Azo dyes

Details Azo dyes Azo dyes

1999-10-01

2001-10-02

Higel, Floyd D. (Department: 1626)

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

Organic compounds

Azo

C008S662000, C008S682000, C008S688000, C534S804000, C534S849000, C106S031770, C106S031800, C106S496000

Reexamination Certificate

active

06297362

ABSTRACT:

The invention relates to new azo dyes, to a process for preparing them and to their use for dyeing and printing paper and other materials, especially as a dye in ink-jet inks.
The dyes of the invention have in the form of their free acids the formula (I)
wherein
R is hydrogen or optionally substituted C
1
-C
6
-alkyl,
R
1
is hydrogen or C
1
-C
6
-alkyl,
R
2
is hydrogen, optionally substituted C
1
-C
6
-alkyl or optionally substituted phenyl,
the ring D is optionally substituted by one or more identical or different substituents selected from the group consisting of C
1
-C
6
-alkyl, C
1
-C
6
-alkoxy, halogen, especially F, Cl and Br, and SO
3
H,
m is 0 or 1,
n is 1, 2 or 3 and as a function of n
X is a mono-, di- or trivalent acyl radical, pyrimidine or 1,3,5-triazine radical which is not fibre-reactive.
Exemplary substituents for optionally substituted alkyl radicals include for example: OH, NR
3
R
4
, where R
3
and R
4
independently of each other are hydrogen, C
1
-C
4
-alkyl, C
2
-C
4
-hydroxyalkyl.
Exemplary substituents for optionally substituted phenyl include for example: C
1
-C
6
-alkyl, C
1
-C
6
-alkoxy, COOH, SO
3
H, F, Cl, Br.
Preferred dyes of the formula (I) are those wherein
R is hydrogen, C
1
-C
6
-alkyl or C
2
-C
4
-hydroxyalkyl,
R
1
is hydrogen or C
1
-C
6
-alkyl,
R
2
is hydrogen, C
1
-C
6
-alkyl, C
2
-C
4
-hydroxyalkyl, C
2
-C
4
-aminoalkyl, especially NR
3
R
4
-substituted C
2
-C
4
-alkyl, wherein
R
3
and R
4
independently of each other represent hydrogen, C
1
-C
4
-alkyl and C
2
-C
4
-hydroxyalkyl or denote optionally C
1
-C
4
-alkyl-, C
1
-C
4
-alkoxy-, HOOC—, HO
3
S—, F—, Cl— and/or Br-substituted phenyl,
and the ring D is optionally substituted by one or more identical or different substituents selected from the group consisting of C
1
-C
4
-alkyl, C
1
-C
4
-alkoxy, F, Cl, Br and SO
3
H.
In a particular embodiment
when n=1 then X is optionally HOOC-substituted C
2
-C
6
-alkanoyl, optionally C
1
-C
4
-alkyl-, C
1
-C
4
-alkoxy-, HO
3
S—, HOOC—, F—, Cl— and/or Br-substituted C
6
-C
10
-aroyl or a radical of the formulae (II), (IIIa) or (IIIb)
wherein
T
1
and T
2
independently of each other are OR
5
, NR
6
R
7
or SR
8
,
wherein
R
5
and R
8
independently of each other are hydrogen, C
1
-C
6
-alkyl, sulpho-, carboxyl- and/or di-C
1
-C
3
-alkylamino-substituted C
2
-C
6
-alkyl or optionally C
1
-C
4
-alkyl-, C
1
-C
4
-alkoxy-, sulpho-, F—, Br— and/or Cl-substituted phenyl,
R
6
is hydrogen, C
1
-C
6
-alkyl or C
2
-C
6
-alkyl optionally substituted by sulphur, hydroxyl, C
1
-C
3
-alkoxy, amino or mono- or disubstituted C
1
-C
3
-alkylamino,
R
7
has the meanings of R
6
independently of R
6
or is optionally C
1
-C
4
-alkyl-, C
1
-C
4
-alkoxy-, carboxyl-, sulpho-, F—, Cl—and/or Br-substituted phenyl or naphthyl, or
R
6
and R
7
combine with the nitrogen atom to which they are attached to form a morpholine radical or an optionally C
1
-C
4
-alkyl-, C
2
-C
4
-hydroxyalkyl- or C
2
-C
4
-aminoalkyl-substituted piperazine radical, and
T
3
is hydrogen, F, Cl, CN, CCl
3
, CCl
2
F or COOH.
In a further particular embodiment
when n=2 X is —CO—, —CO—(CH
2
)
1-4
—CO—, —COC
2
H
2
—CO—, optionally H
3
C—, H
3
CO—, F—, Cl—, Br— and/or HOOC-substituted C
6
-C
10
-diaroyl or a radical of the formulae (IVa), (IVb) or (V)
wherein
T
1
and T
3
are each as defined above and
Z is a radical of the formula
Y is C
2
-C
6
-alkylene or optionally carboxyl- or sulpho-substituted arylene, and
R
9
is hydrogen, C
1
-C
6
-alkyl or C
2
-C
4
-hydroxyalkyl.
In a likewise particular embodiment
when n=3 X is a radical of the formula (VI) or (VII)
wherein T
3
is as defined above.
Particular preference is given to compounds of the formula (I) which conform to the formula (VIII)
wherein
R, R
1
, R
2
, D, X and m are each as defined above,
n is 1 or 2.
Particular preference in this context is given to dyes of the formula (VIII) wherein m=0.
Very particular preference is given to dyes of the formula (VIII) wherein R, R
1
and R
2
are each as defined above, m=0, the ring D does not bear any further substituents, and
X is benzoyl or a radical of the formula (II) when n=1 and CO, COC
2
H
4
CO, COC
2
H
2
CO,
or a radical of the formula (IVa) or (IVb) when n=2.
In a preferred embodiment, the substituents of the compound of the formula (I) and its subformulae have the following meanings:
R
1
and R
2
independently of each other are preferably hydrogen, CH
3
, C
2
H
5
, C
3
H
7
, C
2
H
4
OH, C
2
H
4
SO
3
H, C
3
H
6
OH, C
3
H
6
SO
3
H, C
2
H
4
COOH, C
3
H
6
COOH, C
6
H
5
, C
6
H
4
SO
3
H, C
6
H
4
COOH or C
2
H
4
N(CH
3
)
2
.
R is preferably hydrogen, CH
3
, C
2
H
5
, C
2
H
4
OH.
R
3
and R
4
independently of each other are preferably hydrogen, CH
3
, C
2
H
4
OH.
R
5
is preferably derived from the following HOR
5
compounds: ethylene glycol or isethionic acid (2-hydroxyethanesulphonic acid), water.
R
6
is preferably hydrogen, CH
3
, C
2
H
5
, C
3
H
7
, C
2
H
4
OH, C
2
H
4
OCH
3
or C
3
H
6
OH.
R
7
is preferably hydrogen, C
2
H
4
OH, C
3
H
6
OH, C
2
H
4
SO
3
H, C
2
H
4
COOH, C
3
H
6
SO
3
H, C
3
H
6
COOH, C
6
H
5
, C
6
H
4
SO
3
H, C
6
H
4
COOH or
R
6
and R
7
combine with the nitrogen atom to which they are bonded to preferably denote a radical of the formula
R
8
is preferably derived from the following thiols HSR
8
: 2-mercaptoethanol or 3-mercapto-1-propanesulphonic acid.
R
9
is preferably hydrogen, CH
3
, C
2
H
4
OH.
T
1
and T
2
independently of each other are preferably derived respectively from the following amines T
1
H and T
2
H:
2-aminoethanol, 2-methylaminoethanol, 1-amino-2-propanol, 2-amino-1-propanol, diethanolamine, taurine, N-methyltaurine, glycine, 3-aminopropanoic acid, 3-dimethylamino-1-propylamine, N-2-hydroxyethyl-piperazine, N-2-aminoethylpiperazine, morpholine, aniline, orthanilic acid, methanilic acid, sulphanilic acid, anthranilic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, ammonia.
Z is preferably:
m-phenylenediamine, p-phenylenediamine, 2,4-diaminobenzenesulphonic acid, 2,5-diaminobenzenesulphonic acid, piperazine, 2,5-dimethylpiperazine.
Very particular preference is likewise given to compounds of the formula (I) which conform to the formula (IX)
wherein the substituents are each as defined above.
Very particular preference is given to compounds of the formula (X)
wherein
R is hydrogen, CH
3
or C
2
H
5
,
R
2
is hydrogen, CH
3
, C
2
H
5
, C
3
H
7
, C
4
H
9
or C
6
H
5
, and
T
1
and T
2
are each as defined above and preferably represent OH, NH
2
, NH
2
C
2
H
4
OH, N(C
2
H
4
OH)
2
, NHC
2
H
4
SO
3
H, CH
2
NC
2
H
4
SO
3
H.
The dyes of the formula (D are preferably used in the form of their lithium, sodium, potassium or ammonium salts. Useful ammonium salts are in particular ammonium salts in which 1 to 4 hydrogen atoms are replaced by identical or different C
1
-C
6
-alkyl radicals or hydroxyl- or C
1
-C
3
-alkoxy-substituted C
2
-C
6
-alkyl radicals. Particular preference is given to alkanolamine ammonium salts such as methyldiethanolammonium, dimethylethanolammonium or triethanolammonium and quaternary ammonium ions such as tetramethylammonium and tetraethylammonium.
The invention further provides a process for preparing the compounds of the formula (I) according to the invention, which is characterized in that compounds of the formula (XI)
wherein
R, R
1
, R
2
, D and m are each as defined above, are reacted with compounds of the formula
X(B)
n
,
where
X is as defined above as a function of n,
n is 1, 2 or 3, and
B is a detachable Cl or F radical.
The preferred compounds of the formula X(B)
n
are carbonyl halides, methyl carboxylates and 2,4,6-trifluoro- or 2,4,6-trichloropyrimidines or -1,3,5-triazines with any fluorine or chlorine atoms still present in these reaction products in the 4- and/or 6-position being replaced by HN-, HO- or HS-containing nucleophiles.
Preferred acylating agents of the formula X(B)
n
are carbonyl chlorides, for example acetyl chloride, propionyl chloride, benzoyl chloride, terephthaloyl chloride, succinoyl chloride, fumaroyl chloride, phosgene and carboxylic anhyd

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