1,7-disubstituted perylene-3,4,9,10-tetracarboxylic acids,...

Details 1,7-disubstituted perylene-3,4,9,10-tetracarboxylic acids,... 1,7-disubstituted perylene-3,4,9,10-tetracarboxylic acids,...

1999-09-24

2001-02-06

Aulakh, Charanjit S. (Department: 1612)

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

Organic compounds

Heterocyclic carbon compounds containing a hetero ring...

C106S241000, C106S287210, C106S401000, C106S499000, C524S090000, C008S568000

Reexamination Certificate

active

06184378

ABSTRACT:

DESCRIPTION
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
L
1
and L
2
independently of one another are 1,2-ethylene, 1,2-ethenylene and 1,2-ethynylene;
R
1
and R
2
independently of one another are hydrogen or C
1
-C
30
-alkyl, whose carbon chain can be interrupted by one or more groups —O—, —S—, —NR
3
—, —CO— and/or —SO2— and/or which can be substituted one or more times by —COOR
3
, —SO
3
R
3
, hydroxyl, cyano, C
1
-C
6
-alkoxy, C
5
-C
8
-cycloalkyl or aryl or by a 5- to 7-membered heterocyclic radical which is attached via a nitrogen atom and can include further heteroatoms and/or can be aromatic, R
3
being hydrogen or C
1
-C
6
-alkyl,
and to a process for preparing the perylene-3,4,9,10-tetracarboxylic dianhydrides (I) or the acids (1a) 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 VI
where
X
1
is bromine or is —L—R, where
L is 1,2-ethylene, 1,2-ethenylene or 1,2-ethynylene and
R is hydrogen or C
1
-C
30
-alkyl whose carbon chain can be interrupted by one or more groups —O—, —S—, —NR
3
—, —CO— and/or —SO
2
— and/or which can be substituted one or more times by —COOR
3
, —SO
3
R
3
, hydroxyl, cyano, C
1
-C
6
-alkoxy, C
5
-C
8
-cycloalkyl or aryl or by a 5- to 7-membered heterocyclic radical which is attached via a nitrogen atom and can include further heteroatoms and/or can be aromatic, R
3
being hydrogen or C
1
-C
6
-alkyl;
X
2
is bromine or —L—R;
R
4
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) or the acids (Ia), and to a process for preparing the perylene-3,4,9,10-tetracarboxylic diimides (VI).
Perylene-3,4,9,10-tetracarboxylic acids and their anhydrides are known to be important intermediates for preparing perylimide pigments and perylimide dyes, but are also useful 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 alkaline hydrolysis of the corresponding diimides in a polar protic solvent. The tetraaroxy-substituted diimides themselves are 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. In addition, the dihalogenated perylene-3,4,9,10-tetracarboxylic diimides described in EP-A-39 912 and in DE-A-412 122 are always mixtures of products with differing degrees of halogenation (especially tetra-, tri- and monohalogenated products); it has not been possible to prepare the dihalogenated diimides specifically.
It is therefore 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 above-defined formulae I and Ia (referred to below as dianhydrides I), which may be substituted symmetrically or asymmetrically.
Preferred dianhydrides I are the subject of the subclaim.
We have also discovered a process for preparing the symmetric 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
4
—NH
2
  III
 where R
4
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 aprotic solvent, a palladium complex as catalyst, a copper salt as cocatalyst and a base with a 1-alkyne of the general formula V
H—C—C≡R
1
  V
 in a molar ratio of from 1:2 to 1:4, and
c) hydrolyzing the symmetric, 1,7-disubstituted perylene-3,4,9,10-tetracarboxylic diimides, formed in step b), of the general formula VI′
 after additional reduction of the unsaturated bonds in L
1
, if desired, in the presence of a polar protic solvent and a base to form the symmetric dianhydrides I.
We have also discovered a process for preparing the asymmetric dianhydrides I, which corresponds to the process for preparing the symmetric dianhydrides I in step a) but in which the 1,7-dibromoperylene-3,4,9,10-tetracarboxylic diimides IV are reacted in step b)—which is likewise carried out in the presence of an aprotic solvent, a palladium complex as catalyst, a copper salt as cocatalyst and a base—first with a 1-alkyne of the general formula Va
H—C≡C—R
1
  Va
and then with a different 1-alkyne of the general formula Vb
H—C≡C—R
2
  Vb
in each case in a molar ratio of from 1:1 to 1:2 and the resulting asymmetric 1,7-disubstituted perylene-3,4,9,10-tetracarboxylic diimides of the general formula VI″
are then hydrolyzed, in step c), after additional reduction of the unsaturated bonds in L
1
and L
2
, if desired, in the presence of a polar protic solvent and a base to form the asymmetric dianhydrides I.
We have, furthermore, discovered the 1,7-disubstituted perylene-3,4,9,10-tetracarboxylic diimides of the above-defined formula VI (referred to as perylimides VI), which can likewise be symmetrically or asymmetrically substituted, as intermediates for the dianhydrides I, and processes for preparing the perylimides VI which comprise steps a) and b) of the process for preparing the corresponding dianhydrides I.
Preferred perylimides VI are the subject of the subclaim.
Yet further, 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 also 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.
Each alkyl in the formulae I (including Ia), III, IV, V (including Va and Vb) and VI (including VI′ and VI″) can be either straight-chain or branched. Substituted aromatic radicals can generally have up to three, preferably one or two, of the substituents stated.
Specific examples of suitable radicals R
1
and R
2
(and of their substituents) in addition to hydrogen 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, isodec

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