CA1066272A - Azo dyestuffs - Google Patents
Azo dyestuffsInfo
- Publication number
- CA1066272A CA1066272A CA243,335A CA243335A CA1066272A CA 1066272 A CA1066272 A CA 1066272A CA 243335 A CA243335 A CA 243335A CA 1066272 A CA1066272 A CA 1066272A
- Authority
- CA
- Canada
- Prior art keywords
- alkyl
- alkoxy
- cyano
- chlorine
- phenyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/0025—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds
- C09B29/0029—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds the heterocyclic ring containing only nitrogen as heteroatom
- C09B29/0037—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds the heterocyclic ring containing only nitrogen as heteroatom containing a five-membered heterocyclic ring with two nitrogen atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Coloring (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
Abstract of the Disclosure Disclosed are disperse dyes of formula I, I
in which R1 is an unsubstituted or substituted C1-4alkyl, phenyl or aminocarbonyl radical or an unsubstituted C1-4-alkoxy or alkoxy-(C1-4)-carbonyl radical, R2 is an unsubstituted alkoxy-(C1-4)-carbonyl radical or cyano, with the proviso that it is cyano only when at least one of R1 and R3 is other than methyl, R3 is hydrogen or an optionally substi-tuted C1-4alkyl,cycloalkyl or phenyl radical, and K is the radical of a coupling component selected from the amino-benzene, amino-naphthalene, pyrazo-lone-5, 5-aminopyrazole, pyridone, pyrimidone, tetrahydroquinoline, coumarine or pyrrole series or of the activated methylene group-containing aliphatic series, their production and use.
in which R1 is an unsubstituted or substituted C1-4alkyl, phenyl or aminocarbonyl radical or an unsubstituted C1-4-alkoxy or alkoxy-(C1-4)-carbonyl radical, R2 is an unsubstituted alkoxy-(C1-4)-carbonyl radical or cyano, with the proviso that it is cyano only when at least one of R1 and R3 is other than methyl, R3 is hydrogen or an optionally substi-tuted C1-4alkyl,cycloalkyl or phenyl radical, and K is the radical of a coupling component selected from the amino-benzene, amino-naphthalene, pyrazo-lone-5, 5-aminopyrazole, pyridone, pyrimidone, tetrahydroquinoline, coumarine or pyrrole series or of the activated methylene group-containing aliphatic series, their production and use.
Description
-~ Case lSO-3699 ~ 66~72 The invention relates to mono azo dyestuffs having a pyrazole diazo component radical. ; ~ -Thus, the invention provides disperse dyes of 5 formula I, 1 ~ ~`2 ~ -=N-K I . .
k3 ~ ~
. . .:
in which Rl is (Cl_4)alkyl; (Cl-q)alkYl mono- ;~
substituted by chlorine, bromine, ; - .
cyano or (Cl ~)alkoxy; phenyl; .
phenyl substituted by one or two substituents selected from chlorine, bromine, cyano, nitro, (Cl 4)alkyl : -~
:~ and (Cl_4)alkoxy;
aminocarbonyl; aminocarbonyl ~:
substituted by one or two (Cl 4)-alkyl groups; (Cl 4~alkoxy; or .:
alkoxy(Cl 4)carbonyl;
R2 ls an unsubstituted alkoxy-(Cl 4)-carbonyl radical or cyano, with the . .
provlso that it ls cyano only when at least one of Rl and R3 is other than methyl, R3 is hydrogen; (Cl_4)alkyl; (Cl_4)alkyl monosubstituted by chlorine, bromine, -cyano, hydroxy, (Cl_4)alkoxy, alkyl(Cl 4)carbonyloxy, phenyl, :~
cyclohexyl or a heterocyclic radical; ~ :
~ 1 ~
.: ~ : , . .. . .. . .
;6~,'72 : !
. cycloalkyl; phenyl; or phenyl subst-ltuted by one or two substituents selected from chlorine, bromine, cyallo~ (Cl_4)alkyl, (Cl_4)alkoxy, tr1fluoromethyl and n~tro.
K is the radical of a coupling component selected from the amino-benzene, amino-naphthalene, pyrazo-lone-5, 5-amlnopyrazole, pyridone, pyrimidone, tetrahydroquinoline~ ; -. .
coumarine or pyrrole series or o the activated methylene group-containing aliphatic series.
Any substituent on the coupling component K is chosen -.
15 go as to be compatlble wlth t~le utlllty of the compounds as dl perse dye~.
Substituted alkyl radicals of Rl are preferahly mono ~ substituted by chlorine, bromine or cyano and more partic-`-~ ularly by cyano. Any phenyl raldical of Rl is preferably 20 unsubstitu~ed, The preferred significances of R1 are methyl and cyanomethyl.
-~ Any alkoxycarbonyl of R2 preferably contains 1 or 2 carbon atoms in the alkoxy moiety, The preferred slgnificance of R2, however, is cyano, asæuming, of course, at least one 25 of Rl and R3 is other than methyl, Any substituted phenyl radical of R3 ls preferably ~ ~ubstituted by preferably one substituent selected from - chlorine, bromine, cyano, Cl_4alkyl t Cl_4alkoxy ~ .
:~.
tri~luoromethYl and nitro. Any cycloalkyl of R3 i~
30 p~eferably cyclohexyl, The preferred signlfi-~ B
;6Z7'~
-~ cances of R3 are unsubstituted phenyl and monochlorophenyl.
; As examples of coupling components of the activated methylene group-containing aliphatic series may be ~-~
given the acetoacetic acid anilides and the indane-diones.
The preferxed coupling component radicals as K
are those o~ the aminobenzene series, e.g. of formula (a), N\ (a) in which R4 is hydrogen, methyl, chlorine, bromine, Cl 4alkoxy or phenoxy, R5 is hydrogen or a Cl 4alkyl radical, unsub-- 10 - stituted or substituted by a substituent ;
selected from cyano, chlorine t hydroxyl, , Cl 4alkoxy, formyloxy, chloroacetoxy, :` ' alkyl(Cl 4)carbonyloxy, alkoxy(Cl 4)carbonyl,,alkoxy(Cl 4)carbonyloxy and benzoyloxy, R6 is Cl_4alkyl, unsubstituted or substituted ~- by a substituent selected rom hydroxy, Cl 4alkoxy, cyano, phenyl, phenoxy, formylcxy, : : , :.. .
chloroacetoxy, alkyl(Cl 4)carbonyloxy, . alkoxy(Cl 4)carbonyl, alkoxy(Cl 4)carbonyloxy, :.
benzoxyloxy, phenylaminocarbonyloxy, phthal-~ .
imidyl, ben20sulphomidyl, pyridyl and henzo-thiazolylmercapto; or phenyl, unsubstituted or suhstituted by up to two substituents selected from chlorine, bromine, methyl, methoxy and ethoxy, ' ;~ :
...i. , ,.: , .,: . . ., . .: .
. . . . . . . . . . . . . . .
- 4 - l50-369g ~(~6627Z :~
R7 is hydrogen, chlorine, bromine, cyano, methyl, Cl 4alkoxy, formylamino, alkyl(C1 ~) carbonylamino, benzoylamino, chIoro-, bromo-, or phenoxy-aIkyl(Cl 4)carbonylamino, alkoxy-(Cl 4)carbonylamino, benzyloxycarbonylamino, ~-a1koxy(cl 4)ethoxycarbonylamino or alkyl-sulphonylamino, the radicals (a) being free from -N-C-0- groups, R4 is preferably hydrogen. R5 is preferably o C2 3alkyl, substituted by cyano or alky](C1 2)carbonyloxy.
R6 is preferably C2 3alkyl substituted by alkyl(Cl 2)carbony-loxy. R7 is preferably hydrogen, methyl or alkyl(Cl 4)-carbonylamino.
The invention also provides a process for the production of compounds of formula I, stated above, charact-erised by reacting a diazotised derivative of an amine of formula II, Rl ~ 2~2 II
with a compound of formula H-K.
^~ The diazotisation of the compounds of formula II
and the coupling with the compound HK may be carried out in conventional manner, e.g. at a pH below 5, at a temperature below 20~C, preferably from ~5 to ~5~C and in a medium optionally buffered by an alkali metal salt of a low (e.g.
Cl 4)alkane acid, e.g. sodium acetate.
~ - 5 - 150-3699 ` ~ ~0~6;~7;2 The resulting compounds of formula I may be isolated and purified in conventional manner.
The amines of formula II and the compounds H-K
are either known or may be obtained in conventional manner from available starting materials.
The disperse dyes of formula I are useful for the dyeing or printing of substrates comprising or COnSiStillg ~-of fully or semi-synthetic, hydrophobic, high-molecular weight organic material, e.g. those conventionally dyed or ~ 10 printed using disperse dyes. They are particularly suitable for dyeing or prlnting textile material, whether in fibre, yarn,woven or other form, comprising or cohsisting of linear, ; aromatic polyester, cellulose-~/2-acetate, cellulose tri-acetate and synthe~ic polyamides, on which they build-up well from aqueous suspensions.
, . ..... . . . . . . .
It is especially advantageous to convert the ~ dyestuffs in known manner into dyestuff preparations pr1or ; to their use. For this purpose they are comminuted until their average particle size is 0.01 to 10/u, especially 0.1 - 20 to 5 ~. This comminution may be carried out in the presence -v of a dispersant or filler. For example, the dried dyestuff is ground together with a dispersant, if desired or required -in the presence of a filler, or kneaded with a dispersant to form a paste and then dried under vacuum or spray-dried.
When a suitable proportion of water is added to a preparation manufactured in this manner, it may be used for dyeing or padding from a dilute liquor or for p~inting.
For dyeing from dilute liquors there axe . - , . .
~ .
,- ~ . . . :
, '': ', , ~ ' . . " ' . , ,' , ' ' .
~`', ~;6272 generally used up to about 50g of dyestuff per litre, for paddin~ up to about 150g per litre, preferably up to 100 g per litre, and for printin~ up to about 150 g per kilogram of printing paste. The goods-to-liquor ratio may vary within wide limits, for example from 1:3 to 1:200, pre~erably from 1:3 ~o 1:80.
Dyeing follows the usual practice: Polyester fibres can be dyed in the presence of carriers at temperatures from 80C to 125C or in the absence of carriers under superatmospheric pressure at 100 to 140C,by the exhaustion method. Furthermore, polyester fibres may be padded, impregnated or printed with aqueous dispersions of the new . ~ .
dyestuffs, the dyestuff being heat~set on the impregnated material at 140 to 230C,for example with the aid of steam or air. In the particularly favourable temperature ran~e from 180 to 220C the dyestuffs diffuse rapidly into the polyester fibre without subsequent sublimation, even when the material under treatment is exposed to such a temperature for a prolonged period. In this manner the objectionable fouling of the dyeing apparatus is prevented. Secondary cellulose acetate is preferably dyed between ~5 and 80C and cellulose triacetate at a temperature of up to about 115C. The most advanta~eous p~ range is from 2 to 9, especially from ~ to 8.
As a rule, the usual dispersants, which are preferably anionic or nonionic and may also be used in the form of mixtures of two or more, are added.
, . .. .
... ~ . :
About 0.5 g of dispersant per litre of dyestuff preparation will generally suffice ~hough larger amounts, for example up to about 3 ~ per litre, may be used equally well.
Known anionic dispersants suitable for use in the present process are, for example, condensates from naphthalenesul-phonic acids and formaldehyde, especially dinaphthylmethane-disulphonates, esters of sulphonated succinic acid, Turkey red oil and alkali metal salts of sulphuric acid esters of fatty alcohols, for example sodium laurylsulphate, sodium cetylsulphate, sulphite cellulose waste liquor or alkali metal sulphates of monoglycerides of fatty acids. Examples of known and particularly suitable nonionic dispersants are . . .
the adducts of 3 to 40 mols of ethylene oxide with alkyl-phenols, fatty alcohols or fatty amines and neutral sulphuric acid esters thereof.
In paddiny and printing,the conventional thickeners may be used, for example modified or unmodified natural products, for example alginates, British gum arabic, -~ 20 crystal gum, locust bean flour, gum tragacanth, carboxy~
methyl cellulose, hydroxyethyl cellulose, starches or synthetic products, for example polyacrylamides or poly-vinyl alcohols.
;~''' ' , . ' ' ' ' '''~ ' ' ' ''. '' ~ , .. . ., . , '. ' ~ ' ':' ' , :
, - '10~62~72 .~
The dyeings obtained have satisfactory all-round fastness properties, of particular interest being their fast--~ ness to light, thermofixation, sublimalion and pleating. Other fastness properties which may be mentioned include fastness to water, washing, perspiration, solvents, e.g. dry-cleaning solvents, lubricants, rubblng, cross-dyeing, ozone, gas fumes and chlorine. The dyeings show resistence to various permanent-press processes and to soil release finishes. The dyes show resistence to reduction (when dyeing wool containing lo substrates) and they reserve wool and cotton.
The following Examples in which all parts are by weight and temperatures in degrees centigrade, illustrate the invention.
~ " .
,.~.
. .
:' , ~66'~'7Z
Example 1 20 Parts of 5-amino-4-cyano-1-~-cyanoethyl-3-cyanomethyl-pyrazole are added slowly at 0-5~ to a mixture of 107 parts of nltrosylsulphuric acid (produced by dissolving 7 parts of sodium nitrite in 100 parts of concentrated sulphuric acid), 85 parts of ~lacial acetic acid and 15 parts of propionic acid. A mixture of 85 parts of glacial acetic acid and 15 parts of propionic acid is added at 0-5 to the mixture obtained and it is subsequently stirred at 0-5 for 3 hours. A solution of 28.9 parts of-1-acetylamino-3-N-(2'-ace~oxyethyl)-3-N-(2'-cyanoethyl)-aminobenzene in 85 parts of ylacial acetic acid and 15 parts pf propionic acid is added in drops and the resulting coupling mixture is stirred for 3 hours at 0-5. The reaction mixture is ` then poured with stirring into a mixture consisting of 600 parts of ice and 300 parts of water, whereby the resultant dyestuff is precipitated. It is filtered off, washed with water until free from acid and salt, and dried.
The dyestuff thus obtained dyes synthetic fibres in red shades.
- Application Example 7 Parts of the dyestuff produced in accordance with Example 1 are ground to a fine powder for 48 hours in a ball mill together with 4 parts of dinaphthylmethanedisul-phonic acid sodium, 4 parts of sodium cetyl sulphate and 5 parts of anhydrous sodium sulphate.
1 Part of the dyeing preparation thus obtained : , ; ' ' : , . . .
. "' ' ' ' . ' :. ' 3L~6627Z
is made into a paste with a little water, and the suspension obtained is added through a sieve to a dye bath containing . , , 3 parts of sodium lauryl sulphate in 4000 parts of water.
The liquor ratio is 1:40. Then, 100 parts of purified polyester fibre material are added at 40-50 to the bath, 20 ` parts of a chlorinated benzene, emulsified in water, are added, the bath is heated slowly to 100 and dyeing takes place for 1-2 hours at 95-100. T~e fihres which are dyed in brilliant red are washed, soaped, washed again and dried.
o The even dyeing is very fast to light, cross-dyeing, washing, water, sea water, perspiration, sublimation, gas,fumes, thermofixation, pleating and permanent-pressing.
In the following Tables are given further dyestuffs according to the invention, which may be produced - 15 in a manner similar to that of Example 1.
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t~;~ U ~(d~ a ~a ~a , , ,o~ y u~ I~U~d ~a ~~
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.. _ ...... _ __...... ... . . . _ .......... . ___ .~ ~ :Z . . . . . . . . . .
F~ Y ~o ~a ~a ~a ~a ~a ~a ~a ~ ~a ~~ a _. . ............... . .
s~ '~ ~a ~ ~ 'd ~a ~a ~ ~a r r ~a ra ra ~a ~a .. . . .. _ ._ X O ~ I~ ~ ~ O .~
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~066Z7'~
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a :~ $~ a a O .a ~, a ,~ a h a ~a a a ~ ~ ~ .
. ~ ~ . . .
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o m - .~ u m ~m o ~ v ~: ~ u a) ,~ o 5: o o v~ o o Id p:; ~ ~q y ~ ~ U$ a ~~: y ~ .
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k3 ~ ~
. . .:
in which Rl is (Cl_4)alkyl; (Cl-q)alkYl mono- ;~
substituted by chlorine, bromine, ; - .
cyano or (Cl ~)alkoxy; phenyl; .
phenyl substituted by one or two substituents selected from chlorine, bromine, cyano, nitro, (Cl 4)alkyl : -~
:~ and (Cl_4)alkoxy;
aminocarbonyl; aminocarbonyl ~:
substituted by one or two (Cl 4)-alkyl groups; (Cl 4~alkoxy; or .:
alkoxy(Cl 4)carbonyl;
R2 ls an unsubstituted alkoxy-(Cl 4)-carbonyl radical or cyano, with the . .
provlso that it ls cyano only when at least one of Rl and R3 is other than methyl, R3 is hydrogen; (Cl_4)alkyl; (Cl_4)alkyl monosubstituted by chlorine, bromine, -cyano, hydroxy, (Cl_4)alkoxy, alkyl(Cl 4)carbonyloxy, phenyl, :~
cyclohexyl or a heterocyclic radical; ~ :
~ 1 ~
.: ~ : , . .. . .. . .
;6~,'72 : !
. cycloalkyl; phenyl; or phenyl subst-ltuted by one or two substituents selected from chlorine, bromine, cyallo~ (Cl_4)alkyl, (Cl_4)alkoxy, tr1fluoromethyl and n~tro.
K is the radical of a coupling component selected from the amino-benzene, amino-naphthalene, pyrazo-lone-5, 5-amlnopyrazole, pyridone, pyrimidone, tetrahydroquinoline~ ; -. .
coumarine or pyrrole series or o the activated methylene group-containing aliphatic series.
Any substituent on the coupling component K is chosen -.
15 go as to be compatlble wlth t~le utlllty of the compounds as dl perse dye~.
Substituted alkyl radicals of Rl are preferahly mono ~ substituted by chlorine, bromine or cyano and more partic-`-~ ularly by cyano. Any phenyl raldical of Rl is preferably 20 unsubstitu~ed, The preferred significances of R1 are methyl and cyanomethyl.
-~ Any alkoxycarbonyl of R2 preferably contains 1 or 2 carbon atoms in the alkoxy moiety, The preferred slgnificance of R2, however, is cyano, asæuming, of course, at least one 25 of Rl and R3 is other than methyl, Any substituted phenyl radical of R3 ls preferably ~ ~ubstituted by preferably one substituent selected from - chlorine, bromine, cyano, Cl_4alkyl t Cl_4alkoxy ~ .
:~.
tri~luoromethYl and nitro. Any cycloalkyl of R3 i~
30 p~eferably cyclohexyl, The preferred signlfi-~ B
;6Z7'~
-~ cances of R3 are unsubstituted phenyl and monochlorophenyl.
; As examples of coupling components of the activated methylene group-containing aliphatic series may be ~-~
given the acetoacetic acid anilides and the indane-diones.
The preferxed coupling component radicals as K
are those o~ the aminobenzene series, e.g. of formula (a), N\ (a) in which R4 is hydrogen, methyl, chlorine, bromine, Cl 4alkoxy or phenoxy, R5 is hydrogen or a Cl 4alkyl radical, unsub-- 10 - stituted or substituted by a substituent ;
selected from cyano, chlorine t hydroxyl, , Cl 4alkoxy, formyloxy, chloroacetoxy, :` ' alkyl(Cl 4)carbonyloxy, alkoxy(Cl 4)carbonyl,,alkoxy(Cl 4)carbonyloxy and benzoyloxy, R6 is Cl_4alkyl, unsubstituted or substituted ~- by a substituent selected rom hydroxy, Cl 4alkoxy, cyano, phenyl, phenoxy, formylcxy, : : , :.. .
chloroacetoxy, alkyl(Cl 4)carbonyloxy, . alkoxy(Cl 4)carbonyl, alkoxy(Cl 4)carbonyloxy, :.
benzoxyloxy, phenylaminocarbonyloxy, phthal-~ .
imidyl, ben20sulphomidyl, pyridyl and henzo-thiazolylmercapto; or phenyl, unsubstituted or suhstituted by up to two substituents selected from chlorine, bromine, methyl, methoxy and ethoxy, ' ;~ :
...i. , ,.: , .,: . . ., . .: .
. . . . . . . . . . . . . . .
- 4 - l50-369g ~(~6627Z :~
R7 is hydrogen, chlorine, bromine, cyano, methyl, Cl 4alkoxy, formylamino, alkyl(C1 ~) carbonylamino, benzoylamino, chIoro-, bromo-, or phenoxy-aIkyl(Cl 4)carbonylamino, alkoxy-(Cl 4)carbonylamino, benzyloxycarbonylamino, ~-a1koxy(cl 4)ethoxycarbonylamino or alkyl-sulphonylamino, the radicals (a) being free from -N-C-0- groups, R4 is preferably hydrogen. R5 is preferably o C2 3alkyl, substituted by cyano or alky](C1 2)carbonyloxy.
R6 is preferably C2 3alkyl substituted by alkyl(Cl 2)carbony-loxy. R7 is preferably hydrogen, methyl or alkyl(Cl 4)-carbonylamino.
The invention also provides a process for the production of compounds of formula I, stated above, charact-erised by reacting a diazotised derivative of an amine of formula II, Rl ~ 2~2 II
with a compound of formula H-K.
^~ The diazotisation of the compounds of formula II
and the coupling with the compound HK may be carried out in conventional manner, e.g. at a pH below 5, at a temperature below 20~C, preferably from ~5 to ~5~C and in a medium optionally buffered by an alkali metal salt of a low (e.g.
Cl 4)alkane acid, e.g. sodium acetate.
~ - 5 - 150-3699 ` ~ ~0~6;~7;2 The resulting compounds of formula I may be isolated and purified in conventional manner.
The amines of formula II and the compounds H-K
are either known or may be obtained in conventional manner from available starting materials.
The disperse dyes of formula I are useful for the dyeing or printing of substrates comprising or COnSiStillg ~-of fully or semi-synthetic, hydrophobic, high-molecular weight organic material, e.g. those conventionally dyed or ~ 10 printed using disperse dyes. They are particularly suitable for dyeing or prlnting textile material, whether in fibre, yarn,woven or other form, comprising or cohsisting of linear, ; aromatic polyester, cellulose-~/2-acetate, cellulose tri-acetate and synthe~ic polyamides, on which they build-up well from aqueous suspensions.
, . ..... . . . . . . .
It is especially advantageous to convert the ~ dyestuffs in known manner into dyestuff preparations pr1or ; to their use. For this purpose they are comminuted until their average particle size is 0.01 to 10/u, especially 0.1 - 20 to 5 ~. This comminution may be carried out in the presence -v of a dispersant or filler. For example, the dried dyestuff is ground together with a dispersant, if desired or required -in the presence of a filler, or kneaded with a dispersant to form a paste and then dried under vacuum or spray-dried.
When a suitable proportion of water is added to a preparation manufactured in this manner, it may be used for dyeing or padding from a dilute liquor or for p~inting.
For dyeing from dilute liquors there axe . - , . .
~ .
,- ~ . . . :
, '': ', , ~ ' . . " ' . , ,' , ' ' .
~`', ~;6272 generally used up to about 50g of dyestuff per litre, for paddin~ up to about 150g per litre, preferably up to 100 g per litre, and for printin~ up to about 150 g per kilogram of printing paste. The goods-to-liquor ratio may vary within wide limits, for example from 1:3 to 1:200, pre~erably from 1:3 ~o 1:80.
Dyeing follows the usual practice: Polyester fibres can be dyed in the presence of carriers at temperatures from 80C to 125C or in the absence of carriers under superatmospheric pressure at 100 to 140C,by the exhaustion method. Furthermore, polyester fibres may be padded, impregnated or printed with aqueous dispersions of the new . ~ .
dyestuffs, the dyestuff being heat~set on the impregnated material at 140 to 230C,for example with the aid of steam or air. In the particularly favourable temperature ran~e from 180 to 220C the dyestuffs diffuse rapidly into the polyester fibre without subsequent sublimation, even when the material under treatment is exposed to such a temperature for a prolonged period. In this manner the objectionable fouling of the dyeing apparatus is prevented. Secondary cellulose acetate is preferably dyed between ~5 and 80C and cellulose triacetate at a temperature of up to about 115C. The most advanta~eous p~ range is from 2 to 9, especially from ~ to 8.
As a rule, the usual dispersants, which are preferably anionic or nonionic and may also be used in the form of mixtures of two or more, are added.
, . .. .
... ~ . :
About 0.5 g of dispersant per litre of dyestuff preparation will generally suffice ~hough larger amounts, for example up to about 3 ~ per litre, may be used equally well.
Known anionic dispersants suitable for use in the present process are, for example, condensates from naphthalenesul-phonic acids and formaldehyde, especially dinaphthylmethane-disulphonates, esters of sulphonated succinic acid, Turkey red oil and alkali metal salts of sulphuric acid esters of fatty alcohols, for example sodium laurylsulphate, sodium cetylsulphate, sulphite cellulose waste liquor or alkali metal sulphates of monoglycerides of fatty acids. Examples of known and particularly suitable nonionic dispersants are . . .
the adducts of 3 to 40 mols of ethylene oxide with alkyl-phenols, fatty alcohols or fatty amines and neutral sulphuric acid esters thereof.
In paddiny and printing,the conventional thickeners may be used, for example modified or unmodified natural products, for example alginates, British gum arabic, -~ 20 crystal gum, locust bean flour, gum tragacanth, carboxy~
methyl cellulose, hydroxyethyl cellulose, starches or synthetic products, for example polyacrylamides or poly-vinyl alcohols.
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The dyeings obtained have satisfactory all-round fastness properties, of particular interest being their fast--~ ness to light, thermofixation, sublimalion and pleating. Other fastness properties which may be mentioned include fastness to water, washing, perspiration, solvents, e.g. dry-cleaning solvents, lubricants, rubblng, cross-dyeing, ozone, gas fumes and chlorine. The dyeings show resistence to various permanent-press processes and to soil release finishes. The dyes show resistence to reduction (when dyeing wool containing lo substrates) and they reserve wool and cotton.
The following Examples in which all parts are by weight and temperatures in degrees centigrade, illustrate the invention.
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Example 1 20 Parts of 5-amino-4-cyano-1-~-cyanoethyl-3-cyanomethyl-pyrazole are added slowly at 0-5~ to a mixture of 107 parts of nltrosylsulphuric acid (produced by dissolving 7 parts of sodium nitrite in 100 parts of concentrated sulphuric acid), 85 parts of ~lacial acetic acid and 15 parts of propionic acid. A mixture of 85 parts of glacial acetic acid and 15 parts of propionic acid is added at 0-5 to the mixture obtained and it is subsequently stirred at 0-5 for 3 hours. A solution of 28.9 parts of-1-acetylamino-3-N-(2'-ace~oxyethyl)-3-N-(2'-cyanoethyl)-aminobenzene in 85 parts of ylacial acetic acid and 15 parts pf propionic acid is added in drops and the resulting coupling mixture is stirred for 3 hours at 0-5. The reaction mixture is ` then poured with stirring into a mixture consisting of 600 parts of ice and 300 parts of water, whereby the resultant dyestuff is precipitated. It is filtered off, washed with water until free from acid and salt, and dried.
The dyestuff thus obtained dyes synthetic fibres in red shades.
- Application Example 7 Parts of the dyestuff produced in accordance with Example 1 are ground to a fine powder for 48 hours in a ball mill together with 4 parts of dinaphthylmethanedisul-phonic acid sodium, 4 parts of sodium cetyl sulphate and 5 parts of anhydrous sodium sulphate.
1 Part of the dyeing preparation thus obtained : , ; ' ' : , . . .
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is made into a paste with a little water, and the suspension obtained is added through a sieve to a dye bath containing . , , 3 parts of sodium lauryl sulphate in 4000 parts of water.
The liquor ratio is 1:40. Then, 100 parts of purified polyester fibre material are added at 40-50 to the bath, 20 ` parts of a chlorinated benzene, emulsified in water, are added, the bath is heated slowly to 100 and dyeing takes place for 1-2 hours at 95-100. T~e fihres which are dyed in brilliant red are washed, soaped, washed again and dried.
o The even dyeing is very fast to light, cross-dyeing, washing, water, sea water, perspiration, sublimation, gas,fumes, thermofixation, pleating and permanent-pressing.
In the following Tables are given further dyestuffs according to the invention, which may be produced - 15 in a manner similar to that of Example 1.
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' ' ' '
Claims (12)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A disperse dye of formula I, I
in which R1 is (C1-4)alkyl; (C1-4)alkyl mono-substituted by chlorine, bromine, cyano or (C1-4)alkoxy; phenyl;
phenyl substituted by one or two substituents selected from chlorine, bromine, cyano, nitro, (C1-4)alkyl and (C1-4)alkoxy;
aminocarbonyl; aminocarbonyl substituted by one or two (C1-4)-alkyl groups; (C1-4) alkoxy; or alkoxy (C1-4)carbonyl;
R2 is an unsubstituted alkoxy-(C1-4)-carbonyl radical or cyano, with the proviso that it is cyano only when at least one of R1 and R3 is other than methyl, R3 is hydrogen; (C1-4)alkyl; (C1-4)alkyl monosubstituted by chlorine, bromine, cyano, hydroxy, (C1-4)alkoxy, alkyl(C1-4)carbonyloxy, phenyl, cyclohexyl or a heterocyclic radical;
cycloalkyl; phenyl; or phenyl subst-ituted by one or two substituents selected from chlorine, bromine, cyano, (C1-4)alkyl, (C1-4)alkoxy, trifluoromethyl and nitro.
K is the radical of a coupling component selected from the amino-benzene, amino-naphthalene, pyrazo-lone-5, 5-aminopyrazole, pyridone, pyrimidone, tetrahydroquinoline, coumarine or pyrrole series or of the activated methylene group-containing aliphatic series.
in which R1 is (C1-4)alkyl; (C1-4)alkyl mono-substituted by chlorine, bromine, cyano or (C1-4)alkoxy; phenyl;
phenyl substituted by one or two substituents selected from chlorine, bromine, cyano, nitro, (C1-4)alkyl and (C1-4)alkoxy;
aminocarbonyl; aminocarbonyl substituted by one or two (C1-4)-alkyl groups; (C1-4) alkoxy; or alkoxy (C1-4)carbonyl;
R2 is an unsubstituted alkoxy-(C1-4)-carbonyl radical or cyano, with the proviso that it is cyano only when at least one of R1 and R3 is other than methyl, R3 is hydrogen; (C1-4)alkyl; (C1-4)alkyl monosubstituted by chlorine, bromine, cyano, hydroxy, (C1-4)alkoxy, alkyl(C1-4)carbonyloxy, phenyl, cyclohexyl or a heterocyclic radical;
cycloalkyl; phenyl; or phenyl subst-ituted by one or two substituents selected from chlorine, bromine, cyano, (C1-4)alkyl, (C1-4)alkoxy, trifluoromethyl and nitro.
K is the radical of a coupling component selected from the amino-benzene, amino-naphthalene, pyrazo-lone-5, 5-aminopyrazole, pyridone, pyrimidone, tetrahydroquinoline, coumarine or pyrrole series or of the activated methylene group-containing aliphatic series.
2. A compound of Claim 19 wherein any C1-4alkyl of R1 is unsubstituted or mono-substituted by chlorine, bromine or cyano, wherein any phenyl of R1 is unsubstituted wherein any C1-4alkyl of R3 is unsubstituted or mono-substituted by chlorine, bromine, cyano, hydroxy, C1-4alkoxy, alkyl(C1-4)carbonyloxy, phenyl, cyclohexyl, tetrahydrofuryl or pyridyl, wherein any phenyl radical of R3 is unsubstituted or monosubstituted by chlorine, bromine, cyano, C1-4alkyl, C1-4alkoxy, trifluoro-methyl or nitro, and wherein any cycloalkyl radical of R3 is cyclohexyl.
3. A compound according to Claim 1, wherein K is a a radical of formula (a), (a) in which R4 is hydrogen, methyl, chlorine, bromine, C1-4alkoxy or phenoxy, R5 is hydrogen or a C1-4alkyl radical, unsub-stituted or substituted by a substituent selected from cyano, chlorine, hydroxyl, C1-4alkoxy, formyloxy, chloroacetoxy, alkyl(C1-4)carbonyloxy, alkoxy(C1-4)carbonyl, alkoxy(C1-4)carbonyloxy and benzoyloxy, is C1-4alkyl, unsubstituted or substituted by a substituent selected from hydroxy, C1-4alkoxy, cyano, phenyl, phenoxy, formyloxy, chloroacetoxy, alkyl(C1-4)carbonyloxy, alkoxy(C1-4)carbonyl, alkoxy(C1-4)carbonyloxy, benzoxyloxy, phenylaminocarbonyloxy, phthal-imidyl, benzosulphomidyl, pyridyl and benzo-thiazolylmercapto; or phenyl, unsubstituted or substituted by up to two substituents selected from chlorine, bromine, methyl, methoxy and ethoxy, R7 is hydrogen, chlorine, bromine, cyano, methyl, C1-4alkoxy, formylamino, alkyl(C1-4) carbonylamino, benzoylamino, chloro-, bromo-, or phenoxy-alkyl(C1-4)carbonylamino, alkoxy (C1-4)carbonylamino, benzyloxycarbonylamino, .beta.-alkoxy(C1-4)ethoxycarbonylamino or alkyl-sulphonylamino, the radicals (a) being free from -N-?-O- groups.
4, A compound of Claim 3, wherein R1 is methyl or cyanomethyl, R2 is cyano and R3 is phenyl, unsubstituted or mono-substituted by chlorine.
5. A compound of Claim 3 or 4, in which R4 is hydrogen, R5 is C2-3alkyl substituted by cyano, alkyl(C1-2)-carbonyloxy, alkoxy(C1-2)carbonyl or by alkoxy(C1-2)carbonyl-oxy R6 is C2-3alkyl substituted by alkyl(C1-2)carbonyloxy, and R7 is hydrogen, methyl or alkyl(C1-4)-carbonylamino.
6. A compound of Claim 1, of formula
7. A compound of claim 1, of formula
8. A compound of Claim 1, of formula
9. A compound of Claim 1, of formula
10. A compound of Claim 1, formula
11. A process for the production of a compound of formula 1, stated in Claim 1, characterised by reacting a diazotised derivative of an amine of formula II, II
in which R1, R2 and R3 are as defined in Claim 1, with a compound of formula H-K, in which K is as defined in Claim 1.
in which R1, R2 and R3 are as defined in Claim 1, with a compound of formula H-K, in which K is as defined in Claim 1.
12. A process for dyeing or printing a substrate comprising or consisting of fully or semi-synthetic, hydro-phobic, high molecular weight organic material comprising applying thereto a dyeing or printing medium comprising a compound of Claim 1.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH35075A CH594028A5 (en) | 1975-01-13 | 1975-01-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1066272A true CA1066272A (en) | 1979-11-13 |
Family
ID=4185013
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA243,335A Expired CA1066272A (en) | 1975-01-13 | 1976-01-12 | Azo dyestuffs |
Country Status (11)
| Country | Link |
|---|---|
| JP (1) | JPS5195431A (en) |
| BE (1) | BE837495A (en) |
| BR (1) | BR7600142A (en) |
| CA (1) | CA1066272A (en) |
| CH (1) | CH594028A5 (en) |
| DE (1) | DE2600036C2 (en) |
| ES (1) | ES444242A1 (en) |
| FR (1) | FR2297231A1 (en) |
| GB (1) | GB1531071A (en) |
| IT (1) | IT1063358B (en) |
| NL (1) | NL7600195A (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH663959A5 (en) * | 1984-07-14 | 1988-01-29 | Sandoz Ag | ANIONIC MONOAZO COMPOUNDS WITH HETEROCYCLIC DIAZOCOMPONENT. |
| US5023229A (en) * | 1990-10-31 | 1991-06-11 | Eastman Kodak Company | Mixture of dyes for magenta dye donor for thermal color proofing |
| US5134116A (en) * | 1990-11-02 | 1992-07-28 | Eastman Kodak Company | Mixture of dyes for black dye donor for thermal color proofing |
| US5144015A (en) * | 1990-12-21 | 1992-09-01 | Eastman Kodak Company | Synthesis of pyrazole dyes |
| AU4311897A (en) | 1996-10-01 | 1998-04-24 | Zeneca Limited | Aqueous ink compositions |
| CN1232483A (en) | 1996-10-01 | 1999-10-20 | 曾尼卡有限公司 | Aqueous ink compositions |
| US6864216B2 (en) | 2002-05-22 | 2005-03-08 | Eastman Kodak Company | Thermal magenta donor and dyes |
| JP5847928B2 (en) * | 2012-04-27 | 2016-01-27 | 富士フイルム株式会社 | Coloring composition for inkjet printing, printing method, and fabric |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3336285A (en) * | 1964-03-23 | 1967-08-15 | Eastman Kodak Co | Monoazo compounds prepared from 3-amino-4-cyanopyrazole compounds |
| US3634391A (en) * | 1969-07-25 | 1972-01-11 | Eastman Kodak Co | Pyrazolyl-azo-indole dyestuffs |
-
1975
- 1975-01-13 CH CH35075A patent/CH594028A5/xx not_active IP Right Cessation
-
1976
- 1976-01-02 DE DE19762600036 patent/DE2600036C2/en not_active Expired
- 1976-01-09 NL NL7600195A patent/NL7600195A/en unknown
- 1976-01-09 GB GB80476A patent/GB1531071A/en not_active Expired
- 1976-01-12 JP JP51002155A patent/JPS5195431A/en active Pending
- 1976-01-12 CA CA243,335A patent/CA1066272A/en not_active Expired
- 1976-01-12 BE BE163457A patent/BE837495A/en unknown
- 1976-01-12 BR BR7600142A patent/BR7600142A/en unknown
- 1976-01-12 ES ES444242A patent/ES444242A1/en not_active Expired
- 1976-01-13 IT IT1922276A patent/IT1063358B/en active
- 1976-01-13 FR FR7600681A patent/FR2297231A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| FR2297231A1 (en) | 1976-08-06 |
| BR7600142A (en) | 1976-08-31 |
| ES444242A1 (en) | 1977-10-01 |
| DE2600036A1 (en) | 1976-07-15 |
| BE837495A (en) | 1976-07-12 |
| NL7600195A (en) | 1976-07-15 |
| GB1531071A (en) | 1978-11-01 |
| FR2297231B1 (en) | 1979-08-31 |
| CH594028A5 (en) | 1977-12-30 |
| IT1063358B (en) | 1985-02-11 |
| DE2600036C2 (en) | 1984-08-16 |
| JPS5195431A (en) | 1976-08-21 |
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