EP1819678A1

EP1819678A1 - Rylene tetracarboxylic acid diimides substituted by cyclic amino groups

Info

Publication number: EP1819678A1
Application number: EP05810887A
Authority: EP
Inventors: Martin KÖNEMANN; Jianqiang Qu; Klaus MÜLLEN
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2004-11-29
Filing date: 2005-11-26
Publication date: 2007-08-22
Also published as: KR20070090200A; DE102004057585A1; WO2006058674A1; US20090124732A1; JP2008521766A; CN101068790A

Abstract

The invention relates to rylene tetracarboxylic acid diimides of general formula (I). The invention also relates to the production of said rylene tetracarboxylic acid diimides and to the use thereof for colouring organic and inorganic materials, in particular lacquers, printing inks and plastic materials, as a dispersing auxiliary agent and pigment additive for organic pigments, for producing aqueous polymer dispersions which can be absorbed in the close infrared area of the electromagnetic spectrum, in the production of markings and inscriptions which absorb infrared light and which are invisible to the human eye and as infrared absorbers for heat management.

Description

Rylenetetracarboxylic diimides substituted by cyclic amino groups

description

The present invention relates to novel Rylenetetracarbonsäurediimide of the general formula I.

in which the variables have the following meaning:

R ₁ R 'independently of one another: hydrogen; (1) CrC 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 which may be monosubstituted or polysubstituted by:

(i) C ₁ -C ₁₂ -alkoxy ₁ -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 and / or -SO ₃ R ² ;

(ii) aryl or hetaryl to which are 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, wherein the entire ring system may be monosubstituted or polysubstituted by: Ci-dβ-alkyl, C ₁ - Ci ₂ -alkoxy,

C ¹ -C 6 -alkylthio, -C = CR ¹ , -CR ¹ = CR ¹ _2L, 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 , 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 and / or -SO ₃ R ² may be substituted;

(iii) 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, be anneliert, wherein the entire ring system may be mono- or polysubstituted by: C _r C ₁₈ alkyl, C ₁ - C ₁₂ -Akoxy, CrCe-alkylthio, -CsCR 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 and / or -SO ₃ R ² ;

(iv) a radical -U-aryl which may be monosubstituted or polysubstituted by the abovementioned radicals which are mentioned as substituents for the aryl radicals (ii), where U is a grouping -O-, -S-, -NR ¹ -, -CO-, -SO- or -SO ₂ -; (2) 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 moieties -O-, -S-, -NR ¹ -, -N = CR ¹ -, -CR ¹ = CR ¹ -, -CO-, -SO- and / or -SO ₂ - may be interrupted, which may be fused, where the entire ring system may be mono- or polysubstituted by: the radicals (i), (ii), (iii), (iv) and / or (v) Ci-Cso-alkyl, the carbon chain by one or more -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 ₁₂ -Akoxy ₁ 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 , 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 a - or may be substituted several times by C ₁ - C ₁₈ -alkyl and / or the above radicals mentioned as substituents for alkyl; (3) 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 -, -CsC -, -CR ¹ = CR ¹ -, -CO-, -SO- and / or -SO ₂ - may be interrupted, which may be fused, where the entire ring system may be substituted by the radicals (i), (ii), (iii), (iv), (v) and / or aryl and / or hetarylazo, each represented by C ₁ -C ₁₀ -alkyl, C ₁ -C ₆ -

Alkoxy and / or cyano may be substituted; 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; CrC ₁₈ alkyl, whose carbon chain is represented by one or more moieties

-O-, -S-, -CO-, -SO- and / or -SO ₂ - may be interrupted and the one or more times by C ₁ -C ₁₂ -Akoxy ₁ C _r 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, whose carbon skeleton may be interrupted by one or more groups -O-, -S-, -CO- and / or -SO ₂ - be annelated can, with the entire ring system one or more times by C ₁ -Ci ₂ - Alkyl and / or the above, as substituents for alkyl mentioned radicals can be substituted;

A is a nitrogen-bonded 5 to 9-membered ring whose carbon chain may be interrupted by one or more moieties -O-, -S-, -NR ¹ -, -CO- and / or -SO ₂ -, to the one or two unsaturated or saturated 4- to 8-membered rings may be annelated whose carbon chain may also be interrupted by these groups and / or -N =, where the entire ring system may be mono- or polysubstituted by: hydroxy, nitro, -NHR ² , carboxy, -COOR ² , -CONR ² R ³ or -NR ² COR ³ ;

C 1 -C ₃₀ -alkyl whose carbon chain may be interrupted by one or more groups -O-, -S-, -NR ¹ -, -CO- and / or -SO ₂ - and which may be interrupted by cyano, hydroxy, nitro, C ₁ -C ₆ -alkoxy, -COOR ^2, -CONR ² R ^3, aryl substituted by C ₁ - ₁ -C ₆ -alkoxy can be substituted C ₁₈ alkyl or C, and / or bonded via a nitrogen atom 5- to 7-membered heterocyclic radical containing further heteroatoms and may be aromatic, mono- or polysubstituted;

C ₅ -C ₈ -cycloalkyl whose carbon skeleton may be interrupted by one or more groups -O-, -S- and / or -NR ¹ - and / or which may be mono- or polysubstituted by C ¹ -C ₆ -alkyl;

Aryl or hetaryl, each by CrC ₁₈ alkyl, Ci-C ₆ alkoxy, cyano, nitro, halogen, -CONR ² R ³ , -NR ² COR ³ , -SO ₂ NR ² R ³ and / or aryl or Hetarylazo, which may be substituted in each case by C ₁ -C ₁₀ -AIRyI, C ₁ -C ₆ -alkoxy or cyano, may be mono- or polysubstituted, and where the radicals A may be the same or different for m>1;

X is chlorine or bromine, where the radicals X may be the same or different for x> 1;

ZC ₃ -C ₂₀ -alkyl, C ₃ -C ₂₀ -alken-2-yl or C ₃ -C ₂ o-alkyn-2-yl, whose alkyl chain is in each case represented by one or more groups -O-, -S-, - NR ¹ -, -CO- and / or -SO ₂ - may be interrupted and by cyano, C ₁ -C ₆ -alkoxy, -COOR ² ,

-CONR ² R ³ , aryl which may be substituted by C ₁ -C ₁₈ -alkyl or C ₁ -C ₆ -alkoxy, and / or a 5- to 7-membered heterocyclic radical bonded via a nitrogen atom and containing further heteroatoms may be aromatic, mono- or polysubstituted; 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 annelated, the entire ring system being mono- or polysubstituted by the alkyl radicals (1), cycloalkyl radicals (2), aryl radicals mentioned for R and R ' or hetaryl radicals (3) and / or the radicals (i) and / or (iv) mentioned therein, where the radicals Z may be the same or different for z>1; m is 1 or 2; n 1 to 4 for m = 1;

1 to 6 for m = 2; x 0 to 3 for m = 1, where n + x + z <4; 0 to 5 for m = 2, where n + x + z <6; z o to 3 for m = 1, where n + x + z <4;

O to 5 for m = 2, where n + x + z <6.

Furthermore, the invention relates to the preparation of these Rylenetetracarbonsäurediimide and their use for coloring organic and inorganic materials, in particular paints, printing inks and plastics, as dispersants and pigment additives for organic pigments, for production in the near-infrared region of the electromagnetic spectrum absorbing aqueous polymer dispersions, for the production of the human eye of invisible infrared-absorbing markers and labels and as an infrared absorber for thermal management.

The higher rylenetetracarboxylic diimides (referred to below as "rylenimides" for short) are known to be of particular application-related interest because of their strong absorption in the near-infrared region of the electromagnetic spectrum. For example, WO-A-02/77081 describes the use of quaterrylenetetracarboxylic diimides as infrared absorbers for thermal protection in glass laminates.

In addition to the unsubstituted in the rylene skeleton Rylenimiden based on terrylene and quaterrylene such Rylenimide are known which carry halogen, aryloxy, arylthio, hetaryloxy, hetarylthio, alkyl, alkenyl or alkynyl as substituents on the rylene skeleton (Chem. Eur. J. 3, 219-225 (1997) WO-A-03/104232; WO-A-96/22332; Angew. Chem. 107, 1487-1489 (1995); WO-A-02/76988). Tetrahedron Letters 40, 7047-7050 (1999) discloses N, N'-dicyclohexylperylene-S, N, O-tetracarboxylic diimides bearing 2 pyrrolidyl, piperidyl or morpholinyl radicals in the perylene skeleton.

It is an object of the present invention to provide rylenimides having advantageous application properties which are not only readily incorporated into the respective application media and can be adapted to these media, but also absorb longer wavelengths than the previously known rylenimides.

Accordingly, the rylenimides of formula I defined above were found.

Preferred and particularly preferred rylenimides I are given in the subclaims. Furthermore, a process for the preparation of Rylenimiden the general formula Ia

in which the variables have the meaning mentioned above, which is characterized in that a halogenated Rylenetetracarbonsäurediimid the formula IIa

in which the variables X and x1a have the following meaning:

X halogen; x1a 1 to 4 for m = 1; 1 to 6 for m = 2,

if desired in the presence of a nonacid solvent, with a cyclic amine of formula III

H-A III

or a salt of this amine.

In addition, a process for the preparation of Rylenimiden of the general formula Ib

in which R, R ¹ , A, Z and m have the meaning given at the outset and n1 and z1 have the following meanings:

n1 1 to 3 for m = 1;

1 to 5 for m = 2; z1 1 to 3 for m = 1, where n1 + z1 <4;

1 to 5 for m = 2, where n1 + z1 <6,

found, which is characterized in that a rylenimide of the general formula IIb

in which X and x1b have the following meaning:

X is halogen x1b 1 to 3 for m = 1, where x1b + z1 ≤ 4; 1 to 5 for m = 2, where x1 b + z1 ≤ 6,

if desired, in the presence of a nonacid solvent, with a cyclic amine of the above formula III or a salt of this amine.

Finally, the use of Rylenimide I 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 electrical magnetic spectrum of absorbing aqueous polymer dispersions, for generating invisible to the human eye, infrared light absorbing markers and found as infrared absorbers for thermal management.

As examples of the radicals R, R ¹ , R ¹ , R ² , A, X and Z mentioned in the formulas and their substituents may be mentioned in detail:

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 names isooctyl, isononyl, isodecyl and isotridecyl are trivial and derived from the alcohols obtained by the oxo process) ;

2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-isopropoxyethyl, 2-butoxyethyl, 2- and 3-methoxy-propyl, 2- and 3-ethoxypropyl, 2- and 3-propoxypropyl, 2- and 3-butoxy-propyl , 2- and 4-methoxybutyl, 2- and 4-ethoxybutyl, 2- and 4-propoxy-butyl, 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;

2-methylthioethyl, 2-ethylthioethyl, 2-propylthioethyl, 2-isopropylthio-ethyl, 2-butylthioethyl, 2- and 3-methylthiopropyl, 2- and 3-ethylthiopropyl, 2- and 3-propylthiopropyl, 2 and 3 Butylthiopropyl, 2- and 4-methylthiobutyl, 2- and 4-ethylthio-butyl, 2- and 4-propylthiobutyl, 3,6-dithiaheptyl, 3,6-dithiaoctyl, 4,8-dithianonyl, 3,7-dithiaoctyl , 3,7-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;

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, S.β.θ-trimethyl-Seθ-triazaundecyl, 12-methyl-3,6,9,12-tetraazatridecyl and 3,6,9 , 12-tetramethyl-3,6,9,12-tetraazatridecyl;

(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-methylsulfoxide-butyl, 2- and 4-ethylsulfoxide-butyl, 2- and 4-propylsulfoxide-butyl 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;

Methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentoxy, isopentoxy, neopentoxy, tert-pentoxy and hexoxy;

Methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, sec-butylthio, tert-butylthio, pentylthio, isopentylthio, neopentylthio, tert-pentylthio and hexylthio;

Methylamino, ethylamino, propylamino, isopycapamino, 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-dimethylaminosulfonyl, N, N-diethylaminosulfonyl, N, N-dipropylaminosulfonyl, N, N-diisopropylaminosulfonyl, N, N-dibutylaminosulfonyl, N, N-diisobutylaminosulfonyl, N, N'-di-sec-butylaminosulfonyl , NN-di-tert-butylaminosulfonyl, N, N-Dipentylaminosulfonyl, N, N-Dihexylaminosulfonyl, NN-Diheptylaminosulfonyl, N, N-Dioctylaminosulfonyl, N, N-Dinonylaminosulfonyl, N, N-Didecylaminosulfonyl, N ₁ N- Didodecylaminosulfonyl, N-methyl-N-ethylaminosulfonyl, N-methyl-N-dodecylaminosulfonyl, N-dodecylaminosulfonyl, (N, N-dimethylamino) ethylaminosulfonyl, N ₁ N- (propoxyethyl) dodecylaminosulfonyl, N, N-Diphenylaminosulfonyl, N, N- (4-tert-butylphenyl) octadecylaminosulfonyl and N, N-bis (4-chlorophenyl) aminosulfonyl;

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

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

Chlorine, bromine and iodine;

Phenylazo, 2-naphthylazo, 2-pyridylazo and 2-pyrimidylazo;

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-methylcycloheptyl, 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-, A- and 5-ethylcyclooctyl and 3-, A- and δ-propylcyclooctyl; 3- and 4-hydroxycyclohexyl, 3- and A-nitrocyclohexyl and 3- and 4-chlorocyclohexyl;

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 ;

Phenyl, 2-naphthyl, 2- and 3-pyrryl, 2-, 3- and 4-pyridyl, 2-, A- and 5-pyrimidyl, 3-, A- 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-, A-, 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-, A-, 5-, 6-, 7- and 8- (1,2,3,4-tetrahydroquinolinyl) and 2-, 3-, A-, 5-, 6-, 7- and 8-chromanyl, 2-, A- 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 A-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 A-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-methoxy-phenyl, 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-propoxy-phenyl, 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 A-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 A-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-pyridyloxy, 2-, 3- and 4-pyridylthio, 2-, A- and 5-pyrimidyloxy and 2-, A- and 5- pyrimidylthio; Ethynyl, 1- and 2-propynyl, 1, 2 and 3-butynyl, 1-, 2-, 3- and 4-pentynyl, 3-methyl-1-butynyl, 1-, 2-, 3-, 4- and 5-hexynyl, 3- and 4-methyl-1-pentynyl, 3,3-dimethyl-1-butynyl, 1-heptynyl, 3-, 4- and 5-methyl-1-hexynyl, 3,3-, 3, 4- and 4,4-dimethyl-1-pentynyl, 3-ethyl-1-pentynyl, 1-octynyl, 3, 4, 5 and 6-methyl-1-heptynyl, 3,3-, 3,4 , 3,5-, 4,4- and 4,5-dimethyl-1-hexynyl, 3-, 4- and 5-ethyl-1-hexynyl, 3-ethyl-3-methyl-1-pentynyl, 3 Ethyl 4-methyl-1-pentynyl, 3,3,4- and 3,4,4-trimethyl-1-pentynyl, 1-nonynyl, 1-decynyl, 1-undecynyl and 1-dodecynyl;

4-cyano-1-butynyl, 5-cyano-1-pentynyl, 6-cyano-1-hexynyl, 7-cyano-1-heptynyl and 8-cyano-1-octynyl;

4-hydroxy-1-butynyl, 5-hydroxy-1-pentynyl, 6-hydroxy-1-hexynyl, 7-hydroxy-1-heptynyl, 8-hydroxy-1-octynyl, 9-hydroxy-1-nonynyl, 10 Hydroxy-1-decynyl, 11-hydroxy-1-undecinyl and 12-hydroxy-1-dodecynyl;

4-carboxy-1-butynyl, 5-carboxy-1-pentynyl, 6-carboxy-1-hexynyl, 7-carboxy-1-heptynyl, 8-carboxy-1-octynyl, 4-methylcarboxy-1-butynyl, 5- Methylcarboxy-1-pentynyl, 6-methylcarboxy-1-hexynyl, 7-methylcarboxy-1-heptynyl, 8-methylcarboxy-1-octynyl, 4-ethylcarboxy-1-butynyl, 5-ethylcarboxy-1-pentynyl, 6-ethylcarboxy-1-hexynyl, 7-ethylcarboxy-1-heptynyl and 8-ethylcarboxy-1-octynyl;

1-ethenyl, 1- and 2-propenyl, 1-, 2- and 3-butenyl, 1-, 2-, 3- and 4-pentenyl, 3-methyl-1-butenyl, 1-, 2-, 3- , 4- and 5-hexenyl, 3- and 4-methyl-1-pentenyl, 3,3-dimethyl-1-butenyl, 1-heptenyl, 3-, 4- and 5-methyl-1-hexenyl, 3,3 , 3,4- and 4,4-dimethyl-1-pentenyl, 3-ethyl-1-pentenyl, 1-octenyl, 3, 4, 5 and 6-methyl-1-heptenyl, 3, 3-, 3,4-, 3,5-, 4,4- and 4,5-dimethyl-1-hexenyl, 3-, 4- and 5-ethyl-1-hexenyl, 3-ethyl-3-methyl-1 pentenyl, 3-ethyl-4-methyl-1-pentenyl, 3,3,4- and 3,4,4-trimethyl-1-pentenyl, 1-nonenyl, 1-decenyl, 1-undecenyl and 1- dodecenyl;

4-cyano-1-butenyl, 5-cyano-1-pentenyl, 6-cyano-1-hexenyl, 7-cyano-1-heptenyl and 8-cyano-1-octenyl;

4-hydroxy-1-butenyl, 5-hydroxy-1-pentenyl, 6-hydroxy-1-hexenyl, 7-hydroxy-1-heptenyl, 8-hydroxy-1-octenyl, 9-hydroxy-1-nonenyl, 10-hydroxy-1-decenyl, 11-hydroxy-1-undecenyl and 12-hydroxy-1-dodecenyl;

4-carboxy-1-butenyl, 5-carboxy-1-pentenyl, 6-carboxy-1-hexenyl, 7-carboxy-1-heptenyl, 8-carboxy-1-octenyl, 4-methylcarboxy-1-butenyl, 5-methylcarboxy-1-pentenyl, 6-methylcarboxy-1-hexenyl, 7-methylcarboxy-1-heptenyl, 8-methylcarboxy-1-octenyl, 4-ethylcarboxy-1-butenyl, 5-ethylcarboxy-1-pentenyl, 6- Ethylcarboxy-1-hexenyl, 7-ethylcarboxy-1-heptenyl and 8-ethylcarboxy-1-octenyl.

The terryleneimides I according to the invention can carry up to 6 substituents in the terrylene skeleton, preferably 4 or 2 substituents. The quaterryleneimides I according to the invention can have up to 8 substituents in the quaterrylene skeleton; preferably 6, 4 or 2 substituents. The rylene skeletons are preferably substituted by at least 2 cyclic amino radicals A which, as a constituent of the chromophoric system, cause an unexpectedly strong bathochromic shift of absorption and emission, which is about 110 nm for the terryleneimides and about 60 nm for the quaterryleneimides non-substituted or substituted by other radicals Rylenimiden.

The rylenimides according to the invention are generally produced in the form of product mixtures with different degrees of substitution which, if desired, can be separated by chromatography.

The preparation of the inventive rylenimides Ia, which are substituted exclusively by the cyclic amino radicals A, can advantageously be carried out by reacting the halogenated, preferably chlorinated and particularly preferably brominated, rylenimides IIa with the corresponding amine III.

The halogenated rylenimides IIa and their preparation are known from WO-A-03/104232, 96/22332 and 02/76988 and the earlier German patent application 102004048729.4.

The rylenimides Ib according to the invention, which are substituted in the rylene skeleton both by the cyclic amine radicals A and by (Het) aryloxy and / or (Het) arylthio radicals Z, can be prepared starting from rylenimides IIb, which are already substituted by the radicals Z. and further halogen atoms X carry for exchange with the cyclic amino radicals A.

The rylenimides IIb are likewise known from the abovementioned WO-A-03/104232, 96/22332 and 02/76988 and are obtainable from the halogenated rylenimides IIa by incomplete replacement of the halogen atoms X by the radicals Z.

Rylenimides I according to the invention which carry cyclic amino radicals A, (Het) aryloxy and / or (Het) arylthio radicals Z and halogen atoms X or cyclic amino radicals A and halogen atoms X in the rylene skeleton are analogous in each case by incomplete replacement of the halogen atoms X by the amino radicals A and if appropriate, the radicals Z are available. However, these rylenimides I are only of minor importance.

In the reaction according to the invention of the rylenimide IIa or Mb with the cyclic amine III, a non-acidic solvent may be present as the reaction medium, but the amine III may also itself act as a solvent. Particularly suitable cyclic amines III are piperidines, pyrrolidines, piperazines, morpholines and thiomorpholines (1,4-thiazines), the piperidines, pyrrolidines, piperazines and morpholines being preferred and the piperidines being particularly preferred.

The cyclic amines III can be chemically modified, ie their carbon chain can be interrupted not only by -O-, -S- or -NR ¹ - but also by -CO-, -SO- or -SO ₂ -, they can be a or two aromatic or saturated 4- to 7-membered fused rings whose carbon chain may also be interrupted by said groups, and they may be substituted by the above-mentioned alkyl, cycloalkyl and / or (Het) aryl radicals. However, the unmodified amines III are preferred.

As examples of suitable amines IM may be mentioned in detail:

Piperidine, 2- or 3-methylpiperidine, 6-ethylpiperidine, 2,6- or 3,5-dimethylpiperidine, 2,2,6,6-tetramethylpiperidine, 4-benzylpiperidine, 4-phenylpiperidine, piperidin-4-ol, piperidine pyridine-4-carboxylic acid, piperidine-4-carboxylic acid methyl ester, piperidine-4-carboxylic acid ethyl ester, piperidine-4-carboxylic acid amide, 2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidine 4-ylamine, decahydroquinoline and decahydroisoquinoline;

Pyrrolidine, 2-methylpyrrolidine, 2,5-dimethylpyrrolidine, 2,5-diethylpyrrolidine, tropanol, pyrrolidine-2-carboxylic acid methyl ester, pyrrolidine-2-carboxylic acid ethyl ester, pyrrolidine-2-carboxylic acid benzyl ester, pyrrolidine-2-carboxylic acid amide, 2,2,5, 5-tetramethylpyrrolidine-3-carboxylic acid, 2,2,5,5-tetramethylpyrrolidine-3-carboxylic acid methyl ester, 2,2,5,5-tetra-methylpyrrolidine-3-carboxylic acid ethyl ester, 2,2,5,5-tetramethylpyrrolidine-3 carboxylic acid benzyl ester, pyrrolidin-3-ylamine, (2,6-dimethylphenyl) pyrrolidin-2-ylmethylamine, (2,6-diisopropylphenyl) pyrrolidin-2-ylmethylamine and dodecahydrocarbazole;

Piperazine, diketopiperazine, 1-benzylpiperazine, 1-phenethylpiperazine, 1-cyclohexylpiperazine, 1-phenylpiperazine, 1- (2,4-dimethylphenyl) piperazine, 1- (2-, 3- or 4-methoxyphenyl) -piperazine, 1- (2-, 3- or 4-ethoxyphenyl) piperazine, 1- (2-, 3- or 4-fluorophenyl) piperazine, 1- (2-, 3- or 4-chlorophenyl) piperazine, 1- ( 2-, 3- or 4-bromophenyl) piperazine, 1-, 2- or 3-pyridin-2-ylpiperazine and 1-benzo [1,3] dioxol-4-ylmethylpiperazine;

Morpholine, 2,6-dimethylmorpholine, 3,3,5,5-tetramethylmorpholine, morpholin-2- or 3-ylmethanol, morpholin-2- or 3-ylacetic acid, morpholin-2-or 3-ylacetic acid methyl ester, Morpholine-2- or 3-ylacetic acid ethyl ester, 3-morpholin-3-yl-propionic acid methyl ester, 3-morpholin-3-yl-propionic acid ethyl ester, tert-butyl 3-morpholin-3-yl-propionic acid, morpholine-2-ol or 3-ylacetamide, 3-morpholin-3-yl-propionic acid amide, 3-benzylmorpholine, 3-methyl-2-phenylmorpholine, 2- or 3-phenylmorpholine, 2- (4-methoxyphenyl) morpholine, 2- (4- Trifluoromethylphenyl) morpholine, 2- (4-chlorophenyl) - morpholine, 2- (3,5-dichlorophenyl) morpholine, morpholine-2- or -3-carboxylic acid, morpholine-3-carboxylic acid methyl ester, 3-pyridin-3-ylmorpholine, 5-phenylmorpholin-2-one, 2-Mor - pholin-2-ylethylamine and phenoxazine;

Thiomorpholine, 2- or 3-phenylthiomorpholine, 2- or 3- (4-methoxyphenyl) thiomorpholine, 2- or 3- (4-fluorophenyl) thiomorpholine, 2- or 3- (4-trifluoromethylphenyl) thio- morpholine, 2 or 3- (2-chlorophenyl) thiomorpholine, 4- (2-aminoethyl) thiomorpholine, 3-pyridin-3-ylthiomorpholine, 3-thiomorpholinecarboxylic acid, 6,6-dimethyl-5-oxo-3-thiomorpholinecarboxylic acid, Thiomorpholinone and 2-phenylthiomorpholin-3-one and the thiomorpholine oxides and dioxides.

Instead of the free amines III, their salts, e.g. the salts of inorganic acids, such as the hydrofluorides, hydrochlorides, hydrobromides, hydroiodides, hydrogen sulfates, hydrogen sulfites, Hydrogenphoshate and hydrogen phosphites, or the salts of organic acids, such as the formates, acetates and propionates, are used, from which by addition of base again the amines are released.

If the cyclic amine III is used only as a reactant and not as a solvent at the same time, its amount used is usually from 1 to 10 mol, in particular from 1 to 3 mol, per halogen atom to be exchanged in the rylenimide IIa or IIb.

If desired, the amount of cyclic amine IM can be reduced to almost the stoichiometrically required amount by adding a non-nucleophilic nitrogenous base. Suitable bases are, under the reaction conditions, liquid trialkylamines, in particular tri (C ₃ -C ₆ -alkyl) amines, such as tripropylamine and tributylamine, and especially nitrogen-containing heterocycles, such as pyridine, N-methylpiperidine, N-methylmorpholine, pyrimidine, quinoline , Isoquinoline, quinaldine, diazabicyclononene (DBN) and diazabicycloundecene (DBU).

If a non-nucleophilic base is used, its amount is generally 1 to 5 mol, preferably 1 to 3 mol, per halogen atom to be exchanged in the rylenimide IIa or IIb.

Suitable solvents for the reaction according to the invention of the halogenated rylenimide IIa or IIb with the cyclic amine III are non-acidic solvents which do not protonate the amine III.

One group of preferred solvents are aliphatic carboxylic acid amides, especially N, N-di (C ₁ -C ₆ alkyl) - (Ci-C ₆ carboxylic acid) amides such as N, N-dimethylformamide, N ₁ N-diethylformamide, N, N-dimethylacetamide and N, N-dimethylbutyramide, and lactams, in particular N- (C 1 -C ₆ -alkyl) lactams, such as N-methylpyrrolidone, with dimethylformamide and N-methylpyrrolidone being particularly preferred. Another group of preferred solvents are halogenated aromatic and aliphatic hydrocarbons, such as chlorobenzene, dichlorobenzene and trichlorobenzene, and halogenated methanes and ethanes, for example methylene chloride, chloroform, tribromomethane, tetrachloromethane, tetrabromomethane, 1, 2-dichloro, 1,1- and 1 , 2-dibromo, 1, 1, 1 and 1, 1, 2-trichloro, 1, 1, 1 and 1,1, 2-tribromo, 1, 1, 1, 2 and 1, 1 , 2,2-tetrachloro and 1, 1,1, 2- and 1, 1, 2,2-tetrabromoethane, with methylene chloride, chloroform and chlorobenzene being particularly preferred.

Furthermore, such solvents could be used which dissolve only the amine III, but not the halogenated Rylenimid IIa. In addition to protic, the amine III non-protonating solvents such as water, aliphatic C _r C ₆ alcohols and glycols of the type HO- (C ₂ H ₄ O) ₃ -H with a = 1 to 6 are the di- (C C ₁ -C ₆ -alkyl) ethers of these glycols and aromatic hydrocarbons are mentioned as suitable examples of these solvents.

The amount of solvent is selected in the process according to the invention so that generally 10 to 100 g, preferably 10 to 50 g, of a liquid phase under the reaction conditions per g of halogenated Rylenimid IIa or IIb are present.

The liquid phase is composed of the nonacidic solvent and the cyclic amine III or, if the cyclic amine III simultaneously acts as a solvent, of the amine IM alone and optionally the non-nucleophilic base.

The reaction temperature in the process according to the invention is generally from 30 to 200 ^° C., preferably from 50 to 150 ^° C.

If the selected reaction temperature is above the boiling point of one of the components, it is possible to work in the closed system under the pressure which is being set.

The reaction time is usually 12 h to 10 d, in particular 1 to 5 d.

In terms of process technology, according to the invention, a mixture of rylenimide IIa or IIb and cyclic amine III and, if desired, nonacid solvent and / or nonnucleophilic base are heated to the chosen reaction temperature and stirred at this temperature for 12 h to 10 d.

The workup of the reaction mixture on the Rylenimide I can be done by filtering off the possibly precipitated reaction product or evaporation and subsequent column filtration or column chromatography. For the precipitation of the reaction product are protic solvents such as water, alcohols, in particular Ci-C ₆ alkanols, for example methanol, ethanol, n- and i-propanol, n-, i- and sec-butanol, n-pentanol, amyl alcohol and n- and i-hexanol, ethylene glycol mono (C _r C ₄ alkyl) ether, for example ethylene glycol mono-n-butyl ether, and carboxylic acids, in particular aliphatic Ci-C ₄ -carboxylic acids, for example formic acid, acetic acid, propionic acid and butyric acid ,

The reaction product subsequently isolated by filtration or by evaporation is usually washed with one of these solvents or a dilute inorganic acid, such as sulfuric acid, hydrochloric acid or phosphoric acid, or a combination of solvents, or stirred in these solvents and filtered again.

In addition, recrystallization may be carried out from the chlorinated hydrocarbons or carboxylic acid amides and lactams mentioned as reaction solvents, optionally in combination with the solvents suitable for precipitation or dilute inorganic acids.

By the final column chromatography, the reaction product can be further purified. In addition, the rylenimides I of the different degrees of substitution can be separated from one another.

Suitable eluents for the above-mentioned chlorinated hydrocarbons, with chloroform and methylene chloride are preferred, are, as well as mixtures of esters, such as ethyl acetate, and / or alcohols, for example methanol or ethanol, and aliphatic rule hydrocarbons, for example petroleum ethers with a boiling range 35-120 ⁰ C, or aromatic hydrocarbons, for example benzene, toluene, xylenes, mesitylene and ethylbenzene. Silica gel is usually used as the stationary phase.

With the aid of the process according to the invention, the rylenimides I can be obtained in yields of generally from 30 to 90% and purities of at least 90%.

The rylenimides I according to the invention exhibit strong absorption in the near infrared range at wavelengths of up to 1100 nm and thus advantageously supplement the spectral range accessible with the aid of the hitherto known rylene compounds.

They are suitable for a variety of applications, such as the coloring of high molecular weight organic and inorganic materials, such as paints, printing inks and plastics, as dispersing agents and pigment additives for organic pigments, for production in the near-infrared region of the electromagnetic spectrum absorbing aqueous polymer dispersions, for the production of the human eye invisible, infrared absorbing markers and markings, and as an infrared absorber for thermal management.

Examples

example 1

N, N '- (2,6-diisopropyl) phenyl-1, 6,9,13-tetra- (N-piperidyl) -trylene-3,4: 11,12-tetracarboxylic acid diimide

A mixture of 4.6 g of N, N '- (2,6-diisopropyl) phenyl-1, 6,9,13-tetrabromterrylen- 3,4: 11, 12-tetracarboxylic acid and 60 ml of piperidine was 5 d at 106 ⁰ C stirred. The resulting product was filtered off after cooling the reaction mixture to room temperature, stirred first with 50 ml of ethanol, then with 100 ml of water and finally again with 50 ml of ethanol for 1 h, then filtered off and dried in vacuo.

Column filtration on silica gel with petroleum ether / ethyl acetate (8: 1 v / v) gave 3.9 g of a black solid (yield about 90%) which, according to mass spectroscopic analysis, was a mixture of N ₁ N carrying 2 to 4 piperidyl residues '- (2,6-Diisopropylphenyl) terrylene-3,4: 11,12-tetracarboxylic diimides and showed the following absorption:

λ _m a _x (ε) (methylene chloride) = 791 nm (53 l g ^'1 cm ^-1 ).

Column chromatography on silica gel with chloroform gave 1.5 g of pure N, N '- (2,6-diisopropylphenyl) -1,6,9,13-tetra- (N-piperidyl) -trylene-3,4: 11,12-. tetracarboxylic diimide (34% yield), which showed the following absorption:

λ _max (ε) (acetone) = 538 (4099), 804 (21582) nm (I mor ¹ crτϊ ¹ ); λ _m ax (ε) (chloroform) = 819 nm (23,000 1 mol ^"1 cm ^-1 ).

Example 2

Mixture of N, N '- (2,6-diisopropylphenyl) quaterrylene-3,4: 13,14-tetracarboxylic diimides having 1 to 6 piperidyl radicals in the quaterrylene skeleton

A mixture of 2.9 g of N, N '- (2,6-diisopropylphenyl) hexabromquaterrylen-3,4: 13,14- tetracarboxylic diimide, 30 ml piperidine and 30 ml of dimethylformamide was stirred for 5 d under reflux (106 ⁰ C). The reaction product was precipitated by cooling to room temperature by adding 10 ml of water and 10 ml of ethanol, filtered off, repeatedly stirred with 50 ml of water at 80 ⁰ C and filtered, and finally three times with water / ethanol (1: 1 v / v) and dried then dried in vacuo.

After column filtration on silica gel with toluene / ethyl acetate (10: 1 v / v) 0.96 g of a black solid were obtained (yield about 40%), which according to mass spectroscopic examination of a mixture of 1 to 6 piperidyl residues bearing N ₁ N. '- (2,6-Diisopropylphenyl) terrylene-3,4: 11, 12-tetracarboxylic diimides (position of the piperidyl residues in the hexasubstituted diimide: 1, 6, 8, 11, 16, 19 and 1, 6, 8, 11, 16) , 18) and the following absorption showed:

λ _m a _x (ε) (methylene chloride) = 805 nm (61 l g ^'1 cm ^-1 ).

Example 3

N, N '- (2,6-diisopropylphenyl) -1, 6,11,16-tetra (4-tert-octylphenoxy) -8,18-di (N-piperiyl) -quaterrylene-3,4: 13, 14-tetracarboxylic

A mixture of 1.94 g of an isomeric mixture of N, N '- (2,6-diisopropylphenyl) -1,6,1,16-tetra (4-tert-octylphenoxy) -8, 18- and -8.19 dibromoquaterrylene-3,4: 13,14-tetracarboxylic acid diimide (about 1: 1) and 20 ml of piperidine was stirred at 85 ° C for 5 days.

The reaction mixture was then added to a mixture of 100 ml of water and 100 ml of methanol and stirred at room temperature for 30 minutes before filtration. The moist presscake was stirred in 50 ml of 1m hydrochloric acid for 30 min, filtered off, then stirred in 100 ml of water / methanol (1: 1 v / v), filtered off and dried in vacuo.

There were obtained 1, 86 g of a black solid, which was purified by column filtration on silica gel with toluene. This gave 1.37 g of a black solid (70% yield) which, according to mass spectroscopic analysis, was added to a mixture of tetra (tert-octylphenoxy) dipiperidyl, tetra (tert-octylphenoxy) monopiperidyl, tri (tert. octylphenoxy) dipiperidyl and tri (tert-octylphenoxy) tripiperidyl substituted N, N ^l - (2,6-diisopropylphenyl) quaterrylene-3,4: 13,14-tetracarboxylic diimides and showed the following absorption:

λ _max (ε) (methylene chloride) = 847 (40) nm (g mol ^"1 cm ^{" 1} ).

Column chromatography on silica gel with methylene chloride gave 1.1 g of an isomeric mixture of N, N '- (2,6-diisopropylphenyl) -1,6,11,16-tetra (4-tert-octylphenoxy) -8.18 and -8,19-di (N-piperidyl) quaterrylene-3,4: 13,14-tetracarboxylic acid diimide (about 1: 1) (55% yield), which showed the following absorption: λmax (ε) (acetone) = 489 (13015), 878 (75,000) nm (1 mol ^"1 cnT ¹ ), λ _m a _x (ε) (chloroform) = 910 nm (105,000 l mol ^{" 1} crrT ¹ ).

Example 4

Mixture of N, N '- (2,6-diisopropylphenyl) quaterrylene-3,4: 13,14-tetracarboxylic diimides having 3 to 5 piperidyl radicals in the quaterrylene skeleton

A mixture of 20.23 g of N, N '- (2,6-diisopropylphenyl) hexabromoquaterrylene-3,4: 13,14-tetracarboxylic diimide, 210 ml of piperidine and 210 ml of N-methylpyrrolidone was heated to 117 ° C. with stirring for 122 hours ,

After cooling to 8O ⁰ C, the reaction mixture was precipitated to 500 ml of water. The mixture was stirred at 8O ⁰ C for 3 h. The precipitated reaction product was filtered off, washed with warm water and then dried in vacuo.

After column filtration on silica gel with toluene / ethyl acetate (10: 1 v / v), 3.23 g of a black solid were obtained (yield about 42%), which, according to mass spectroscopic examination, a mixture of 3 to 5 N, N piperidyl residues '- (2,6-Diisopropylphenyl) terrylene-3,4: 11, 12-tetracarboxylic diimides and showed the following absorption:

λ _m ax (ε) (methylene chloride) = 877 nm (51 l g ^-1 cm ^-1 ).

Claims

claims

1. rylenetetracarboximides of the general formula

in which the variables have the following meaning:

R, R ¹ independently of one another: hydrogen;

(1) Ci-C ₃ o-alkyl, whose carbon chain by one or more Grup pierungen -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:

(i) C ₁ -C ₁₂ -alkoxy, CrC 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 and / or -SO ₃ R ² ;

(ii) 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, wherein the entire ring system may be mono- or polysubstituted by: C _r C ₁₈ alkyl, C ₁ -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 , aryl and / or hetaryl, each by d-Ciβ-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 and / or -SO ₃ R ² may be substituted;

(iii) 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, be anneliert, wherein the entire ring system one or more times may be substituted by: C ₁ -C ₁₈ -alkyl C ₁ ₁ -C ₂ -alkoxy, CRCE 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 and / or -SO ₃ R ² ; (iv) a radical -U-aryl which may be monosubstituted or polysubstituted by the abovementioned radicals which are mentioned as substituents for the aryl radicals (ii), where U is a grouping -O-, -S-, -NR ¹ -, -CO-, -SO- or -SO ₂ -;

(2) 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 groupings -O-, -S-, -NR ¹ -, -N = CR ¹ -, -CR ¹ = CR ¹ -, -CO-, -SO- and / or -SO ₂ - may be interrupted, which may be fused, where the entire ring system may be mono- or polysubstituted by: the radicals (i), (ii), (iii), (iv) and / or (v) CrC 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: Ci-C ₁₂ alkoxy, CrCe 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 , aryl and / or saturated or unsaturated C ₄ -C ₇ -cycloalkyl, whose carbon skeleton is represented 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, wherein the aryl and cycloalkyl radicals may each be mono- or polysubstituted by C ₁ -C ₁₈ - alkyl and / or the above, as substituents for alkyl radicals may be substituted;

(3) 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 -, -C ≡C-, -CR ¹ = CR ¹ -, -CO-, -SO- and / or -SO ₂ - may be fused, wherein the entire ring system may be substituted by the radicals (i), (ii )

(iii), (iv), (v) and / or aryl and / or hetarylazo, each of which substituted by C ₁ - C ₁₀ alkyl may be substituted, C ₁ -C ₆ -alkoxy and / or cyano; 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 ₁₈ -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 one or more times by C _r Ci ₂ alkyl and / or the above, as substituents may be substituted for radicals mentioned for alkyl; A is a nitrogen-bonded 5 to 9-membered ring, whose

Carbon chain can be interrupted by one or more groups -O-, -S-, -NR ¹ -, -CO- and / or -SO ₂ - be annealed to the one or two unsaturated or saturated A- to 8-membered rings can, whose carbon chain can also be interrupted by these groups and / or -N =, wherein the entire ring system may be mono- or polysubstituted by: hydroxy, nitro, -NHR ² , carboxy, -COOR ² , -CONR ² R ³ or -NR ² COR ³ ; Ci-C ₃ -alkyl, whose carbon chain by one or more -O-, -S-, -NR ¹ -, -CO- and / or -SO ₂ - and may be interrupted by cyano, hydroxy, nitro, C _r C ₆ alkoxy, -COOR ^2, -CONR ² R ^3,

Aryl, which may be substituted by C ₁ -C ₁₈ -alkyl or C ₁ -C ₆ -alkoxy, and / or a bonded via a nitrogen atom 5- to 7-membered heterocyclic radical containing further heteroatoms and may be aromatic, one or more times may be substituted; C ₅ -C ₈ -cycloalkyl, whose carbon skeleton is replaced by one or more

Grouping -O-, -S- and / or -NR ¹ - interrupted and / or which may be mono- or polysubstituted by C ₁ -C ₆ -A ^ yI; Aryl or hetaryl, each by d-dβ-alkyl, C ₁ -C ₆ -alkoxy, cyano, nitro, halogen, -CONR ² R ³ , -NR ² COR ³ , -SO ₂ NR ² R ³ and / or aryl - or het-arylazo, which may be substituted by d-Cio-alkyl, C ₁ -C ₆ -alkoxy or cyano, may be monosubstituted or polysubstituted, and wherein the radicals A may be the same or different for m>1; X is chlorine or bromine, where the radicals X may be the same or different for x>1; ZC ₃ -C ₂₀ -alkyl, C ₃ -C ₂₀ -alken-2-yl or C ₃ -C ₂₀ -alkyne-2-yl, their alkyl chain in each case by one or more groups -O-, -S-, -NR ¹ -, -CO- / or -SO ₂ and - can be interrupted and the by cyano, C ₁ -C ₆ - alkoxy, -COOR ^2, -CONR ² R ^3, aryl substituted by dC ₁₈ alkyl or C ₁ -C ₆ - alkoxy, and / or a 5- to 7-membered heterocyclic radical bonded via a nitrogen atom, which contain further heteroatoms and may be aromatic, mono- or polysubstituted;

Aryloxy, arylthio, hetaryloxy or hetarylthio, to which in each case further saturated or unsaturated 5- to 7-membered rings whose carbon skeleton by one or more groups -O-, -S-, -NR ¹ -, -N = CR ¹ -

-CO-, -SO- and / or -SO ₂ - may be interrupted, can be anneliert, wherein the entire ring system one or more times by the for R and R ¹ mentioned alkyl radicals (1), cycloalkyl radicals (2), aryl or hetaryl radicals (3) and / or the radicals mentioned therein (i) and / or (iv) may be substituted, wherein the radicals Z for z 1 may be the same or different; m is 1 or 2; n 1 to 4 for m = 1;

1 to 6 for m = 2; x 0 to 3 for m = 1, where n + x + z <4,

0 to 5 for m = 2, where n + x + z <6; z 0 to 3 for m = 1, where n + x + z <4,

0 to 5 for m = 2, where n + x + z <6.

2. rylenetetracarboximides of the general formula I according to claim 1, in which the variables have the following meanings:

R, R 'are independently hydrogen;

C ₁ -C ₃₀ -alkyl whose carbon chain can be interrupted by one or more groups -O-, -S-, -NR ¹ -, -CO- and / or -SO ₂ - and which is interrupted by cyano, C ₁ -C ₆ -Alkoxy ₁ aryl which may be substituted by C ₁ -C ₁₈ -alkyl or C ₁ -C ₆ -alkoxy and / or a 5- to 7-membered heterocyclic radical bonded via a nitrogen atom and containing further heteroatoms and may be aromatic, mono- or polysubstituted;

C ₅ -C ₈ -cycloalkyl whose carbon skeleton by one or more groups -O-, -S- and / or -NR ¹ - interrupted and / or which may be mono- or polysubstituted by C ₁ -Ce-AKyI; Aryl or hetaryl, which is represented by C ₁ -C _1S -alkyl, C ₁ -C ₆ -alkoxy, cyano, nitro, halogen, -CONR ² R ³ , -SO ₂ NR ² R ³ , -COOR ² , -SO ₃ R ² and / or aryl- or hetarylazo, which may each be substituted by C ₁ -C ₁₀ -alkyl, C ₁ -C ₆ -alkoxy or cyano, may be monosubstituted or polysubstituted;

R ^{1 is} hydrogen or C ₁ -C ₆ -alkyl;

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

C ₁ -C ₁₈ -alkyl which may be substituted by C ₁ -C ₆ -alkoxy, halogen, hydroxy, carboxy and / or cyano; Aryl or hetaryl, which may be substituted by the above, for alkyl radicals and by C ₁ -C ₆ -alkyl may be substituted;

A is a nitrogen-bonded 5 to 9-membered ring, whose

Carbon chain can be interrupted by one or more moieties -O-, -S-, -NR ¹ -, -CO- and / or -SO ₂ - be annealed to the one or two unsaturated or saturated 4- to 8-membered rings can, their carbon chain also by these groupings and / or -N = may be interrupted, wherein the entire ring system may be monosubstituted or polysubstituted by: hydroxy, nitro, -NR ² R ³ , -COOR ² , -CONR ² R ³ or -NR ² COR ³ ; C 1 -C ₃₀ -alkyl whose carbon chain may be interrupted by one or more groups -O-, -S-, -NR ¹ -, -CO- and / or -SO ₂ - and which may be interrupted by cyano, hydroxy, nitro , C _r C ₆ alkoxy, -COOR ^2, -CONR ² R ^3, aryl substituted by C ₁ -C ₁₈ -alkyl or C _r C ₆ alkoxy may be substituted, and / or bonded via a nitrogen atom 5- to 7-membered heterocyclic radical containing further heteroatoms and may be aromatic, may be mono- or polysubstituted;

C ₅ -C ₈ -cycloalkyl whose carbon skeleton may be interrupted by one or more groups -O-, -S- and / or -NR ¹ - and / or which may be mono- or polysubstituted by C ¹ -C ₆ -alkyl; Aryl or hetaryl, each represented by C ₁ -C ₁₈ -alkyl, C ₁ -C ₆ -alkoxy, cyano, nitro, halogen, -CONR ² R ³ , -NR ² COR ³ , -SO ₂ NR ² R ³ and / or aryl- or

Hetarylazo, which may be substituted in each case by C ₁ -C ₄ -alkyl, C ₁ -C ₆ -alkoxy or cyano, may be mono- or polysubstituted, and where the radicals A may be identical or different for m>1; X is chlorine or bromine, where the radicals X may be the same or different for x>1;

ZC ₃ -C ₂ -alkyl, C ₃ -C ₂₀ alkene-2-yl or C ₃ -C ₂₀ alkyne-2-yl, whose alkyl chain in each case by one or more -O-, -S-, - NR ¹ -, -CO- and / or -SO ₂ - may be interrupted and by cyano, C ₁ -C ₆ - alkoxy, -COOR ² , -CONR ² R ³ , aryl, by C _r C ₁₈ alkyl or C ₁ -C ₆ - alkoxy, and / or a nitrogen atom bonded via a 5- to 7-membered heterocyclic radical containing further heteroatoms and may be aromatic, mono- or polysubstituted;

Aryloxy, arylthio, hetaryloxy or hetarylthio, each one or more times by one or more of those mentioned for R, of

Substituted hydrogen may be substituted, wherein the radicals Z may be the same or different for z> 1; m is 1 or 2; n 1 to 4 for m = 1; 1 to 6 for m = 2; x O to 3 for m = 1, where n + x + z <4,

O to 5 for m = 2, where n + x + z <6; z o to 3 for m = 1, where n + x + z <4,

O to 5 for m = 2, where n + x + z <6.

3. rylenetetracarboximides of the general formula I according to claim 1, in which the variables have the following meaning: R, R ^{1 are} independently hydrogen;

C ₁ -C ₃₀ -alkyl whose carbon chain may be interrupted by one or more groups -O- and / or -CO- and which is substituted by cyano, C ₁ -C ₆ -alkoxy, aryl which is represented by C ₁ -C ₁₈ - AIkYl or C ₁ -C ₆ -alkoxy may be substituted, and / or a 5- to 7-membered heterocyclic radical bonded via a nitrogen atom, which contain further heteroatoms and may be aromatic, mono- or polysubstituted; C ₅ -C ₈ -cycloalkyl which may be mono- or polysubstituted by C _r C ₆ -alkyl;

Phenyl, naphthyl, pyridyl or pyrimidyl, which are each represented by C ₁ -C ₁₈ -alkyl, C ₁ -C ₆ -alkoxy, cyano, nitro, halogen, -CONR ² R ³ , -SO ₂ NR ² R ³ and / or phenyl- or naphthylazo, each of which may be substituted by C ₁ -C ₁₀ alkyl, C _r C ₆ alkoxy or cyano, may be mono- or polysubstituted;

R ^{1 is} hydrogen or C ₁ -C ₆ -alkyl;

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

C ₁ -C ₁₈ alkyl which may be substituted by C ₁ -C ₆ -alkoxy, halogen, hydroxy, carboxy and / or cyano; Aryl or hetaryl, which may be substituted by the above radicals mentioned for alkyl and by C ₁ -C ₆ -AlkYl;

A is a nitrogen atom-bonded, 5 to 7-membered ring whose carbon chain may be interrupted by one or more groups -O-, -S-, -NR ¹ -, -CO- and / or -SO ₂ -, to the one or two unsaturated or saturated 4- to 8-membered rings may be annelated, the carbon chain of which may likewise be interrupted by these groups and / or -N =, where the entire ring system may be monosubstituted or polysubstituted by C ₁ - C ₂₄ -alkyl, which may be substituted by aryl, which may carry C ₁ -C ₁₈ -alkyl as substituent, where the radicals A may be the same or different for m>1;

Z is phenoxy, phenylthio, pyridyloxy, pyrimidyloxy, pyridylthio or pyrimidylthio which may each be mono- or polysubstituted by C 1 -C ₁₂ -alkyl which may be substituted by aryl and / or aryl, where the radicals Z are z> 1 may be the same or different; m is 1 or 2; n 2 to 4 for m = 1; 2 to 6 for m = 2; z 0 to 2 for m = 1, where n + z <4, 0 to 4 for m = 2, where n + z <6.

4. A process for the preparation of Rylentetracarbonsäurediimiden the general formula Ia

in which the variables have the meaning given in claim 1, characterized in that a halogenated rylenetetracarboxylic acid diimide of the formula IIa

in which X and x1a have the following meanings:

X halogen; x1a 1 to 4 for m = 1; 1 to 6 for m = 2,

if desired in the presence of a nonacid solvent, with a cyclic amine of the formula III

HA

or a salt of this amine.

5. A process for the preparation of Rylenetetracarbonsäurediimiden of the general formula Ib

in which R ₁ R ¹ , A, Z and m have the meaning given in claim 1 and n1 and z1 have the following meanings:

n1 1 to 3 for m = 1;

1 to 5 for m = 2; z1 1 to 3 for m = 1, where n1 + z1 <4;

1 to 5 for m = 2, where n1 + z1 <6,

characterized in that a rylenimide of the general formula IIb

in which X and x1b have the following meaning:

X halogen; x1 b 1 to 3 for m = 1, where x1 b + z1 <4; 1 to 5 for m = 2, where x1 b + z1 <6,

HA

or a salt of this amine.

6. Use of Rylenetetracarbonsäurediimiden of the formula I according to the

Claims 1 to 3 for coloring organic and inorganic materials.

7. Use according to claim 6, characterized in that the high molecular weight materials are paints, printing inks or plastics.

8. Use of Rylenetetracarbonsäurediimiden of the formula I according to claims 1 to 3 as a dispersing aid and pigment additives for organic pigments.

9. Use of Rylenetetracarbonsäurediimiden of the formula I according to claims 1 to 3 for the preparation in the near-infrared region of the electromagnetic spectrum absorbing aqueous polymer dispersions.

10. Use of Rylenetetracarbonsäurediimiden of the formula I according to claims 1 to 3 for the production of invisible to the human eye, infrared light absorbing markers and labels.

11. Use of Rylenetetracarbonsäurediimiden of the formula I according to claims 1 to 3 as an infrared absorber for thermal management.