Thermochromic rylene dyes

Details Thermochromic rylene dyes Thermochromic rylene dyes

2002-02-27

2002-11-26

Powers, Fiona T. (Department: 1626)

Organic compounds -- part of the class 532-570 series

Organic compounds

Heterocyclic carbon compounds containing a hetero ring...

C546S100000, C524S089000, C524S090000

Reexamination Certificate

active

06486319

ABSTRACT:

The present invention relates to novel rylene dyes of the general formula I
where
R is hydrogen or C
1
-C
30
-alkyl, whose carbon chain may be interrupted by one or more —O—, —S—, —NR
1
—, —CO— and/or —SO
2
— groups and which may be monosubstituted or polysubstituted by cyano, C
1
-C
6
-alkoxy, aryl, which may be substituted by C
1
-C
18
-alkyl or C
1
-C
6
-alkoxy, or a 5- to 7-membered heterocyclic radical which is bonded via a nitrogen atom and may contain further heteroatoms and may be aromatic; C
5
-C
8
-cycloalkyl, whose carbon skeleton may be interrupted by one or more —O—, —S— and/or —NR
1
— groups and which may be monosubstituted or polysubstituted by C
1
-C
6
-alkyl; aryl or hetaryl, each of which may be monosubstituted or polysubstituted by C
1
-C
18
-alkyl, C
1
-C
6
-alkoxy, cyano, —CONHR
2
, —NHCOR
2
and/or aryl- or hetarylazo, each of which may be substituted by C
1
-C
10
-alkyl, C
1
-C
6
-alkoxy or cyano;
R′ is C
2
-C
30
-alkyl, whose carbon chain may be interrupted by one or more —O— and/or —CO— groups and which may be monosubstituted or polysubstituted by cyano, C
1
-C
6
-alkoxy, C
5
-C
8
-cycloalkyl, whose carbon skeleton may be interrupted by one or more —O—, —S— and/or —NR
1
— groups and which may be C
1
-C
6
-alkyl-substituted, aryl, which may be substituted by C
1
-C
18
-alkyl or C
1
-C
6
-alkoxy, or a 5- to 7-membered heterocyclic radical which is bonded via a nitrogen atom and which may contain further heteroatoms and which may be aromatic;
methyl, which is monosubstituted or disubstituted by aryl, hetaryl and/or C
5
-C
8
-cycloalkyl, each of which may be substituted by C
1
-C
18
-alkyl or C
1
-C
6
-alkoxy;
C
5
-C
8
-cycloalkyl, whose carbon skeleton may be interrupted by one or more —O—, —S— and/or —NR
1
— groups and which may be monosubstituted or polysubstituted by C
1
-C
6
-alkyl;
R
1
is hydrogen or C
1
-C
6
-alkyl;
R
2
is hydrogen; C
1
-C
18
-alkyl; aryl or hetaryl, each of which may be substituted by C
1
-C
6
-alkyl, C
1
-C
6
-alkoxy or cyano; n is 0 or 1,
and to the preparation of these dyes, and to their use for coloring high-molecular-weight organic and inorganic materials.
The present invention furthermore relates to the preparation of 9-bromoperylene-3,4-dicarboximides of the general formula IIIa and aminorylenedicarboximides of the general formula V, and to novel 9-aminoperylene-3,4-dicarboximides of the general formula Va
where:
R
3
hydrogen or C
1
-C
30
-alkyl, whose carbon chain may be interrupted by one or more —O—, —S—, —NR
1
—, —CO— and/or —SO
2
— groups and which may be monosubstituted or polysubstituted by cyano, C
1
-C
6
-alkoxy, aryl, which may be substituted by C
1
-C
18
-alkyl or C
1
-C
6
-alkoxy, or a 5- to 7-membered heterocyclic radical which is bonded via a nitrogen atom and may contain further heteroatoms and may be aromatic; C
5
-C
8
-cycloalkyl, whose carbon skeleton may be interrupted by one or more —O—, —S— and/or —NR
1
— groups and which may be monosubstituted or polysubstituted by C
1
-C
6
-alkyl; aryl or hetaryl, each of which may be monosubstituted or polysubstituted by C
1
-C
18
-alkyl, C
1
-C
6
-alkoxy, cyano, —CONHR
2
, —NHCOR
2
and/or aryl- or hetarylazo, each of which may be substituted by C
1
-C
10
-alkyl, C
1
-C
6
-alkoxy or cyano, where
R
1
is hydrogen or C
1
-C
6
-alkyl;
R
2
is hydrogen C
1
-C
18
-alkyl; aryl or hetaryl, each of which may be substituted by C
1
-C
6
-alkyl, C
1
-C
6
-alkoxy or cyano;
as intermediates for the rylene dyes (I).
Perylene-3,4-dicarboximides which are substituted on the imide nitrogen atom, unsubstituted perylene-3,4-dicarboximide and perylene-3,4-dicarboximides which are substituted on the perylene skeleton are suitable not only as pigment precursors, but are themselves also advantageously employed as pigments and fluorescent dyes. The perylene-3,4-dicarboximides substituted on the perylene skeleton which have been disclosed hitherto are substituted in the 1,6-, 1,7-, 1,6,9-, 1,7,9- and 1,6,7,12-position and also only in the 9-position. The perylene skeleton in each case carries a halogen atom, in particular a bromine atom, in the 9-position (WO-A-96/22331, EP-A-596 292 and WO-A-97/22607 and the references cited therein, and Dyes and Pigments 16, pages 19-25 (1991)). EP-A-657 436 and Liebigs Annalen 1995, pages 1229-1244, also describe an N-(1-hexylheptyl)-9-aminoperylene-3,4-dicarboximide which is prepared by nitrating the corresponding N-substituted perylene-3,4-dicarboximide using dinitrogen tetraoxide followed by reduction with metallic iron in the presence of hydrochloric acid. However, this process is restricted to perylene-3,4-dicarboximides carrying unsubstituted alkyl groups on the imide nitrogen atom and gives exclusively isomer mixtures (1- and 9-isomers), which are difficult to purify, in low yields. Corresponding N-substituted 4-aminonaphthalene-1,8-dicarboximides are disclosed in Yuki Gosei Kagaku Kyokaishi 12, pages 504-508 (1956) (see Chemical Abstracts 51:8052a (1957)).
EP-A-648 817 describes fluorescent dyes containing imide groups whose imide nitrogen atom, for reversible solubilization, has been converted into a carbamate function, which renders the dye soluble in the application medium and can be re-cleaved thermally. Inter alia, unsubstituted perylene-3,4-dicarboximide whose NH function is reacted correspondingly is also listed here as fluorescent dye. Since the solubilization takes place via the imide nitrogen atom there is no possibility of modifying the dye on the nitrogen atom by specific substitution. In addition, the hue of the dye does not change on thermal removal of the alkoxycarbonyl protecting group, and the dye is therefore not thermochromic.
It is an object of the present invention to provide further dyes having advantageous applicational properties which can in particular not only be incorporated readily into the respective application medium and matched to this medium, but are also thermochromic.
We have found that this object is achieved by the rylene dyes of the formula I defined at the outset.
Preferred rylene dyes are given in the subclaim.
We have also found a process for the preparation of the rylene dyes of the general formula I which comprises
a) regioselectively monobrominating a perylene-3,4-dicarboximide of the general formula IIa
 using elemental bromine in the presence of an aliphatic monocarboxylic acid,
b1) reacting the 9-bromoperylene-3,4-dicarboximide of the general formula IIIa
 formed in step a) or a 4-bromonaphthalene-1,8-dicarboximide of the general formula IIIb
 prepared in a known manner by imidation of 4-bromonaphthalene-1,8-dicarboxylic anhydride with a benzophenonimine of the general formula IV
 where
R″, R′″, independently of one another, are hydrogen, C
1
-C
6
-alkyl or C
1
-C
6
-alkoxy and
x, y, independently of one another, are an integer from 1 to 3,
in the presence of an aprotic organic solvent, a transition-metal catalyst system and a base in an aryl-N coupling reaction and
b2) hydrolyzing the resultant ketimine in the presence of an acid and in the presence of a polar, aprotic solvent to give an aminorylenedicarboximide of the general formula V
 and
c) subsequently reacting the latter with a dicarbonate of the general formula VI
in the presence of a polar, aprotic solvent and in the presence of a base to give the rylene dye I.
We have also found a process for the preparation of aminorylenedicarboximides of the general formula V, which comprises reacting a bromorylenedicarboximide of the general formula III with a benzophenonimine of the general formula IV in the presence of an aprotic organic solvent, a transition-metal catalyst system and a base in an aryl-N coupling reaction to give the corresponding ketimine, and subsequently hydrolyzing the latter in the presence of an acid and in the presence of a polar, aprotic solvent.
In addition, we have found the 9-aminoperylene-3,4-dicarboximides of the formula Va defined at the outset as intermediates for the rylene dyes of the general formula I.
We have also found a process for the preparation of the 9

Affiliated with

Also associated with

Rating

Thermochromic rylene dyes does not yet have a rating. At this time, there are no reviews or comments for this patent.

If you have personal experience with Thermochromic rylene dyes, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Thermochromic rylene dyes will most certainly appreciate the feedback.

Rate now

Comments { 0 }

Profile ID: LFUS-PAI-O-2988389