Organic compounds -- part of the class 532-570 series – Organic compounds – Azoxy
Reexamination Certificate
2001-09-13
2004-04-27
Powers, Fiona T. (Department: 1626)
Organic compounds -- part of the class 532-570 series
Organic compounds
Azoxy
C534S570000, C534S572000, C008S636000, C008S681000
Reexamination Certificate
active
06727351
ABSTRACT:
The present invention relates to novel azoxy dyes of the general formula I in the form of the free acid
where
n is 0 or 1, each
R
1
is selected from the group consisting of methoxy, hydroxyl and carboxyl, each
R
2
is selected from the group consisting of carboxyl, amino, C
1
-C
4
-alkylamino, allylamino, benzylamino and methoxycarbonylmethylamino, and the phenyl rings A may additionally be substituted by C
1
-C
8
-alkyl, unsubstituted or methyl- or halogen-substituted phenyl, hydroxyl, amino, nitro, halogen, carboxyl, N-benzylcarbamoyl, unsubstituted or nitro-, halogen-, C
1
-C
4
-alkoxy- or acetoxy-substituted phenylcarbamoyl and naphthylcarbamoyl or be benzofused,
their copper complexes, a process for preparing the copper complex dyes, azoxy dyes of the formula I in their partially or completely deacylated form, their copper complexes, colorants comprising these azoxy dyes and/or their copper complexes and their use for dyeing and printing natural or synthetic substrates.
CH-A-193 343, CH-A-196 252, CH-A-196 259, CH-A-196 260, CH-A-196 264, DE-A-26 51 369, EP-A-648 814 and EP-A-43 792 describe azoxy dyes containing various hydroxyaminonaphthalenesulfonic acids and their copper complexes.
DE-A-28 44 597 teaches a process for preparing copper-containing azoxy dyes whose coupling component is a 4-hydroxy-6-sulfophenylaminonaphthalene-2-sulfonic acid.
The prior art dyes are dull and frequently provide unlevel dyeings.
It is an object of the present invention to provide dyes which do not have the abovementioned disadvantages and which possess good application properties.
We have found that this object is achieved by the above-described dyes and their copper complexes.
Any alkyl appearing in the abovementioned formula may be straight-chain or branched.
Additionally substituted phenyl rings A may each bear 1, 2, 3 or 4, preferably 1 or 2, substituents, which may be different.
Halogen is fluorine, chlorine, bromine or iodine.
R
2
is for example methylamino, ethylamino, propylamino, isopropylamino, butylamino, isobutylamino, sec-butylamino and tert-butylamino.
Substituents for the phenyl rings A include for example methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-, 3- or 4-bromophenyl, 2-, 3- or 4-methylphenyl, 2-, 3- or 4-nitrophenylcarbamoyl, 2-, 3- or 4-methoxyphenylcarbamoyl, 2-methoxy-4-nitro- and 2-methoxy-5-nitrophenylcarbamoyl, 2-, 3- or 4-ethoxyphenylcarbamoyl and 2-, 3- or 4-acetoxyphenylcarbamoyl.
In the description part and in the claims, the dyes of the formulae I, VI, VII, VIII and IX are depicted in the form of the free acids, but preferably they are present as salts, especially as alkali metal salts, and are isolated as salts from the synthesis. The formula depiction as free acid must therefore, as customary in the dye literature, be considered equivalent to the depiction as salt.
Suitable cations are derived from metal or ammonium ions. Metal ions are in particular the lithium, sodium or potassium ions. Ammonium ions for the purposes of the present invention are unsubstituted or substituted ammonium cations. Substituted ammonium cations include for example monoalkyl-, dialkyl-, trialkyl-, tetraalkyl- or benzyltrialkyl-ammonium cations for example diethanolammonium or cations derived from nitrogenous five- or six-membered saturated heterocycles, such as pyrrolidinium, piperidinium, morpholinium, piperazinium or N-alkylpiperazinium cations or their N-monoalkyl- or N,N-dialkyl-substituted products. Alkyl is here to be understood as meaning in general straight-chain or branched C
1
-C
20
-alkyl, which may be substituted by 1 or 2 hydroxyl groups and/or interrupted by from 1 to 4 oxygen atoms in ether function.
The dyes may be prepared by reacting an aminohydroxynaphthalenesulfonic acid of the formula II
where n is 0 or 1, with an anhydride of the formula III
where B is a single bond or imino, C
1
-C
4
-alkylimino or phenylimino and A is as defined above, in a weakly alkaline medium to form a coupling component of the formula IV
This coupling component may be coupled with nitroanilines of the formula V
where R
1
is as defined above, as diazo component in a conventional manner before two resultant nitromonoazo dyes are reductively linked via an azoxy bridge to form the dyes of the invention.
The reducing agents used are preferably reducing sugars, for example D-glucose, in aqueous alkaline solution. The solution may be rendered alkaline for example by means of an alkali metal hydroxide such as sodium hydroxide or lithium hydroxide. Such reductions are common knowledge and described for example in EP-A-43 792. In addition, a reduction with customary reducing agents such as aldehydes e.g. formaldehyde or hydrazine hydrate is possible.
Suitable aminohydroxynaphthalenesulfonic acids II include for example 1-amino-8-hydroxynaphthalene-4,6-disulfonic acid, 2-amino-8-hydroxynaphthalene-6-sulfonic acid, 3-amino-8-hydroxynaphthalene-6-sulfonic acid, 4-amino-8-hydroxynaphthalene-6-sulfonic acid and particularly preferably 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid.
Examples of anhydrides III are
phthalic anhydrides such as phthalic anhydride, 3-methyl-, 4-methyl-, 3,6-dimethyl-, 4-tert-butyl-, 3,4,5,6-tetramethyl-, 3-o-tolyl-, 3,6-diphenyl-, 3-hydroxy-, 4-carboxy-, 3-amino-, 3-nitro-, 4-nitro-4-(2,4-dichlorophenyl)carbamoyl-, 4-(3,4-dichlorophenyl)carbamoyl-, 4-(2-methoxy-5-chlorophenyl)carbamoyl-, 4-(3-nitrophenyl)carbamoyl-, 4-(2-methoxy-4-nitrophenyl)carbamoyl-, 4-(2-methoxy-5-nitrophenyl)carbamoyl, 4-(4-acetamidophenyl)carbamoyl-, 4-(2-ethoxyphenyl)carbamoyl-, 4-naphthylcarbamoyl-, 4-benzylcarbamoyl-, 3-fluoro-, 4-fluoro-, 3,4,5,6-tetrafluoro-, 3,6-difluoro-, 3,4-difluoro-, 3-chloro-, 4-chloro-, 3,6-dichloro-, 4,5-dichloro-, 3,4,5,6-tetrachloro-, 4-bromo-, 3,4,5,6-tetrabromo-, 3,4,5,6-tetraiodo- and 3-(4-bromo)phenyl-phthalic anhydride,
isatoic anhydrides such as isatoic anhydride, 6-methyl-, 6-hydroxy-, 5-hydroxy-, 4-carboxy-, 4-nitro-, 5-nitro-, 5-amino-, 6-fluoro-, 5-chloro-, 6-chloro-, 3,5-dichloro-, 5-bromo-, N-methyl-, N-ethyl-, N-benzyl-, N-allyl-, N-methyl-5-nitro-, N-methyl-5-chloro-, N-methyl-6-chloro- and N-methoxycarbamoylmethyl-isatoic anhydride, and also
naphthalene-1,2-dicarboxylic and naphthalene-2,3-dicarboxylic anhydrides.
The present invention further provides copper complex dyes and their mixtures which are obtainable by reacting dyes I with at least 0.1 mol equivalent of a copper donor. Preferably, 0.1-2 mol of a copper donor is used per mole of dye. Amounts above 2 mol equivalents are possible, but have no influence on the product. Incomplete formation of 2:1 complexes, i.e., the use of <2 mol equivalents of the copper donors, provides mixtures of the uncomplexed, singly copper-complexed and doubly copper-complexed dyes.
The copper complex dyes conform to the general formula VI in the form of the free acid
where at least one of M
1
and M
2
is copper(II) and any which is not is hydrogen and methyl, and n, R
2
and A are each as defined above. When M
1
or M
2
is hydrogen and methyl, the methyl radical will form the methoxy group on the phenyl ring and the hydrogen will form the hydroxyl group on the naphthalene structure.
Copper complex dyes obtained by reaction with 0.5-1.7 mol, especially 0.5-1.5 mol, of copper donor per mole of dye are preferred.
The copper donors used may be salts which contain the copper as cation, for example copper sulfate, copper chloride or copper acetate. In some cases, the use of complex copper compounds is of advantage, for example in the form of copper-ammine complexes, such as coppertetrammine sulfates from copper sulfate and ammonia, pyridine or monoethanolamine, or in the form of compounds which contain the copper in complexed form, for example complex copper compounds of the alkali metal salts of aliphatic aminocarboxylic acids or hydroxycarboxylic acids, as of glycocoll, of lactic acid and in particular of tartaric acid, such as sodium copper tartrate.
The treatment with the copper donor takes place in an aqueous or organic/aqueous medium, for example at
Etzbach Karl-Heinz
Kräh Claudia
Sens Rüdiger
Tresch Rainer
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