EP2087042A1

EP2087042A1 - Pentarylene and hexarylene tetracarboxylic acid diimides, and production thereof

Info

Publication number: EP2087042A1
Application number: EP07822006A
Authority: EP
Inventors: Jianqiang Qu; Neil Gregory Pschirer; Rüdiger Sens
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2006-11-02
Filing date: 2007-10-30
Publication date: 2009-08-12
Also published as: JP2010508326A; CN101573414B; US8202994B2; CN101573414A; WO2008052981A1; US20100059716A1

Abstract

The invention relates to methods for producing pentarylene and hexarylene tetracarboxylic acid diimides of general formula (!) or (Ia) or the mixtures thereof, pentarylene and hexarylene tetracarboxylic acid diimides having a high substitution rate, and the use thereof.

Description

Pentarylene and Hexarylentetracarbonsäurediimide and their preparation

description

The present invention relates Pentarylen- and Hexarylentetracarbonsäurediimide and their preparation and use.

Rylenetetracarboxylic diimides are known to be of particular application interest due to their strong absorption in the near-infrared (NIR) region of the electromagnetic spectrum.

Thus, for example, WO-A 02/77081 describes the use of quaterrylenetetracarboxylic diimides as infrared absorbers for thermal protection in glass laminates.

Pentarylene and hexarylene derivatives, which are unsubstituted or have a low degree of substitution, are described by N.G. Pschirer et al., Angew. Chem. Int. Ed. 45 (2006), 1401-1404.

Similar pentarylene and hexarylene derivatives are also described in DE-A 10 2005 018241.

Despite the already described pentarylene and hexarylene derivatives and their use in connection with their absorption capacity in the NIR, there is a need for further, in particular highly substituted, derivatives and to processes for their preparation.

It is therefore an object of the present invention to provide such derivatives and processes for their preparation which are of particular interest, in particular because of their absorption capacity, and which, owing to the simplest possible production processes, should be easy to prepare despite their comparatively high degree of substitution.

This object is achieved by a process for the preparation of pentarylene and hexarylene tetracarboxylic diimides containing the steps

(a) coupling of at least one terrylene or quaterrylene compound of the formula (II)

with at least one compound of the formula (III) or (IIIa)

in which

Y, Y ^{1 are} both halogen or one of Y, Y ^{1 is} halogen and the other is B (OFT) ₂ ;

Each R, R ^{A is} independently the same or different of the following radicals:

Aryloxy, arylthio, hetaryloxy or hetarylthio, to which in each case further saturated or unsaturated 5- to 7-membered rings whose carbon skeleton is represented by one or more groups -O-, -S-, -NR ¹ -, -N = CR ¹ -, -CO-, -SO- and / or -SO ₂ - may be interrupted, wherein the entire ring system is mono- or polysubstituted by the radicals (i), (ii), (iii), (iv) and / or (v) may be substituted:

(i) C 1 -C ₃₀ -alkyl whose carbon chain is replaced by one or more

Groupings -O-, -S-, -NR ¹ -, -N = CR ¹ -, -C≡C-, -CR ¹ = CR ¹ -, -CO-, -SO- and / or -SO ₂ - interrupted and which may be may be mono- or polysubstituted by d-C ₂ alkoxy, Ci-C ₆ alkylthio, -C≡CR ^1, -CR ¹ = CR ¹ _2, hydroxyl, mercapto, halogen, cyano, nitro , -NR ² R ³ , -NR ² COR ³ , -CONR ² R ³ , -SO ₂ NR ² R ³ , -COOR ² , -SO ₃ R ² , -PR ² R ³ , -POR ² R ³ ,

Aryl and / or saturated or unsaturated C ₄ -C ₇ -cycloalkyl, whose carbon skeleton is represented by one or more groups -O-, -S-, -NR ¹ -, -N = CR ¹ -, -CR ¹ = CR ¹ -, -CO-, -SO- and / or -SO ₂ - may be interrupted, wherein the aryl and cycloalkyl radicals in each case one or more times by Ci-Ci8-alkyl and / or the above, as substituents for

Alkyl radicals may be substituted;

(ii) C ₃ -C ₈ -cycloalkyl, whose carbon skeleton is represented by one or more moieties -O-, -S-, -NR ¹ -, -N = CR ¹ -, -CR ¹ = CR ¹ -, -CO-, -SO- and / or -SO ₂ - may be interrupted and to the further saturated or unsaturated 5- to 7-membered rings whose carbon skeleton by one or more groups -O-, -S-, -NR ¹ -, -N = CR ¹ -, - CR ¹ = CR ¹ -, -CO-, -SO- and / or -SO ₂ - may be interrupted, the entire ring system may be monosubstituted or polysubstituted by: C _r -C ₈ alkyl, C _r C ₂ alkoxy, C _r C ₆ alkylthio, -

C≡CR ¹ , -CR ¹ = CR ¹ ₂ , hydroxy, mercapto, halogen, cyano, nitro, -NR ² R ³ , -NR ² COR ³ , -CONR ² R ³ , -SO ₂ NR ² R ³ , - COOR ² , -SO ₃ R ² , -PR ² R ³ and / or - POR ² R ³ ;

(iii) aryl or hetaryl to which further saturated or unsaturated 5- to

7-membered rings whose carbon skeleton is represented by one or more moieties -O-, -S-, -NR ¹ -, -N = CR ¹ -, -CR ¹ = CR ¹ -, -CO-, -SO- and / or -SO ₂ - may be interrupted, be anneliert, wherein the entire ring system may be mono- or polysubstituted by: Ci-Ci8-alkyl, C _r Ci ₂ alkoxy, C _r C ₆ alkylthio, -C≡CR ¹ , CR ¹ = CR ¹ ₂ ,

Hydroxy, mercapto, halogen, cyano, nitro, -NR ² R ³ , -NR ² COR ³ , -CONR ² R ³ , -SO ₂ NR ² R ³ , -COOR ² , -SO ₃ R ² , -PR ² R ³ , -POR ² R ³ , aryl and / or hetaryl, each represented by C ₁ -C 18 -alkyl, C 1 -C 12 -alkoxy, hydroxy, mercapto, halogen, cyano, nitro, -NR ² R ³ , -NR ² COR ^3, -CONR ² R ^3, - SO ₂ NR ² R ^3, -COOR ^2, -SO ₃ R ^2, -PR ² R ³ and / or -POR ² R ³ may be substituted; (iv) a radical -U-aryl which may be monosubstituted or polysubstituted by the abovementioned radicals which are mentioned as substituents for the aryl radicals (iii), where U is a grouping -O-, -S-, -NR ¹ -, -CO-, -SO- or -SO ₂ -;

(v) C _r Ci2 alkoxy, C _r C ₆ alkylthio, -C≡CR ^1, -CR ¹ = CR ¹ _2, hydroxyl, mer- capto, halogen, cyano, nitro, -NR ² R ^3, -NR ² COR ^3, -CONR ² R ^3, - SO ₂ NR ² R ^3, -COOR ^2, -SO ₃ R ^2, -PR ² R ³ and / or -POR ² R ^3;

each R 'is independently hydrogen;

dC ₃ o-alkyl, whose carbon chain is represented by one or more moieties -O-, -S-, -NR ¹ -, -N = CR ¹ -, -C≡C-, -CR ¹ = CR ¹ -, -CO- , -SO- and / or -SO ₂ - may be interrupted and may be mono- or polysubstituted by the substituents mentioned for the radicals R radicals (ii), (iii), (iv) and / or (v) ;

C ₃ -C ₈ -cycloalkyl to which further saturated or unsaturated 5- to 7-membered rings whose carbon skeleton is replaced by one or more groups -O-, -S-, -NR ¹ -, -N = CR ¹ -, - CR ¹ = CR ¹ -, -CO-, -SO- and / or -SO ₂ - may be annelated, wherein the entire ring system by the substituents for the radicals R mentioned radicals (i), (ii) (iii), (iv) and / or (v) may be substituted; or

Aryl or hetaryl to which further saturated or unsaturated 5- to 7-membered rings, the carbon skeleton by one or more groups -O-, -S-, -NR ¹ -, -N = CR ¹ -, -CR ¹ = CR ¹ -, -CO-, -SO- and / or -SO ₂ - may be interrupted, which may be fused, wherein the entire te ring system may be substituted by the substituents as for the

Radicals R mentioned radicals (i), (ii), (iii), (iv), (v), aryl and / or hetarylazo, each by Ci-Ci _O alkyl, Ci-C ₆ -Akoxy and / or Cyano may be substituted;

each R "is independently of one another hydrogen, C 1 -C ₃₀ -alkyl, C ₅ -C ₈ -

Cycloalkyl, aryl or hetaryl is or joined together to form a 5- to 7-membered ring containing the two oxygen atoms and the boron atom, to which unsaturated or saturated rings can be fused and which can be attached to the carbon atoms by up to 4Ci-C ₃₀ - Alkyl, C ₅ -C ₈ cycloalkyl, aryl or hetaryl groups may be substituted; R ^{1 is} hydrogen or C ¹ -C ₈ -alkyl, where the radicals R ^{1 may be} identical or different if they occur more than once;

R ² , R ^{3 are} independently hydrogen;

C 1 -C 6 -alkyl whose carbon chain may be interrupted by one or more groups -O-, -S-, -CO-, -SO- and / or -SO ₂ - and which is mono- or polysubstituted by C 1 -C ₁₂ -alkoxy , C ₁ -C ₆ -alkylthio, hydroxy, mercapto, halogen, cyano, nitro and / or -COOR ¹ may be substituted;

Aryl or hetaryl, to each of which further saturated or unsaturated 5- to 7-membered rings, the carbon skeleton by one or more groups -O-, -S-, -CO- and / or -SO ₂ - may be interrupted, be annelated can, wherein the entire ring system may be mono- or polysubstituted by Ci-Ci ₂ alkyl and / or the above, as substituents for alkyl radicals may be substituted;

and wherein m, m1, n, n1 satisfy at least one of the following conditions:

m = 1, m1 = 0 and n, n1 are integers whose sum gives a number from 5 to 8;

m = 2 and n, n1 are integers whose sum gives a number from 0 to 8, where the reaction is with (purple);

m = 1, m1 = 1 and n, n1 are integers whose sum gives a number from 5 to 12;

m = 2, m1 = 0 and n, n1 are integers whose sum gives a number from 0 to 12;

(b) Cyclodehydration of the reaction product obtained in step (a) to give a rylene compound of general formula (I) or (Ia)

(I)

(Ia) or mixtures thereof.

For the process according to the invention, m, m1, n, n1 satisfy at least one of the following conditions.

For the preparation of Pentarylentetracarbonsäurediimiden a corresponding Terrylene and a corresponding perylene (m = 1, m1 = 0) are implemented, where n, n1 are integers whose sum is a number from 5 to 8, ie 5, 6, 7 or 8, preferably 5 or 6 results. Examples of n + n1 are 6 + 2, 5 + 3, 4 + 4, 6 + 1.5 + 2, 4 + 3, 3 + 4, 6 + 0, 5 + 1, 4 + 2, 2 + 4, 3 + 3, 5 + 0, 4 + 1, 1 + 4, 3 + 2, 2 + 3. Preferred for n + n1 are 4 + 4,4 + 2,2 + 4,3 + 2.

Furthermore, Pentarylentetracarbonsäurediimide can be obtained by a corresponding Quaterrylen (m = 2) is used and n, n1 are integers whose sum is a number from 0 to 8, ie 0, 1, 2, 3, 4, 5, 6, 7 or 8, preferably 4, 5 or 6, furthermore preferably 5, 6, 7 or 8, in particular 5 or 6, the reaction being carried out with a corresponding naphthalene of the formula (IIIa). Examples of n + n1 are 8 + 0, 7 + 0, 6 + 0, 5 + 0, 4 + 0, 3 + 0, 2 + 0, 1 + 0, 0 + 0, 7 + 1, 6 + 1, 5 + 1.4 + 1.3 + 1.2 + 1, 1 + 1.0+ 1. Preferred for n + n1 are 6 + 0.5 + 0.4 + 0.3 + 0, 2 + 0.6 + 1.5 + 1.4 + 1.3 + 1.2 + 1; more preferred are 6 + 0.5 + 0.4 + 0.3 + 0. For the preparation of Hexarylentetracarbonsäurediimiden two corresponding

Terrylene (m = 1, m1 = 1) implemented, where n, n1 are integers whose sum is a number from 5 to 12, ie 5, 6, 7, 8, 9, 10, 11 or 12, preferably 5, 6 , 7 or 8 results. Examples of n + n1 are 6 + 6, 6 + 4, 4 + 6, 5 + 5, 6 + 3, 3 + 6, 5 + 4, 4 + 5, 6 +

2, 2 + 6, 5 + 3, 3 + 5, 4 + 4, 6 + 1, 1 + 6, 5 + 2, 2 + 5, 4 + 3, 3 + 4, 6 + 0, 0 + 6, 5 + 1, 1 + 5, 4 + 2, 2 + 4, 3 + 3, 5 + 0, 0 + 5, 4 + 1, 1 + 4, 3 + 2, 2 + 3. Preferred for n + n1 4 + 4, 4 + 3, 3 + 4, 3 + 3.

Furthermore, hexarylene tetracarboxylic diimides can be obtained by reacting a corresponding quaterrylene (m = 2) and a corresponding perylene (m1 = 0), where n, n1 are integers whose sum gives a number from 0 to 12, ie 0, 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12, preferably 4, 5, 6, 7, or 8, especially 5, 6, 7, or 8. Examples of n + n1 are 8 + 0, 7 + 0, 6 + 0, 5 + 0, 4 + 0, 3 + 0, 2 + 0, 1 + 0, 0 + 0, 8 + 1, 7 + 1, 6 + 1, 5 + 1, 4 + 1, 3 + 1, 2 + 1, 1 + 1, 0 + 1, 8 + 2, 7 + 2, 6 + 2, 5 + 2, 4 + 2, 3 + 2, 2 + 2, 1 + 2, 0 + 2, 8 + 3, 7 + 3, 6 + 3, 5 + 3, 4 +

3, 3 + 3, 2 + 3, 1 + 3, 0 + 3, 8 + 4, 7 + 4, 6 + 4, 5 + 4, 4 + 4, 3 + 4, 2 + 4, 1 + 4, 0 + 4. Preferred for n + n1 are 6 + 4, 5 + 4, 4 + 4, 3 + 4, 6 + 2, 6 + 0, 5 + 2, 5 + 0, 4 + 2, 4 + 0, 2 + 2, 2 + 0; particularly preferred are 6 + 4, 4 + 4, 6 + 2, 4 + 2, 6 + 0, 4 + 0.

In a particularly preferred embodiment of the process according to the invention for the preparation of pentarylene- and hexarylenetetracarboxylic acid diimides, the reaction with a quaternarylene compound has the general formula (II, m = 2).

Therefore, another object of the present invention is a method according to the invention, wherein m = 2.

Furthermore, the object is achieved by Pentarylentetracarbonsäurediimide of the general formula (I) or mixtures thereof, wherein n and n1 are integers whose sum is a number from 5 to 8, ie 5, 6, 7 or 8, preferably 5 or 6, and R, R ^A , R ', m, m1 have the abovementioned meaning. Examples of n + n1 are 6 + 2, 5 + 3, 4 + 4, 6 + 1, 5 + 2, 4 + 3, 3 + 4, 6 + 0, 5 + 1, 4 + 2, 2 + 4, 3 + 3, 5 + 0, 4 + 1, 1 + 4, 3 + 2, 2 + 3. Preferred for n + n1 are 4 + 4, 4 + 2, 2 + 4, 3 + 2.

The pentarylene compounds according to the invention can therefore be obtained by means of the process according to the invention by coupling a corresponding terrylene compound with the corresponding perylene compound. The pentarylene compounds according to the invention have a high degree of substitution, in which the radicals R and R ^A together are present at least five times. However, the sum of the substituents R and R ^A is not more than 8. The object is further achieved by Pentarylentetracarbonsäurediimide of the general formula (Ia) or mixtures thereof, wherein n and n1 are integers whose sum is a number from 5 to 8, ie 5, 6, 7 or 8, preferably 5 or 6, and R, R ^A , R ', m have the abovementioned meaning. Examples of n + n1 are 8 + 0, 7 + 1, 7 + 0, 6 + 1, 6 + 0, 5 + 1, 5 + 0, 4 + 1. Preferred for n + n1 are 6 + 0, 5 + 0, 4 + 0.

The pentarylene compounds according to the invention can thus be obtained by means of the process according to the invention by coupling a corresponding quaterrylene compound with the corresponding naphthalene compound. The pentarylene compounds according to the invention have a high degree of substitution, in which the radicals R and R ^A together are present at least five times. However, the sum of the substituents R and R ^A is not more than 8.

The object is further achieved by Hexarylentetracarbonsäurediimide the general formula (I) or mixtures thereof, wherein n and n1 are integers whose

Sum 5 to 12, ie 5, 6, 7, 8, 9, 10, 11 or 12, preferably 5, 6, 7 or 8, and R, R ^A , R ', m, m1 have the abovementioned meaning. Examples of n + n1 are 8 + 0, 7 + 0, 6 + 0, 5 + 0, 8 + 1, 7 + 1, 6 + 1, 5 + 1, 4 + 1, 8 + 2, 7 + 2, 6 + 2, 5 + 2,

4 + 2, 3 + 2, 8 + 3, 7 + 3, 6 + 3, 5 + 3, 4 + 3, 3 + 3, 2 + 3, 8 + 4, 7 + 4, 6 + 4, 5 + 4, 4 + 4, 3 + 4, 2 + 4, 1 + 4. Preferred for n + n1 are 6 + 0, 5 + 0, 6 + 2, 5 + 2, 4 + 2, 6 + 4, 5

+ 4, 4 + 4.

The hexarylene compounds according to the invention can thus be obtained by means of the process according to the invention by coupling a corresponding quaterrylene compound with the corresponding perylene compound. The hexarylene compounds according to the invention have a high degree of substitution, in which the radicals R and R ^A together are present at least five times. However, the sum of the substituents R and R ^A is at most 12.

The starting compounds according to the formulas (II), (III), (IIIa) are known from the prior art or can be prepared by means of syntheses of analogous compounds known from the literature. In particular, terrylene and Quaterrylenderivate that can serve as starting materials for the process of the invention for the preparation of pentarylene and Hexarylentetracarbonsäurediimiden are described in the German patent application with the application number 10 2005 021362. In addition, the preparation of hexarylene and Pentarylentetracarbonsäurediimiden in DE-A 10 2005 018241 is described. A preparation of the imide compounds according to the invention can be carried out analogously.

The process according to the invention for the preparation of pentarylene- and hexarylene-tetracarboxylic diimides comprises, as a first step (a), the coupling of at least one rylen- or quaterrylene compound of the formula (II) with at least one compound of the formula (III) or (IIIa), where the linking of the two building blocks takes place in each case with the aid of the groups Y and Y ¹ .

In this case, Y and Y ^{1 may be} halides, by means of which the desired binding of the two aromatic building blocks is made possible with the aid of a catalytic coupling. It is also possible that one of the radicals Y, Y ^{1 may be} a halide and the other a boronic acid or a similar compound of the formula B (OFT) ₂ . A coupling then takes place via the so-called Suzuki reaction. Preferably, in both cases, the halides are bromide or chloride.

The preparation of the diimides according to the invention by means of the process according to the invention is preferably carried out in the presence of an organic solvent, if desired in admixture with water, and a transition metal catalyst and a base, wherein as stated above, one of the two building blocks, a Boronäurede- derivative and the other may represent a halide. Such a boronic acid derivative is obtainable, for example, by reacting the corresponding halogenated aromatic with the aid of diboranes of the general formula (IV) (RO) ₂ BB (OR ^" ) ₂ in the presence of an aprotic organic solvent, a transition metal catalyst and a base.

Suitable diboranes of the general formula (IV) are, in particular, bis (1, 2 and 1, 3-diolato) diboranes, tetraalkoxydiboranes, tetracycloalkoxydiboranes and tetra (het) aryloxydiboranes and also their mixed forms. Examples of these compounds are: bis (pinacolato) diborane, bis (1, 2-benzodiolato) -diborane, bis (2,2-dimethyl-1,3-propanediolato) diborane, bis (1,1,3,3 -tetramethyl-1,3-pandiolato) diborane, bis (4,5-pinanediolato) diborane, bis (tetramethoxy) diborane, bis (tetra-cyclopentoxy) diborane, bis (tetraphenoxy) diborane and bis (4-pyridiyloxy) diborane ,

Preference is given to diboranes of the general formula (IV) in which the two radicals R located on a boron atom are bonded together to form a five-membered or six-membered ring containing the two oxygen atoms and the boron atom. Aromatic or saturated, and also bicyclic, rings having 5 to 7 C atoms can be fused to the five- or six-membered rings formed as ring members. All rings or ring systems may be substituted by up to 4 C 1 -C ₃₀ -alkyl, C ₅ -C ₈ -cycloalkyl, aryl and / or hetaryl radicals, preferably they are substituted by up to 4 C _r C ₄ -alkyl radicals , Examples of these preferred diboranes are the above-mentioned bis (1, 2 and 1, 3-diolato) -diborane, with bis (pinacolato) diborane being particularly preferred. The molar ratio of diborane of the general formula (IV) to the halogenated aromatic is generally from 0.8: 1 to 3: 1, in particular from 1, 5: 1 to 2: 1.

Suitable solvents are in principle all aprotic solvents which are stable under the reaction conditions to bases having a boiling point above the selected reaction temperature in which the starting materials are completely dissolved at reaction temperature and the catalysts and bases used at least partially, so that largely homogeneous reaction conditions are present. Both nonpolar aprotic and polar aprotic solvents can be used.

Examples of preferred non-polar aprotic solvents are solvents boiling at> 100 ⁰ C from the following groups: aliphatic (especially C ₈ -C ₈ alkanes) unsubstituted, alkyl-substituted cycloaliphatic and fused (especially unsubstituted C ₇ -C ₁₀ cycloalkanes , C ₆ -C ₈ cycloalkanes substituted by one to three -C ₆ - alkyl groups are substituted, polycyclic saturated hydrocarbons having 10 to 18 carbon atoms), alkyl and cycloalkyl-substituted aromatics (especially benzene substituted by one to three alkyl groups CrCβ or a C ₅ -C ₈ -cycloalkyl radical is substituted) and fused aromatics which may be alkyl-substituted and / or partially hydrogenated (in particular naphthalene which is substituted by one to four C ₁ -C ₆ -alkyl groups) and mixtures of these solvents.

Specific examples of particularly preferred solvents include: octane, isooctane, nonane, isononane, decane, isodecane, undecane, dodecane, hexadecane and octadecane; Cycloheptane, cyclooctane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, propylcyclohexane, isopropylcyclohexane, dipropylcyclohexane, butylcyclohexane, tert-butylcyclohexane, methylcycloheptane and methylcyclooctane; Toluene, o-, m- and p-xylene, 1, 3,5-trimethylbenzene (mesitylene), 1, 2,4- and 1,2,3-trimethylbenzene, ethylbenzene, propylbenzene, isopropylbenzene, butylbenzene, isobutylbenzene, tert-butylbenzene and cyclohexylbenzene; Naphtha-Nn, decahydronaphthalene (decalin), 1- and 2-methylnaphthalene, and 1- and 2-ethylnaphthalene; Combinations of the aforementioned solvents, as they can be obtained from the high-boiling, partially or fully hydrogenated fractions of thermal and catalytic cracking processes in crude oil or naphtha, for example mixtures of Exsol ^® type and alkylbenzene ^® Solvesso® type.

Very particularly preferred solvents are xylene (all isomers), mesitylene and especially toluene.

Examples of suitable polar aprotic solvents are N, N-disubstituted aliphatic see carboxamides (especially N, N-di-C _r C ₄ _{alkyl-Ci-C4-carboxamides),} nitrogen-containing heterocycles and aprotic ethers (especially cyclic ethers, di- aryl ethers and di-C _r C ₆ alkyl ethers of monomeric and oligomeric C ₂ -C ₃ alkylene glycols which may contain up to 6 alkylene oxide units, especially diethylene glycol di-C ₄ alkyl ethers).

Specific examples of particularly suitable solvents are: N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide and N, N-dimethylbutyramide; N-methyl-2-pyrrolidone, quinoline, isoquinoline, quinaldine, pyrimidine, N-methylpiperidine and pyridine; Tetrahydrofuran, dioxane, diphenyl ether, diethylene glycol dimethyl, diethyl, dipropyl, diisopropyl, di-n-butyl, di-sec-butyl and di-tert.-butyl ethers, diethylene glycol methyl ethyl ether, triethylene glycol dimethyl and diethyl ether and triethylene glycol methyl ethyl ether.

The amount of solvent is generally 10 to 1000 ml, preferably 20 to 300 ml, per g of halogenated aromatics.

Particularly suitable transition metal catalysts are palladium complexes which, in turn, are generally used in amounts of from 1 to 20 mol%, in particular from 2 to 10 mol%, based on the halogenated aromatic compounds.

Examples of such catalysts are tetrakis (triphenylphosphine) palladium (0), tetrakis (tris-o-tolylphosphine) palladium (0), [1,2-bis (diphenylphosphino) ethane] palladium (II) chloride, [1, 1'-bis (diphenylphosphino) ferrocene] palladium (II) chloride, bis (triethylphosphine) palladium (II) chloride, bis (tricyclohexylphosphine) palladium (II) acetate, (2,2'-bipyridyl) palladium ( II) chloride, bis (triphenylphosphine) palladium (II) chloride, tris (dibenzylideneacetone) dipalladium (O), 1,5-cyclooctadiene palladium (II) chloride, bis (acetonitrile) palladium (II) chloride and bis (benzonitrile) palladium (II) chloride, palladium (II) acetate, whereby [1,1 '- bis (diphenylphosphino) ferrocene] palladium (II) chloride, tetrakis (triphenylphosphine) palladium (0) and palladium (II) acetate are preferred.

In general, the simultaneous presence of free ligand molecules, e.g. tri (tert-butyl) phosphine, tri (i-butyl) phosphine, triphenylphosphine and tris (o-tolyl) phosphine and 2-dicyclohexylphosphino-2,6-dimethoxybiphenyl. Usual amounts are 80 to 500 mol%, preferably 100 to 300 mol%, based on the transition metal catalyst.

The bases used are preferably the alkali metal salts, in particular the sodium and especially the potassium salts, weak organic and inorganic acids, such as sodium acetate, potassium acetate, sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate, phosphates, fluorides such as potassium fluoride. Preferred bases are the acetates, especially potassium acetate. In general, 1 to 5 mol, preferably 2 to 4 mol, of base are used per mole of halogenated aromatic.

The reaction temperature is usually from 20 to 180 ⁰ C, especially at 60 to 120 ⁰ C.

The reaction time is usually 0.5 to 30 hours, in particular 1 to 20 hours.

From a technical point of view, the preparation of the boronic acid derivatives is expediently carried out as follows:

The halogenated aromatic and solvent are added, the diborane of the general formula (IV), the transition metal catalyst and the base are added in succession and the mixture is heated for 0.5 to 30 h under protective gas to the desired reaction temperature. After cooling to room temperature, the solid components are filtered from the reaction mixture and the solvent is distilled off under reduced pressure.

The Suzuki reaction of the boronic acid derivative thus prepared with the corresponding halogenated aromatic can in principle be used under analogous conditions to produce the product in step (a) of the process according to the invention, wherein instead of the diborane the corresponding boronic acid derivative is reacted with the corresponding halogenated aromatic ,

However, the reaction of the boronic acid derivative with the halogenated aromatic is preferably carried out in the presence of an organic solvent, if desired in admixture with water, and of a transition metal catalyst and a base, the molar ratio of boronic acid derivative to halogenated aromatic being generally 0.8: 1 to 3 : 1, preferably 0.9: 1 to 2: 1.

Suitable solvents are all solvents in which the reactants are completely dissolved at reaction temperature and the catalysts and bases used at least partially, so that substantially homogeneous reaction conditions are present.

For example, octane, isooctane, nonane, isononane, decane, isodecane, undecane, dodecane, hexadecane and octadecane are suitable; Cycloheptane, cyclooctane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, propylcyclohexane, isopropylcyclohexane, dipropylcyclohexane, butylcyclohexane, tert-butylcyclohexane, methylcycloheptane and methylcyclooctane; Toluene, o-, m- and p-xylene, 1, 3,5-trimethylbenzene (mesitylene), 1, 2,4- and 1, 2,3-trimethylbenzene, ethylbenzene, propylbenzene, isopropylbenzene, butylbenzene, isobutylbenzene, tert. Butylbenzene and cyclobutene lohexylbenzol; Naphthalene, decahydronaphthalene (decalin), 1- and 2-methylnaphthalene, and 1- and 2-ethylnaphthalene; Combinations of the aforementioned solvents, as they can be obtained from the high-boiling, partially or fully hydrogenated fractions of thermal and catalytic cracking processes in crude oil or naphtha, for example mixtures of Exsol ^® type and alkylbenzene Vesso ^® from sol type.

The amount of solvent is usually from 10 to 1000 ml, preferably from 20 to 100 ml per g of boronic acid derivative.

Preferably, water is used as an additional solvent. In this case, 10 to 1000 ml, in particular 250 to 500 ml, of water per I of organic solvent are generally used.

Palladium complexes are likewise preferably used as transition metal catalysts. The amount of catalyst used is usually 1 to 20 mol%, in particular 1, 5 to 5 mol%, based on the boronic acid derivative.

As the base alkali metal salts of weak acids are preferred, the carbonates, such as sodium carbonate and especially potassium carbonate are particularly preferred. Phosphates, such as sodium or potassium phosphate, are also preferred here. In general, the amount of base is from 0.1 to 10 mol, in particular from 0.2 to 5 mol, per mole of boronic acid derivative.

The reaction temperature is generally from 20 to 180 ⁰ C, preferably 60 to 120 ⁰ C. It is used in step b) water, so it is recommended not to carry out the reaction at temperatures above 100 ° C, since it is otherwise possible to operate under pressure.

The reaction is usually completed in 0.5 to 48 hours, especially in 5 to 20 hours.

In terms of process technology, it is expedient to proceed as follows: The boronic acid derivative and the halogenated aromatic as well as solvent are introduced, transition metal catalyst and the base, preferably dissolved in water or a water / alcohol mixture, are added and the mixture is heated for 0.5 to 48 h under protective gas to the desired reaction temperature. After cooling to room temperature, the organic phase is separated from the reaction mixture and the solvent is distilled off under reduced pressure.

The purity of the product thus produced from step (a) of the process according to the invention for the preparation of the pentarylene- and hexarylenetetracarboximides is generally sufficient for the further reaction in step (b). Optionally, the crude product can be further purified by washing with water and, if desired, a suitable organic solvent, in particular a chlorinated aliphatic or aromatic hydrocarbon, or by column chromatography on silica gel with a mixture of methylene chloride and hexane or pentane or with toluene as eluent.

The yield in step a) of the process according to the invention is usually from 20 to 95%.

In addition to the Suzuki reaction described above, which requires a corresponding boronic acid derivative, a direct coupling, in particular in homo couplings, can also be carried out by halides.

In this case, the reaction of the correspondingly halogenated aromatic compounds of the formula (II) and (III) or (IIIa) can be carried out in the presence of a diborane of the general formula (IV). Finally, a Suzuki reaction also takes place, but the corresponding boronic acid derivative is only generated in situ.

The coupling can be carried out, for example, in the presence of 30 to 70 mol%, based on the halogenated aromatic, of a diborane of the general formula (IV), a transition metal catalyst, a base and an aprotic solvent according to a Suzuki coupling reaction, wherein the in In situ formed Boronsäurederivat not intermediately isolated, but is reacted directly with the remaining halogenated aromatic.

In this process variant, the procedure is analogous to the above, but for example, only 30 to 70 mol% of diborane of the general formula (IV), based on the halogenated aromatic used. As a rule, 1 to 20 mol%, preferably 5 to 10 mol%, of transition metal catalyst and 1 to 5 mol, preferably 2 to 3 mol, of base are used per mole of halogenated aromatic th. The aprotic organic solvent is usually used in amounts of from 10 to 100 ml, in particular from 20 to 50 ml, per g of halogenated aromatic compounds.

The reaction temperature is generally from 20 to 100 ⁰ C, preferably at 60 to 80 ⁰ C, and the reaction time at 12 to 72 h, preferably 24 to 48 h.

In terms of process technology, it is expedient to proceed as follows:

The halogenated aromatic and solvent are added, the diborane of the general formula (IV), the transition metal catalyst and the base are added in succession and the mixture is heated to the desired reaction temperature for 12 to 72 hours. After cooling to room temperature, the organic phase is separated from the reaction mixture and the solvent is distilled off under reduced pressure.

Again, the purity of the product obtained is usually sufficient for the subsequent cyclodehydration in step (b) of the process according to the invention. Further purification is possible, for example, by column chromatography.

The yield is usually 80 to 95%.

In addition, it is possible to carry out a direct coupling of the halogenated aromatics (halogen compound) without the use of a diborane.

This coupling can take place, for example, in the presence of an organic transition metal complex as a catalyst, free ligand molecules and an aprotic solvent in the sense of a homo-coupling.

Suitable inert diluents are, for example, aliphatic carboxylic acid amides, such as N, N-dimethylformamide and N, N-dimethylacetamide, aliphatic and cycloaliphatic ethers, such as 1,2-dimethoxyethane, and aromatics, such as benzene, toluene and xylene, wherein N, N-dimethylformamide and N, N-dimethylacetamide are preferred.

The amount of diluent is usually 20 to 100 g, preferably 25 to 45 g per gram of halogen compound.

In the case of the organic transition metal complexes serving as catalyst, in addition to the known palladium complexes, such as tetrakis (triphenylphosphine) palladium (0), in particular nickel complexes are suitable, for example bis (triphenyl-) phosphine) nickel (II) chloride, tetrakis (triphenylphosphine) nickel (0), [1, 2-bis (diphenylphosphino) etane] nickel (II) chloride and preferably bis (1, 5-cyclooctadiene) nickel (0). The catalysts can also be obtained by the addition of transition metal salts or compounds, free ligands such as cyclooctadiene, bipyridyl, triphenylphosphine, trifluorophosphine, -η, δ- and π-bonded olefins, cycloolefins, aromatics and antiaromata, carbonyls, hydrogen and Halogen as well as their mixtures and, if necessary, produce oxidizing and reducing agents.

In general, 40 to 150 mol%, preferably 50 to 100 mol%, of organic transition metal complex based on the halogen compound used.

In general, the simultaneous presence of free ligand molecules, in particular mixtures of cyclooctadiene and bipyridyl in the molar ratio of 1: 1 to 8: 1, is always recommended. In this case, amounts of usually 80 to 900 mol%, preferably 80 to 200 mol%, preferably based on the halogen compound suitable.

The coupling temperature is generally 40 to 80 ^° C., preferably 60 to 70 ^° C.

The reaction time is usually 24 to 48 h, in particular 36 to 48 h.

In terms of process technology, this direct coupling is advantageously carried out by initially introducing the halogen compound, the organometallic catalyst and free ligand molecules in the inert diluent and, if appropriate under a protective gas, heating to the desired reaction temperature for 24 to 48 h. After cooling, the reaction mixture in water, which may optionally contain methanol, is a dilute inorganic acid, eg. As dilute hydrochloric acid, and filtered from the precipitate formed, washed with water and dried in vacuo.

The purity of the product according to the invention thus produced is generally sufficient for the subsequent cyclodehydration in step (b) of the process according to the invention. If appropriate, the product can additionally be further purified by column chromatography on silica gel with a mixture of methylene chloride and hexane or pentane as the eluent.

The yield is generally 70 to 90%.

In step (b) of the process according to the invention, the cyclodehydration of the reaction product obtained in step (a) takes place. The Cyclodehydrierung can in a

Having hydroxy and amino functions and a substantially undissolved Base-containing organic reaction medium or in the presence of a base-stable, high-boiling, organic solvent and an alkali or alkaline earth metal-containing base and a nitrogen-containing auxiliary base are made.

The first-mentioned process variant is preferred. In particular, amino alcohols having from 2 to 20, preferably from 2 to 10, carbon atoms are suitable as the organic reaction medium. The carbon chain of these alcohols may be interrupted by oxygen atoms in ether function. Examples of particularly suitable solvents are ethanolamine, triethanolamine and diethanolamine, with ethanolamine being preferred. It is also possible to use mixtures of alcohols and amines, each having a boiling point of at least 70 ⁰ C and are liquid at the reaction temperature.

Usually, 1, 5 to 150 ml, preferably 5 to 50 ml, reaction medium per gram of starting compound used.

As in the reaction medium substantially insoluble base are the alkali metal salts, in particular the sodium salts and v.a. the potassium salts, weak organic and preferably weak inorganic acids, such as formates, acetates, propionates, bicarbonates, and more preferably carbonates, especially sodium carbonate, and more preferably. Potassium carbonate.

In general, the amount of base is 1 to 10 mol, preferably 2 to 5 mol, per mole of starting compound.

The reaction temperature is generally from 40 to 200 ⁰ C, in particular from 80 to 160 ° C.

The reaction time is usually 0.5 to 64 hours, preferably 1 to 12 hours.

In terms of process technology, it is expedient to proceed by stirring a mixture of starting compound, solvent and base under inert gas at the desired reaction temperature for 0.5 to 24 h and the product of the formula (I) or (Ia) according to the invention, after cooling to room temperature, by addition of a Alcohols, such as ethanol, or precipitated by water from the reaction mixture, filtered off and washed with water.

The purification of the rylene compound according to the invention can be carried out by

Catalyst residues are removed by rapid filtration over silica gel, washed with a halogenated aliphatic hydrocarbon such as methylene chloride. Residues of unreacted starting materials can be purified by column chromatography be removed on silica gel with methylene chloride as eluent or by repeated washing with hexane or pentane.

The yield is generally 90 to 100%.

As a product according to the inventive method for the preparation of pentarylene and Hexarylentetracarbonsäuredimiden diimides of general formula (I) or (Ia)

(I)

(Ia)

or mixtures thereof.

Here, the variables R, R ^A , R 'have the following meaning:

Each R, R ^A independently are the same or different of the following radicals:

Aryloxy, arylthio, hetaryloxy or hetarylthio, to which in each case further saturated or unsaturated 5- to 7-membered rings whose carbon skeleton is represented by one or more groups -O-, -S-, -NR ¹ -, -N = CR ¹ -, -CO-, -SO- and / or -SO ₂ - be interrupted can be fused, wherein the entire ring system may be mono- or polysubstituted by the radicals (i), (ii), (iii), (iv) and / or (v):

(i) C 1 -C ₃₀ -alkyl whose carbon chain is represented by one or more moieties -O-, -S-, -NR ¹ -, -N = CR ¹ -, -C≡C-, -CR ¹ = CR ¹ -, -CO-, -SO- and / or -SO ₂ - may be interrupted and which may be mono- or polysubstituted by: C ¹ -C ₂ -alkoxy, C ₁ -C ₆ -alkylthio, -C≡CR ¹ , -CR ¹ = CR ¹ 2, hydroxy, mercapto, halogen, cyano, nitro, -NR ² R ³ , -NR ² COR ³ , -CONR ² R ³ , -SO ₂ NR ² R ³ , -COOR ² , -SO ₃ R ² , -PR ² R ³ , -POR ² R ³ , aryl and / or saturated or unsaturated C ₄ -C ₇ -CyCl oa I ky I, whose

Carbon skeleton by one or more moieties -O-, -S-, -NR ¹ -, -N = CR ¹ -, -CR ¹ = CR ¹ -, -CO-, -SO- and / or -SO ₂ - be interrupted can, wherein the aryl and cycloalkyl radicals may each be mono- or polysubstituted by d-Ci8-alkyl and / or the above, as substituents for alkyl radicals may be substituted;

(ii) C ₃ -C ₈ -cycloalkyl, whose carbon skeleton is represented by one or more moieties -O-, -S-, -NR ¹ -, -N = CR ¹ -, -CR ¹ = CR ¹ -, -CO-, -SO- and / or -SO ₂ - may be interrupted and to the further saturated or unsaturated 5- to 7-membered rings whose carbon skeleton by one or more groups -O-, -S-, -NR ¹ -, -N = CR ¹ -, - CR ¹ = CR ¹ -, -CO-, -SO- and / or -SO ₂ - may be interrupted, wherein the entire ring system may be monosubstituted or polysubstituted by: Ci ₈ alkyl, _{d-Ci2-alkoxy,} Ci-C ₆ -alkylthio, - C≡CR ^1, -CR ¹ = CR ¹ _2, hydroxyl, mercapto, halogen, cyano, nitro, -NR ² R ^3,

-NR ² COR ³ , -CONR ² R ³ , -SO ₂ NR ² R ³ , -COOR ² , -SO ₃ R ² , -PR ² R ³ and / or - POR ² R ³ ;

(iii) aryl or hetaryl, to which further saturated or unsaturated 5- to 7-membered rings, their carbon skeleton by one or more

Groupings -O-, -S-, -NR ¹ -, -N = CR ¹ -, -CR ¹ = CR ¹ -, -CO-, -SO- and / or -SO ₂ - may be interrupted, be annelated , where the entire ring system may be mono- or polysubstituted by: C _r C ₁₈ alkyl, C _r C ₁₂ alkoxy, C _r C ₆ alkylthio, -C≡CR ^1, -CR ¹ = CR ¹ _2, hydroxyl , Mercapto, halogen, cyano, nitro, -NR ² R ³ , -NR ² COR ³ , -

CONR ² R ³ , -SO ₂ NR ² R ³ , -COOR ² , -SO ₃ R ² , -PR ² R ³ , -POR ² R ³ , aryl and / or hetaryl, each by C _r Ci8-alkyl, d-C ₂ alkoxy, hydroxyl, mercapto, halogen, cyano, nitro, -NR ² R ^3, -NR ² COR ^3, -CONR ² R ^3, - SO ₂ NR ² R ^3, -COOR ^2, -SO ₃ R ² , -PR ² R ³ and / or -POR ² R ³ may be substituted; (iv) a radical -U-aryl which may be monosubstituted or polysubstituted by the abovementioned radicals which are mentioned as substituents for the aryl radicals (iii), where U is a grouping -O-, -S-, -NR ¹ -, -CO-, -SO- or -SO ₂ -;

each R 'is independently hydrogen;

dC ₃ o-alkyl, whose carbon chain is replaced by one or more moieties -O-, -S-, -NR ¹ -, -N = CR ¹ -, -C≡C-, -CR ¹ = CR ¹ -, -CO -, -SO- and / or -SO ₂ - may be interrupted and the mono- or polysubstituted by the substituents mentioned for the radicals R radicals (ii), (iii), (iv) and / or (v) be substituted can;

C ₃ -C ₈ -cycloalkyl to which further saturated or unsaturated 5- to 7-membered rings whose carbon skeleton is replaced by one or more groups -O-, -S-, -NR ¹ -, -N = CR ¹ - , -CR ¹ = CR ¹ -, -CO-, -SO- and / or

-SO ₂ - may be interrupted, be anneliert, wherein the entire ring system by the substituents for the radicals R mentioned radicals (i), (ii), (iii), (iv) and / or (v) may be substituted ; or

Aryl or hetaryl to which further saturated or unsaturated 5- to 7-membered rings, the carbon skeleton by one or more groups -O-, -S-, -NR ¹ -, -N = CR ¹ -, -CR ¹ = CR ¹ -, -CO-, -SO- and / or -SO ₂ - may be interrupted, may be anneliert, wherein the entire ring system may be substituted by the substituents for the radicals R mentioned radicals (i), (ii), (iii), (iv), (v), aryl and / or hetarylazo, each of which may be substituted by C ₁ -C ₁₀ -alkyl, C ₁ -C ₆ -alkoxy and / or cyano.

Here, the variables R ", R ¹ to R ^{2 have} the following meaning:

Each R "is independently hydrogen, C _r C ₃ o-alkyl, C ₅ -C ₈ cycloalkyl, aryl or hetaryl or joined together to form a 5- to 7-membered ring containing the two oxygen atoms and the boron atom to which unsaturated or saturated rings may be annelated and which may be substituted on the carbon atoms by up to 4 Ci-C ₃₀ alkyl, Cs-Cβ-cycloalkyl, aryl or hetaryl groups; R ¹ is hydrogen or C ¹ -C ₁₈ -alkyl, where the radicals R ^{1 may be} identical or different if they occur more than once;

R ² , R ³ are independently hydrogen; C 1 -C 6 -alkyl whose carbon chain may be interrupted by one or more groups -O-, -S-, -CO-, -SO- and / or -SO ₂ - and which is mono- or polysubstituted by CrCl ₂ Alkoxy, C 1 -C ₆ -alkylthio, hydroxy, mercapto, halogen, cyano, nitro and / or - COOR ¹ ; Aryl or hetaryl, to each of which further saturated or unsaturated 5- to 7-membered rings, the carbon skeleton by one or more groups -O-, -S-, -CO- and / or -SO ₂ - may be interrupted, be annelated can, wherein the entire ring system may be mono- or polysubstituted by d-Ci ₂ alkyl and / or the above, as substituents for alkyl radicals may be substituted.

As examples of the radicals R, R ^A , R ', R ", R ¹ to R ³ mentioned in the formulas and their substituents may be mentioned in detail:

Examples of alkyls are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, 2-methylpentyl, heptyl, 1-ethylpentyl,

Octyl, 2-ethylhexyl, isooctyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl (the above designations isooctyl, isononyl, isodecyl and isotridecyl are

Trivial designations and are derived from the alcohols obtained after the oxo process); The numbers given as indices after the symbol "C" refer to the

Minimum and maximum number of C atoms of the alkyls.

Examples of oxygen-interrupted alkyls are 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-isopropoxyethyl, 2-butoxyethyl, 2- and 3-methoxypropyl, 2- and 3-ethoxypropyl, 2- and 3-propoxypropyl, 2- and 3-butoxypropyl, 2- and 4-methoxybutyl, 2- and 4-ethoxybutyl, 2- and 4-propoxybutyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 4,8-dioxanonyl, 3, 7-dioxaoctyl, 3,7-dioxanonyl, 4,7-dioxo-octyl, 4,7-dioxanonyl, 2- and 4-butoxybutyl, 4,8-dioxadecyl, 3,6,9-trioxadecyl, 3,6,9 Trioxaundecyl, 3,6,9-trioxadodecyl, 3,6,9,12-tetraoxatridecyl and 3,6,9,12-tetraoxatetradecyl;

Examples of alkyls interrupted by sulfur are 2-methylthioethyl, 2-ethylthioethyl, 2-propylthioethyl, 2-isopropylthioethyl, 2-butylthio-ethyl, 2- and 3-methylthiopropyl, 2- and 3-ethylthiopropyl, 2- and 3-propylthiopropyl, 2- and 3-butylthiopropyl, 2- and 4-methylthiobutyl, 2- and 4-ethylthiobutyl, 2- and 4-propylthiobutyl, 3,6-dithiaheptyl, 3,6-dithiaoctyl, 4,8-dithianonyl, 3, 7-dithiaoctyl, 3,7-di- thianonyl, 2- and 4-butylthiobutyl, 4,8-dithiadecyl, 3,6,9-trithiadecyl, 3,6,9-trithia-undecyl, 3,6,9-trithiadodecyl, 3,6,9,12-tetrathiatridecyl and 3,6,9,12-tetrathiatetra-decyl;

Examples of alkyls interrupted by amino groups are 2-monomethyl- and 2-monoethylaminoethyl, 2-dimethylaminoethyl, 2- and 3-dimethylaminopropyl, 3-monoisopropylaminopropyl, 2- and 4-monopropylaminobutyl, 2- and 4-dimethylaminobutyl, 6-methyl-3 , 6-diazaheptyl, 3,6-dimethyl-3,6-diazaheptyl, 3,6-di-azaoctyl, 3,6-dimethyl-3,6-diazaoctyl, 9-methyl-3,6,9-triazadecyl, 3 , 6,9-trimethyl-3,6,9-triazadecyl, 3,6,9-triazaundecyl, 3,6,9-trimethyl-3,6,9-triazaundecyl, 12-methyl-3,6,9,12 tetraazatridecyl and 3,6,9,12-tetramethyl-3,6,9,12-tetraazatridecyl;

Further examples of alkyl groups which are interrupted and / or have substituents are

(I-ethylethylidene) aminoethylene, (1-ethylethylidene) aminopropylene, (1-ethylethylidene) aminobutylene, (1-ethylethylidene) aminodecylene and (1-ethylethylidene) aminododecylene;

Propan-2-one-1-yl, butan-3-one-1-yl, butan-3-one-2-yl and 2-ethyl-pentan-3-one-1-yl;

2-Methylsulfoxidoethyl, 2-Ethylsulfoxidoethyl, 2-Propylsulfoxidoethyl, 2-Isopropylsulf- oxidoethyl, 2-Butylsulfoxidoethyl, 2- and 3-Methylsulfoxidopropyl, 2- and 3-Ethylsulf- oxidopropyl, 2- and 3-Propylsulfoxidopropyl, 2- and 3- Butylsulfoxidopropyl, 2- and 4-methylsulfoxidobutyl, 2- and 4-ethylsulfoxidobutyl, 2- and 4-propylsulfoxidobutyl and 4-butylsulfoxidobutyl;

2-methylsulfonylethyl, 2-ethylsulfonylethyl, 2-propylsulfonylethyl, 2-isopropylsulfonyl-ethyl, 2-butylsulfonylethyl, 2- and 3-methylsulfonylpropyl, 2- and 3-ethylsulfonylpropyl, 2- and 3-propylsulfonylpropyl, 2- and 3-butylsulfonylproypl, 2- and 4-methylsulfonylbutyl, 2- and 4-ethylsulfonylbutyl, 2- and 4-propylsulfonylbutyl and 4-butylsulfonylbutyl;

Carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, 5-carboxypentyl, 6-carboxyhexyl, 8-carboxyctyl, 10-carboxydecyl, 12-carboxydodecyl and 14-carboxytetradecyl;

Sulfomethyl, 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, 5-sulfopentyl, 6-sulfohexyl, 8-sulfooctyl, 10-sulfodecyl, 12-sulfododecyl and 14-sulfotetradecyl;

2-hydroxyethyl, 2- and 3-hydroxypropyl, 1-hydroxyprop-2-yl, 3- and 4-hydroxybutyl, 1-hydroxybut-2-yl and 8-hydroxy-4-oxo-octyl; 2-cyanoethyl, 3-cyanopropyl, 3- and 4-cyanobutyl, 2-methyl-3-ethyl-3-cyanopropyl, 7-cyano-7-ethylheptyl and 4-methyl-7-methyl-7-cyanoheptyl;

2-chloroethyl, 2- and 3-chloropropyl, 2-, 3- and 4-chlorobutyl, 2-bromoethyl, 2- and 3-bromopropyl and 2-, 3- and 4-bromobutyl;

2-nitroethyl, 2- and 3-nitropropyl and 2-, 3- and 4-nitrobutyl;

Examples of alkyloxy are methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert. Butoxy, pentoxy, isopentoxy, neopentoxy, tert. Pentoxy and hexoxy;

Examples of alkylthio are methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, sec-butylthio, tert. Butylthio, pentylthio, isopentylthio, neopentylthio, tert-pentylthio and hexylthio;

Examples of triply bonded radicals are ethynyl, 1- and 2-propynyl, 1-, 2- and 3-butynyl, 1-, 2-, 3- and 4-pentynyl, 1-, 2-, 3-, 4- and 4-pentynyl 5-hexynyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8- and 9-decynyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10- and 1-1-dodecynyl and 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 1- 1- , 12-, 13-, 14-, 15-, 16- and 17-octadecinyl;

Examples of radicals having double bond are ethenyl, 1- and 2-propenyl, 1-, 2- and 3-butenyl, 1-, 2-, 3- and 4-pentenyl, 1-, 2-, 3-, 4- and 5-hexenyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8- and 9-decenyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10- and 1-1-dodecenyl and 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11-, 12-, 13-, 14-, 15-, 16- and 17-octadecenyl;

Examples of further radicals are

Methylamino, ethylamino, propylamino, isopryplamino, butylamino, isobutylamino, pentylamino, hexylamino, dimethylamino, methylethylamino, diethylamino, dipropylamino, diisopropylamino, dibutylamino, diisobutylamino, dipentylamino, dihexylamino, dicyclopentylamino, dicyclohexylamino, dicycloheptylamino, diphenylamino and dibenzylamino;

Formylamino, acetylamino, propionylamino and benzoylamino;

Carbamoyl, methylaminocarbonyl, ethylaminocarbonyl, propylaminocarbonyl, butylaminocarbonyl, pentylaminocarbonyl, hexylaminocarbonyl, heptylaminocarbonyl, octylaminocarbonyl, nonylaminocarbonyl, decylaminocarbonyl and phenylaminocarbonyl; Aminosulfonyl, N, N-dimethylaminosulphonyl, N, N-diethylaminosulphonyl, N-methyl-N-ethylaminosulfonyl, N-methyl-N-dodecylaminosulfonyl, N-Dodecylaminosulfonyl, (N ₁ N-dimethylamino) ethylaminosulfonyl, N, N- (propoxyethyl) dodecylaminosulfonyl, N, N-diphenylaminosulfonyl, N, N- (4-tert-butylphenyl) octadecylaminosulfonyl and N, N-bis (4-chlorophenyl) aminosulfonyl;

Methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, hexoxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl, phenoxycarbonyl, (4-tert-butylphenoxy) carbonyl and (4-chlorophenoxy) carbonyl;

Methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, isopropoxysulfonyl, butoxysulfonyl, isobutoxysulfonyl. Butoxysulfonyl, hexoxysulfonyl, dodecyloxysulfonyl, octadecyloxysulfonyl, phenoxysulfonyl, 1- and 2-naphthyloxysulfonyl, (4-tert-butylphenoxy) sulfonyl and (4-chlorophenoxy) sulfonyl;

Diphenylphosphino, di (o-tolyl) phosphino and diphenylphosphine oxido;

Halogens are chlorine, bromine and iodine;

Aryl or hetarylazo are, for example, phenylazo, 2-naphthylazo, 2-pyridylazo and 2-pyrimidylazo;

Optionally substituted cycloalkyls are, for example, cyclopropyl, cyclobutyl, cyclopentyl, 2- and 3-methylcyclopentyl, 2- and 3-ethylcyclopentyl, cyclohexyl, 2-, 3- and 4-methylcyclohexyl, 2-, 3- and 4-ethylcyclohexyl, 3 and 4-propylcyclohexyl, 3- and 4-isopropylcyclohexyl, 3- and 4-butylcyclohexyl, 3- and 4-sec-butylcyclohexyl, 3- and 4-tert-butylcyclohexyl, cycloheptyl, 2-, 3- and 4-methyl cycloheptyl, 2-, 3- and 4-ethylcycloheptyl, 3- and 4-propylcycloheptyl, 3- and 4-isopropylpropylcycloheptyl, 3- and 4-butylcycloheptyl, 3- and 4-sec-butylcycloheptyl, 3- and 4- tert-butylcycloheptyl, cyclooctyl, 2-, 3-, 4- and 5-methylcyclooctyl, 2-, 3-, 4- and 5-ethylcyclooctyl and 3-, 4- and 5-propylcyclooctyl; 3- and 4-hydroxycyclohexyl, 3- and 4-nitrocyclohexyl and 3- and 4-chlorocyclohexyl. The indices indicated by the symbol "C" refer to the minimum and maximum number of C atoms of the cycloalkyls.

Examples of optionally interrupted cycloalkyls are

1-, 2- and 3-cyclopentenyl, 1-, 2-, 3- and 4-cyclohexenyl, 1-, 2- and 3-cycloheptenyl and 1-, 2-, 3- and 4-cyclooctenyl;

2-dioxanyl, 1-morpholinyl, 1-thiomorpholinyl, 2- and 3-tetrahydrofuryl, 1-, 2- and 3-pyrrolidinyl, 1-piperazyl, 1-diketopiperazyl and 1-, 2-, 3- and 4-piperidyl; Optionally condensed and / or substituted and / or interrupted aryl and hetaryl groups should have at least 3 to 14 ring atoms, preferably 5 to 10 ring atoms, and are for example

Phenyl, 2-naphthyl, 2- and 3-pyrryl, 2-, 3- and 4-pyridyl, 2-, 4- and 5-pyrimidyl, 3-, 4- and 5-pyrazolyl, 2-, 4- and 5 -imidazolyl, 2-, 4- and 5-thiazolyl, 3- (1, 2,4-triazyl), 2- (1, 3,5-triazyl), 6-quinaldyl, 3, 5, 6 and 8-quinolinyl, 2-benzoxazolyl, 2-benzothiazolyl, 5-benzothiadiazolyl, 2- and 5-benzimidazolyl and 1- and 5-isoquinolyl;

1-, 2-, 3-, 4-, 5-, 6-, and 7-indolyl, 1-, 2-, 3-, 4-, 5-, 6-, and 7-isoindolyl, 5- (4-methyliso - indolyl), 5- (4-phenylisoindolyl), 1-, 2-, 4-, 6-, 7- and 8- (1,2,3,4-tetrahydroisoquinolinyl), 3- (5-phenyl) - ( 1, 2,3,4-tetrahydroisoquinolinyl), 5- (3-dodecyl- (1,2,3,4-tetrahydroisoquinolinyl), 1-, 2-, 3-, 4-, 5-, 6-, 7- and 8- (1,2,3,4-tetrahydroquinolinyl) and 2-, 3-, 4-, 5-, 6-, 7- and 8-chromanyl, 2-, 4- and 7-quinolinyl, 2 - (4-phenylquinolinyl) and 2- (5-ethyl-quinolinyl);

2-, 3- and 4-methylphenyl, 2,4-, 3,5- and 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2-, 3- and 4-ethylphenyl, 2,4-, 3 , 5- and 2,6-diethylphenyl, 2,4,6-triethylphenyl, 2-, 3- and 4-propylphenyl, 2,4-, 3,5- and 2,6-dipropylphenyl, 2,4,6- Tripropylphenyl, 2-, 3- and 4-isopropylphenyl, 2,4-, 3,5- and 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, 2-, 3- and 4-butylphenyl, 2,4- , 3,5- and 2,6-dibutylphenyl, 2,4,6-tributylphenyl, 2-, 3- and 4-isobutylphenyl, 2,4-, 3,5- and 2,6-diisobutylphenyl, 2,4, 6-triisobutylphenyl, 2-, 3- and 4-sec-butylphenyl, 2,4-, 3,5- and 2,6-di-sec-butylphenyl and 2,4,6-tri-sec-butyl-phenyl; 2-, 3- and 4-methoxyphenyl, 2,4-, 3,5- and 2,6-dimethoxyphenyl, 2,4,6-trimethoxyphenyl, 2-, 3- and 4-ethoxyphenyl, 2,4- , 3,5- and 2,6-diethoxyphenyl, 2,4,6-triethoxyphenyl, 2-, 3- and 4-propoxyphenyl, 2,4-, 3,5- and 2,6-dipropoxyphenyl, 2-, 3 and 4-isopropoxyphenyl, 2,4- and 2,6-diisopropoxyphenyl and 2-, 3- and 4-butoxyphenyl; 2-, 3- and 4-chlorophenyl and 2,4-, 3,5- and 2,6-dichlorophenyl; 2-, 3- and 4-hydroxyphenyl and 2,4-, 3,5- and 2,6-dihydroxyphenyl; 2-, 3- and 4-cyanophenyl; 3- and 4-carboxyphenyl; 3- and 4-carboxamidophenyl, 3- and 4-N-methylcarboxamidophenyl and 3- and 4-N-ethylcarboxamidophenyl; 3- and 4-acetylaminophenyl, 3- and 4-propionylaminophenyl and 3- and 4-butyluraminophenyl; 3- and 4-N-phenylamino-phenyl, 3- and 4-N- (o-tolyl) aminophenyl, 3- and 4-N- (m-tolyl) aminophenyl and 3- and 4- (p-tolyl) aminophenyl ; 3- and 4- (2-pyridyl) aminophenyl, 3- and 4- (3-pyridyl) aminophenyl, 3- and 4- (4-pyridyl) aminophenyl, 3- and 4- (2-pyrimidyl) aminophenyl and 4- (4-pyrimidyl) aminophenyl;

4-phenylazophenyl, 4- (1-naphthylazo) -phenyl, 4- (2-naphthylazo) -phenyl, 4- (4-naphthyl-azo) -phenyl, 4- (2-pyrylazo) -phenyl, 4- (3-pyridyl-azo) -phenyl , 4- (4-Pyridylazo) phenyl, 4- (2-pyrimidylazo) phenyl, 4- (4-pyrimidylazo) phenyl and 4- (5-pyrimidylazo) phenyl; Phenoxy, phenylthio, 2-naphthoxy, 2-naphthylthio, 2-, 3- and 4-pyylindyloxy, 2-, 3- and 4-pyridylthio, 2-, 4- and 5-pyrimidyloxy and 2-, 4- and 5- pyrimidylthio.

The diimides of the general formulas (I) and (Ia) or mixtures thereof according to the invention are preferably those in which R and R ^{A have} the same meaning.

The diimides of the general formulas (I) and (Ia) or mixtures thereof according to the invention are likewise preferably those in which R, R ^{A are,} independently of one another, aryloxy or arylthio, the entire ring system being mono- or polysubstituted by Radicals (i), (ii), (iii), (iv) and / or (v) may be substituted as indicated above. It is particularly preferred if R, R ^A can be mono- or poly-substituted by a radical (i) independently of one another.

Likewise preferably, the diimides of the general formulas (I) and (Ia) or mixtures thereof according to the invention are those in which R, R ^{A are} independently of one another

in which

X is O or S is and

R ⁴ , R ⁵ , R ⁶ independently of one another may be hydrogen or the radicals (i), (ii), (iii), (iv) and / or (v) as specified above, with the proviso that at least one of the radicals R ⁴ , R ^{6 is} not hydrogen. Particularly preferred is that when R ^{4 is} C 15 C ₃₀ alkyl or C ₃ C ₈ cycloalkyl, no ternary carbon atom occurs at the 1 position.

It is further preferred that both R ^{4 are} not hydrogen and R ⁵ , R ^{6 is} hydrogen or that R ^{6 is} not hydrogen and R ⁴ , R ^{5 are} hydrogen.

Likewise preferably, the diimides of the general formulas (I) and (Ia) or mixtures thereof according to the invention are those in which each R 'independently of one another is C 1 -C ₃₀ -alkyl or aryl, where the entire ring system is mono- or polysubstituted by the radicals (i), (ii), (iii), (iv) and / or (v) as indicated above, may be substituted. Particularly preferably, R 'is monosubstituted or polysubstituted by a radical (i). Also preferably, all R 'are the same.

The diimides of the general formula (I) and (Ia) according to the invention exhibit strong absorption in the infrared range at wavelengths from 700 to 1100 nm. Their functionalization can be selected in a targeted manner so that they can be adapted directly to the desired intended use.

They are useful in a variety of applications such as the coloring of high molecular weight organic and inorganic materials, e.g. of paints, printing inks and plastics, for the production in the near infrared region of the electromagnetic spectrum of absorbing aqueous polymer dispersions, for the production of invisible to the human eye, infrared absorbing markers and labels, as infrared absorbers for thermal management, as IR Iaserstrahlen absorbing materials in the welding treatment of Plastic parts, as semiconductors in organic electronics, as emitters in electro- and chemiluminescence applications as well as active components in photovoltaics.

Examples

example 1

Preparation of N- (2,6-Diisopropylphenyl-1, 6,11,15-tetra [4- (1,1,3,3-tetramethylbutyl) phenoxy] -13- (4- [N- (2,6 -diisopropylphenyl)] - naphthalene-1, 8-dicarboxylic acid imide) quaterrylene-3,4-dicarboxylic acid imide

To a N2 stirred mixture of 0.028 g (0.058 mmol) N- (2,6-diisopropylphenyl-4- (4,4,5,5-tetramethyl-1,2,3-dioxaboran-2-yl) -naphthalene 1,8-dicarboxylic acid imide and 0.07 g (0.044 mmol) of N- (2,6-diisopropylphenyl-1,6,11,15-tetra [4- (1,1,3,3-tetramethylbutyl) -phenoxy ] -13-cholro-quaterrylene-3,4-dicarboximide in 15 ml of toluene were first treated with a solution of 0.042 g (0.3 mmol) of potassium carbonate in 2 ml of water and then 0.01 g (0.004 mmol) of palladium (II) - acetate and 0.36 g (0.009 mmol) of 2-dicyclohexylphosphino-2,6-dimethoxybiphenyl The mixture was heated to 85 ° C. under N 2 and stirred at this temperature for 24 hours After cooling to room temperature, the organic phase was separated off and the solvent removed in vacuo The crude product was subjected to column chromatography on silica gel with a 1: 1 mixture of methylene chloride and hexane as eluent.

25 mg of product were obtained in the form of a green solid, which corresponds to a yield of 31%. Analytical data:

UV-Vis (CHCl3): λmax = 759 nm;

MS (Maldi): m / z (rel. Int.) = 1900.9 (100%) [M +].

Example 2

Cyclodehydration to N, N'-bis (2,6-diisopropylphenyl) -1,6,11,20-tetra [4- (1,1,3,3-tetramethylbutyl) phenoxy] pentarylene-3,4: 15,16 -tetracarbonsäuredimid

A mixture of 0.05 g (0.03 mmol) product from Example 1, 0.12 g (0.86 mmol) Ka liumcarbonat and 2.0 ml of ethanolamine, and 1, 0 ml Deiethylglycoldientylether was heated to 120 ⁰ C under a nitrogen atmosphere heated. After 24 h, much of the starting material was observed by means of TLC. After 64 h, starting material was completely converted.

After cooling, the reaction product was precipitated onto water, filtered off, washed with hot water and finally with hexane until the effluent became colorless. The residue was subjected overnight to Soxleth extraction with hexane. The product was dried in vacuo at 70 ⁰ C.

There were obtained 0.03 g of product in the form of a black-green solid, which corresponds to a yield of 60%.

Analytical data:

UV-Vis (CHCl3): λmax = 863, 777 nm;

MS (Maldi): m / z (rel. Int.) = 1899.2 (100%) [M +].

Example 3

Preparation of N- (2,6-Diisopropylphenyl-1, 6, 8, 11, 15, (17) 18-hexa [4- (1,1,3,3-tetramethylbutyl) -phenoxy] -13- (4- [N- (2,6-diisopropylphenyl)] - naphthalene-1, 8-dicarboxylic acid imide) quaterrylene-3,4-dicarboxylic acid imide

To a N2 stirred mixture of 0.03 g (0.06 mmol) N- (2,6-diisopropylphenyl-4- (4,4,5,5-tetramethyl-1,3,2-dioxaboran-2-yl) naphthalene-1,8-dicarboximide and 0.10 g (0.052 mmol) of N- (2,6-diisopropylphenyl-1, 6, 8, 1, 15, (17), 18-penta [4- (1,1 , 3,3-tetramethylbutyl) -phenoxy] -13-cholro-quaterrylene-3,4-dicarboxylic acid imide in 15 ml of toluene were first a solution of 0.042 g (0.3 mmol) of potassium carbonate in 2 ml of water and then 0.01 g (0.004 mmol) of palladium (II) acetate and 0.36 g (0.009 mmol) of 2-dicyclohexylphosphino-2,6-dimethoxybiphenyl. The mixture was heated to 85 ° C under N 2 and stirred at this temperature for 24 h. After cooling to room temperature, the organic phase was separated and the solvent removed in vacuo. The crude product was subjected to a column chromatography on silica gel with a 1: 1 mixture of methylene chloride and hexane as eluent.

There were obtained 25 mg of product in the form of a green solid, which corresponds to a yield of 21%.

Analytical data:

UV-Vis (CH 2 Cl 2): λ max = 760 nm; MS (Maldi): m / z (rel. Int.) = 2310.9 (100%) [M +].

Example 4

Cyclodehydration to N, N'-bis (2,6-diisopropylphenyl) -1, 6,8,11, 20, (22) 23-hexa [4- (1,1,3,3-tetramethylbutyl) phenoxy] pentarylene 3,4: 15,16-tetracarbonsäuredimid

A mixture of 0.05 g (0.038 mmol) of Example 3, 0.12 g (0.86 mmol) of potassium carbonate and 2.0 ml of ethanolamine, and 1, 0 ml Deiethylglycoldientylether was heated to 120 ⁰ C under a nitrogen atmosphere. After 24 h, much of the starting material was observed by means of TLC. After 64 h, starting material was completely converted.

After cooling, the reaction product was precipitated onto water, filtered off, washed with hot water and finally with hexane until the effluent became colorless. The residue was subjected overnight to Soxleth extraction with hexane. The product was dried in vacuo at 70 ⁰ C domestic product.

There were obtained 0.027 g of product in the form of a black-green solid, which corresponds to a yield of 55%.

UV-Vis (CH 2 Cl 2): λ max = 865, 779 nm;

MS (Maldi): m / z (rel. Int.) = 2309.1 (100%) [M +]. Example 5

Preparation of N- (2,6-Diisopropylphenyl-1,1,1,1,1-tetra [4- (1,1,3,3-tetramethylbutyl) -phenoxy] -13- (9- [N- (2, 6-diisopropylphenyl)] - 1,6-bis [4- (1,1,3,3-tetramethylbutyl) phenoxy] perylene-3,4-dicarboxylic acid imide) quaterrylene-3,4-dicarboxylic acid imide

To a N2 stirred mixture of 0.059 g (0.058 mmol) N- (2,6-diisopropylphenyl-1,6-bis [4- (1,1,3,3-tetramethylbutyl) -phenoxy] -9- (4, 4,5,5-tetramethyl-1,3,2-dioxaboran-2-yl) -prerylene-3,4-dicarboxylic acid imide and 0.07 g (0.044 mmol) N- (2,6-diisopropylphenyl-1, 6, 1,1-Tetra [4- (1,1,3,3-tetramethylbutyl) -phenoxy] -13-cholroquaterrylene-3,4-dicarboximide in 15 ml toluene was first treated with a solution of 0.042 g (0.3 mmol) of potassium carbonate in 2 ml of water and then 0.01 g (0.004 mmol) of palladium (II) acetate and 0.36 g (0.009 mmol) of 2-dicyclohexylphosphino-2,6-dimethoxybiphenyl were added After cooling to room temperature, the organic phase was separated and the solvent removed in vacuo, The crude product was subjected to column chromatography on silica gel with a 1: 1 mixture of methylene chloride and hexane as the eluent ,

There were obtained 30 mg of product in the form of a black-green solid, which corresponds to a yield of 28%.

Analytical data:

UV-Vis (CH 2 Cl 2): λ max = 757, 528 nm;

MS (Maldi): m / z (rel. Int.) = 2433.2 (100%) [M +].

Example 6

Cyclodehydration to N, N'-bis (2,6-diisopropylphenyl) -1, 6,10,15,20,25-hexa [4- (1,1,3,3-tetramethylbutyl) phenoxy] hexarylene-3,4 : 17,18-tetracarbonsäuredimid

A mixture of 0.05 g (0.03 mmol) liumcarbonat product from Example 5, 0.12 g (0.86 mmol) Ka and 2.0 mL ethanolamine and 1, 0 mL was heated to 120 ⁰ C under a nitrogen atmosphere , After 24 h, much of the starting material was observed by means of TLC. After 64 h, starting material was completely converted.

After cooling, the reaction product was precipitated onto water, filtered off, washed with hot water and finally with hexane until the effluent became colorless. the Overnight residue was subjected to Soxleth extraction with hexane. The product was dried in vacuo at 70 ⁰ C.

There were obtained 0.031 g of product in the form of a blue-green solid, which corresponds to a yield of 60%.

Analytical data:

UV-Vis (CH 2 Cl 2): λ max = 942, 841 nm; MS (Maldi): m / z (rel. Int.) = 2431, 5 (100%) [M +].

IR (KBr): v (cm-1) = 2958, 2360, 2342, 1703, 1668, 1589, 1567, 1537, 1503, 1472, 1409, 1364, 1320, 1279, 1211, 1 179, 1105, 1056, 875 , 837;

Example 7

Preparation of N- (2,6-diisopropylphenyl-1,6,9,14-tetra [2,6-diisopropylphenoxy] -1-1- (1 1 - [N- (2,6-diisopropylphenyl)] - 1, 6 bis [2,6-diisopropylphenoxy] terrylene-3,4-dicarboxylic acid imide) terrylene-3,4-dicarboxylic acid imide

A mixture of 0.47 g (0.33 mol) of N- (2,6-diisopropylphenyl-1,6,9,14-tetra (2,6-diisopropylphenoxy) -1 1 - (4,4,5,5 -tetramethyl-1,3,2-dioxaboran-2-yl) -terrenylene-3,4-dicarboxylic acid imide, 0.41 g (0.30 mmol) of N- (2,6-diisopropylphenyl-1, 6, 9, 14 tetra (2,6-diisopropylphenoxy) -1-bromo-terrylene-3,4-dicarboximide and 25 ml of toluene were stirred at room temperature under N 2, and after 10 min, 0.035 g (0.030 mmol) of Pd (PPh 3) 4 and 0 , 3 g of potassium carbonate in the 5.5 ml of water and ethanol (10: 1), then the mixture was heated to 85 ° C under N 2 and stirred for 72 hours at this temperature.

The cooled reaction mixture was subjected to column chromatography on silica gel with CHCl 3: ethyl acetate (19: 1) as eluent.

There were obtained 0.43 g of product, which corresponds to a yield of 53%.

Analytical data:

1 H-NMR: (500 MHz, CD2CI2, 25 ⁰ C): δ = 9.8 (d, 4H), 9.5 (d, 4H), 7.85 (s, 4H), 7.8 -7 , 1 (m, 36 H), 3.15 (m, 16H), 2.6 (m, 4H), 1, 4-0.9 (m 120 H) UV-Vis (CHCl 3): λ max (ε) = 698 (163,000) (M-1 cm-1); MS (Maldi): m / z (rel. Int.) = 2617.3 (100%) [M +]. Example 8

Cyclodehydration to N, N'-bis (2,6-diisopropylphenyl) -1, 6,9,12,15,20,23,26-octa (2,6-diisopropylphenylphenoxy) hexarylene-3,4: 17,18 -tetracarbonsäuredimid

A mixture of 0.210 g (0.080 mmol) of product from Example 7, 0.610 g (4.4 mmol) of potassium carbonate and 10 ml of ethanolamine was heated to 120 ⁰ C under nitrogen atmosphere. After 24 h, much of the starting material was observed by means of TLC. After 64 h, starting material was completely converted.

There were obtained 0.131 g of product in the form of a green solid, which corresponds to a yield of 63%.

Analytical data:

UV-Vis (CHCl3): λmax = 973, 862 nm;

MS (Maldi): m / z (rel. Int.) = 2615.5 (100%) [M +].

Claims

claims

1. A process for the preparation of Pentarylen- and Hexarylentetracarbonsäurediimi- the containing the steps

with at least one compound of the formula (III) or (IIIa)

in which

Y, Y ^{1 are} both halogen or one of Y, Y ^{1 is} halogen and the other B is (OR ") ₂ ; Each R, R ^{A is} independently the same or different of the following radicals:

Aryloxy, arylthio, hetaryloxy or hetarylthio, to which in each case further saturated or unsaturated 5- to 7-membered rings, the carbon skeleton by one or more groups -O-, -S-, -NR ¹ -, -N = CR ¹ -, -CO-, -SO- and / or -SO ₂ - may be fused, wherein the entire ring system one or more times by the radicals (i), (ii), (iii), (iv) and / or (v) may be substituted:

(i) C ¹ -C 30 -alkyl whose carbon chain is represented by one or more moieties -O-, -S-, -NR ¹ -, -N = CR ¹ -, -OC-, -CR ¹ = CR ¹ -, -CO -, -SO- and / or -SO ₂ - may be interrupted and may be mono- or polysubstituted by d-C ₂ alkoxy, Ci-C ₆ alkylthio, -C≡CR ^1, -CR ¹ = CR ¹ ₂ , hydroxy, mercapto, halogen, cyano, nitro, -NR ² R ³ ,

-NR ² COR ³ , -CONR ² R ³ , -SO ₂ NR ² R ³ , -COOR ² , -SO ₃ R ² , -PR ² R ³ , -POR ² R ³ , aryl and / or saturated or unsaturated C ₄ -C ₇ -cycloalkyl, whose carbon skeleton is represented by one or more moieties -O-, -S-, -NR ¹ -, -N = CR ¹ -, -CR ¹ = CR ¹ -, -CO-, -SO- and / or -SO ₂ - may be interrupted, wherein the aryl and cycloalkyl radicals may each be monosubstituted or polysubstituted by C 1 -C ₈ -alkyl and / or the abovementioned radicals mentioned as substituents for alkyl;

(ii) C ₃ -C ₈ -cycloalkyl, whose carbon skeleton is represented by one or more moieties -O-, -S-, -NR ¹ -, -N = CR ¹ -, -CR ¹ = CR ¹ -, -CO-, -SO- and / or -SO ₂ - may be interrupted and to the further saturated or unsaturated 5- to 7-membered rings whose carbon skeleton by one or more groups -O-, -S-, -NR ¹ -, -N = CR ¹ -, - CR ¹ = CR ¹ -, -CO-, -SO- and / or -SO ₂ - may be interrupted, may be annelated, wherein the entire ring system may be mono- or polysubstituted by: dC ^ -alkyl, C ₁ -C ₂ -alkoxy, -C ₆ -alkylthio, - C≡CR ^1, -CR ¹ = CR ¹ _2, hydroxyl, mercapto, halogen, cyano, nitro, -NR ² R ^3, -NR ² COR ³ , -CONR ² R ³ , -SO ₂ NR ² R ³ , -COOR ² , -SO ₃ R ² , -PR ² R ³ and / or - POR ² R ³ ;

(iii) aryl or hetaryl, to which further saturated or unsaturated 5- to 7-membered rings whose carbon skeleton is replaced by one or more moieties -O-, -S-, -NR ¹ -, -N = CR ¹ -, -CR ¹ = CR ¹ -, -CO-, -SO- and / or -SO ₂ - may be interrupted, the entire ring system may be mono- or polysubstituted by: C _r Ci ₈ alkyl, C _r C ₁₂ alkoxy, C _r C ₆ alkylthio, -C≡CR ¹ , -CR ¹ = CR ¹ ₂ , Hydroxy, mercapto, halogen, cyano, nitro, -NR ² R ³ , -NR ² COR ³ , -CONR ² R ³ , -SO ₂ NR ² R ³ , -COOR ² , -SO ₃ R ² , -PR ² R ^3, -POR ² R ^3, aryl and / or hetaryl, each of d-Ci ₈ alkyl, d-C ₂ alkoxy, hydroxyl, mercapto, halogen, cyano, nitro, -NR ² R ^3, -NR ² COR ^3, -CONR ² R ^3, - SO ₂ NR ² R ^3, -COOR ^2, -SO ₃ R ^2, -PR ² R ³ and / or -POR ² R ³ may be substituted;

(iv) a radical -U-aryl which may be monosubstituted or polysubstituted by the abovementioned radicals which are mentioned as substituents for the aryl radicals (iii), where U is a grouping -O-, -S-, -NR ¹ -, -CO-, -SO- or -SO ₂ -;

(v) C _r C ₂ alkoxy, Ci-C ₆ alkylthio, -C≡CR ^1, -CR ¹ = CR ¹ _2, hydroxyl, mercapto, halogen, cyano, nitro, -NR ² R ^3, -NR ² COR ^3, -CONR ² R ^3, - SO ₂ NR ² R ^3, -COOR ^2, -SO ₃ R ^2, -PR ² R ³ and / or -POR ² R ^3;

each R 'is independently hydrogen;

C 1 -C ₃₀ -alkyl whose carbon chain is replaced by one or more groupings -O-, -S-, -NR ¹ -, -N = CR ¹ -, -C≡C-, -CR ¹ = CR ¹ - , -CO-, -SO- and / or -SO ₂ - may be interrupted and the one or more times by the radicals mentioned as substituents for the radicals R (ii), (iii), (iv) and / or (v ) may be substituted;

Aryl or hetaryl to which further saturated or unsaturated 5- to 7-membered rings, the carbon skeleton by one or more groups -O-, -S-, -NR ¹ -, -N = CR ¹ -, -CR ¹ = CR ¹ -, -CO-, -SO- and / or -SO ₂ - may be interrupted, may be anneliert, wherein the entire ring system may be substituted by the substituents for the radicals R mentioned radicals (i), (ii), (iii), (iv), (v), aryl and / or hetarylazo, each of which may be substituted by C ₁ -C 10 -alkyl, C ₁ -C ₆ -alkoxy and / or cyano; each R "independently of one another is hydrogen, C 1 -C ₃ -alkyl, C ₅ -C ₈ -cycloalkyl, aryl or hetaryl or linked together to form a 5- to 7-membered ring containing the two oxygen atoms and the boron atom, to the unsaturated or saturated rings can be annelated and that at the carbon atoms by up to 4

C 1 -C ₃₀ alkyl, C ₅ -C ₈ cycloalkyl, aryl or hetaryl groups may be substituted;

R, ¹ is hydrogen or Ci-C ₈ alkyl, where the radicals R ¹ may be the same or comparable eliminated if they occur several times;

R ² , R ^{3 are} independently hydrogen;

C 1 -C ₈ -alkyl whose carbon chain may be interrupted by one or more groups -O-, -S-, -CO-, -SO- and / or -SO ₂ - and which is mono- or polysubstituted by C 1 -C ₁₂ - Alkoxy, C ₁ -C ₆ -alkylthio, hydroxy,

Mercapto, halogen, cyano, nitro and / or -COOR ¹ may be substituted;

Aryl or hetaryl, to which in each case further saturated or unsaturated 5- to 7-membered rings, the carbon skeleton by one or more

Groupings -O-, -S-, -CO- and / or -SO ₂ - may be interrupted, wherein the entire ring system is mono- or polysubstituted by d-Ci ₂ alkyl and / or the above, as substituents may be substituted for alkyl radicals;

and wherein m, m1, n, n1 satisfy at least one of the following conditions:

m = 1, m1 = 0 and n, n1 are integers whose sum gives a number from 5 to 8;

m = 1, m1 = 1 and n, n1 are integers whose sum is a number of

5 to 12 results;

m = 2, m1 = 0 and n, n1 are integers whose sum gives a number from 0 to 12; (b) Cyclodehydration of the reaction product obtained in step (a) to give a rylene compound of general formula (I) or (Ia)

(I)

(Ia) or mixtures thereof.

2. The method according to claim 1, characterized in that m = 2.

3. Pentarylentetracarbonsäurediimid the general formula (I) or mixtures thereof, wherein n and n1 are integers whose sum gives a number from 5 to 8 and R, R ^A , R ', m, m1 have the meaning given in claim 1.

4. Pentarylentetracarbonsäurediimid the general formula (Ia) or mixtures thereof, wherein n and n1 are integers whose sum gives a number from 5 to 8 and R, R ^A , R ', m have the meaning given in claim 1.

5. Hexarylenetetracarboxylic acid diimide of the general formula (I) or mixtures thereof, wherein n and n1 are integers whose sum gives a number from 5 to 12 and R, R ^A , R ', m, m1 have the meaning given in claim 1.

6. Diimide or mixtures thereof according to one of claims 3 to 5, characterized in that R and R ^{A have} the same meaning.

7. Diimide or mixtures thereof according to one of claims 3 to 6, characterized in that R, R ^A are each independently aryloxy or arylthio, the entire ring system being mono- or polysubstituted by the radicals (i), (ii), (iii), (iv) and / or (v) as specified in claim 1 may be substituted.

8. Diimide or mixtures thereof according to claim 7, characterized in that R, R ^A independently of one another or more times by a radical (i) may be substituted.

9. Diimide or mixtures thereof according to claim 7 or 8, characterized in that R, R ^A independently

are,

in which

X is O or S is and

R ⁴ , R ⁵ , R ⁶ independently of one another may be hydrogen or the radicals (i), (ii), (iii), (iv) and / or (v) as specified in claim 1, with the proviso that at least one of Radicals R ⁴ , R ^{6 is} not hydrogen.

10. A diimide according to claim 9, characterized in that when R ^{4 is} C ₁ -C 30 alkyl or C ₃ -C 8 cycloalkyl, no ternary carbon atom occurs in the 1-position.

1 1. Diimide or mixtures thereof according to claim 9 or 10, marked thereby, that both R ^{4 are} not hydrogen and R ⁵ , R ^{6 is} hydrogen or that R ^{6 is} not hydrogen and R ⁴ , R ^{5 are} hydrogen.

12. Diimide or mixtures thereof according to one of claims 3 to 11, characterized in that each R 'independently of one another is C ₁ -C 30 -alkyl or aryl, where the entire ring system is mono- or polysubstituted by the radicals (i), (ii) , (i-ii), (iv) and / or (v) as specified in claim 1 may be substituted.

13. Diimide or mixtures thereof according to claim 12, characterized in that R 'is mono- or polysubstituted by a radical (i).

14. Use of a diimide or mixtures thereof according to any one of claims 3 to 13 for coloring high molecular weight organic and inorganic materials, as a dispersing aid and pigment additives for organic pigments, for production in the near-infrared region of the electromagnetic spectrum of absorbing aqueous polymer dispersions, for the production of the human eye non-visible, infrared-absorbing markers and labels, as infrared absorbers for thermal management, as IR laser-absorbing materials in the welding treatment of plastic parts, as semiconductors in organic electronics, as emitters in electro- and chemiluminescence applications or as an active component in photovoltaics.