Core-extended perylene bisimides

Details Core-extended perylene bisimides Core-extended perylene bisimides

2001-03-20

2002-12-10

Aulakh, Charanjit S. (Department: 1625)

Compositions: coating or plastic

Coating or plastic compositions

Heterocyclic

C546S031000, C546S028000, C544S233000, C544S245000, C106S001150, C106S400000, C430S078000

Reexamination Certificate

active

06491749

ABSTRACT:

The present invention relates to nucleus-extended perylenebisimides of general formulae (I) and (II)
wherein
R
1
and R
2
are each independently of the other unsubstituted or substituted C
1
-C
24
alkyl, C
1
-C
24
cycloalkyl, or C
6
-C
10
aryl, and
A
1
and A
3
are each independently of the other —S—, —S—S—, —CH═CH—, R
3
OOC—C(—)═C(—)—COOR
3
, —N═N— or —N(R
4
)—, or a linkage selected from the group consisting of the organic radicals of formulae (III), (IV), (V), (VI) and (VII)
wherein
R
3
is hydrogen, C
1
-C
24
alkyl or C
1
-C
24
cycloalkyl,
R
4
is unsubstituted or substituted C
1
-C
24
alkyl, C
1
-C
24
cycloalkyl, phenyl, benzyl, —CO—C
1
—C
4
alkyl, —CO—C
6
H
5
or C
1
-C
4
alkylcarboxylic acid (C
1
-C
4
alkyl) ester, and
A
2
is a linkage of formula (III), (IV) or (V),
also to intermediates for the preparation of compounds (I) and (II) and to processes for the preparation of those intermediates and also to processes for the preparation of compounds (I) and (II), and to the use thereof as colourants.
Perylenes, as is known (see Heterocycles, Vol. 40, No. 1, (1995) 477-500), are photostable fluorescent dyes that are often distinguished by high fluorescence quantum yields. A disadvantage thereof is, however, that perylenes have a low degree of solubility in aqueous media.
Chem. Ztg. (1975), 99, 92-93 describes, inter alia, nucleus-extended perylenes that are obtainable by Diels-Alder reaction of 4-phenyl-1,2,4-triazoline-3,5-dione with perylene and that may exhibit absorptions at 600 nm.
Further Diels-Alder reactions on perylenes are described in Heterocycles, Vol. 40, No. 1, 1995. J. Org. Chem. USSR, (1986), 22, 943-946 describes the preparation of thio- and dithio-cyclic derivatives of perylene-3,4,9,10-tetracarboxylic acid. Furthermore, J. Org. Chem. USSR, (1980), 16, 762-7 describes a process for the preparation of nitrogen-cyclic derivatives of perylene-3,4,9,10-tetracarboxylic acid.
The problem underlying the invention was accordingly to provide further nucleus-extended perylenes, especially nucleus-extended perylenebisimides, that preferably as fluorescent dyes have good fastness to heat and to light; perylenes suitable as NIR dyes or as fluorescent markers were also to be provided.
Accordingly, there have been found the nucleus-extended perylenebisimides of general formulae (I) and (II) defined at the beginning.
C
1
-C
24
Alkyl is, for example, methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl, n- or neo-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, heneicosyl, docosyl or tetracosl, preferably 1-(C
1
-C
9
alkyl)-C
2
-C
10
alkyl, such as 1-methyl-ethyl, 1-ethyl-n-propyl, 1-n-propyl-n-butyl, 1-n-butyl-n-pentyl, 1-n-hexyl-1-n-heptyl, 1-n-heptyl-1-n-octyl, 1-n-octyl-1-n-nonyl or 1-n-nonyl-1-n-decyl, or C
1
-C
8
alkyl, such as methyl, ethyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl, n- or neo-pentyl, n-hexyl, n-heptyl or n-octyl and especially C
1 -C
4
alkyl, such as methyl, ethyl, n- or iso-propyl or n-, iso-, sec- or tert-butyl.
C
3
-C
14
Cycloalkyl is, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, cyclotridecyl or cyclotetradecyl, preferably C
5
-C
8
cycloalkyl, such as cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.
Especially preferred compounds of formulae (I) and (II) are those wherein R
1
and/or R
2
denote a secondary alkyl radical, such as 1-(C
1
-C
9
alkyl)-C
2
-C
10
alkyl, especially those wherein the radical R
1
has a so-called “swallowtail structure”, such as 1-methyl-ethyl, 1-ethyl-n-propyl, 1-n-propyl-n-butyl, 1-n-butyl-n-pentyl, 1-n-hexyl-1-heptyl, 1-n-heptyl-1-n-octyl, 1-n-octyl-1-n-nonyl, 1-n-nonyl-1-decyl, or an aromatic radical, especially the phenyl radical, very especially C
1
-C
6
alkyl-substituted phenyl, such as 2,6-di-tert-butylphenyl and 2,5-di-tert-butylphenyl.
C
6
-C
10
Aryl is, for example, phenyl or 1- or 2-naphthyl, especially phenyl.
—CO—C
1
-C4Alkyl is —CO-methyl, —CO-ethyl, —CO-n-propyl, —CO-isopropyl, or —CO-n-, —CO-iso-, —CO-sec- or —CO-tert-butyl.
C
1
-C
4
Alkylcarboxylic acid (C
1
-C
4
alkyl) ester is, for example, methylcarboxylic acid methyl ester, methylcarboxylic acid ethyl ester, methylcarboxylic acid n-propyl ester, methylcarboxylic acid isopropyl ester, methylcarboxylic acid n-butyl ester or methylcarboxylic acid isobutyl ester, methylcarboxylic acid sec-butyl ester or methylcarboxylic acid tert-butyl ester or ethylcarboxylic acid methyl ester, ethylcarboxylic acid ethyl ester, ethylcarboxylic acid n-propyl ester, ethylcarboxylic acid isopropyl ester, ethylcarboxylic acid n-butyl ester, ethylcarboxylic acid sec-butyl ester or ethylcarboxylic acid tert-butyl ester, n-propylcarboxylic acid methyl ester or n-butylcarboxylic acid methyl ester.
Hal is, for example, halide and denotes fluoride, chloride, bromide or iodide.
Especially preferred perylene-3,4:9,10-tetracarboxylic acid bisimides of general formulae (I) and (II) are those wherein R
1
and R
2
are each independently of the other 1-n-hexyl-1-heptyl, 2,5-di-tert-butylphenyl, 1-nonyl-1-decyl or 1-n-butyl-n-pentyl; very especially R
2
is R
1
.
Very special preference is given to perylene-3,4:9,10-tetracarboxylic acid bisimides of general formulae (I) and (II) wherein A
1
is —S—, NR
4
, —CH═CH—, R
3
OOC—C(−) ═C(−)—COOR
3
, or a linkage of formula (III), (IV), (V), (VI) or (VII) and A
2
and A
3
are an organic radical of formula (V) or A
2
and A
3
are each independently of the other an organic radical of formula (III), (IV) or (V).
Preferred perylenes of the present invention are the compounds of formulae (VIII) to (XX) given below, wherein R
1
and R
2
are especially each independently of the other 1-hexyl-1-heptyl, 2,5-di-tert-butylphenyl, 1-nonyl-1-decyl or 1-butyl-pentyl,
very especially R
1
and R
2
in (VII) are 1-n-hexyl-1-heptyl, 2,5-di-tert-butylphenyl or 1-butylpentyl, and
wherein very especially R
1
and R
2
are 1-n-hexyl-1-heptyl, and
wherein preferably
R
4
is unsubstituted or substituted C
1
-C
24
alkyl, C
1
-C
24
cycloalkyl, phenyl, and especially cyclohexyl or 2,5-di-tert-butylphenyl, and
R
1
and R
2
are very especially 1-n-hexyl-1-heptyl, and
wherein
R
1
and R
2
are very especially 1-n-hexyl-1-heptyl, and
wherein
R
1
and R
2
are very especially 1-n-hexyl-1-heptyl, and
wherein
R
1
and R
2
are very especially 1-n-hexyl-1-heptyl, 2,5-di-tert-butylphenyl or 1-n-butyl-n-pentyl, and
wherein preferably
R
4
is unsubstituted or substituted C
1
-C
24
alkyl, phenyl, benzyl, —CO—C
1
-C
4
alkyl, —CO—C
6
H
5
or C
1
-C
4
alkylcarboxylic acid (C
1
-C
4
alkyl) ester, and especially C
1
-C
4
alkyl, more especially methyl, benzyl, —CH
2
COOC
2
H
5
, —COCH
3
or —CO-phenyl, and
R
1
and R
2
are very especially 1-n-hexyl-1-heptyl, 2,5-di-tert-butylphenyl or 1-n-butyl-n-pentyl, and
wherein
R
1
and R
2
are very especially 1-n-hexyl-1-heptyl, 2,5-di-tert-butylphenyl or 1-n-butyl-n-pentyl, and
wherein
R
1
and R
2
are very especially 1-n-hexyl-1-heptyl, 2,5-di-tert-butylphenyl or 1-n-butyl-n-pentyl, and
wherein especially
R
4
is substituted or unsubstituted phenyl, and
R
1
and R
2
are very especially 1-n-hexyl-1-heptyl, and
wherein preferably
R
3
is C
1
-C
4
alkyl, especially methyl or ethyl, and
R
1
and R
2
are very especially 1-n-hexyl-1-heptyl, and
wherein
R
1
and R
2
are very especially 1-n-hexyl-1-heptyl, and
wherein especially
R
4
is phenyl, and
R
1
and R
2
are very especially 1-n-hexyl-1-heptyl, and
wherein especially
R
4
is phenyl, and
R1 and R
2
are very especially 1-n-hexyl-1-heptyl.
The perylenebisimides (I) according to the invention wherein A
1
is A
4
, wherein A
4
is a linkage selected from the group consisting of the organic radicals of formulae (III), (IV), (V) and (VII), and perylenebisimides (II) wherein A
2
is A
5
, wherein A
5
is a linkage of formula (III) or (V), and A
1
is A
6
, wherein A
6
is a linkage of formula (V), a

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