1,7-Diaroxy- or 1,7-arylthio-substituted...

Details 1,7-Diaroxy- or 1,7-arylthio-substituted... 1,7-Diaroxy- or 1,7-arylthio-substituted...

2000-08-02

2001-12-04

Aulakh, C. S. (Department: 1625)

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

Organic compounds

Heterocyclic carbon compounds containing a hetero ring...

C106S493000, C106S499000, C252S301170, C252S301260, C252S301350, C008S568000

Reexamination Certificate

active

06326494

ABSTRACT:

The present invention relates to novel, 1,7-disubstituted perylene-3,4,9,10-tetracarboxylic dianhydrides of the general formula I and perylene-3,4,9,10-tetracarboxylic acids of the general formula Ia
where
R is aryloxy, arylthio, hetaryloxy or hetarylthio each of which can be substituted one or more times by 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/or can be substituted one or more times by —COOR
1
, —SO
3
R
1
, hydroxyl, cyano, C
1
-C
6
-alkoxy, C
5
-C
8
-cycloalkyl or a 5- to 7-membered heterocyclic radical which is attached via nitrogen and can contain further heteroatoms, or can be substituted one or more times by C
1
-C
6
-alkoxy, cyano, —COOR
1
or —SO
3
R
1
, where R
1
is hydrogen or C
1
-C
6
-alkyl
and to a process for the preparation of the perylene-3,4,9,10-tetracarboxylic dianhydrides (I) or of the acids (Ia) and to their use as pigments, laser dyes and precursors for preparing fluorescent dyes, polymeric colorants, pigments and pigment additives.
The invention additionally relates to novel 1,7-disubstituted perylene-3,4,9,10-tetracarboxylic diimides of the general formula
where
R is aryloxy, arylthio, hetaryloxy or hetarylthio each of which can be substituted one or more times by 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/or can be substituted one or more times by —COOR
1
, —SO
3
R
1
, hydroxyl, cyano, C
1
-C
6
-alkoxy, C
5
-C
8
-cycloalkyl or a 5- to 7-membered heterocyclic radical which is attached via nitrogen and can contain further heteroatoms, or can be substituted one or more times by C
1
-C
6
-alkoxy, cyano, —COOR
1
or —SO
3
R
1
, where R
1
is hydrogen or C
1
-C
6
-alkyl, and
R
2
is C
4
-C
30
-alkyl whose carbon chain can be interrupted by one or more groups —O—, —S— or —CO—, or is C
5
-C
8
-cycloalkyl or aryl which can be substituted one or more times by C
1
-C
6
-alkyl or C
1
-C
6
-alkoxy,
as intermediates for the perylene-3,4,9,10-tetracarboxylic dianhydrides (I) and the acids (Ia) and to a process for the preparation of the perylene-3,4,9,10-tetracarboxylic diimides (VI).
Perylene-3,4,9,10-tetracarboxylic acids and their anhydrides are known as important intermediates for the preparation of perylimide pigments and perylimide dyes, but are also suitable themselves for coloring, or pigmenting, high molecular mass organic materials.
In addition to unsubstituted perylene-3,4,9,10-tetracarboxylic acid, which can be obtained by hydrolyzing perylene-3,4,9,10-tetracarboxylic diimide in concentrated sulfuric acid at about 200° C., there is particular interest in perylene tetracarboxylic acids which are substituted in the perylene skeleton and whose properties in use, such as solubility, inherent color and fluorescence, can be tailored by introducing suitable substituents.
WO-A-94/25504 discloses 1,6,7,12-tetraaroxy-substituted perylene-3,4,9,10-tetracarboxylic dianhydrides prepared by hydrolyzing the corresponding diumides under alkaline conditions in a polar protic solvent. The tetraaroxy-substituted diimides themselves have been obtained by reacting the tetrachlorinated diimides with arylates (EP-A-227 980).
1,7-disubstituted perylene-3,4,9,10-tetracarboxylic acids such as the novel compounds (Ia), which like all perylene-3,4,9,10-tetracarboxylic acids are generally in the form of the dianhydrides, have not been disclosed to date. Even the dihalogenated perylene-3,4,9,10-tetracarboxylic diimides described in EP-A-39 912 and DRP 412 122 are always mixtures of products with different degrees of halogenation (especially tetra-, tri- and monohalogenated products); it was not possible to prepare specifically the dihalogenated diimides.
It is an object of the invention to provide novel, disubstituted perylene-3,4,9,10-tetracarboxylic acids and dianhydrides.
We have found that this object is achieved by the 1,7-disubstituted perylene-3,4,9,10-tetracarboxylic dianhydrides and the corresponding acids of the formulae I and Ia defined at the outset (referred to below as dianhydrides I).
Preferred dianhydrides I are the subject of the subclaim.
The object has additionally been achieved by a process for the preparation of the dianhydrides I, which comprises
a) reacting 1,7-dibromoperylene-3,4,9,10-tetracarboxylic dianhydride (II) or
1,7-dibromoperylene-3,4,9,10-tetracarboxylic acid (IIa), in the presence of a polar aprotic solvent and in the presence or absence of an imidation catalyst, with a primary amine of the general formula III
R
2
—NH
2
  III
in which R
2
is C
4
-C
30
-alkyl whose carbon chain can be interrupted by one or more groups —O—, —S— or —CO—, or is C
5
-C
8
-cycloalkyl or aryl which can be substituted one or more times by C
1
-C
6
-alkyl or C
1
-C
6
-alkoxy,
b) reacting the 1,7-dibromoperylene-3,4,9,10-tetracarboxylic diimides, formed in step a), of the general formula IV
in the presence of an inert aprotic solvent and of a non-nucleophilic or only weakly nucleophilic base with an aromatic alcohol or thioalcohol of the general formula V
H—R  V
and
hydrolyzing the 1,7-disubstituted perylene-3,4,9,10-tetracarboxylic diimides, formed in step b), of the general formula VI
in the presence of a polar protic solvent and a base to give the dianhydrides I.
In addition we have discovered the 1,7-disubstituted perylene-3,4,9,10-tetracarboxylic diimides of the formula VI defined at the outset (referred to below as perylimides VI) as intermediates for the dianhydrides I, and processes for the preparation of the perylimides VI which comprise steps a) and b) of the process for the preparation of the corresponding dianhydrides I.
Preferred perylimides VI are the subject of the subclaim.
We have also found a second process for the preparation of the dianhydrides I, which comprises reacting 1,7-dibromoperylene-3,4,9,10-tetracarboxylic dianhydride (II) or 1,7-dibromoperylene-3,4,9,10-tetracarboxylic acid (IIa) with an aromatic alcohol or thioalcohol of the formula V in the presence of an aprotic solvent and of an inorganic base.
Additionally, we have found a process for the preparation of 1,7-dibromoperylene-3,4,9,10-tetracarboxylic dianhydride (IIa) or 1,7-dibromoperylene-3,4,9,10-tetracarboxylic acid by brominating perylene-3,4,9,10-tetracarboxylic dianhydride or, respectively, perylene-3,4,9,10-tetracarboxylic acid in 100% by weight sulfuric acid, which comprises brominating in the presence of iodine at from 80 to 90° C. and metering in the bromine slowly.
Moreover, we have discovered the use of the dianhydrides I as pigments, laser dyes and precursors for preparing fluorescent dyes, polymeric colorants, pigments and pigment additives.
Finally, we have discovered the use of the perylimides VI as pigments and dyes for coloring high molecular mass organic materials and inorganic materials, as laser dyes and as organic materials for electroluminescence applications.
Suitable unsubstituted radicals R are phenoxy, phenylthio, 2-naphthyloxy, 2-naphthylthio, 2-, 3- and 4-pyridyloxy, 2-, 3- and 4-pyridylthio, 2-, 4- and 5-pyrimidyloxy and 2-, 4- and 5-pyrimidylthio, with phenoxy and 2-naphthyloxy being preferred.
Alkyl substituents of radicals R (and alkyl radicals R
1
and R
2
)) can be either straight-chain or branched.
Specific examples of these substituents (or, respectively, of substituents thereof) 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 terms isooctyl, isononyl, isodecyl and isotridecyl are trivial names and derive from the alcohols obtained by oxo synthesis—cf. in this context Ullmanns Encyklopädie der technischen Chemie, 4th Edition, Volume 7, 215-217, and Volume 11, 435 and 436);
2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-isopropoxyethyl, 2-butoxyethyl, 2- and 3-methoxypropy

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