Y is independently as defined in claim 1;

m is 3, wherein 0, 1,2 or 3 of the m Y groups are different from hydrogen; and is

n is 4, wherein 0, 1,2 or 3 of the n Y groups are different from hydrogen;

wherein:

a2) there is provided an isopropenylbenzene compound (II),

wherein:

X^2aselected from F, Cl, Br, I, O-benzyl, CH₃SO₃And CF₃SO₃；

Each Y is independently selected from hydrogen, C₁-C₆Alkyl radical, C₁-C₆Alkoxy radical, C₃-C₈Cycloalkyl radical, C₃-C₈Cycloalkoxy, phenyl and phenoxy, wherein the cyclic rings in the last-mentioned four groups are each unsubstituted or substituted by 1,2 or 3C₁-C₆Alkyl substitution; and is

z is 3, wherein 0, 1,2 or 3 of the z Y groups are different from hydrogen;

b2) dimerizing an isopropenylbenzene compound of formula (II) in the presence of an acidic catalyst to produce a compound of formula (III):

c2) subjecting a compound of formula (III) to amination with a bis (trialkylsilyl) amino alkali metal in the presence of a palladium complex catalyst followed by removal of the trialkylsilyl protecting group to give a compound of formula (V):

d2) arylating the compound of formula (V) with at least aromatic compounds of formula (VI) in the presence of a palladium complex catalyst and a base,

Ar-X^2b(VI)，

wherein X^2bSelected from F, Cl, Br, I, O-benzyl, CH₃SO₃And CF₃SO₃，

Thereby obtaining the compound of formula (i.a.a.).

13. The process as claimed in claim 12, wherein only aromatic compounds of the formula (VI) are used in step d2) to give compounds of the formula (i.a-a), in which all Ar groups have the same meaning.

A process for preparing a mixture of compounds (I.A.a.1) and (I.B.a.1),

wherein each Ar is independently as defined in any one of claims 1 and 4 to 8 at ;

wherein:

a3) providing a mixture of 5(6) -amino-1- (4' -aminophenyl) -1,3, 3-trimethylindane compounds of formulae (VIIa) and (VIIb);

b3) arylating a mixture of compounds of formula (VIIa) and (VIIb) with at least aromatic compounds of formula (VI) in the presence of a palladium complex catalyst and a base,

Ar-X^2b(VI)，

wherein X^2bSelected from F, Cl, Br, I, O-benzyl, CH₃SO₃And CF₃SO₃；

To give a mixture of compounds of formula (i.a.a. a1) and (i.b.a 1).

15. processes for preparing a mixture of compounds of formula (I.C.a) and (I.D.a),

wherein:

each Ar is independently as defined in any one of claims 1 and 4 to 8 at ;

each Y is independently as defined in claim 1;

m is 3, wherein 0, 1,2 or 3 of the m Y groups are different from hydrogen; and is

n is 4, wherein 0, 1,2 or 3 of the n Y groups are different from hydrogen;

wherein:

a4) there is provided an isopropenylbenzene compound of the formula (IX),

wherein:

X^2cselected from F, Cl, Br, I, O-benzyl, CH₃SO₃And CF₃SO₃；

z is 4, wherein 0, 1,2 or 3 of the z Y groups are different from hydrogen;

b4) dimerizing an isopropenylbenzene compound of formula (IX) in the presence of an acidic catalyst to produce compounds of formulae (Xa) and (Xb),

c4) aminating a mixture of compounds of formulae (Xa) and (Xb) with at least aromatic amines of formula (IV) in the presence of a palladium complex catalyst and a base,

Ar₂-NH (IV)，

to give a mixture of compounds of formula (i.c.a) and (i.d.a).

16. A process for the preparation of a compound of formula (I.E.a),

wherein:

each Ar is independently as defined in any one of claims 1 and 4 to 8 at ;

each Y is independently as defined in claim 1;

m is 2, wherein 0, 1 or 2 of the m Y groups are different from hydrogen; and is

n is 3, wherein 0, 1 or 2 of the n Y groups are different from hydrogen;

wherein:

a5) there is provided an isopropenylbenzene compound of the formula (XI),

wherein:

each X^2dIndependently selected from F, Cl, Br, I, O-benzyl, CH₃SO₃And CF₃SO₃；

z is 2, wherein 0, 1 or 2 of the z Y groups are different from hydrogen;

b5) dimerizing an isopropenylbenzene compound of formula (XI) in the presence of an acidic catalyst to produce a compound of formula (XII),

c5) subjecting compound (XII) to amination with bis (trialkylsilyl) amino alkali metal in the presence of a palladium complex catalyst, followed by removal of the trialkylsilyl protecting group, to give a compound of formula (XIII),

d5) arylating compound (XIII) with at least aromatic compounds of formula VI in the presence of a palladium complex catalyst and a base,

Ar-X^2b(VI)，

wherein X^2bSelected from F, Cl, Br, I, O-benzyl, CH₃SO₃And CF₃SO₃；

Thereby obtaining the compound of formula (i.e. a).

17. processes for the preparation of a compound of formula (I.E.a),

wherein:

each Ar is independently as defined in any one of claims 1 and 4 to 8 at ;

each Y is independently as defined in claim 1;

wherein:

a6) providing a1, 1, 3-trimethyl-3-phenylindane compound of formula (XII),

wherein X^2dSelected from F, Cl, Br, I, O-benzyl, CH₃SO₃And CF₃SO₃；

b6) Aminating compound (XII) with at least aromatic amines of formula (IV) in the presence of a palladium complex catalyst and a base

Ar₂-NH (IV)，

Thereby obtaining the compound of formula (i.e. a).

18. Use of a compound of formula I as defined in any of claims 1 to 8 or a mixture of compounds of formula (I) as defined in claims 9 or 10 or a composition comprising at least two different compounds of formula I as defined in claim 1,

-as Hole Transport Material (HTM) in organic electronic devices,

-as Electron Blocking Material (EBM) in organic electronic devices,

use as semiconductor material in Organic Field Effect Transistors (OFETs), in particular Thin Film Transistors (TFTs),

-in Organic Solar Cells (OSC), solid-state dye-sensitized solar cells (DSSC) or perovskite solar cells, in particular as hole transport material in organic solar cells, as replacement for liquid electrolytes in dye-sensitized solar cells, as hole transport material in perovskite solar cells,

for Organic Light Emitting Diodes (OLEDs), in particular for displays on electronic devices and lighting systems,

for electrophotography, in particular as a photoconductive material in Organic Photoconductors (OPC),

-for organic optical detectors, organic photoreceptors, organic field quenching devices (O-FQDs), light emitting electrochemical cells (LECs) and organic laser diodes.

19, organic field effect transistors comprising a substrate having at least gate structures, a source electrode and a drain electrode, and as semiconducting material at least compounds of formula I as defined in any of claims 1 to 8 or a mixture of compounds of formula (I) as defined in claims 9 or 10 or a composition comprising at least two different compounds of formula I as defined in claim 1.

20, substrates comprising a plurality of organic field effect transistors, at least of said field effect transistors comprising at least compounds of formula I as defined in any of claims 1 to 8 or a mixture of compounds of formula (I) as defined in claims 9 or 10 or a composition comprising at least two different compounds of formula I as defined in claim 1.

21, semiconductor units comprising at least substrates as defined in claim 20.

22, electroluminescent device comprising an upper electrode, a lower electrode, an electroluminescent layer and optionally an auxiliary layer, wherein at least of the electrodes are transparent, wherein the electroluminescent device comprises at least compounds of formula I as defined in any of claims 1 to 8 or a mixture of compounds of formula (I) as defined in claim 9 or 10 or a composition comprising at least two different compounds of formula I as defined in claim 1.

23. An electroluminescent device as claimed in claim 22 comprising at least compounds of the formula I as defined in any of claims 1 to 8 or a mixture of compounds of the formula (I) as defined in claims 9 or 10 or a composition comprising at least two different compounds of the formula I as defined in claim 1 in the hole-transporting layer or the electron-blocking layer.

24. An electroluminescent device as claimed in claim 22 or 23 in the form of an organic light-emitting diode (OLED).

25. A process for preparing a compound of formula (V),

wherein:

each Y is independently as defined in claim 1;

m is 3, wherein 0, 1,2 or 3 of the m Y groups are different from hydrogen; and is

n is 4, wherein 0, 1,2 or 3 of the n Y groups are different from hydrogen;

wherein:

a2) there is provided an isopropenylbenzene compound (II),

wherein:

X^2aselected from F, Cl, Br, I, O-benzyl, CH₃SO₃And CF₃SO₃；

z is 3, wherein 0, 1,2 or 3 of the z Y groups are different from hydrogen;

b2) dimerizing an isopropenylbenzene compound of formula (II) in the presence of an acidic catalyst to produce a compound of formula (III),

c2) the compound of formula (III) is subjected to an amination reaction with a bis (trialkylsilyl) amino alkali metal in the presence of a palladium complex catalyst followed by removal of the trialkylsilyl protecting group to give the compound of formula (V).

26, A process for preparing a compound of formula (V),

wherein:

each Y is independently as defined in claim 1;

m is 3, wherein 0, 1,2 or 3 of the m Y groups are different from hydrogen; and is

n is 4, wherein 0, 1,2 or 3 of the n Y groups are different from hydrogen;

wherein:

a7) provided are halogenated 1,3, 3-trimethylindane compounds of formula XXI,

wherein Hal is chlorine, bromine or iodine;

b7) (ii) copper-promoted amidation of a compound of the formula (XXI) with an amide of the formula XXII,

wherein R is²⁰Is hydrogen, C₁-C₁₀Alkyl radical, C₃-C₈Cycloalkyl or CH₂-(C₆-C₁₀Aryl groups);

to give the diamide of the formula (XXIII),

c7) hydrolysis of the diamide of formula (XXIII) gives the compound of formula (V).

27. The method of claim 25 or 26, wherein zero of the m Y groups is different from hydrogen and zero of the n Y groups in the compound of formula V is different from hydrogen.

28, kinds of 6-amino-1- (4' -aminophenyl) -1,3, 3-trimethylindane,

it is obtainable by a process wherein:

a2.1) providing the isopropenylbenzene compound (II.1),

wherein X^2aSelected from F, Cl, Br, I, O-benzyl, CH₃SO₃And CF₃SO₃；

b2.1) dimerizing the isopropenylbenzene compound of formula (II.1) in the presence of an acidic catalyst to give the compound of formula (III.1),

c2.1) amination of the compound of formula (III.1) with a bis (trialkylsilyl) amino alkali metal in the presence of a palladium complex catalyst followed by removal of the trialkylmethylsilyl protecting group to give 6-amino-1- (4' -aminophenyl) -1,3, 3-trimethylindane;

a7.1) providing a halogenated 1,3, 3-trimethylindan compound of the formula XXI.1,

wherein Hal is chlorine, bromine or iodine;

b7.1) copper-promoted amidation of the compounds of the formula (XXI.1) with amides of the formula XXII,

wherein R is²⁰Is hydrogen, C₁-C₁₀Alkyl radical, C₃-C₈Cycloalkyl or CH₂-(C₆-C₁₀Aryl groups);

to give the diamide of the formula (XXIII.1),

c7.1) hydrolysis of the diamide of formula (XXIII.1) to give the compound 6-amino-1- (4' -aminophenyl) -1,3, 3-trimethylindane.

6-amino-1- (4 '-aminophenyl) -1,3, 3-trimethylindane comprising less than 1% by weight of regioisomeric impurities selected from 5-amino-1- (4' -aminophenyl) -1,3, 3-trimethylindane, 4-amino-1- (4 '-aminophenyl) -1,3, 3-trimethylindane, or 7-amino-1- (4' -aminophenyl) -1,3, 3-trimethylindane.

30. 6-amino-1- (4' -aminophenyl) -1,3, 3-trimethylindane according to claim 29, which has an LC purity of equal to or greater than 99.0%.

Background

"organic electronic devices" are primarily concerned with the development, characterization and application of novel materials and manufacturing methods for producing electronic components based on small organic molecules or polymers with desired electronic properties. These include, inter alia, Organic Field Effect Transistors (OFETs), Organic Thin Film Transistors (OTFTs), organic electroluminescent devices, Organic Light Emitting Diodes (OLEDs), Organic Solar Cells (OSCs), such as excitonic solar cells, dye-sensitized solar cells (DSSCs) or perovskite solar cells, electrophotography, in particular photoconductive materials in Organic Photoconductors (OPCs), organic optical detectors, organic photoreceptors, Organic Field Quenching Devices (OFQDs), light-emitting electrochemical cells (LECs) and organic laser diodes. In many cases, organic semiconductors have advantages over classical inorganic semiconductors, such as better substrate compatibility and better processability of semiconductor components based thereon. It allows, inter alia, the processing of flexible substrates and the adjustment of their interfacial orbital energy according to the specific field of application. The great potential for development is attributed to organic field effect transistors, for example in memory elements and integrated optoelectronic devices. Organic Light Emitting Diodes (OLEDs) take advantage of the material properties of a material that emits light when excited by an electrical current. Even today, OLEDs are of interest as a replacement for liquid crystal displays for producing flat visual display units. Due to the extremely compact design and the inherently lower power consumption, devices comprising OLEDs are particularly suitable for mobile applications, for example for mobile phones, laptops, etc.

By "organic photovoltaic device" is meant the use of an organic component to convert radiant energy (primarily solar energy) directly into electrical energy. In contrast to inorganic solar cells, in organic solar cells the light does not directly generate free carriers, but first forms excitons, i.e. electrically neutral excited states in the form of electron-hole pairs. These excitons may be separated at a suitable photovoltaic interface (organic donor-acceptor interface or interface with an inorganic semiconductor). For this reason, excitons generated in the volume of organic material must be diffusible to the photovoltaic interface. The diffusion of excitons to the active interface thus plays a key role in organic solar cells. There is a great need to develop materials for light-induced excited states which have a maximum transmission width and a high mobility (high exciton diffusion length) and are therefore advantageously suitable for use as active materials in so-called excitonic solar cells.

DSSC has several advantages over silicon-based solar cells, such as lower production and material costs, because inexpensive metal oxide semiconductors such as titanium dioxide can be used without requiring high purity, other advantages include its flexibility, transparency, and light weight, DSSC's structure is typically based on a transparent substrate (e.g., glass) coated with a transparent conductive layer (working electrode), n-type conductive metal oxide is typically applied in or near the electrode, such as nanoporous TiO₂The function of DSSC is based on the fact that light is absorbed by the dye and electrons are transferred from the excited dye to the n-type semiconducting metal oxide semiconductor and migrate thereon to the anode, although dye-sensitized solar cells are currently the most efficient alternative to solar cell technology, there is a continuing need for further improvements to ₂) However, in many cases, liquid DSSCs have durability issues, such as electrode corrosion and electrolyte leakage, and is therefore seeking suitable alternatives to liquid electrolytes for hole conduction.

Another approach in solar cell technology is the use of organometallic perovskites as light trapping compounds, these solar cells are referred to as perovskite-sensitized solar cells (PSC). actual PSC based on lead iodide allows energy conversion efficiencies of over 9%. variants of PSC are hybrid solar cells based on methyl ammonium lead iodide chloride as a crystalline perovskite absorber material₂O₃Not acting as an n-type oxide but as a mid-scale "architecture" on which the device is structured.

Photoconductivity is optical and electrical phenomena in which a material becomes conductive due to absorption of electromagnetic radiation, such as visible, ultraviolet, infrared or gamma radiation, an Organic Photoconductor (OPC) is a component of an Electrophotographic (EP) printer, a latent image, which is a pattern of surface charges, is created on the OPC, which is then contacted with a development system containing charged marking particles, by uniformly charging the OPC surface, followed by selective irradiation, thereby locally creating opposite charges, which then move to the surface and locally neutralize the deposited charges.

Among the aforementioned applications, there is a continuing need for novel compounds having advantageous properties. They should be obtained by efficient and economical synthetic routes.

it is generally known that certain triarylamines are suitable for use in organic electronic applications.

WO 2012/034627 describes compounds of formula (a):

wherein:

ar is an aromatic ring system;

Ar¹、Ar²is an aromatic or heteroaromatic ring system having 6 to 60C atoms;

r is selected from the group consisting of: H. d, F, Cl, Br, I, CN, Si (R)²)₃(ii) a A linear, alkoxy or thioalkyl group having 1 to 40C atoms or a branched or cyclic alkyl, alkoxy or thioalkyl group having 3 to 40C atoms; an aromatic or heteroaromatic ring system having 6 to 60C atoms; or an aralkyl group having 5 to 60 aromatic ring atoms,

m is 0, 1,2 or 3;

n is, identically or differently at each occurrence, 0, 1,2, 3 or 4;

p is 0, 1 or 2.

The compounds are used in electronic devices, preferably selected from the group consisting of: organic electroluminescent devices, organic integrated circuits, organic field effect transistors, organic thin film transistors, organic light emitting transistors, organic solar cells, organic dye sensitized solar cells, organic optical detectors, organic photoreceptors, organic field quenching devices, light emitting electrochemical cells, organic laser diodes and organic plasmon light emitting devices, in particular for use in organic electroluminescent devices.

There is a continuing need for new organic compounds with good electronic application properties. They should be prepared from readily available educts by an efficient and economical preparation process.

It has now surprisingly been found that the indane derivatives of the invention are suitable for use as hole conductors (p-type semiconductors, electron donors) in organic photovoltaic devices. They are particularly suitable as Hole Transport Materials (HTM) or Electron Blocking Materials (EBM).

Brief description of the invention

Accordingly, in an th aspect, the invention relates to compounds of formula (I):

wherein:

x is independently at each occurrence selected from the formula-A- (NAr)₂) Wherein:

ar is independently at each occurrence selected in each case from unsubstituted or substituted aryl groups, wherein two groups Ar bonded to the same nitrogen atom may also form, together with nitrogen atom , a fused ring system having 3 or more than 3 unsubstituted or substituted rings;

y is independently at each occurrence selected from hydrogen, C₁-C₆Alkyl radical, C₁-C₆Alkoxy radical, C₃-C₈Cycloalkyl radical, C₃-C₈Cycloalkoxy, phenyl and phenoxy, wherein the cyclic rings in the last-mentioned four radicals are each unsubstituted or substituted by 1,2 or 3C₁-C₆An alkyl group and wherein the phenyl ring bonded to the single bond of the phenyl indane moiety carries at least Y groups in as hydrogen ortho-positions relative to the phenyl ring of the phenyl indane moiety;

k is 1 or 2;

l is 1 or 2;

m is 2 or 3, wherein 0, 1,2 or 3 of the m Y groups are different from hydrogen;

n is 3 or 4, wherein 0, 1,2 or 3 of the n Y groups are different from hydrogen;

the sum of k and m is 4 and the sum of l and n is 5.

A further aspect relates to a mixture of compounds of formula (I) wherein k and l are each 1, i.e. to a mixture of compounds of formulae (i.a.a.) and (i.b.a):

wherein:

each Y is independently as defined briefly above and in the detailed description below;

each Ar is independently as defined briefly above and in the detailed description below;

m is 3, wherein 0, 1,2 or 3 of the m Y groups are different from hydrogen; and is

n is 4, wherein 0, 1,2 or 3 of the n Y groups are different from hydrogen;

and to a method of making the mixture.

A further aspect relates to mixtures of compounds of formula (I) wherein k and l are each 1, i.e. to mixtures of compounds of formulae (I.C.a) and (I.D.a)

Wherein:

each Y is independently as defined briefly above and in the detailed description below;

each Ar is independently as defined briefly above and in the detailed description below;

m is 3, wherein 0, 1,2 or 3 of the m Y groups are different from hydrogen; and is

n is 4, wherein 0, 1,2 or 3 of the n Y groups are different from hydrogen.

And to a method of making the mixture.

Another aspect relates to methods of preparing the compounds of formula (I).

A further aspect of the invention relates to the use of a compound of the invention or a composition (mixture) comprising at least two different compounds of the invention as defined in the brief description above and in the detailed description below as Hole Transport Material (HTM) in organic electronic devices, as Electron Blocking Material (EBM) in organic electronic devices, as semiconductor material, in particular as hole transport material in organic solar cells, as replacement for liquid electrolytes in dye-sensitized solar cells, as hole transport material in perovskite solar cells, Organic Light Emitting Diodes (OLEDs), in particular for displays on electronic devices and lighting systems, for electrophotography, in particular as photoconductive material in Organic Photoconductors (OPCs), for organic optical detectors, organic photoreceptors, organic field quenching devices (O-FQDs), light emitting electrochemical cells (LECs) and organic laser diodes.

A further aspect of the invention relates to organic field effect transistors comprising a substrate having at least gate structures, a source and a drain, and as semiconductor material at least compounds of formula (I) as defined above briefly and in the following detailed description.

A further aspect of the invention relates to substrates comprising a plurality of organic field effect transistors, wherein at least of the field effect transistors comprise at least compounds of formula (I) as defined above briefly and in the detailed description below.

A further aspect of the invention relates to semiconductor units comprising a substrate as defined above.

A further aspect of the invention relates to electroluminescent devices comprising an upper electrode, a lower electrode (wherein at least of the electrodes are transparent) and an electroluminescent layer and optionally an auxiliary layer, wherein the electroluminescent device comprises at least compounds of formula I as defined above briefly and in the detailed description below.

A further aspect of the invention relates to two methods of preparing a compound of formula (V):

wherein:

each Y is independently as defined briefly above and in the detailed description below;

m is 3, wherein 0, 1,2 or 3 of the m Y groups are different from hydrogen; and is

n is 4, wherein 0, 1,2 or 3 of the n Y groups are different from hydrogen.

The compounds of formula (V) are valuable intermediates for the compounds of the invention and are generally used in chemical syntheses.

A further aspect of the invention relates to an intermediate compound of 6-amino-1- (4' -aminophenyl) -1,3, 3-trimethylindane:

it is obtainable by a process wherein:

a2.1) providing an isopropenylbenzene compound (II.1):

wherein X^2aSelected from F, Cl, Br, I, O-benzyl, CH₃SO₃And CF₃SO₃；

b2.1) dimerizing an isopropenylbenzene compound of formula (II.1) in the presence of an acidic catalyst to yield a compound of formula (III.1):

a7.1) provides a halogenated 1,3, 3-trimethylindan compound of the formula XXI.1:

wherein:

hal is chlorine, bromine or iodine;

b7.1) copper-promoted amidation of the compounds of the formula (XXI.1) with amides of the formula XXII,

wherein:

R²⁰is hydrogen, C₁-C₁₀Alkyl radical, C₃-C₈Cycloalkyl or CH₂-(C₆-C₁₀Aryl groups); to give a diamide of the formula (XXIII.1):

c7.1) hydrolysis of the diamide of formula (XXIII.1) to give the compound 6-amino-1- (4' -aminophenyl) -1,3, 3-trimethylindane.

Yet another aspect of the invention relates to an intermediate compound 6-amino-1- (4 '-aminophenyl) -1,3, 3-trimethylindan comprising less than 1% by weight of regioisomeric impurities selected from the group consisting of 5-amino-1- (4' -aminophenyl) -1,3, 3-trimethylindan, 4-amino-1- (4 '-aminophenyl) -1,3, 3-trimethylindan, and 7-amino-1- (4' -aminophenyl) -1,3, 3-trimethylindan.

These and other aspects of the invention are described in the following paragraphs.

Detailed Description

The compounds of general formula (I) and the process for their preparation have at least of the following advantages:

the compounds of formula (I) are characterized by good thermal and environmental stability. Most of the compounds (I) have a high glass transition temperature. It is generally sublimable, can be purified by partial sublimation and allows the device to be manufactured by physical vapor deposition.

The preferred application of the compounds (I) is as Hole Transport Materials (HTM) or Electron Blocking Materials (EBM).

OFETs, especially OTFTs, prepared from compounds of formula (I) are characterized by at least of high charge transport mobility, high on/off ratio, low threshold voltage and air stability.

The compound of formula (I) further has good performance in OPV applications it allows excited states (excitons) generated by absorbed photons to be transported over very large distances, i.e. it has a good exciton diffusion length.

The present invention further allows for the provision of compounds of formula (I) wherein the size of the semiconductor bandgap is adjusted to make very efficient use of sunlight.

The process of the invention allows for the extremely efficient and economical synthesis of a wide variety of compounds of formula (I). Thus, the compound (I) having optimized properties can be easily provided for the intended use.

Described herein are compounds of formula (I):

wherein (X)_k、(X)_l、(Y)_mAnd (Y)_nAs described in the summary of the invention and in the detailed description below. The asterisk (—) in formula (I) denotes an asymmetric carbon atom. Thus, the present invention provides both pure enantiomers and enantiomeric mixtures of the compounds of formula (I). The invention also provides the use of pure enantiomers and enantiomeric mixtures of compounds of formula (I). Depending on the type of substitution, the compounds of the formula (I) may have further chiral centers, in which case they are present in the form of mixtures of diastereomers. The compounds of formula (I) may be obtained in enantiomerically enriched or pure form by standard methods known in the art, including for example chiral separation or by preparing the compounds of formula (I) using a suitable chiral 1,1, 3-trimethyl-3-phenylindane compound as starting material. Suitable compounds of formula (I) also include all possible regioisomers and mixtures thereof.

It should be noted that in the formulae shown herein, methyl groups may be indicated by solid lines. Thus, for example, the solid lines at the 1 and 3 positions in formula (I) shown below represent methyl groups attached at the 1 and 3 positions of the compound of formula (I), and the solid lines at the 9 position of 9, 9-dimethylfluorene shown below represent two methyl groups:

it should be noted that generally, unless the formulae are otherwise clearly indicated, no hydrogen atom is depicted in the formulae in other words, in the specific formulae of the present application, a hydrogen atom is explicitly shown, but in most cases, is not shown as a convention.

As used in this specification and the claims, the singular forms "," "," and "the" include the plural forms unless the context clearly dictates otherwise.

The definitions of the variables specified in the above formula use collective terms that generally denote the corresponding substituents. Definition C_n-C_mThe number of possible carbon atoms in the respective substituents or substituent moieties is given in each case.

The expression "halogen" denotes in each case fluorine, bromine, chlorine or iodine, especially chlorine, bromine or iodine. Similarly, the term "halo" denotes in each case fluorine, chlorine, bromine or iodine.

The term "unbranched" as used herein is also referred to as straight-chain.

The term "C" as used herein_n-C_mAlkyl "means having n to m carbon atoms, e.g. 1-2 (" C)₁-C₂Alkyl "), 1-4 ('C')₁-C₄Alkyl ") or 1 to 6 (" C ")₁-C₆Alkyl ") branched or unbranched saturated hydrocarbon radicals of carbon atoms. C₁-C₂Alkyl is methyl or ethyl. Except for C₁-C₂Alkyl radicals other than those mentioned, C₁-C₄Examples of alkyl are propyl, isopropyl, butyl, 1-methylpropyl (sec-butyl), 2-methylpropyl (isobutyl) or 1, 1-dimethylethyl (tert-butyl). Except for C₁-C₄Alkyl radicals other than those mentioned, C₁-C₆Examples of alkyl are pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2-dimethylpropyl, 1-ethylpropyl, 1-dimethylpropyl, 1, 2-dimethylpropyl, hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2-dimethylbutylCyclobutyl, 2, 3-dimethylbutyl, 3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1, 2-trimethylpropyl, 1,2, 2-trimethylpropyl, 1-ethyl-1-methylpropyl or 1-ethyl-2-methylpropyl.

The term "CH" as used herein₂-(C₆-C₁₀Aryl) "means benzyl, 1-naphthylmethyl or 2-naphthylmethyl.

Similarly, the term "C_n-C_mAlkoxy "refers to a straight or branched alkyl group attached to the rest of the molecule via an oxygen atom at any bond in the alkyl group and having n to m carbon atoms, for example 1-2 carbon atoms or 1-4 carbon atoms or 1-6 carbon atoms (as mentioned above). C₁-C₂Alkoxy is methoxy or ethoxy. Except for C₁-C₂Alkoxy radicals other than those mentioned, C₁-C₄Examples of alkoxy are n-propoxy, 1-methylethoxy (isopropoxy), butoxy, 1-methylpropoxy (sec-butoxy), 2-methylpropoxy (isobutoxy) or 1, 1-dimethylethoxy (tert-butoxy). Except for C₁-C₄Alkoxy radicals other than those mentioned, C₁-C₆Examples of alkoxy are pentyloxy, 1-methylbutyloxy, 2-methylbutyloxy, 3-methylbutyloxy, 1-dimethylpropyloxy, 1, 2-dimethylpropyloxy, 2, 2-dimethylpropyloxy, 1-ethylpropyloxy, hexyloxy, 1-methylpentyloxy, 2-methylpentyloxy, 3-methylpentyloxy, 4-methylpentyloxy, 1-dimethylbutyloxy, 1, 2-dimethylbutyloxy, 1, 3-dimethylbutyloxy, 2, 2-dimethylbutyloxy, 2, 3-dimethylbutyloxy, 3-dimethylbutyloxy, 1-ethylbutyloxy, 2-ethylbutyloxy, 1, 2-trimethylpropyloxy, 1,2, 2-trimethylpropyloxy, 2-methylpropyloxy, 1-methylpropyloxy, 1, 1-ethyl-1-methylpropoxy or 1-ethyl-2-methylpropoxy.

The term "C" as used herein_n-C_mCycloalkyl "refers to a monocyclic n-to m-membered saturated alicyclic group having, for example, 3 to 8 carbon atoms. C₃-C₈Examples of cycloalkyl are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.

Similarly, the term "C_n-C_mCycloalkoxy "refers to a monocyclic n-to m-membered saturated alicyclic group bonded to the skeleton via an O linkage, e.g. C₃-C₈Cycloalkyl (as mentioned above).

The term "aryl" as used herein refers to monocyclic, bicyclic, tricyclic and tetracyclic aromatic hydrocarbon radicals having 6 to 18 ring carbon atoms, wherein the rings are all fused or two aromatic rings may also be joined by a chemical bond and selected from-CH₂A divalent group of-O-, -S-or-N (H) -are linked to each other. Examples include phenyl, naphthyl, anthracenyl, phenanthrenyl, fluorenyl, dibenzofuranyl, dibenzothienyl, carbazolyl, 11H-benzo [ b ]]Fluorenyl, naphtho [2,3-b ]]Benzofuranyl, naphtho [2,3-b ]]Benzothienyl and 5H-benzo [ b]The carbazolyl-aryl group may be substituted at , two, three, four, more than four, or all substitutable positions suitable substituents are typically C₁-C₆Alkyl radical, C₁-C₆Alkoxy, carbazol-9-yl (N-bonded carbazolyl), unsubstituted or C-bonded₁-C₄Alkyl radical, C₁-C₄Alkoxy and phenyl substituted in which the phenyl in the moiety thereof may be substituted by 1,2, 3 or 4 substituents selected from C₁-C₄Alkyl and C₁-C₄Different or the same substituent of the alkoxy group. Furthermore, suitable substituents attached at the aryl group are usually also diphenylamino, C₅-C₈Cycloalkyl, phenyl, biphenyl, bitriphenyl, naphthyl, anthracenyl and phenanthryl, wherein the cyclic rings in the last-mentioned 8 radicals are each unsubstituted or are selected from C by 1,2, 3,4 or 5₁-C₄Alkyl radical, C₁-C₄Alkoxy and carbazol-9-yl (unsubstituted or substituted by C)₁-C₄Alkyl radical, C₁-C₄Alkoxy and phenyl substituted) wherein the phenyl groups on the moiety thereof may be substituted with 1,2, 3 or 4 substituents selected from C₁-C₄Alkyl and C₁-C₄Different or the same substituent of the alkoxy group. Furthermore, bonded to fluorenyl groups or 11H-benzo [ b ]]Two substituents of the fluorenyl group, having the same carbon atom as , may form an alkylene group (CH2) r from wherein r is 4,5,6 or 7, thus forming a 5-to 8-membered saturated carbonA ring, in which 1 or 2 hydrogen atoms in the radical may be replaced by a radical C₁-C₄Alkyl or C₁-C₄Alkoxy radicals instead of, or bound to, fluorenyl or 11H-benzo [ b ]]Two substituents of the fluorenyl group, which substituents are identical to the carbon atom, may be taken together to form an alkylene group (CH2) r wherein r is 4,5,6 or 7, thus forming a 5-8 membered saturated carbocyclic ring which may be benzofused to or two phenyl groups wherein the phenyl rings are optionally substituted by 1,2, 3 or 4 identical or different C' s₁-C₄Alkyl or C₁-C₄Alkoxy substitution.

If a moiety is described as "optionally substituted," the moiety may be unsubstituted or substituted.

If a moiety is described as "substituted," then a non-hydrogen group replaces a hydrogen group of any substitutable atom of the moiety, if there are more than substitutions on the moiety, then each non-hydrogen group may be the same or different (unless otherwise specified).

The statements made above and below for preferred aspects of the invention, for example for the variables X and Y and for preferred meanings of the indices n, m, l and k of the compounds of the formula (I), apply in each case independently or in particular in combination to the preferred compounds of the formula (I) and the use according to the invention:

preference is given to compounds of the formula (I) in which k is 1 and l is 1.

Likewise, preference is given to compounds of the formula (I) in which k is 2 and l is 2.

A more preferred embodiment of the invention relates to compounds of formula (I) wherein k is 1 and l is 1.

Of these, preference is given to compounds of formula (i.a), wherein m, n, Y, a and Ar are as defined above and herein below for compounds of formula (I):

of the compounds of formula (I) wherein k is 1 and l is 1, compounds of formula (I.B) are likewise preferred, wherein m, n, Y, a and Ar are as defined above and below for the compounds of formula (I):

among the compounds of formula (I), wherein k is 1 and l is 1, compounds of formula (i.c) are likewise preferred, wherein m, n, Y, a and Ar are as defined above and below for the compounds of formula (I):

among the compounds of formula (I) wherein k is 1 and l is 1, preference is likewise given to compounds of formula (i.d) wherein m, n, Y, a and Ar are as defined above and below for the compounds of formula (I):

another more preferred embodiment of of the present invention relates to compounds of formula (I) wherein k is 2 and l is 2 among these, compounds of formula (i.e.) are preferred, wherein m, n, Y, a and Ar are as defined above and below for compounds of formula (I):

as is readily understood by those skilled in the art, with respect to compounds of formula (I), X (i.e., -A-NAr)₂) And the preferences given for Y also apply to the compounds of formulae (i.a), (I.B), (i.c), (i.d) and (i.e) as defined below.

In embodiments, X represents A-N (Ar)₂Wherein the group A is a divalent phenylene group. Independently of their occurrence, A is preferably selected from the group of formulae (A1), (A2) and (A3),

wherein:

# are the bonding sites of the benzene ring and the nitrogen atom, respectively; and is

R^a、R^b、R^c、R^dAnd R^eEach, if present, is independently selected from hydrogen, straight and branched C₁-C₄Alkyl and straight and branched C₁-C₄An alkoxy group.

In specific embodiments, each group A in formula (I) is a divalent phenylene group as defined above in more specific embodiments, each group A in formula (I) is a divalent phenylene group and all groups A have the same meaning^a、R^b、R^c、R^dAnd R^eEach (if present) is hydrogen. Also preferably, the group R^a、R^b、R^c、R^dAnd R^eAt least of which (if present) are different from hydrogen and the remaining radicals R^a、R^b、R^c、R^dAnd R^eEach (if present) is hydrogen. More preferably, R^a、R^b、R^c、R^dAnd R^e of (if present) are methoxy or methyl and the remaining R's are^a、R^b、R^c、R^dAnd R^eEach (if present) is hydrogen.

In another embodiment of the invention, X is NAr₂I.e. the group a is a chemical bond. However, among the compounds of formula (I), those in which each group a is mono-valent (I) are more preferred.

Thus, among the compounds of formula (I) wherein each group a is a single bond, compounds of formula (i.a.a.):

wherein m, n, Y and Ar are as defined above for the compound of formula (I).

Those skilled in the art will readily understand that for compounds of formula (I) and (I.A) for (Y)_m、(Y)_nAnd Ar also apply to formula (i.a.a) as defined below.

Among the compounds of formula (I) in which the individual groups a are single bonds, preference is likewise given to compounds of formula (i.b.a) in which m, n, Y and Ar are as defined above for the compounds of formula (I):

as readily understood by those skilled in the art, reference to compounds of formula (I) and (I.B) is directed to (Y)_m、(Y)_nAnd Ar also applies to formula (i.b.a) as defined below.

Among the compounds of formula (I) in which the individual groups a are single bonds, preference is likewise given to compounds of formula (i.c.a) in which m, n, Y and Ar are as defined above for the compounds of formula (I):

those skilled in the art will readily understand that for compounds of formula (I) and (I.C) for (Y)_m、(Y)_nAnd Ar also apply to formula (i.c.a) as defined below.

Among the compounds of formula (I) in which the individual groups a are single bonds, preference is likewise given to compounds of formula (i.d.a) in which m, n, Y and Ar are as defined above for the compounds of formula (I):

those skilled in the art will readily understand that for compounds of formulae (I) and (I.D) for (Y)_m、(Y)_nAnd Ar also applies to formula (i.d.a) as defined below.

Among the compounds of formula (I) in which the individual groups a are single bonds, preference is likewise given to compounds of formula (i.e. a) in which m, n, Y and Ar are as defined above for the compounds of formula (I):

as is readily understood by those skilled in the art, with respect to compounds of formula (I) and (i.e.) for (a), (b), (c), (dY)_m、(Y)_nAnd Ar also applies to formula (i.e. a) as defined below.

Preference is given to compounds of the formulae (I), (I.A), (I.B), (I.C), (I.D), (I.E), (I.A.a), (I.B.a), (I.C.a), (I.D.a) and (I.E.a), where the group Ar, independently of its occurrence, is selected from unsubstituted or substituted phenyl, unsubstituted or substituted naphthyl, unsubstituted or substituted phenanthryl, unsubstituted or substituted anthracyl, unsubstituted or substituted fluorenyl, unsubstituted or substituted C-bonded carbazolyl, unsubstituted or substituted dibenzofuranyl, unsubstituted or substituted dibenzothiophenyl or 2 groups Ar, together with the nitrogen atom to which they are attached, form unsubstituted or substituted N-bonded carbazolyl.

More preferably, each Ar, independently of its occurrence, is selected from:

phenyl, biphenyl, bitriphenyl, tetraphenyl, wherein phenyl, biphenyl, bitriphenyl and tetraphenyl are unsubstituted or are substituted with or more, for example 1,2, 3,4 or more than 4 substituents R^Ar1Substitution;

naphthyl, anthryl, phenanthryl, fluorenyl, spirofluorenyl, C-bonded carbazolyl, dibenzofuranyl and dibenzothienyl, wherein the naphthyl, phenanthryl, fluorenyl, spirofluorenyl, C-bonded carbazolyl, dibenzofuranyl and dibenzothienyl are unsubstituted or are substituted by or more, for example 1,2, 3,4 or more than 4 substituents R^Ar2Substitution; or

2 groups Ar with the nitrogen atom to which they are attached may form N-bonded carbazolyl, which is unsubstituted or substituted with or more substituents R^Ar3Substitution;

wherein:

each R^Ar1Independently selected from C₁-C₆Alkyl radical, C₁-C₆Alkoxy, carbazol-9-yl, wherein carbazol-9-yl may be substituted by 1,2, 3 or 4 groups selected from C₁-C₄Alkyl radical, C₁-C₄Alkoxy and phenyl, wherein the phenyl group may be substituted with 1,2, 3 or 4 substituents selected from C₁-C₄Alkyl and C₁-C₄Alkoxy, diphenylamino, C₅-C₈Cycloalkyl and naphthyl, wherein the cyclic rings in the last-mentioned three radicals are each unsubstituted or substituted by 1,2, 3 or 4 substituents selected from C₁-C₄Alkyl radical, C₁-C₄Alkoxy and carbazol-9-yl, wherein the carbazol-9-yl group may be substituted with 1,2, 3 or 4 substituents selected from C₁-C₄Alkyl radical, C₁-C₄Alkoxy and phenyl, wherein the phenyl group may be substituted with 1,2, 3 or 4 substituents selected from C₁-C₄Alkyl and C₁-C₄Different or the same substituent of alkoxy;

each R^Ar2Independently selected from C₁-C₆Alkyl radical, C₁-C₆Alkoxy, carbazol-9-yl, wherein carbazol-9-yl may be substituted by 1,2, 3 or 4 groups selected from C₁-C₄Alkyl radical, C₁-C₄Alkoxy and phenyl, wherein the phenyl group may be substituted with 1,2, 3 or 4 substituents selected from C₁-C₄Alkyl and C₁-C₄Alkoxy, diphenylamino, C₅-C₈Cycloalkyl and phenyl, wherein the cyclic rings in the last-mentioned three radicals are each unsubstituted or substituted by 1,2, 3 or 4 substituents selected from C₁-C₄Alkyl radical, C₁-C₄Alkoxy and carbazol-9-yl, wherein the carbazol-9-yl group may be substituted with 1,2, 3 or 4 substituents selected from C₁-C₄Alkyl radical, C₁-C₄Alkoxy and phenyl, wherein the phenyl group may be substituted with 1,2, 3 or 4 substituents selected from C₁-C₄Alkyl and C₁-C₄Different or identical substituents of alkoxy, and furthermore, in the case of fluorenyl, two geminal radicals R^Ar2May form alkylene (CH)₂)_rWherein r is 4,5,6 or 7, wherein 1 or 2 hydrogen atoms in the group may be replaced by methyl or methoxy; and is

Each R^Ar3Independently selected from C₁-C₆Alkyl radical, C₁-C₆Alkoxy, diphenylamino and phenyl, of which the last two groupsEach of which is unsubstituted or substituted by 1,2, 3 or 4 substituents selected from C₁-C₄Alkyl and C₁-C₄Different or the same substituent of the alkoxy group.

Specific examples of the group Ar include groups of the following formulae (AR-I) to AR-XLIV):

wherein # in each case denotes the bonding site of the nitrogen atom;

in the formulae AR-I, AR-II, AR-III, AR-IV, AR-V, AR-VI, AR-VII, AR-VIII, AR-IX, AR-X, AR-XI, AR-XII, AR-XIII, AR-XIV, AR-XV, AR-XVI, AR-XVII, AR-XVIII, AR-XIX, AR-XX, AR-XXI, AR-XXII, and AR-XXIII:

R¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶、R¹⁷、R¹⁸and R¹⁹If present, independently of one another, from hydrogen, straight-chain or branched C₁-C₄Alkyl, straight-chain or branched C₁-C₄Alkoxy and carbazol-9-yl, wherein carbazol-9-yl may be substituted by 1,2, 3 or 4 groups selected from C₁-C₄Alkyl, aryl, heteroaryl, and heteroaryl,C₁-C₄Alkoxy, phenyl, tolyl, xylyl,

Different or the same substituents of the group and the anisyl group;

in the formulae AR-XXIV, AR-XXV, AR-XXVI, AR-XXVII, AR-XXVIII, AR-XXIX, AR-XXX, AR-XXXI, AR-XXXII, AR-XXXIII, AR-XXXIV, AR-XXXV, AR-XXXVI, AR-XXXVII, AR-XXXVIII, AR-XXXIV, AR-XXIX, AR-XL, AR-XLI, AR-XLII, AR-XLIII, and AR-XLIV: r¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R^9a、R^9b、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵And R¹⁶If present, independently of one another, from hydrogen, straight-chain or branched C₁-C₄Alkyl, straight-chain or branched C₁-C₄Alkoxy, carbazol-9-yl and phenyl, wherein carbazol-9-yl and phenyl are unsubstituted or substituted by 1,2 or 3 substituents selected from C₁-C₄Alkyl radical, C₁-C₄Alkoxy, phenyl, tolyl, xylyl,

Different or the same substituents of the group and the anisyl group; and the number of the first and second electrodes,

furthermore, R in the formulae AR-XXIV, AR-XXV and AR-XXVI^9aAnd R^9bMay form an alkylene radical (CH) from ₂)_rWherein r is 4,5 or 6, wherein 1 or 2 hydrogen atoms in the group may be replaced by methyl or methoxy.

In the formulae AR-I, AR-II, AR-III, AR-IV, AR-V, AR-VI, AR-VII, AR-VIII, AR-IX, AR-X, AR-XI, AR-XII, AR-XIII, AR-XIV, AR-XV, AR-XVI, AR-XVII, AR-XVIII, AR-XIX, AR-XX, AR-XXI, AR-XXII and AR-XXIII, the radicals R¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶、R¹⁷、R¹⁸And R¹⁹If present, is preferably selected from hydrogen, C₁-C₂Alkyl radical, C₁-C₂Alkoxy and carbazol-9-yl, which may be substituted by 1 or 2 groups selected from C₁-C₂Alkyl radical, C₁-C₂Alkoxy, phenyl, tolyl, xylyl,

Substituents of the group and anisyl. In particular, each radical R¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶、R¹⁷、R¹⁸And R¹⁹If present, from the group consisting of hydrogen, methyl, methoxy and carbazol-9-yl which is unsubstituted or substituted by 1 or 2 substituents selected from methyl, methoxy, phenyl, tolyl, xylyl,

The same or different substituents of the group and the anisyl group.

In the formulae AR-XXIV, AR-XXV, AR-XXVI, AR-XXVII, AR-XXVIII, AR-XXIX, AR-XXX, AR-XXXI, AR-XXXII, AR-XXXIII, AR-XXXIV, AR-XXXV, AR-XXXVI, AR-XXXVII, AR-XXXVIII, AR-XXXIX, AR-XL, AR-XLI, AR-XLII, AR-XLIII and AR-XLIV, R is¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵And R¹⁶If present, is generally selected from hydrogen, C₁-C₂Alkyl radical, C₁-C₂Alkoxy and carbazol-9-yl, which may be substituted by 1 or 2 groups selected from C₁-C₂Alkyl radical, C₁-C₂Alkoxy, phenyl, tolyl, xylyl,

Substituent of the group and anisyl; r^9aAnd R^9bIf present, are generally hydrogen, C independently of one another₁-C₂Alkyl, phenyl or form a radical- (CH)₂)₄-or- (CH)₂)₅-. In particular, each radical R¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵And R¹⁶If present, is selected from hydrogen, methyl, methoxy and carbazol-9-yl, which may be substituted by 1 or 2 groups selected from methyl, methoxy, phenyl, tolyl, xylyl,

Substituents of the group and anisyl. In particular, R^9aAnd R^9bIf present, independently of one another, hydrogen, methyl, phenyl or form a radical- (CH)₂)₄-or- (CH)₂)₅-。

The above-mentioned groups Ar of the formulae (AR-I) to (AR-XLIV) bonded to the nitrogen atom may be combined with each other as desired. Here, radicals of the formulae (AR-I), (AR-II), (AR-III), (AR-IV), (AR-V), (AR-VI), (AR-VIII), (AR-IX), (AR-X), (AR-XIV), (AR-XXIII), (AR-XXIV), (AR-XXV), (AR-XXIX), (AR-XXX), (AR-XXXI), (AR-XXXII), (AR-XXXIII), (AR-XXXIV), (AR-XXXV) and (AR-XXXVI) are particularly preferred.

Specific examples of the group Ar include phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2, 4-dimethylphenyl, 2, 6-dimethylphenyl, 3, 5-dimethylphenyl, 2,4, 6-trimethylphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-phenylphenyl, 3-phenylphenyl, 4- (o-tolyl) phenyl, 4- (m-tolyl) phenyl, 4- (p-tolyl) phenyl, 4- (2, 6-dimethylphenyl) phenyl, 1-methyl-4-phenyl, 2-methyl-4-phenyl, 3-methylphenyl-phenyl, 2-methylphenyl-4-methylphenyl-phenyl, 2-methylphenyl, 4-methoxyphenyl, 2, 6-dimethyl-4-phenyl, 3-methyl-4- (o-tolyl) phenyl, 3-methyl-4- (m-tolyl) phenyl, 3-methyl-4- (p-tolyl) -phenyl, 3-methyl-4- (2,4, 6-trimethylphenyl) phenyl, 3-methyl-4- (2, 4-dimethylphenyl) -phenyl, 3-methyl-4- (2, 6-dimethylphenyl) phenyl, 4- (4-methoxyphenyl) phenyl, 4-methoxy-3-phenyl, 3-methoxy-4-phenyl, 2-methoxy-5-phenyl, m-tolyl, m, 2-methoxy-4, 5-diphenyl-phenyl, 3, 4-diphenylphenyl, 3, 5-diphenylphenyl, 3- (4-phenylphenyl) phenyl, 4- (4-phenylphenyl) phenyl, 3- (3, 5-diphenylphenyl) phenyl, 4-diphenylaminophenyl, 1-naphthyl, 2-naphthyl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-dimethylfluoren-2-yl, 9-methyl-9-phenyl-fluoren-2-yl, 9-diphenylfluoren-2-yl, 9-dimethylfluoren-3-yl, 9-methyl-9-phenyl-fluoren-3-yl, etc, 9, 9-diphenylfluoren-3-yl, 9-dimethylfluoren-4-yl, 9-methyl-9-phenyl-fluoren-4-yl, 9-diphenylfluoren-4-yl, dibenzofuran-2-yl, dibenzothiophen-2-yl, dibenzofuran-3-yl, dibenzothiophen-3-yl, 9-methylcarbazol-2-yl, 9-phenylcarbazol-2-yl, 9-methylcarbazol-3-yl, 9-phenylcarbazol-3-yl, 4- (1-naphthyl) phenyl, 4- (2-naphthyl) phenyl, 4- (carbazol-9-yl) -phenyl, 9-dimethylfluoren-4-yl, 9-methylthiophen-2-yl, 9-phenylcarbazol-3-yl, 4- (3, 6-dimethoxycarbazol-9-yl) phenyl, 4- (3, 6-dimethylcarbazol-9-yl) phenyl, 9' -spirobi (fluoren) -2-yl,

Wherein # represents a bonding site of a nitrogen atom

Also preferably, 2 groups Ar form together with the nitrogen atom to which they are attached an N-bonded carbazolyl group which is unsubstituted or substituted with or more, e.g. 1,2, 3,4 or more than 4 substituents R^Ar3Is substituted in which R^Ar3As defined above. In particular, R independently of its occurrence^Ar3Is phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl. Specific examples include carbazol-9-yl, 3-phenylcarbazol-9-yl, 3- (o-tolyl) carbazol-9-yl, 3- (m-tolyl) carbazol-9-yl), 3- (p-tolyl) carbazol-9-yl, 3- (o-anisyl)) Carbazol-9-yl, 3- (m-anisyl) carbazol-9-yl), 3- (p-anisyl) carbazol-9-yl, 3, 6-diphenylcarbazol-9-yl, 3, 6-bis (o-tolyl) carbazol-9-yl, 3, 6-bis (m-tolyl) carbazol-9-yl, 3, 6-bis (p-tolyl) carbazol-9-yl, 3, 6-bis (o-anisyl) carbazol-9-yl, 3, 6-bis (m-anisyl) carbazol-9-yl, 3, 6-bis (p-anisyl) carbazol-9-yl, 3, 6-dimethylcarbazol-9-yl and 3, 6-dimethoxycarbazol-9-yl.

In particular, independently of its occurrence, the group NAr₂Selected from the formulae (A-1) to (A-83) listed in Table A below.

Table a:

# denotes the binding site to the rest of the molecule.

In particular, withIndependently of its occurrence, the group NAr₂A group selected from formulae (1) to (38):

wherein # represents the side of the bond to the rest of the compound.

Preference is given to compounds of the formula (I), (I.A), (I.B), (I.C), (I.D), (I.E), (I.A.a), (I.B.a), (I.C.a), (I.D.a) and (I.E.a), in which all radicals NAr₂Further are preferred compounds of formula (I), (I.A), (I.B), (I.C), (I.D), (I.E), (I.A.a), (I.B.a), (I.C.a), (I.D.a) and (I.E.a), wherein all groups Ar have the same meaning.

Preference is given to compounds of the formulae (I), (I.A), (I.B), (I.C), (I.D), (I.E), (I.A.a), (I.B.a), (I.C.a), (I.D.a) and (I.E.a), where, independently of their occurrence, Y is as defined above. Of these, preferred are those in which, independently of their occurrence, each (Y)_mSelected from the group consisting of: hydrogen, C₁-C₄Alkyl radical, C₁-C₄Alkoxy, phenyl, tolyl, xylyl,

Phenyl, phenoxy, O-tolyl, O-xylyl and O-

Radicals, in particular hydrogen, methyl, methoxy and phenyl. In particular, 0 or 1 of the m Y groups is different from hydrogen.

Bonded in ortho-position on the phenyl ring relative to the phenylindane moiety pieces (Y)_nMust be hydrogen and the rest (Y)_nIndependently of one another, are preferably selected from the following groups: hydrogen, C₁-C₄Alkyl radical, C₁-C₄Alkoxy, phenyl, tolyl, xylyl,

Phenyl, phenoxy, O-tolyl, O-xylyl and O-

Radicals, in particular hydrogen, methyl, methoxy and phenyl. In particular, two groups (Y) bonded in ortho-position on the phenyl ring relative to the phenylindane moiety_nAre all hydrogen. In particular, the group (Y) bonded to the benzene ring is not ortho-positioned with respect to the phenylindane moiety_nMay be different from hydrogen. In particular, 0 or 1 of the n Y groups is different from hydrogen.

Examples of preferred compounds are the individual compounds of the formulae (I.A.a.1), (I.A.1), (I.A.2), (I.A.3), (I.A.4), (I.B.a.1), (I.B.1), (I.B.2), (I.B.3), (I.B.4), (I.C.a.1), (I.C.a.2), (I.C.a.3), (I.C.a.4), (I.C.1), (I.C.2), (I.C.3), (I.C.4), (I.D.a.1), (I.D.1), (I.D.2), (I.D.3), (I.D.4) and (I.E.a.1) which are summarized in tables 1 to 24 below.

TABLE 1

A.a.1 compound of formula I.A.a.1 wherein the radical NAr₂In each case corresponds to line of table B.

TABLE 2

A.1 compounds of the formula I.A.1, in which the radical NAr₂In each caseIn this case corresponding to line of table B.

TABLE 3

A.2 Compounds of the formula I.A.2, in which the radical NAr₂In each case corresponds to line of table B.

TABLE 4

A.3 Compounds of the formula I.A.3, in which the radical NAr₂Corresponds in each case to line of table B

TABLE 5

A.4 compounds of the formula I.A.4, in which the radical NAr₂In each case corresponds to line of table B.

TABLE 6

A compound of formula I.B.a.1 wherein the radical NAr₂In each case corresponds to line of table B.

TABLE 7

A compound of the formula I.B.1, wherein the radical NAr₂In each case corresponds to line of table B.

TABLE 8

A compound of the formula I.B.2, wherein the radical NAr₂In each case corresponds to line of table B.

TABLE 9

A compound of formula I.B.3 wherein the radical NAr₂In each case corresponds to line of table B.

Watch 10

A compound of formula I.B.4 wherein the group NAr₂In each case corresponds to line of table B.

TABLE 11

A.1 compound of formula I.C.a.1 wherein the radical NAr₂In each case corresponds to line of table B.

TABLE 12

A.2 compound of formula I.C.a.2 wherein the radical NAr₂In each case corresponds to line of table B.

Watch 13

A.3 compound of formula I.C.a.3 wherein the radical NAr₂In each case corresponds to line of table B.

TABLE 14

A.4 compound of formula I.C.a.4, wherein the radical NAr₂In each case corresponds to line of table B.

Watch 15

A compound of formula I.C.1, wherein the radical NAr₂In each case corresponds to line of table B.

TABLE 16

A compound of formula I.C.2, wherein the radical NAr₂In each case corresponds to line of table B.

TABLE 17

A compound of formula I.C.3 wherein the radical NAr₂In each case corresponds to line of table B.

Watch 18

A compound of formula I.C.4, wherein the radical NAr₂In each case corresponds to line of table B.

Watch 19

A compound of formula I.D.a.1 wherein the radical NAr₂In each case corresponds to line of table B.

Watch 20

A compound of formula I.D.1 wherein the radical NAr₂In each case corresponds to line of table B.

TABLE 21

A compound of formula I.D.2 wherein the radical NAr₂In each case corresponds to line of table B.

TABLE 22

A compound of formula I.D.3 wherein the radical NAr₂In each case corresponds to line of table B.

TABLE 23

A compound of formula I.D.4 wherein the radical NAr₂In each case corresponds to line of table B.

Watch 24

A compound of formula I.E.a.1 wherein the radical NAr₂Corresponds in each case to line of table B and is connected to two groups NAr of the phenyl indan moiety₂Two groups NAr having the same meaning and attached to a benzene ring₂Have the same meaning.

TABLE B

Particularly preferred embodiments of the present invention relate to the compounds of formula I shown below and to the enantiomers thereof.

OMe means OCH₃。

Likewise especially preferred are mixtures (compositions) of compounds of formula (I) comprising compounds of formulae (i.a.a.) and (i.b.a):

wherein:

each Y is independently as defined above; and is

Each Ar is independently as defined above;

m is 3, wherein 0, 1,2 or 3 of the m Y groups are different from hydrogen; and is

n is 4, wherein 0, 1,2 or 3 of the n Y groups are different from hydrogen.

In particular, the group NAr attached to the phenylindane moiety of the compound of formula (i.a.a.)₂Having a group NAr linked to the phenylindane moiety of a compound of formula (I.B.a)₂A group NAr having the same meaning and attached to the benzene ring in the compound of formula (I.A.a.)₂Have the same meaning as in the compounds of formula (i.b.a).

Thus, a further aspect of the invention relates to a mixture of compounds of formula (I) comprising compounds of formulae (i.a.a.) and (i.b.a), wherein Y and Ar are as defined herein, in particular each Y and each Ar have of the meanings mentioned as preferred.

Examples of preferred compositions of compounds of formula (i.a.a.1) and (i.b.a.1) are summarized in table 25 below.

TABLE 25

A mixture of compounds of formula (I.A.a.1) and (I.B.a.1) wherein the group NAr attached to the phenylindane moiety of the compound of formula (I.A.a.1)₂Having a group NAr linked to the phenyl indan moiety of a compound of formula (I.B.a.1)₂The same meaning, and is attached to the benzene ring of the compound of formula (I.A.a.1)₂Having a group NAr with a ring attached to a compound of formula (I.B.a.1)₂The same meaning, and the group NAr₂In each case corresponding to line of table B.

Also preferred are mixtures of compounds of formula (I) comprising compounds of formulae (i.c.a) and (i.d.a):

wherein:

each Y is independently as defined above; and is

Each Ar is independently as defined above;

m is 3, wherein 0, 1,2 or 3 of the m Y groups are different from hydrogen; and is

n is 4, wherein 0, 1,2 or 3 of the n Y groups are different from hydrogen.

In particular, the group NAr attached to the phenylindane moiety of the compound of formula (i.c.a)₂Having a group NAr linked to the phenylindane moiety of a compound of formula (I.D.a)₂A group NAr having the same meaning and attached to the benzene ring in the compound of formula (I.C.a.)₂Have the same meaning as in the compounds of formula (i.d.a).

Thus, a further aspect of the invention relates to a mixture of compounds of formula (I) comprising compounds of formulae (i.c. a) and (i.d. a) wherein Y and Ar are as defined herein, in particular each Y and each Ar have of the meanings mentioned as preferred.

Examples of preferred mixtures of compounds of formula (i.c. a.1) and (i.c. a.1) are summarized in table 26 below.

Watch 26

A mixture of compounds of formula (I.C.a.1) and (I.D.a.1) wherein the group NAr attached to the phenylindane moiety of the compound of formula (I.C.a.1)₂Having a group NAr linked to the phenyl indan moiety of a compound of formula (I.D. a.1)₂The same meaning, and is attached to the benzene ring of the compound of formula (I.C. a.1)₂Having a group NAr with a ring attached to a compound of formula (I.D.a.1)₂The same meaning, and the group NAr₂In each case corresponding to line of table B.

In specific embodiments, the compound of formula (I) is selected from the compounds specified in the examples, either as a pure enantiomer or as a mixture of two enantiomers.

The compounds of formula (I) of the invention and the starting materials for their preparation can be prepared analogously to known organic chemistry methods as described in standard works of organic chemistry. The compounds of formula (I) may be prepared by various routes.

The compounds of the formula (I) can advantageously be prepared by the methods described below or in the synthetic description of the working examples or by standard methods of organic chemistry. If not otherwise indicated, the substituents, variables and indices are as defined above for formula (I).

Accordingly, another aspect of the invention is a process for preparing compound (i.a.a.):

wherein:

each Ar is independently as defined above;

each Y is independently as defined above;

m is 3, wherein 0, 1,2 or 3 of the m Y groups are different from hydrogen; and is

n is 4, wherein 0, 1,2 or 3 of the n Y groups are different from hydrogen;

wherein:

a1) there is provided an isopropenylbenzene compound of the formula (II),

wherein:

X^2aselected from F, Cl, Br, I, O-benzyl, CH₃SO₃And CF₃SO₃；

Each Y is independently selected from hydrogen and C₁-C₆Alkyl radical, C₁-C₆Alkoxy radical, C₃-C₈Cycloalkyl radical, C₃-C₈Cycloalkoxy, phenyl and phenoxy, wherein the cyclic rings in the last-mentioned 4 groups are each unsubstituted or substituted by 1,2 or 3C₁-C₆Alkyl substitution; and is

z is 3, wherein 0, 1,2 or 3 of the z Y groups are different from hydrogen;

b1) dimerizing an isopropenylbenzene compound of formula (II) in the presence of an acidic catalyst to produce a compound of formula (III):

c1) aminating a compound of formula (III) with at least aromatic amines of formula (IV) in the presence of a palladium complex catalyst and a base:

Ar₂NH(IV)，

thereby obtaining the compound of formula (i.a.a.).

Step a1)

The compounds of formula (II) are commercially available or can be prepared, for example, by the pot method by reacting the corresponding acetophenone compound of formula (XIV) with a methyl magnesium halide of formula (XV) by a grignard reaction to give the corresponding 2-phenyl-propan-2-ol of formula (XVI) the acid-catalyzed dehydration of the alcohol of formula (XVI) gives the compound of formula (II) as described in scheme 1.

Scheme 1:

in scheme 1, z, Y and X^2aThe Grignard addition reaction is typically carried out at a temperature of 0-60 ℃, preferably 10-40 ℃ as defined above and Hal means chlorine or bromine the dehydration is typically carried out at the same temperature as the Grignard reaction the amount of Grignard reagent (XV) is 1.0-1.4 equivalents relative to the acetophenone compound XIV the suitable acids for dehydration are polyphosphoric acid, sulfuric acid, hydrochloric acid, trifluoroacetic acid, p-toluenesulfonic acid the reaction can advantageously be carried out in the form of a pot reaction the aryl Grignard is known to undergo the same reaction as the alkyl Grignard, hence the compounds of formula (II) can also be prepared using acetone and a suitable aryl Grignard reagent.

Step b1)

The dimerization may be carried out in the presence of an acidic catalyst. Suitable catalysts are, for example, polyphosphoric acid, sulfuric acid, hydrochloric acid, trifluoroacetic acid, p-toluenesulfonic acid, acidic ion exchangers and earth containing acidic montmorillonite, preferably trifluoroacetic acid. The acid catalyst is typically used as a solvent and is therefore present in large excess. The reaction is generally carried out at a temperature of from 40 to 120 ℃.

Step c1)

The compounds of the formula I.A.a.a.can be obtained by coupling reactions between the compounds III and the corresponding diarylamines (IV) in the presence of palladium catalysts according to the Buchwald-Hartwig reaction. Suitable palladium catalysts or catalyst precursors are, for example, bis (dibenzylideneacetone) palladium (0) (Pd (dba)₂) Tris (dibenzylideneacetone) dipalladium (0) (Pd)₂(dba)₃) [1, 1-bis (diphenylphosphino) -ferrocene]Palladium (II) dichloride (PdCl)₂(dppf)), palladium chloride (PdCl)₂) Bis (acetonitrile) palladium chloride (Pd (ACN))₂Cl₂) [1, 3-bis (2, 6-diisopropylphenyl) imidazol-2-ylidene](3-Chloropyridyl) Palladium dichloride (PEPSI-iPr), dichloro [1, 3-bis (2, 6-di-3-pentylphenyl) imidazol-2-ylidene](3-Chloropyridinyl) palladium (PEPSI-iPlet) or palladium acetate (Pd (OAc)₂). Preferably, theThe catalyst is palladium acetate, Pd (dba)₂Or Pd₂(dba)₃. The reaction is generally carried out in the presence of a ligand. The ligand is any molecule capable of coordinating with the palladium precursor and promoting the Buchwald-Hartwig reaction, preferably a dialkylbiarylphosphine or tri-tert-butylphosphine. Examples of dialkylbiarylphosphine ligands include 2-dicyclohexylphosphino-2 '- (N, N-dimethylamino) biphenyl (DavePhos), 2-dicyclohexylphosphino-2', 4',6' -triisopropylbiphenyl (Xphos), 2-dicyclohexylphosphino-2 ',6' -dimethoxybiphenyl (Sphos), 2-di-tert-butylphosphino-2 ',4',6 '-triisopropylbiphenyl (tBuXPhos), (2-biphenyl) dicyclohexylphosphine, 2- (dicyclohexylphosphino) biphenyl (CyJohnPhos), (2-biphenyl) di-tert-butylphosphino (JohnPhos), 2-dicyclohexylphosphino-2', 6 '-diisopropoxybiphenyl (RuPhos), 2-di-tert-butylphosphino-2' -methylbiphenyl (tBuMePhos), 2-di-tert-butylphosphino-3, 4,5, 6-tetramethyl-2 ',4',6' -triisopropyl-1, 1' -biphenyl 2-di-tert-butylphosphino-2 ' -methylbiphenyl (tBuMePhos), 2-di-tert-butylphosphino-3, 4,5, 6-tetramethyl-2 ',4',6' -triisopropyl-1, 1' -biphenyl (tetramethyltBuXPhos) and 2- (dicyclohexylphosphino) 3, 6-dimethoxy-2 ',4',6' -triisopropyl-1, 1' -biphenyl (BrettPhos). The palladium catalyst and phosphine ligand are preferably used in a molar ratio of from about 0.5 to about 5 moles of ligand per mole of palladium catalyst.

Typically, the reaction is carried out in the presence of a base, such as an alkali metal alkoxide, an alkaline earth metal alkoxide, an alkali metal carbonate or an alkaline earth metal carbonate, an alkali metal amide or a trialkylamine. Preferably, the base is sodium tert-butoxide, cesium carbonate, lithium bis (trimethylsilyl) amide, sodium bis (trimethylsilyl) amide, potassium bis (trimethylsilyl) amide, lithium diisopropylamide or lithium dicyclohexylamide. More preferably, the base is sodium tert-butoxide.

The reaction is generally carried out in a solvent. Suitable solvents are, for example, aliphatic hydrocarbons, such as pentane, hexane, cyclohexane and petroleum ether; aromatic hydrocarbons such as toluene, o-xylene, m-xylene, and p-xylene; ethers, such as diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran and dimethoxyethane, amides, such as dimethylformamide or N-methylpyrrolidone. The reaction temperature is usually 50 to 130 ℃. The reaction is typically carried out under an inert atmosphere (e.g., under dry nitrogen or argon).

Compounds of formula (i.a.a.) may also be prepared by the following process, wherein:

a2) there is provided an isopropenylbenzene compound (II),

wherein:

X^2aselected from F, Cl, Br, I, O-benzyl, CH₃SO₃And CF₃SO₃；

z is 3, wherein 0, 1,2 or 3 of the z Y groups are different from hydrogen;

b2) dimerizing an isopropenylbenzene compound of formula (II) in the presence of an acidic catalyst to produce a compound of formula (III):

d2) arylating a compound of formula (V) with at least aromatic compounds of formula (VI) in the presence of a palladium complex catalyst and a base:

Ar-X^2b(VI)，

wherein X^2bSelected from F, Cl, Br, I, O-benzyl, CH₃SO₃And CF₃SO₃Thereby obtaining the compound of formula (i.a.a.).

Step a2) and step b2)

Suitable reaction conditions are described above in step a1) and step b 1).

Step c2)

The diamino compound of formula (V) can be prepared from compounds having a labile leaving group X^2aBy reacting a compound of formula (III) with a compound of formula M-N (Si (R')₃)₂(wherein M is an alkali metal and R' may be the same or different C₁-C₆Alkyl) alkali metal salts of hexaalkyldisilazane (dililazide), especially lithium bis (trimethylsilyl) amide, and subsequent hydrolysis. Examples of suitable palladium catalysts are tris (dibenzylideneacetone) dipalladium (0) or PdCl₂(dppf), optionally in the presence of a tri (substituted) phosphine, for example a triarylphosphine such as triphenylphosphine or tritolylphosphine, a tri (cyclo) alkylphosphine such as tri-n-butylphosphine, tri-tert-butylphosphine, tricyclohexylphosphine or 2- (dicyclohexylphosphino) biphenyl. The reaction of the compound (III) with an alkali metal hexaalkyldisilamine can be carried out in a manner analogous to the Buchwald-Hartig coupling. Alkali metal hexaalkyldisilanes are commercially available or can be generated in situ from the corresponding amines by strong bases, for example, alkali metal alkoxides such as potassium tert-butoxide, or alkali metal hydrides, lithium hydride, sodium hydride, and the like. Removal of the trialkylsilyl group is achieved simply by aqueous work-up, preferably under acidic conditions, e.g. aqueous hydrochloric acid, sulfuric acid, etc., or using a fluoride ion source, e.g. HF, KF, ammonium fluoride or HF-pyridine.

Step d2)

Suitable reaction conditions are described above in step c1), in some embodiments of of the amination reaction in step d2), the reactants include a aromatic compound of formula (VI) and a second aromatic compound of formula (VI), wherein the aromatic compound of formula (VI) is different from the second aromatic compound of formula (VI), in embodiments, only aromatic compounds of formula (VI) are used in step d2), thereby providing a compound of formula (i.a.a.) wherein all Ar groups have the same meaning.

The compounds of formula (V) are particularly useful intermediate compounds, for example for the preparation of compounds of formula (I) according to the invention or for the preparation of triarylamine compounds other than those according to the invention.

US 3,856,752 describes processes for preparing a mixture of 6-amino-1- (4 '-aminophenyl) -1,3, 3-trimethylindane of formula (B) and 5-amino-1- (4' -aminophenyl) -1,3, 3-trimethylindane of formula (C) in 71% yield.

The resulting diamine product was a mixture of 62% 6-amino-and 38% 5-amino-1- (4' -aminophenyl) -1,3, 3-trimethylindane (as indicated by NMR analysis). the inventors have found that the reaction mixture may also contain small amounts of regioisomeric impurities, namely 4-amino-1- (4' -aminophenyl) -1,3, 3-trimethylindane and/or 7-amino-1- (4' -aminophenyl) -1,3, 3-trimethylindane.regioisomers are different from the compounds of formulas (B) and (C), yet have different reaction properties that may be undesirable for certain uses.

Thus, another aspect of the invention provides processes for the preparation of intermediate compounds of formula (V) in embodiments of this aspect the process comprises steps a2), b2) and c2) as described above, in particular a process comprising steps a2), b2) and c2) as described above is used for the preparation of intermediate compounds of formula (V) wherein zero of the m Y groups is different from hydrogen and zero of the n Y groups is different from hydrogen.

In another embodiment of this aspect, the invention provides processes for preparing an intermediate compound of formula (V), comprising the steps of:

a7) providing a halogenated 1,3, 3-trimethylindan compound of formula XXI:

wherein Hal is chlorine, bromine or iodine;

b7) copper-promoted amidation of a compound of formula (XXI) with an amide of formula (XXII):

wherein R is²⁰Is hydrogen, C₁-C₁₀Alkyl radical, C₃-C₈Cycloalkyl or CH₂-(C₆-C₁₀Aryl groups); to give a diamide of formula (XXXIII):

c7) hydrolysis of the diamide of formula (XXIII) gives the compound of formula (V).

Step a7)

The compound of formula (XXI) may be prepared as described above in step b 2).

Step b7)

In the formula XXII, R²⁰Preferably straight chain C₁-C₁₀Alkyl or branched C₃-C₁₀An alkyl group. In a preferred embodiment, the amide of formula XXII is pivaloamide. The amination process can be carried out using copper catalysts, for example copper (I) compounds, in the sense of a Goldberg-type reaction. Suitable copper (I) compounds are copper (I) oxide, bromide or iodide, especially copper (I) iodide. The amount of copper (I) compound is typically 5 to 20 mol%, based on the amount of the compound of formula (XXI). The reaction is generally carried out in the presence of a ligand such as dimethylethylenediamine (dmeda) or 1, 2-cyclohexanediamine. The ligand is typically present in 0.01 to 300 mol%, based on the amount of catalyst. Typically, the reaction is carried out in an inert aprotic solvent, such as an ether, e.g. dimethoxyethane or dioxaneOr amides, such as dimethylformamide or N-methylpyrrolidone, or aromatic solvents, such as toluene. The reaction is generally carried out in the presence of a base. Suitable bases are alkali metal carbonates, especially potassium carbonate; or alkali metal phosphates such as potassium carbonate. Typically, the reaction is carried out at a temperature of 60-180 ℃ under an inert atmosphere.

Step c7)

The amides may be hydrolyzed under basic or acidic conditions. Suitable basic conditions are, for example, treatment of the amide (XXIII) with an alkali metal hydroxide, for example KOH or NaOH in an alcohol, followed by addition of water. Suitable alcohols are, for example, C₁-C₄Alkanols, for example n-butanol. Suitable acidic conditions are, for example, treatment of the amide (XXIII) with aqueous acids, for example mineral acids, such as sulfuric acid, hydrochloric acid, nitric acid or phosphoric acid, or with hydrobromic acid or hydroiodic acid.

In particular, the above process comprising steps a7), b7) and c7) is used for the preparation of intermediate compounds of formula (V) wherein zero of the m Y groups is different from hydrogen and zero of the n Y groups is different from hydrogen.

Another aspect of the invention relates to the intermediate compound 6-amino-1- (4' -aminophenyl) -1,3, 3-trimethylindan, which is also known as 3- (4-aminophenyl) -1,1, 3-trimethyl-indan-5-amine,

it is obtainable by a process wherein:

a2.1) providing the isopropenylbenzene compound (II.1),

wherein X^2aSelected from F, Cl, Br, I, O-benzyl, CH₃SO₃And CF₃SO₃；

b2.1) dimerizing an isopropenylbenzene compound of formula (II.1) in the presence of an acidic catalyst to yield a compound of formula (III.1):

a7.1) provides a halogenated 1,3, 3-trimethylindan compound of the formula XXI.1:

wherein Hal is chlorine, bromine or iodine;

b7.1) copper-promoted amidation of the compounds of the formula (XXI.1) with amides of the formula XXII,

wherein R is²⁰Is hydrogen, C₁-C₁₀Alkyl radical, C₃-C₈Cycloalkyl or CH₂-(C₆-C₁₀Aryl groups); to give a diamide of the formula (XXIII.1):

c7.1) hydrolysis of the diamide of formula (XXIII.1) to give the compound 6-amino-1- (4' -aminophenyl) -1,3, 3-trimethylindane.

Steps a2.1), b2.1), c2.1), a7.1), b7.1) and c7.1)

Suitable reaction conditions are described above in steps a2), b2), c2), a7), b7) and c7), respectively.

Another aspect of the invention relates to the compound 6-amino-1- (4 '-aminophenyl) -1,3, 3-trimethylindan comprising less than 1% by weight of regioisomeric impurities selected from the group consisting of 5-amino-1- (4' -aminophenyl) -1,3, 3-trimethylindan, 4-amino-1- (4 '-aminophenyl) -1,3, 3-trimethylindan, and 7-amino-1-4' -aminophenyl) -1,3, 3-trimethylindan.

Another aspect of the invention relates to a process for preparing a mixture of compounds (i.a.a.1) and (i.b.a.1):

wherein each Ar is independently as defined in any of claims 1 and 4-8, wherein:

a3) providing a mixture of 5(6) -amino-1- (4' -aminophenyl) -1,3, 3-trimethylindane compounds of formulae (VIIa) and (VIIb);

b3) arylating a mixture of compounds of formula (VIIa) and (VIIb) with at least aromatic compounds of formula (VI) in the presence of a palladium complex catalyst and a base,

Ar-X^2b(VI)

wherein X^2bSelected from F, Cl, Br, I, O-benzyl, CH₃SO₃And CF₃SO₃(ii) a To give a mixture of compounds of formula (i.a.a. a1) and (i.b.a 1).

Step a3)

The compounds of formulae (VIIa) and (VIIb) may be prepared, for example, as described in US 3,856,752, US 3,983,092 or US 4,026,876.

Step b3)

Suitable reaction conditions are described above in step c1), in some embodiments of of the amination reaction in step b3), the reactants include a aromatic compound of formula (VI) and a second aromatic compound of formula (VI), wherein the aromatic compound of formula (VI) is different from the second aromatic compound of formula (VI), in particular embodiments, only aromatic compounds of formula (VI) are used in step b3), thereby obtaining a mixture of compounds of formula (i.a.a.1) and (i.b.a.1), wherein all Ar groups have the same meaning.

The obtained mixture of compounds of formula (i.a.a.1) and (i.b.a.1) is optionally subjected to at least separation and/or purification steps the separation and/or purification steps can be achieved by usual methods known to the skilled person, e.g. recrystallisation or separation on a suitable stationary phase and combinations of these measures.

Another aspect of the invention relates to methods of preparing a mixture of compounds of formula (i.c.a) and (i.d.a):

wherein:

each Ar is independently as defined above;

each Y is independently as defined above;

m is 3, wherein 0, 1,2 or 3 of the m Y groups are different from hydrogen; and is

n is 4, wherein 0, 1,2 or 3 of the n Y groups are different from hydrogen;

wherein:

a4) there is provided an isopropenylbenzene compound of the formula (IX),

wherein:

X^2cselected from F, Cl, Br, I, O-benzyl, CH₃SO₃And CF₃SO₃；

z is 4, wherein 0, 1,2 or 3 of the z Y groups are different from hydrogen;

b4) dimerizing an isopropenylbenzene compound of formula (IX) in the presence of an acidic catalyst to produce compounds of formulae (Xa) and (Xb):

c4) aminating a mixture of compounds of formulae (Xa) and (Xb) with at least aromatic amines of formula (IV) in the presence of a palladium complex catalyst and a base:

Ar₂NH (IV)，

to give a mixture of compounds of formula (i.c.a) and (i.d.a).

Step a4)

The compounds of formula (IX) are commercially available or can be prepared, for example, in a similar manner to that described in step a 1).

Steps b4) and c4)

Suitable reaction conditions are described above in step b1) and step c1), respectively.

The resulting mixture of compounds of formula (i.c.a) and (i.d.a) is optionally subjected to at least separation and/or purification steps the separation and/or purification steps can be achieved by common methods known to the skilled person, such as recrystallisation or separation on a suitable stationary phase and combinations of these measures.

Another aspect of the invention relates to processes for preparing compounds of formula (i.e. a):

wherein:

each Ar is independently as defined in any one of claims 1 and 4 to 8 at ;

each Y is independently as defined in claim 1;

m is 2, wherein 0, 1 or 2 of the m Y groups are different from hydrogen; and is

n is 3, wherein 0, 1 or 2 of the n Y groups are different from hydrogen;

wherein:

a5) providing an isopropenylbenzene compound of formula (XI);

wherein:

each X^2dIndependently selected from F, Cl, Br, I, O-benzyl, CH₃SO₃And CF₃SO₃；

z is 2, wherein 0, 1 or 2 of the z Y groups are different from hydrogen;

b5) dimerizing an isopropenylbenzene compound of formula (XI) in the presence of an acidic catalyst to produce a compound of formula (XII):

c5) amination of compound (XII) with bis (trialkylsilyl) amino alkali metal in the presence of a palladium complex catalyst followed by removal of the trialkylsilyl protecting group affords compound of formula (XIII):

d5) arylating compound (XIII) with at least aromatic compounds of formula VI in the presence of a palladium complex catalyst and a base:

Ar-X^2b(VI)

wherein X^2bSelected from F, Cl, Br, I, O-benzyl, CH₃SO₃And CF₃SO₃；

Thereby obtaining the compound of formula (i.e. a).

Step a5)

The compounds of formula (IX) are commercially available or can be prepared, for example, in analogy to the methods described in step a 1).

Steps b5), c5) and d5)

Suitable reaction conditions are described above in steps b2), c2) and d2), respectively.

Another aspect of the invention are methods of preparing a compound of formula (i.e. a):

wherein:

each Ar is independently as defined above;

each Y is independently as defined above;

wherein:

a6) providing a1, 1, 3-trimethyl-3-phenylindane compound of formula (XII):

wherein X^2dSelected from F, Cl, Br, I, O-benzyl, CH₃SO₃And CF₃SO₃；

b6) Aminating compound (XII) with at least aromatic amines of formula (IV) in the presence of a palladium complex catalyst and a base:

Ar₂NH (IV)

thereby obtaining the compound of formula (i.e. a).

Step a6)

The compounds of formula (IX) are commercially available or can be prepared, for example, in analogy to the methods described in step a 1).

Steps b6) and c6)

Suitable reaction conditions are described above in step b1) and step c1), respectively.

Wherein X is phenylene-NAr₂The compounds of the formula (I) can be prepared, for example, byBy suitable A-NAr₂Various C-C coupling reactions of derivatives and 1,1, 3-trimethyl-3-phenyl-indane derivatives. Suitable coupling reactions are, for example, the Suzuki reaction and the Stille reaction. For example, a compound of formula XVII:

wherein:

each X^2eIs B (OR)^B1)(OR^B2) Radical or Sn (R)^Sn)₃Group, wherein R^B1And R^B2Independently of one another, hydrogen or C₁-C₄Alkyl or R^B1And R^B2 form C₂-C₆Alkanediyl moieties, e.g. ethane-1, 2-diyl, propane-1, 3-diyl or 1,1,2, 2-tetramethylethane-1, 2-diyl, and wherein R^SnIs C₁-C₆Alkyl radical, C₃-C₆A cycloalkyl group or a phenyl group, or a substituted or unsubstituted cycloalkyl group,

y is as defined above;

k is 1 or 2;

l is 1 or 2;

m is 2 or 3, wherein 0, 1,2 or 3 of the m Y groups are different from hydrogen;

n is 3 or 4, wherein 0, 1,2 or 3 of the n Y groups are different from hydrogen;

the sum of k and m is 4 and the sum of l and n is 5;

can be reacted with a suitable compound of formula (XVIII):

Hal-A-NAr₂(XVIII)

wherein:

a is as defined herein and is selected from the group consisting of,

ar is as defined herein

Hal is bromine or chlorine.

The reaction of the compound of the formula (XVII) with the compound (XVIII) can be carried out in a manner analogous to known coupling reactions in the presence of suitable transition metal catalysts, in particular palladium catalysts. Typical reaction conditions are those for Stille coupling (see, e.g., Stille et al, Angew. chem. int. Ed. Engl.1986, 25, 508; J. Eluguero et al, Synthesis 1997, 5, 563-566) or Suzuki coupling (see, e.g., A. Suzuki et al, chem. Rev.1995, 95, 2457-16083; N.ZHE et al, J.Med. chem.2005, 48(5), 1569-1609; Young et al, J.Med. chem.2004, (47), 1547-1552; C.Slee et al, bioorg. Med. chem.Lett.2001, 3243-3253). Boronated compounds (XVII) can be prepared via a Miyaura boronation reaction, for example by treating a compound of formula (XIX) with a bisboronic acid or boronic ester:

wherein each LG1 is selected from bromo, chloro or trifluoromethanesulfonate, Y is as defined above and k, l, m and n are as defined above.

Wherein X is phenylene-NAr₂The compounds of formula (I) can also be prepared under the reaction conditions of the Suzuki coupling as described in scheme 2 below.

Scheme 2

In scheme 2, m, n, k, l, LG1, R^B1、R^B2Y, A and Ar are as defined above. The borated compound (XX) can be prepared in a manner similar to that described for compound (XVII).

Electronic devices herein mean devices that include at least layers containing at least organic compounds, however, components herein can also include inorganic materials or layers that are also built up entirely from inorganic materials.

The invention therefore furthermore relates to the use of individual compounds of the formulae (I), (i.a.a.1), (i.a.1), (i.a.2), (i.a.3), (i.a.4), (i.b.a.1), (i.b.1), (i.b.2), (i.b.3), (i.b.4), (i.c.a.1), (i.c.a.2), (i.c.a.3), (i.c.a.4), (i.c.1), (i.c.2), (i.c.3), (i.c.4), (i.d.a.1), (i.d.1), (i.d.2), (i.d.3), (i.d.4) and (i.e.a.1), or of mixtures of compounds of the formulae (i.a) and (i.b.a) or of mixtures of compounds of the formulae (i.c.a) and (i.d.a) or of mixtures of compounds of the general formulae (i.c.a) and (i.d.a):

-as Hole Transport Material (HTM) in organic electronic devices,

-as Electron Blocking Material (EBM) in organic electronic devices,

use as semiconductor material in Organic Field Effect Transistors (OFETs), in particular Thin Film Transistors (TFTs),

for Organic Light Emitting Diodes (OLEDs), in particular for displays on electronic devices and lighting systems,

for electrophotography, in particular as a photoconductive material in Organic Photoconductors (OPC),

-for organic optical detectors, organic photoreceptors, organic field quenching devices (O-FQDs), light emitting electrochemical cells (LECs) and organic laser diodes.

The compounds of the invention are particularly suitable for use as Hole Transport Materials (HTM) in organic electronic devices. HTMs are used in a wide range of electronic devices and applications, such as organic Electroluminescent (EL) devices and solar cells.

The compounds of the present invention can be used as the only HTM or in combination with at least other HTMs suitable other hole transport materials are well known in the art and preferred hole transport materials for the combination are spiro-OMeTAD, 2',7,7' -tetrakis- (N, N '-di-4-methoxy-3, 5-dimethylanilino) -9,9' -spirofluorene, tris (p-anisyl) amine, N, N, N ', N' -tetrakis (4-methoxyphenyl) -1,1 '-biphenyl-4, 4' diamine, 2, 7-bis [ N, N-bis (4-methoxy-phenyl) amino]-9, 9-spirobifluorene, poly (3-hexylthiophene) (P3HT), poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonate) (PEDOT: PSS), poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine](PTAA), NiO and V₂O₅。

Suitable additives are, for example, pyridine compounds such as tert-butylpyridines, imidazoles or polymer additives such as poly (4-vinylpyridine) or copolymers thereof with, for example, vinylstyrene or alkyl methacrylates, as disclosed in WO2013/026563 claims 1-15 and pages 15-17.

The compounds of the present invention used as HTM may be combined with lithium salts as described in phys.

The usefulness of pyridines is described in sol energy mate. & sol Cells, 2007, 91, 424-.

In addition, the compounds of the invention used as HTM may be doped with p-type dopants, for example N (C)₆H₅Br)₃、SbCl₆、V₂O₅、MoO₃、WO₃、RuO₄、Re₂O₃、F₄-TCNQ (tetrafluoro-tetracyanoquinodimethane), HAT-CN (1,4,5,8,9, 11-hexaazatris-phenylene-hexacyano-nitrile), F6-TCNNQ (1,3,4,5,7, 8-hexafluorotetracyanonaphthoquinodimethane available from Novaled), NDP-9 (p-type dopant from Novaled), or Co complex salt combinations. Suitable dopants are described in chem.mater., 2013, 25, 2986-. Suitable [3 ] as described in EP 2180029A1 may also be used]-radialene (r).

The invention furthermore relates to electroluminescent arrangements comprising an upper electrode, a lower electrode, wherein at least of the electrodes are transparent electroluminescent layers, and optionally an auxiliary layer, wherein the electroluminescent arrangement comprises at least compounds of the formula (I). the above-described preferred embodiments are likewise applicable to substrates, in particular at least compounds of the formula I), (I.A.a.1), (I.A.1), (I.A.2), (I.A.3), (I.A.4), (I.B.a.1), (I.B.1), (I.B.2), (I.B.3), (I.B.4), (I.C.a.1), (I.C.a.2), (I.C.a.3), (I.C.a.4), (I.C.1), (I.C.2), (I.C.3), (I.C.4), (I.D.a.1), (I.D.2), (I.D.3) and (I.D.4) for the transport of electrons or of the compounds (I.A.1).

The present invention is also directed to electroluminescent devices in the form of Organic Light Emitting Diodes (OLEDs). in an organic light emitting device, an electron blocking layer is disposed adjacent to the light emitting layer.

OLEDs can be used in various applications, such as monochromatic or polychromatic displays, in illumination system applications or in medical and/or cosmetic applications, such as phototherapy.

Organic electroluminescent devices, in particular in the form of OLEDs, comprise a cathode, an anode and at least light-emitting layers, which may also comprise, in addition to these layers, other layers, for example or more in each case hole-injecting, hole-transporting, hole-blocking, electron-transporting, electron-injecting, exciton-blocking, electron-blocking and/or charge-generating layers.

The organic electroluminescent device herein may comprise light-emitting layers or a plurality of light-emitting layers if a plurality of light-emitting layers are present, these preferably have the sum of a plurality of emission maxima of 380-750nm, resulting in white light emission overall, i.e. various light-emitting compounds capable of emitting fluorescence or phosphorescence are used in the light-emitting layers, particularly preferred is a system with three light-emitting layers, wherein the three layers show blue, green and orange or red light emission (for the basic structure, see e.g. WO 2005/011013.) it is possible herein that all light-emitting layers are fluorescent or that all light-emitting layers are phosphorescent or that or more light-emitting layers are fluorescent and or more other layers are phosphorescent.

According to the embodiments described above, the compounds of the invention may be used herein in different layers, depending on the precise structure. Preference is given to preferred embodiments of the organic electroluminescent devices comprising compounds of the formula (I) either as hole-transport material in hole-transport or hole-injection or electron-blocking layers or as matrix material for fluorescent or phosphorescent emitters, in particular phosphorescent emitters. The preferred embodiments described above are also suitable for the described use in organic electronic devices.

In a preferred embodiment of the present invention, the compounds of the formula (I) or preferred embodiments are used as hole-transporting or hole-injecting materials in hole-transporting or hole-injecting layers. The light emitting layer herein may be fluorescent or phosphorescent.

The hole injection layer is typically a layer that helps to inject electrons from the anode into the organic layer. The hole injection layer may be positioned proximate to the anode.

The hole transport layer transports holes from the anode to the light emitting layer and is located between the hole injection layer and the light emitting layer.

To enhance the hole transport characteristics, a doped hole transport layer may be employed. The architecture of practical OLEDs typically improves quantum efficiency by using graded heterojunctions. In a graded heterojunction architecture, the composition of hole and electron transporting materials varies continuously within a light emitting layer having a doped emitter. The graded heterojunction architecture combines the benefits of both conventional architectures by improving charge injection while balancing charge transport in the light emitting region.

In yet another preferred embodiment of the invention, the compound of formula (I) or a preferred embodiment thereof is used in an electron blocking layer.

The compounds of the formula (I) or preferred embodiments thereof are particularly preferably used in hole-transport layers or electron-blocking layers.

In another preferred embodiment of the invention, the compounds of formula (I) or preferred embodiments thereof are used as matrix materials for fluorescent or phosphorescent compounds, especially for phosphorescent compounds, in the light-emitting layer the organic electroluminescent devices herein may comprise light-emitting layers or a plurality of light-emitting layers, wherein at least light-emitting layers comprise at least compounds of the invention as matrix materials.

If the compounds of the formula (I) or preferred embodiments thereof are used as matrix materials for light-emitting compounds in the light-emitting layer, they are preferably used in combination with or more phosphorescent materials (triplet emitters). phosphorescence means, in the sense of the present invention, emission from excited states having a spin multiplet >1, in particular from excited triplet states.

The mixture comprising the compound of the formula (I) or the preferred embodiments and the luminescent compound comprises 99.9 to 1% by weight, preferably 99 to 10% by weight, particularly preferably 97 to 60% by weight, in particular 95 to 80% by weight, of the compound of the formula (1) or the preferred embodiments, based on the entire mixture comprising emitter and matrix material. Accordingly, the mixture comprises from 0.1 to 99% by weight, preferably from 1 to 90% by weight, particularly preferably from 3 to 40% by weight, in particular from 5 to 20% by weight, of the emitter, based on the entire mixture comprising emitter and matrix material. In particular, the limits stated above apply if the layer is applied from solution. The same values apply if the layers are applied by vacuum evaporation, wherein the percentages in this case represent% by volume in each case.

Furthermore, the present invention relates again to organic field effect transistors comprising a substrate having at least gate structures, a source and a drain, and at least of the above-described compounds of the formula I as semiconductor materials.

Furthermore, the present invention relates again to substrates comprising a plurality of organic field effect transistors, at least of which comprise at least compounds of the formula I.

Furthermore, the present invention relates to semiconductor units comprising at least substrates as defined above.

The compounds of the invention, i.e. at least compounds of formula (I), (i.a.a.1), (i.a.1), (i.a.2), (i.a.3), (i.a.4), (i.b.a.1), (i.b.1), (i.b.2), (i.b.3), (i.b.4), (i.c.a.1), (i.c.a.2), (i.c.a.3), (i.c.a.4), (i.c.1), (i.c.2), (i.c.3), (i.c.4), (i.d.a.1), (i.d.1), (i.d.2), (i.d.3), (i.d.4) and (i.e.a.1) may advantageously be used as htm in solar cells, respectively, which may also be used in place of the liquid electrolytes of conventional DSSCs to provide solid state DSSC devices.

The compounds of the invention are then preferably used in a photosensitive nanoparticle layer comprising a sensitizing dye or perovskite and at least compounds of the invention.

In an th embodiment, the compounds of the invention are used in DSSCs the structure of DSSCs is generally based on a transparent substrate, which is coated with a transparent conducting layer (working electrode), an n-type conducting metal oxide is generally applied to or near the electrode, for example, nanoporous TiO about 2-20 μm thick₂And (3) a layer. In turn, a monolayer of a photosensitive dye is typically adsorbed on its surface, which can be converted to an excited state by light absorption. This layer carrying the photosensitizing dye is commonly referred to as the light absorbing layer of the DSSC. The counter electrode may optionally have a catalytic layer of metal, for example platinum, with a thickness of a few μm.

In principle, all sensitizing dyes are suitable, provided that the LUMO energy state is slightly above the conduction band edge of the photoelectrode to be sensitized. Examples of dyes are disclosed in Nanoenergy, de Souza, Flavio leiando, Leite, Edson Roberto (ed.), Springer, ISBN 978-3-642-31736-1, pages 58-74 or black dyes as described in US 8,383,553. Preferred dyes are described in WO 2015049031a1, which is incorporated herein by reference.

In principle, the perovskite material contained in the device of the invention may be the portion of the charge transport layer, but may also be the portion of other layers or architectures within the device.

Suitable perovskite materials may comprise two materials corresponding to formula Xa_p-_xXb (x), wherein Xa and Xb are each independently selected from Cl, Br or I, and x is greater than 0 and less than 3. Suitable calcium titaniumMineral materials are also disclosed in claims 52-71 and 72-79 of WO 2013/171517, which is incorporated herein by reference in its entirety. A suitable perovskite material is CsSnl₃、CH₃NH₃Pbl₂Cl、CH₃NH₃Pbl₃、CH₃NH₃Pb(l_1-xBr_x)₃、CH₃NH₃Snl₂Cl、CH₃NH₃Snl₃Or CH₃NH₃Sn(l_1-xBr_x)₃Wherein 0 is<x<1。

Preferred perovskite materials are disclosed on page 18, lines 5 to 17 of WO 2013/171517. As stated, the perovskite is typically selected from CH₃NH₃PbBrl₂、CH₃NH₃PbBrCl₂、CH₃NH₃PblBr₂、CH₃NH₃PWCl₂、CH₃NH₃SnF₂Br、CH₃NH₃SnF₂l and (H)₂N＝CH-NH₂)Pbl_3zBr_3(1-z)Wherein z is greater than 0 and less than 1.

Furthermore, the inventive charge transport layer as described above or the inventive device as described above or below may comprise an insulator, such as alumina as described in Michael m.lee et al, Science, 338, 643, 2012.

Furthermore, the charge transport layer of the present invention or the device of the present invention as described before or below may comprise semiconductor oxide nanoparticles. The charge transport layer of the invention or the device of the invention preferably comprises semiconductor oxide nanoparticles.

According to a preferred embodiment of the invention, the semiconductor is based on a material selected from the group consisting of: si, TiO₂、SnO₂、Fe₂O₃、WO₃、ZnO、Nb₂O₅、CdS、ZnS、PbS、Bi₂S₃、CdSe、GaP、InP、GaAs、CdTe、CuInS₂And/or CuInSe₂。

Preferably, the charge transport layer of the invention as described above is present on a glass support or a plastic or metal foil, optionallyTogether with TiO₂Preferably, the support is electrically conductive.

Further, the present invention relates to electronic or optoelectronic devices comprising a charge transport layer as described or preferred above preferably the invention further relates to a solid state dye sensitized solar cell comprising a charge transport layer as described or preferred above a suitable device architecture of the invention comprising a mixed halide perovskite is described in claims 52-71 and 72-79 of WO 2013/171517, the entire contents of which are incorporated herein by reference.

Suitable device architectures of the present invention further comprising a dielectric architecture together with a perovskite material are described in claims 1-90 of WO2013/171518 or claims 1-94 of WO 2013/171520, which are incorporated herein by reference in their entirety.

claims 1 and 3-14 of the descriptor WO 2014/020499, the entirety of which is incorporated herein by reference, of a suitable device architecture of the invention comprising a semiconductor and a perovskite material₂。

Suitable device architectures of the present invention comprising planar heterojunctions are described in claims 1-39 of WO 2014/045021, which is herein incorporated by reference in its entirety, the device is characterised by a thin film having a light absorbing or light emitting perovskite disposed between an n-type (electron conducting) layer and a p-type (hole conducting) layer.

-providing th and second electrodes;

the substrate may be rigid or flexible, as for the choice of th and second electrodes per se.

Abbreviations used in the examples hereinafter are:

a/a is area percentage; al is aluminum; BPhen is 4, 7-diphenyl-1, 10-phenanthroline, commercially available from LuminescScience Technology corp, taiwan; c60 is a fullerene, available from CreaPhys GmbH Dresden, germany; the EBL is an electron blocking layer, and the EIL is an electron injection layer; EML is a light-emitting layer; ETL is an electron transport layer; f6TCNNQ is 2,2' - (perfluoronaphthalene-2, 6-diyl) dipropionadinitrile, available from Novaled AG, germany; GC is gas chromatography; HAT-CN or HAT (CN)₆Is 1,4,5,8,9, 11-hexaazabiphenylene-hexanenitrile, available from Jilin OLED MaterialTech co, LTD, china; HBL is a hole blocking layer; HIL is a hole injection layer; HPLC is high performance liquid chromatography; the HTL is a hole transport layer; iPrOH is isopropanol; ir (MDQ)₂(acac) is bis (2-methyldibenzo [ f, h)]Quinoxaline) (acetylacetone) iridium (III), available from luminescences Technology corp., taiwan; the ITO is indium tin oxide; LiQ is 8-hydroxyquinonyl lithium, available from Nichem Fine Technology co.ltd, taiwan; NDP-9, NHT-18, Novaled n-type dopant, available from Novaled AG, Germany; NPB is N, N '-bis (naphthalen-1-yl) -N, N' -bis (phenyl) benzidine, commercially available from Sensient, germany; OMe is methoxy; pd (dba)₂Bis (dibenzylideneacetone) palladium (0); pd₂(dba)₃Tris (dibenzylideneacetone) dipalladium (0); RuPhos is 2-dicyclohexylphosphino-2 ',6' -diisopropoxybiphenyl; SPhos is 2-dicyclohexyl-phosphino-2 ',6' -dimethoxybiphenyl; TDSF is 1,3, 5-triazine-2, 4-diphenyl-6- (9,9' -spiro-bis [ 9H-fluorene)]-2-yl, available from Nichem Fine Technology co.ltd., taiwan; THF is tetrahydrofuran; v/v is volume/volume; ZnPc is a zinc phthalocyanine, which is available from CreaPhys GmbH Dresden, germany.

Preparation examples

I. Preparation of intermediates

The starting materials used in the examples are commercially available or can be synthesized by one of ordinary skill in organic chemistry trained to follow routine laboratory procedures, such as described in the examples below.

a)1,3, 3-trimethylindane compounds

a1) 5-chloro-3- (4-chlorophenyl) -1,1, 3-trimethylindane

51.8g (155.4mmol) of methylmagnesium chloride (3M in THF) were added at room temperature under argon over a period of 1 hour20g (129.5mmol) of 4' -chloroacetophenone were added. After 1 hour, the reaction mixture was poured onto 40mL of hydrochloric acid (36% strength in water, commercially available). The phases were separated and saturated NaHCO was used₃The organic phase was separated and 0.5g (2.6mmol) of p-toluenesulfonic acid hydrate was added, the mixture was evaporated to dryness, the crude solid was dissolved in 40mL of trifluoroacetic acid and heated at 85 ℃ for 3 hours, the trifluoroacetic acid was removed by distillation and the crude product was crystallized from 2-propanol to obtain the title compound as a white powder (12g, 60%; purity according to GC: 99.0%).

a2) 5-fluoro-3- (4-fluorophenyl) -1,1, 3-trimethylindane

The title compound is prepared in analogy to the procedure described for 5-chloro-3- (4-chlorophenyl) -1,1, 3-trimethylindan. Yield: 73 percent; purity according to GC: 99.0 percent.

a3) 5-bromo-3- (4-bromophenyl) -1,1, 3-trimethylindan

The title compound is prepared in analogy to the procedure described for 5-chloro-3- (4-chlorophenyl) -1,1, 3-trimethylindan. Yield: 76%; purity according to GC: 98.5 percent.

a4)3- [3, 5-bis (tetrachlorobenzoquinone (bromonyl)) phenyl ] -4, 6-bis (tetrabromo-p-benzoquinone) -1,1, 3-trimethyl-2H-indene

30.0g (95mmol) of tribromobenzene were dissolved in 60mL of anhydrous THF. 105mL of isopropylmagnesium chloride lithium chloride complex (1.3M in THF) were added dropwise under an argon atmosphere. The reaction mixture was stirred at room temperature for 2 hours, followed by dropwise addition of 15mL (204mmol) of acetone. After an additional 4 hours, 150mL NH was added₄Saturated aqueous solution of Cl. The mixture was then expanded with tert-butyl methyl ether and water. The organic phase was separated and washed twice with water, MgSO₄Dried and evaporated to dryness.

The crude product was dissolved in 220mL toluene and 0.3g (1.6mmol) p-toluenesulfonic acid hydrate was added the mixture was heated to reflux in a dean-Stark trap for 2 hours after cooling with 5% NaHCO₃The mixture was washed three times with aqueous solution and MgSO₄Dried and evaporated to dryness. The crude product was dissolved in 50mL heptane and 5mL sulfuric acid was added. The reaction mixture was added at 85 deg.CThe heat was applied for 18 hours. After cooling, the mixture was filtered through celite and evaporated to dryness. The crude product was crystallized from toluene/methanol. The product was obtained as a white solid (13.21g, 50%; purity according to GC: 99%). a5) 6-amino-1- (4' -aminophenyl) -1,3, 3-trimethylindane

50.38g (164mmol) of 5-chloro-3- (4-chlorophenyl) -1,1, 3-trimethylindan are dissolved in 50mL of anhydrous THF. 1.50g (1.6mmol) Pd were added₂(dba)₃And 1.38g (4mmol) of 2- (dicyclohexylphosphino) biphenyl, and 400mL (400mmol) of lithium bis (trimethylsilyl) amide in THF was added to the reaction mixture. The reaction mixture was heated at 75 ℃ under an argon atmosphere for 18 hours. After cooling, aqueous hydrochloric acid (32%) was added until pH 2 was reached, and the mixture was stirred at room temperature for a further 2 hours. The phases were separated and the aqueous phase was washed twice with tert-butyl methyl ether. The aqueous phase was separated and the pH of the aqueous phase was adjusted to pH 9 by addition of aqueous NaOH solution (33%). The aqueous phase was extracted three times with tert-butyl methyl ether. The combined organic phases were washed with water and MgSO₄Dried and evaporated to dryness. After column chromatography (dichloromethane/heptane), the crude product was crystallized from toluene/heptane. The title compound (22.2g, 50%; purity according to GC: 98% (a/a) was obtained as an off-white powder.

a6)5(6) -amino-1- (4' -aminophenyl) -1,3, 3-trimethylindane

The mixture may be obtained as described in example 3 of US 3,856,752.

a7) [3- (4-borono) -1,1, 3-trimethyl-indan-5-yl ] boronic acid

3.88g (9.84mmol) of 5-bromo-3- (4-bromophenyl) -1,1, 3-trimethyl-indan are dissolved in 39mL of THF under an argon atmosphere. The solution was cooled to-78 ℃ and 9.1mL of an n-butyllithium solution (2.7M in heptane, 24.6mmol) were added. Stirring was continued for 1 hour and 6.8mL (29.5mmol) of triisopropyl borate were added. The solution was allowed to warm to room temperature and then cooled to 0 ℃. 100mL of 1M HCl solution was added and the volatiles were evaporated under reduced pressure. The remaining aqueous suspension was basified to pH 10 with 1M NaOH solution, heated to 75 ℃ and filtered under vacuum. The solution was adjusted to pH 1 with 1M HCl and 150mL CH was added₂Cl₂. The organic phase is separated and purified with 100mL CH₂Cl₂the/iPrOH 10:1v/v wash the aqueous phase twice. The combined organic phases were evaporated to dryness. The title compound was obtained as a white foam (3.38g, 99%). a8)3- (4-aminophenyl) -1,1, 3-trimethyl-indan-5-amine

100g (254mmol) of 5-bromo-3- (4-bromophenyl) -1,1, 3-trimethylindan, 64.2g (634mmol) of pivaloamide and 87.7g K from example a3₂CO₃(634mmol) was suspended in 400mL dioxane. Under an argon atmosphere, 7.25g (38.0mmol) of CuI and 6.71g (76.1mmol) of dimethylenediamine were added. The suspension was heated to reflux for 16 hours and cooled to room temperature. The suspension was filtered and washed with 100mL dioxane and 250mL NH₃The aqueous solution washes the filter cake. Furthermore, 20mLNH was used₃The filter cake was washed with aqueous solution and then again with water. The crude product was dried under vacuum. Obtaining N- [4- [6- (2, 2-dimethylpropanoyl-amino) -1,3, 3-trimethyl-indan-1-yl as a colorless solid]Phenyl radical]2, 2-dimethyl-propionamide (110g, 99% of theory).

68.4g (1.22mol) of KOH are suspended in 200mL of n-butanol. 100g (230mmol) of N- [4- [6- (2, 2-dimethylpropanoylamino) -1,3, 3-trimethyl-indan-1-yl ] phenyl ] -2, 2-dimethyl-propionamide are added in small portions under an argon atmosphere. The resulting suspension was heated to reflux for 3 hours and cooled to 80 ℃.200 mL of water was added. The lower aqueous phase was separated and the organic phase was washed with 200mL of water. The aqueous phases were combined, allowed to cool to room temperature and extracted with 100mL of methyl tert-butyl ether. All organic phases were combined and volatiles were removed under heating. 200mL of water was added and the water was removed under heating until all remaining n-butanol was removed. The residue was crystallized by adding 200mL of cyclohexane and cooled to room temperature. The suspension was filtered and the filter cake was washed with cyclohexane and water and the crude product was dried under vacuum. The title product was obtained as a light brown solid (55.2g, 90% of theory).

b) Preparation of aromatic amines

b1) N- (4-methoxyphenyl) -4-phenyl-aniline

To a suspension of 11.6g (50.0mmol) of 4-bromo-1, 1' -biphenyl, 9.20g (74.7mmol) of 4-methoxyaniline and 7.18g (74.7mmol) of sodium tert-butoxide in 150mL of toluene under an argon atmosphere was added 0.29g of (1).00mmol) Tri-tert-butylphosphine tetrafluoroborate and 1.4g (1.00mmol) Pd₂(dba)₃. The mixture was heated at 90 ℃ for 19 hours. After cooling, the mixture was added to 100mL NH₄Cl half-saturated aqueous solution. The mixture was expanded with 100mL of ethyl acetate and the organic phase was separated. The aqueous phase was washed with ethyl acetate and the combined organic phases were washed with a saturated solution of NaCl. Separating the organic phase with MgSO₄Dried and evaporated to dryness. The product was purified by column chromatography (cyclohexane/dichloromethane) to give the title compound as an off-white solid (7.1g, 51%).

b2) N' - (4-biphenylyl) -N, N-diphenyl-1, 4-benzenediamine

Under an argon atmosphere, 17.8g (55.0mmol) of 4-bromo-N, N-diphenylaniline, 8.46g (50.0mmol) of [1,1' -biphenyl]To a suspension of (E) -4-amine and 7.18g (74.7mmol) of sodium tert-butoxide in 150mL of toluene were added 0.29g (1.00mmol) of tri-tert-butylphosphine tetrafluoroborate and 1.04g (1.00mmol) of Pd₂(dba)₃. The mixture was heated at 90 ℃ for 19 hours. After cooling, the mixture was added to 100mL NH₄Cl half-saturated aqueous solution. The mixture was expanded with 100mL of ethyl acetate and the organic phase was separated. The aqueous phase was washed with ethyl acetate and the combined organic phases were washed with a saturated solution of NaCl. Separating the organic phase with MgSO₄Dried and evaporated to dryness. The product was purified by column chromatography (cyclohexane/dichloromethane) to give the title compound as an off-white solid (12.4g, 60%).

b3) N- (9, 9-Dimethylfluoren-2-yl) -9, 9-dimethyl-fluoren-2-amine

To a suspension of 22.6g (82.7mmol) of 2-bromo-9, 9-dimethyl-9H-fluorene, 17.3g (82.7mmol) of 9, 9-dimethyl-9H-fluoren-2-amine and 23.8g (248.1mmol) of sodium tert-butoxide in 300mL of toluene under an argon atmosphere were added 0.96g (3.31mmol) of tri-tert-butylphosphine tetrafluoroborate and 3.03g (3.31mmol) of Pd2(dba)₃. The mixture was heated at 90 ℃ for 19 hours. After cooling, 40mL NH was added₄Saturated aqueous solution of Cl. After 30 minutes, the combined phases were filtered through celite and expanded with 500mL dichloromethane and 250mL water. The organic phase was separated and the aqueous phase was washed with 200mL of dichloromethane. The combined organic phases were washed with a saturated solution of NaCl and MgSO₄Dried and evaporated to dryness. The crude solid was crystallized from toluene to give the title compound as a white solid (20.0g, 60%).

b4) N- (9, 9-dimethylfluoren-2-yl) dibenzofuran-2-amine

9.0g (36.4mmol) of 2-bromodibenzo [ b, d ] under an argon atmosphere]To a suspension of furan, 11.4g (54.6mmol) of 9, 9-dimethyl-9H-fluoren-2-amine and 10.5g (109.2mmol) of sodium tert-butoxide in 200mL of toluene were added 0.42g (1.46mmol) of tri-tert-butylphosphine tetrafluoroborate and 1.33g (1.46mmol) of Pd2(dba)₃. The mixture was heated at 90 ℃ for 15 hours. After cooling, 100mL of a saturated aqueous solution of NH4Cl was added. After 30 minutes, the combined phases were filtered through celite and expanded with 100mL of toluene. The organic phase was separated and the aqueous phase was washed with 100mL of toluene. The combined organic phases were washed with MgSO₄Dried and evaporated to dryness. The crude solid was crystallized from toluene/cyclohexane. The crude solid was purified by column chromatography (heptane/dichloromethane) to give the title compound as a white solid (6.9g, 51%).

Preparation of the Compound of formula (I)

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