Claims
- 1. A monoazo dye of the formula ##STR331## wherein R.sub.2 is hydrogen, halogen, C.sub.1-4 -alkyl, trifluoromethyl, ##STR332## R.sub.3 is C.sub.1-4 -alkyl or phenyl, R.sub.4 is hydrogen, methyl or ethyl, and R.sub.7 and R.sub.8 are each independently hydrogen, C.sub.1-4 -alkyl, C.sub.1-4 -hydroxyalkyl, C.sub.5-7 -cycloalkyl, phenyl or phenyl which is substituted by halogen, trifluoromethyl or C.sub.1-4 -alkyl, and R.sub.9 is phenyl or phenyl substituted by C.sub.1-4 -alkyl or halogen, or naphthyl.
Priority Claims (1)
| Number |
Date |
Country |
Kind |
| 1246/83 |
Mar 1983 |
CHX |
|
Parent Case Info
This application is a continuation of application Ser. No. 06/584,176 filed Feb. 27, 1984, now U.S. Pat. No. 4,954,563.
The present invention has for its object to provide novel monoazo dyes which are suitable for dyeing natural and synthetic polyamides from an aqueous bath, which furthermore dye said materials in shades in the range from yellow to orange and, in addition to having good fastness properties such as lightfastness, wetfastness and resistance to formaldehyde, in particular do not give rise to thermochromism. It has now been found that the monoazo dyes of the formula (1) below meet these requirements.
Accordingly, the invention relates to monoazo dyes of the formula ##STR4## wherein R.sub.1 is hydrogen, C.sub.1 --C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, halogen, C.sub.2 -C.sub.4 alkanoylamino or is an unsubstituted or substituted arylsulfonyl, aryloxy or arylcarbonyl radical; R.sub.2 is hydrogen, halogen, an unsubstituted or substituted alkyl, aryloxy or aryloxysulfonyl radical or a radical of the formula ##STR5## R.sub.3 is an unsubstituted or substituted alkyl or aryl radical; R.sub.4 is hydrogen or alkyl; and R.sub.5 and R.sub.6 are each independently hydrogen or an unsubstituted or substituted alkyl, cycloalkyl or aryl radical, with the proviso that R.sub.1 may not be hydrogen or halogen if R.sub.2 is an unsubstituted or substituted aryloxysulfonyl radical, a radical of the formula ##STR6## or the trifluoromethyl group, and the sulfo group is attached to the benzene ring of the indole radical.
R.sub.1 as C.sub.1 -C.sub.4 alkyl is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl.
R.sub.1 as C.sub.1 -C.sub.4 alkoxy is methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy or tert-butoxy.
R.sub.1 as C.sub.2 -C.sub.4 alkanoylamino is e.g. acetylamino, propionylamino or butyrylamino.
Where R.sub.1 is an unsubstituted or substituted arylsulfonyl, aryloxy or arylcarbonyl radical, the aryl moiety is preferably a radical of the benzene or naphthalene series which may be further substituted, for example by C.sub.1 -C.sub.4 alkyl groups such as methyl and ethyl, C.sub.1 -C.sub.4 alkoxy groups such as methoxy and ethoxy, halogen such as fluorine, chlorine and bromine, and C.sub.1 -C.sub.6 alkanoylamino groups such as acetylamino, and hydroxyl.
R.sub.1 and/or R.sub.2 as halogen may be fluorine, chlorine or bromine.
Where R.sub.2 is an unsubstituted or substituted aryloxy or aryloxysulfonyl radical, the aryl moiety is a radical of the benzene or naphthalene series which may be further substituted, for example by C.sub.1 -C.sub.4 alkyl groups such as methyl and ethyl, C.sub.1 -C.sub.4 alkoxy groups such as methoxy and ethoxy, halogen such as fluorine, chlorine and bromine, C.sub.1 -C.sub.6 alkanoylamino groups such as acetylamino, and hydroxyl.
Unsubstituted or substituted alkyl radicals R.sub.2, R.sub.3, R.sub.5 or R.sub.6 are preferably each independently a straight chain or branched C.sub.1 -C.sub.12 alkyl, preferably C.sub.1 -C.sub.4 alkyl, radical which may be further substituted, for example by halogen such as fluorine, chlorine or bromine, hydroxyl, cyano, C.sub.1 -C.sub.4 alkoxy such as methoxy or ethoxy, and C.sub.1 -C.sub.6 alkanoyl groups such as the acetyl or propionyl group, and the benzoyl group. The alkyl radical R.sub.3 can also be substituted by sulfo. Typical examples of alkyl radicals R.sub.2, R.sub.3, R.sub.5 and R.sub.6 are: methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl and trifluoromethyl.
Unsubstituted or substituted aryl radicals R.sub.3, R.sub.5 and R.sub.6 are preferably each independently a radical of the benzene or naphthalene series which can be further substituted, for example by C.sub.1 -C.sub.4 alkyl groups such as methyl, C.sub.1 -C.sub.4 alkoxy groups such as methoxy and ethoxy, halogen such as fluorine, chlorine or bromine, trifluoromethyl, C.sub.1 -C.sub.6 alkanoylamino groups such as acetylamino, and hydroxyl and carboxyl. The aryl radical R.sub.3 can also be substituted by sulfo. In particular, an aryl radical R.sub.3, R.sub.5 and R.sub.6 is a phenyl radical which can be substituted by methyl, trifluoromethyl and chlorine.
An alkyl radical R.sub.4 is preferably a straight chain or branched C.sub.1 -C.sub.12 alkyl and, most preferably, a C.sub.1 -C.sub.8 alkyl radical. Typical examples of such alkyl radicals are: methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, pent-1-yl, pent-3-yl, hept-1-yl, hept-3-yl and oct-1-yl.
R.sub.5 and R.sub.6 as unsubstituted or substituted cycloalkyl may each preferably be independently a cycloalkyl group containing 5- to 7-membered rings which may be further substituted, for example by C.sub.1 C.sub.4 alkyl such as methyl. The cyclohexyl group is preferred.
Preferred monoazo dyes of the formula (1) are those wherein R.sub.1 is hydrogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, halogen, C.sub.2 -C.sub.4 alkanoylamino, a phenylsulfonyl, naphthylsulfonyl, phenoxy or phenylcarbonyl radical, each unsubstituted or substituted by C.sub.1 -C.sub.4 alkyl or halogen, R.sub.2 is hydrogen, halogen, C.sub.1 -C.sub.4 alkyl, tri-fluoromethyl, a phenoxy or phenoxysulfonyl radical, each unsubstituted or substituted by C.sub.1 -C.sub.4 alkyl or halogen, or is ##STR7## R.sub.3 is C.sub.1 -C.sub.4 alkyl or phenyl, R.sub.4 is hydrogen or C.sub.1 -C.sub.8 -alkyl, and R.sub.7 and R.sub.8 are each independently hydrogen C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 hydroxyalkyl, C.sub.5 -C.sub.7 cycloalkyl, phenyl or phenyl which is substituted by halogen, trifluoromethyl or C.sub.1 -C.sub.4 -alkyl.
Particularly preferred monoazo dyes are those of the formula ##STR8## wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are as defined for formula (1).
More particularly preferred monoazo dyes are those of the formula (2), wherein R.sub.1 is hydrogen, methyl, chlorine, methoxy, ethoxy, o-methylphenoxy, phenoxy, acetylamino, phenylsulfonyl, p-methylphenylsulfonyl, p-chlorophenylsulfonyl, naphthylsulfonyl, p-methylbenzoyl or p-chlorobenzoyl, R.sub.2 is hydrogen, chlorine, methyl, trifluoromethyl, o-methylphenoxy, o-chlorophenoxy, o-chlorophenoxysulfonyl, --SO.sub.2 NH.sub.2, N--C.sub.1 -C.sub.2 alkylaminosulfonyl, N,N-dimethylaminosulfonyl. N-methyl-N-.beta.-hydroxyethylaminosulfonyl, N-methyl-n-cyclohexylaminosulfonyl, N-phenylaminosulfonyl, N-o-methylphenylaminosulfonyl, N-o-chlorophenylaminosulfonyl, N-m-trifluoromethylphenylaminosulfonyl, N-ethyl-N-phenylaminosulfonyl, --CONH.sub.2 or --CON(CH.sub.3).sub.2, R.sub.3 is methyl or phenyl, and R.sub.4 is hydrogen, methyl, ethyl or octyl.
Further preferred monoazo dyes are those of the formula ##STR9## wherein R.sub.1, R.sub.2 and R.sub.4 are as defined for formula (1), in particular the monoazo dyes of the formula (3), wherein R.sub.1 is hydrogen, methyl, chlorine, methoxy, phenoxy, acetylamino, phenylsulfonyl, naphthylsulfonyl, p-methylphenylsulfonyl or p-chlorophenylsulfonyl, R.sub.2 is hydrogen, chlorine, trifluoromethyl, --SO.sub.2 NH.sub.2, N-methyl-N-cyclohexylaminosulfonyl, phenylaminosulfonyl or N-ethyl-N-phenylaminosulfonyl, and R.sub.4 is hydrogen or methyl.
Preferred monoazo dyes are also those of the formula ##STR10## wherein R.sub.2, R.sub.3 and R.sub.4 are as defined for formula (2) and R.sub.9 is a phenyl radical which is unsubstituted or substituted by C.sub.1 -C.sub.4 alkyl and halogen, or naphthyl.
In the monoazo dyes of the formula (4), the symbols have the following preferred meanings: R.sub.2 is hydrogen, R.sub.3 is phenyl, R.sub.4 is hydrogen and R.sub.9 is phenyl.
A valuable representative is the monoazo dye of the formula ##STR11## The present invention also relates to a process for the preparation of the monoazo dyes of the formula (1), which comprises diazotising a diazo component of the formula ##STR12## and coupling the diazonium compound to a coupling component of the formula ##STR13## wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 in formulae (6) and (7) are as defined for formula (1).
The diazotisation of the diazo component of the formula (6) is normally carried out by treatment with nitrous acid in an aqueous solution of mineral acid at low temperature, and the coupling to the coupling component of the formula (7) is carried out in the acid, neutral or alkaline pH range.
It is preferred to diazotise diazo components of the formula (6), wherein R.sub.1 is hydrogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, halogen, C.sub.2 -C.sub.4 alkanoyl-amino, a phenylsulfonyl, naphthylsulfonyl, phenoxy or phenylcarbonyl radical, each unsubstituted or substituted by C.sub.1 -C.sub.4 -alkyl or halogen, R.sub.2 is hydrogen, halogen, C.sub.1 -C.sub.4 alkyl, trifluoromethyl, a phenoxy or phenoxysulfonyl radical, each unsubstituted or substituted by C.sub.1 -C.sub.4 alkyl or halogen, or is ##STR14## R.sub.7 and R.sub.8 are each independently hydrogen, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 hydroxyalkyl, C.sub.5 -C.sub.7 cycloalkyl, phenyl or phenyl which is substituted by halogen, trifluoromethyl or C.sub.1 -C.sub.4 alkyl, and to couple the diazonium compound to a coupling component of the formula (7), wherein R.sub.3 is C.sub.1 -C.sub.4 alkyl or phenyl and R.sub.4 is hydrogen or C.sub.1 -C.sub.8 alkyl. It is preferred to use a coupling component of the formula ##STR15## wherein R.sub.3 and R.sub.4 have the above meanings.
A preferred embodiment of the process comprises diazotising a diazo component of the formula (6), wherein R.sub.1 is hydrogen, methyl, chlorine, methoxy, ethoxy, o-methylphenoxy, phenoxy, acetylamino, phenylsulfonyl, p-methylphenylsulfonyl, p-chlorophenylsulfonyl, naphthylsulfonyl, p-methylbenzoyl or p-chlorobenzoyl; R.sub.2 is hydrogen, chlorine, methyl, trifluoromethyl, o-methylphenoxy, o-chlorophenoxy, o-chlorophenoxysulfonyl, --SO.sub.2 NH.sub.2, N--C.sub.1 -C.sub.2 alkylaminosulfonyl, N,N-dimethylaminosulfonyl. N-methyl-N-.beta.-hydroxyethylaminosulfonyl, N-methyl-N-cyclohexylaminosulfonyl, N-phenylaminosulfonyl, N-o-methylphenylaminosulfonyl, N-o-chlorophenylaminosulfonyl, N-m-trifluoromethylphenylaminosulfonyl, N-ethyl-N-phenylaminosulfonyl, --CONH.sub.2 or --CON(CH.sub.3).sub.2, and coupling the diazonium compound to a coupling component of the formula (8), wherein R.sub.3 is methyl or phenyl and R.sub.4 is hydrogen, methyl, ethyl or octyl.
Another preferred embodiment of the process comprises diazotising a diazo component of the formula (6), wherein R.sub.1 is hydrogen, methyl, chlorine, methoxy, phenoxy, acetylamino, phenylsulfonyl, naphthylsulfonyl, p-methylphenylsulfonyl or p-chlorophenylsulfonyl, R.sub.2 is hydrogen, chlorine, trifluoromethyl, --SO.sub.2 NH.sub.2, N-methyl-N-cyclohexylaminosulfonyl, phenylaminosulfonyl or N-ethyl-N-phenylaminosulfonyl, and coupling the diazonium compound to a coupling component of the formula (9), wherein R.sub.4 is hydrogen or methyl.
Yet another preferred embodiment of the process comprises diazotising a diazo component of the formula (10) ##STR16## wherein R.sub.2 is as defined for formula (2) and R.sub.9 is phenyl or phenyl which is substituted by C.sub.1 -C.sub.4 alkyl and halogen, or naphthyl, and coupling the diazonium compound to a coupling component of the formula (8).
It is preferred to use a diazo component of the formula (10), wherein R.sub.2 is hydrogen and R.sub.9 is phenyl, and a coupling component of the formula (8), wherein R.sub.3 is phenyl and R.sub.4 is hydrogen.
The particularly valuable monoazo dye of the formula (5) is prepared by diazotising 2-amino-1,1'-diphenylsulfone and coupling the intermediate to 2-phenylindole-5-sulfonic acid.
The diazo components of the formula (6) are known and are prepared by methods which are known per se.
Representative examples of the wide range of possible diazo components are: 2-amino-1,1'-diphenylsulfone, 2-amino-4-chloro-1-phenyl-2'-naphthylsulfone, 2-amino-4'-methyl-1,1'-diphenylsulfone, 2-amino-4'-chloro-1,1'-diphenylsulfone, 2-amino-1-phenyl-2'-naphthylsulfone, 4-amino-4'-methyl-1,1'-diphenylsulfone, 4-amino-4'-chloro-1,1'-diphenylsulfone, 4-amino-1,1'-diphenylsulfone, 4-amino-1-phenyl-2'-naphthylsulfone, 2-amino-4,4'-dimethyl-1,1'-diphenylsulfone, 2-amino-4-methyl-1,1'-diphenylsulfone, 2-amino-4-methyl-4'-chloro-1,1'-diphenylsulfone, 2-amino-4,4'-dichloro-1,1'-diphenylsulfone, 2-amino-4-chloro-4'-methyl-1,1'-diphenylsulfone, 2-amino-4-trifluoromethyl1,1'-diphenylsulfone, 2-amino-4-trifluoromethyl-4'-methyl-1,1'-diphenylsulfone, 2-amino-4'-chloro-1,1'-diphenylsulfone-4-sulfamide, 2-amino-1,1'-diphenylsulfone-4-sulfonamide, 2-amino-4'-methyl-1,1'-diphenylsulfone-4-sulfamide, 2-amino-4'-methyl-1,1'-diphenylsulfone-4-N-methylsulfamide, 2-amino-4' -methyl-1,1'-diphenylsulfone-4-N,N-dimethylsulfamide, 2-amino-4'-methyl-1,1'-diphenylsulfone-4-carboxamide, 2-amino-4'-chloro-1,1'-diphenylsulfone-4-carboxamide, 2-amino-4'-methyl-1,1'-diphenylsulfone-4-N,N-dimethylcarboxamide, 2-amino-4'-chloro-1,1'-diphenylsulfone-4-N,N-dimethylcarboxamide, aniline-4-sulfamide, aniline-4-N-methylsulfamide, anilin-4-N-ethylsulfamide, aniline-2-N-methyl-N-.beta.-hydroxyethylsulfamide, aniline-4- N-methyl-N-.beta.-hydroxyethylsulfamide, aniline-4-N,N-dimethylsulfamide, aniline-4-N-phenylsulfamide, 2-chloro-5-(4'-methylphenylcarbonyl)aniline, 2-amino-1-phenyl-2'-naphthylsulfone-4-sulfamide, aniline-2-N-ethyl-N-phenylsulfamide, 2-chloro-5(4'-chlorophenylcarbonyl)aniline, anilin-4-N(2'-methylphenyl)sulfamide, anilin-4-N(2'-chlorophenyl)sulfamide, anilin-4-N-(3'-trifluoromethylphenyl)sulfamide, anilin-2-N-methyl-N-cyclohexylsulfamide, 4-methylaniline-3-N-phenylsulfamide, 4-methylaniline-3-N-ethyl-N-phenylsulfamide, 2-trifluoromethyl-4-acetylaminoaniline, 2-chloroaniline, 2-methoxy-5-chloroaniline, aniline, 2-ethoxyaniline, 2-(2'-chlorophenoxy)-5-chloroaniline, anilin-3-N-ethyl-N-phenylsulfamide, 2,4-di(o-methylphenoxy)aniline, 2-phenoxyaniline-5-N-ethyl-N-phenylsulfamide, 2-(2'-methylphenoxy)aniline, 2-methoxyaniline-5-sulfamide, 2-phenoxyaniline, 2-phenoxy-5-chloroaniline, 2,3- or 3,4- or 2,4- or 2,5- or 3,5- or 2,6-dichloroaniline, 2-(2'-chlorophenoxysulfonyl)5-methylaniline.
Representative examples of the large number of possible coupling components are: 2-phenylindole-5-, -6- or -7-sulfonic acid, 2-methylindole-5-, -6- or -7-sulfonic acid, 1-octyl-2-methylindole-5-sulfonic acid, 1-methyl-2-phenylindole-5-, -6- or -7-sulfonic acid, 1-ethyl-2-methylindole-5-, -6- or -7-sulfonic acid, 1-octyl-2-methylindole-6- or -7-sulfonic acid, 2-p-sulfophenylindole, 2-p-sulfophenyl-1-methylindole, 2-o-sulfophenylindole and 2-o-sulfophenyl-1-methylindole.
The 2-methyl- or 2-phenylindolesulfonic acids employed as coupling components which contain the sulfo group in the benzene ring of the indole are obtained e.g. by reacting phenylhydrazines with ketones by Fischer's indole synthesis (q.v. U.S. Pat. No. 1,866,956), or by sulfonating unsubstituted or substituted indoles in accordance with German patent 137 117. In this last mentioned process it is established that the sulfo group is introduced in the 5-position of the indole at least in the case of 2-phenylindole and 2-methyl-N-octylindole.
The 2-sulfophenylindoles used as coupling components which can be substituted in the 1-position by alkyl are obtained e.g. by reacting phenylhydrazines with corresponding ketones by Fischer's indole synthesis (q.v. U.S. Pat. No. 1,866,956).
The dyes of the formula (1) are suitable for dyeing and printing materials which contain amide groups, for example textile fibres, textile filaments and textile fabrics made from wool, silk and polyurethane fibres, and in particular for dyeing and printing synthetic polyamide, using conventional dyeing methods. The dyes of formula (1) are distinguished by brilliance and tinctorial strength, good exhaust properties and build-up, resistance to formaldehyde and by good general fastness properties such as lightfastness, rubfastness, fastness to acid and alkali, wetfastness, in particular fastness to washing, water, hot water and perspiration, and they afford level dyeings.
It is to be singled out for special mention that the dyes of formula (1) combine readily with other acid dyes and are particularly suitable for dyeing or printing by the trichromatic method.
Particular attention is drawn to the fact that the dyes of formula (1) produce dyeings which have very good constancy of shade even when subjected to the increases in temperature occurring e.g. in drying, thermofixing, steaming and ironing.
The dyes of the formula (1) are obtained either in the form of their free sulfonic acid or of salts thereof. Examples of suitable salts are the alkali metal salts, alkaline earth metal salts or ammonium salts, or the salts of an organic amine. Typical examples are the sodium, lithium, potassium or ammonium salts or the salt of triethanolamine.
The invention is illustrated by the following Examples, in which parts are by weight. The relationship between parts by weight and parts by volume is the same as that between the gram and the cubic centimeter.
US Referenced Citations (9)
| Number |
Name |
Date |
Kind |
| 978439 |
Dressel et al. |
Dec 1910 |
|
| 1113622 |
Hauptmann et al. |
Oct 1914 |
|
| 1835393 |
Hentrick et al. |
Dec 1931 |
|
| 3255173 |
Dehnert et al. |
Jun 1966 |
|
| 3925350 |
Wolfrum et al. |
Dec 1975 |
|
| 3993619 |
Kruckenburg et al. |
Nov 1976 |
|
| 4000123 |
Sommer et al. |
Dec 1976 |
|
| 4060521 |
vor der Bruck et al. |
Nov 1977 |
|
| 4248774 |
Hugl et al. |
Feb 1981 |
|
Foreign Referenced Citations (18)
| Number |
Date |
Country |
| 0013609 |
Jul 1980 |
EPX |
| 0042357 |
Dec 1981 |
EPX |
| 0084320 |
Jul 1983 |
EPX |
| 0102325 |
Mar 1984 |
EPX |
| 226240 |
Sep 1910 |
DE2 |
| 269213 |
Jan 1914 |
DE2 |
| 501107 |
Jul 1930 |
DE2 |
| 1812812 |
Jul 1970 |
DEX |
| 2715135 |
Oct 1978 |
DEX |
| 3201112 |
Jul 1983 |
DEX |
| 12465 |
Apr 1901 |
FRX |
| 321521 |
Jan 1903 |
FRX |
| 670014 |
Nov 1929 |
FRX |
| 1366250 |
Jun 1969 |
FRX |
| 73-00699 |
Jul 1973 |
NLX |
| 284652 |
Apr 1929 |
GBX |
| 1384508 |
Feb 1975 |
GBX |
| 2002018 |
Feb 1979 |
GBX |
Continuations (1)
|
Number |
Date |
Country |
| Parent |
584176 |
Feb 1984 |
|
Patent Grant
4997921
