CA1097622A - Water-soluble dyestuffs, process for preparing them and their use for dyeing and printing cellulose and polyamide fiber materials - Google Patents
Water-soluble dyestuffs, process for preparing them and their use for dyeing and printing cellulose and polyamide fiber materialsInfo
- Publication number
- CA1097622A CA1097622A CA291,703A CA291703A CA1097622A CA 1097622 A CA1097622 A CA 1097622A CA 291703 A CA291703 A CA 291703A CA 1097622 A CA1097622 A CA 1097622A
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- Prior art keywords
- formula
- carbon atoms
- hydrogen
- dyestuff
- methyl
- Prior art date
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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
- C09B29/06—Monoazo dyes prepared by diazotising and coupling from coupling components containing amino as the only directing group
- C09B29/08—Amino benzenes
- C09B29/0801—Amino benzenes containing acid groups, e.g. COOH, SO3H, PO3H2, OSO3H, OPO3H2; SO2NHSO2R or salts thereof, R being hydrocarbonyls
- C09B29/0803—Amino benzenes containing acid groups, e.g. COOH, SO3H, PO3H2, OSO3H, OPO3H2; SO2NHSO2R or salts thereof, R being hydrocarbonyls containing SO3H, OSO3H
-
- 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
- C09B29/0003—Monoazo dyes prepared by diazotising and coupling from diazotized anilines
- C09B29/0007—Monoazo dyes prepared by diazotising and coupling from diazotized anilines containing acid groups, e.g. CO2H, SO3H, PO3H2, OSO3H, OPO2H2; Salts thereof
-
- 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
- C09B29/06—Monoazo dyes prepared by diazotising and coupling from coupling components containing amino as the only directing group
- C09B29/08—Amino benzenes
-
- 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
- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
- C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
- C09B62/443—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring the reactive group being alternatively specified
- C09B62/447—Azo dyes
- C09B62/45—Monoazo dyes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Coloring (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Novel water-soluble dyestuffs had been found which, in the form of the free acid, have the formula (I) (1) in which R1 is hydrogen, alkyl having from 1 to 4 carbon atoms, benzyl, benzyl substituted in the benzene nucleus by methyl and/or chlorine, or is hydroxyalkyl having from 2 to 4 carbon atoms or hydroxyalkyl having from 2 to 4 carbon atoms and esterified with an inorganic or organic acid, cyanoalkyl having from 2 to 4 carbon atoms in the alkyl moiety, carboxy, carbonamido or carbalkoxyalkylene each having from 1 to 4 carbon atoms in the alkyl or alkylene moiety, halogenoalkyl having 2 or 3 carbon atoms, or halogenoalkenyl having 2 or 3 carbon atoms, R2 is hydrogen, methyl, ethyl or halogen, R3 is hydrogen, halogen, methyl, ethyl, methoxy, ethoxy or nitro, R4 is hydrogen, halogen, methyl, ethyl, methoxy, ethoxy or nitro and their salts. The novel dyestuffs can be prepared by coupling the corresponding diazo component of the amine of formula wherein R3 and R4 is defined above and W is hydroxy or sulfato, with a compoud of formula with R1, R2 and W defined aove, and subsequently esterifying the resulting azo compound when containing W as hydroxy, by means of a sulfatization agent. The novel dyestuffs are very well suitable for the dyeing of cellulose fiber materials ac-cording to known methods of applying and fixing fiber-reac-tive dyestuffs, furthermore also well suitable for the dyeing of natural and synthetic polyamide fibers.
- 1a -
Novel water-soluble dyestuffs had been found which, in the form of the free acid, have the formula (I) (1) in which R1 is hydrogen, alkyl having from 1 to 4 carbon atoms, benzyl, benzyl substituted in the benzene nucleus by methyl and/or chlorine, or is hydroxyalkyl having from 2 to 4 carbon atoms or hydroxyalkyl having from 2 to 4 carbon atoms and esterified with an inorganic or organic acid, cyanoalkyl having from 2 to 4 carbon atoms in the alkyl moiety, carboxy, carbonamido or carbalkoxyalkylene each having from 1 to 4 carbon atoms in the alkyl or alkylene moiety, halogenoalkyl having 2 or 3 carbon atoms, or halogenoalkenyl having 2 or 3 carbon atoms, R2 is hydrogen, methyl, ethyl or halogen, R3 is hydrogen, halogen, methyl, ethyl, methoxy, ethoxy or nitro, R4 is hydrogen, halogen, methyl, ethyl, methoxy, ethoxy or nitro and their salts. The novel dyestuffs can be prepared by coupling the corresponding diazo component of the amine of formula wherein R3 and R4 is defined above and W is hydroxy or sulfato, with a compoud of formula with R1, R2 and W defined aove, and subsequently esterifying the resulting azo compound when containing W as hydroxy, by means of a sulfatization agent. The novel dyestuffs are very well suitable for the dyeing of cellulose fiber materials ac-cording to known methods of applying and fixing fiber-reac-tive dyestuffs, furthermore also well suitable for the dyeing of natural and synthetic polyamide fibers.
- 1a -
Description
~7~
The present inventio~ provides a water soluble dyestuff having, in the form of the free acid, the formula (1): -~ N = N ~ ~ _ / 1 (1) in which Rl is hydrogen, alkyl having from 1 to 4 carbon atoms, benzyl, benzyl substituted in the benzene nucleus by methyl and/or chlorine, or is hydroxy-alkyl having from 2 to 4 carbon atoms ox hydroxyalkyl having from 2 to 4 carbon atoms and esterified with an inorganic or organic acid, cyanoalkyl ha~ing from 2 to 4 carbon atoms in the alkyl moiety, carboxy, carbonamido or carbalkoxyalkylene each having from 1 to 4 carbon atoms in the alkyl or alkyelenemoiety, halogenalkyl having 2 or 3 c æ bon atcms, or halogen~alkenyl having 2 or 3 caxbon atoms, R2 is hydrogen, methyl, ethyl or halogen, R3 is hydrogen, halogen, methyl, ethyl, methoxy, ethoxy or nitro, R4 is hydrogen halogen, methyl, ethylt me~hoxy, ethoxy, nitro, and a salt thereof.
More particulaxly, the present invention provides novel and valuable water-soluble dyestuffs having t~ formula ~1) in the form of the free acid ~ N = N ~ N / Rl --~ / \1=/ \ CH2-CH2-OS03H (1) CH -O S ~ R4 R2 . ' ', .
~7~
in which the radicals Rl to R4, identical or different to each other, have the follcwing meaning: Rl represents hydrogen, aIkyl having from 1 to 4 carbon atoms, benzyl optionally substituted by methyl and/or chlorine, hydroxy-alkyl having from 2 -to 4 carbon atoms, hydroxyalkyl having from 2 to 4 carbon a-toms and esterified with an inorganic or organic acid, for example sulfato-alkyl, phosphato-alkyl, acetoxyalkyl, propionyloxyalkyl or phenyl-sulfonyloxy-alkyl, or represents cyanoalkyl having from 2 -to 4 carbon atoms in the alkyl moiety, carboxy, carbonamido or carbalkoxyalkylene each having from 1 to 4 carbon atoms in the aIkyl or alkylene moiety, halogenoalkyl having-2 or 3 carbon atoms, preferably chloroalkyl, or halogenoalken~ having 2 or 3 carbon atoms, for example bromo- or chloroalkenyl, R2 represents hydrogen, methyl or ethyl, preferably methyl, or a halogen atom, for example chlorine, bromine or fluorine, preferably chlorine, R3 represents hydrogen, halogen, for example chlorine, bromine - 2a -~a~
.
7~;~2 or fluorine, preferably chlorine or bromine, methyl or ethyl, preferably methyl, methoxy or ethoxy, preferably methoxy or ~
nitro, R4 represents hydrogen, halogen, for example chlorine, bro-mine or fluorine, preferably chlorine or bromine, methyl or ethyl, preferably methyl, methoxy or ethoxy, preferab-ly methoxy, or nitro.
The dyestuffs of the instant invention of formula (1) '`whërëin the~~-sulfato-ethy-lsul-on~l~group is standing in tha diazocomponent in para-position to the azo group, are pre-ferred, especially those dyestuffs which posse~s, in form of the free acid, the general formula (1a) .. . .. ... ~
~ N = N ~ ~1 j CH2-0 S ~ R2 2 2 0s03H (1~. 3 wherein R3 and R2 are defined as aboYe.
Especially preferred and advantageous in the dyestuff having in form of the free acid the formula (lb1 , . _ . .. .. .. . . .. . . . ... ...
f~ N = N ~3 CE~2-CH
CH ~-O s~f CH2 -CX2-0s03H ~ lb) OS03~
HOE 76/~ 275 7~
The novel d~estuffs are preferably present in the form - of their salts, especially alkali metal salts, for example sodium or potassium salts, or alkaline earth metal salts, for example calcium salts, and are used preferably in the form of the aforesaid salts.
The present invention also provides a process for the preparation of the dyestuffs of formula ~1) or of their salts, which comprises diazotizing an aromatic amine of the formula (2~
~-C~2-CH2-o2s ~NR~
. . . . . . ...
or a salt thereo~ prefexably an alkali metal or alkalin~
earth metal salt, in which R3 and R4 have the aforesaid mean-ing and W stands for the hydroxy or sulfato group, and coupl-ing it with a coupling component of the formula (3) , . . .. , ., ., . ., .. .., ., .. ., .. _ . _ _ ... . .. .
lE~< ' ~ 2 CH~-CM2-W
or a salt thereof, pre~erably an alkali met~l or alkaline earth metal salt, in which ~1' R2 and W have the aforesaid meaning, and, in the case o~ the preparation o~ a dyestuff o~ the formula (4) , .. , .. . , . . , . .. .. . , ; . ......
~ N=N ~ R ~ ~~
! CH2-2S ~ \ ~4 IlH2 R4 l2 CH2-CH2-w W
- . - : - -', . ' ~ .
.
:. , 7~
in which R1, R2, R3 and R4 have the aforesaid meaning and one or ~oth radicals W represent hydroxy, transforming this dyestuff of formula (4) into its ~ulfuric acid semi-ester compound of formula (1) or its salts by means of a sulfa-tization agent.
The acid compounds of formula (1) are transformed in-to their salts or vice versa by methods known to the expert, for example by neutralization or acidification with a strong inorganic acid, for example sulfuric acid.
Suitable diazo components of formula (2) for preparing the dyestuffs of the invention are especially 4-B-sulfatoethylsulfonyl-aniline, 3-~-sulfatoethylsulfonyl-aniline,
The present inventio~ provides a water soluble dyestuff having, in the form of the free acid, the formula (1): -~ N = N ~ ~ _ / 1 (1) in which Rl is hydrogen, alkyl having from 1 to 4 carbon atoms, benzyl, benzyl substituted in the benzene nucleus by methyl and/or chlorine, or is hydroxy-alkyl having from 2 to 4 carbon atoms ox hydroxyalkyl having from 2 to 4 carbon atoms and esterified with an inorganic or organic acid, cyanoalkyl ha~ing from 2 to 4 carbon atoms in the alkyl moiety, carboxy, carbonamido or carbalkoxyalkylene each having from 1 to 4 carbon atoms in the alkyl or alkyelenemoiety, halogenalkyl having 2 or 3 c æ bon atcms, or halogen~alkenyl having 2 or 3 caxbon atoms, R2 is hydrogen, methyl, ethyl or halogen, R3 is hydrogen, halogen, methyl, ethyl, methoxy, ethoxy or nitro, R4 is hydrogen halogen, methyl, ethylt me~hoxy, ethoxy, nitro, and a salt thereof.
More particulaxly, the present invention provides novel and valuable water-soluble dyestuffs having t~ formula ~1) in the form of the free acid ~ N = N ~ N / Rl --~ / \1=/ \ CH2-CH2-OS03H (1) CH -O S ~ R4 R2 . ' ', .
~7~
in which the radicals Rl to R4, identical or different to each other, have the follcwing meaning: Rl represents hydrogen, aIkyl having from 1 to 4 carbon atoms, benzyl optionally substituted by methyl and/or chlorine, hydroxy-alkyl having from 2 -to 4 carbon atoms, hydroxyalkyl having from 2 to 4 carbon a-toms and esterified with an inorganic or organic acid, for example sulfato-alkyl, phosphato-alkyl, acetoxyalkyl, propionyloxyalkyl or phenyl-sulfonyloxy-alkyl, or represents cyanoalkyl having from 2 -to 4 carbon atoms in the alkyl moiety, carboxy, carbonamido or carbalkoxyalkylene each having from 1 to 4 carbon atoms in the aIkyl or alkylene moiety, halogenoalkyl having-2 or 3 carbon atoms, preferably chloroalkyl, or halogenoalken~ having 2 or 3 carbon atoms, for example bromo- or chloroalkenyl, R2 represents hydrogen, methyl or ethyl, preferably methyl, or a halogen atom, for example chlorine, bromine or fluorine, preferably chlorine, R3 represents hydrogen, halogen, for example chlorine, bromine - 2a -~a~
.
7~;~2 or fluorine, preferably chlorine or bromine, methyl or ethyl, preferably methyl, methoxy or ethoxy, preferably methoxy or ~
nitro, R4 represents hydrogen, halogen, for example chlorine, bro-mine or fluorine, preferably chlorine or bromine, methyl or ethyl, preferably methyl, methoxy or ethoxy, preferab-ly methoxy, or nitro.
The dyestuffs of the instant invention of formula (1) '`whërëin the~~-sulfato-ethy-lsul-on~l~group is standing in tha diazocomponent in para-position to the azo group, are pre-ferred, especially those dyestuffs which posse~s, in form of the free acid, the general formula (1a) .. . .. ... ~
~ N = N ~ ~1 j CH2-0 S ~ R2 2 2 0s03H (1~. 3 wherein R3 and R2 are defined as aboYe.
Especially preferred and advantageous in the dyestuff having in form of the free acid the formula (lb1 , . _ . .. .. .. . . .. . . . ... ...
f~ N = N ~3 CE~2-CH
CH ~-O s~f CH2 -CX2-0s03H ~ lb) OS03~
HOE 76/~ 275 7~
The novel d~estuffs are preferably present in the form - of their salts, especially alkali metal salts, for example sodium or potassium salts, or alkaline earth metal salts, for example calcium salts, and are used preferably in the form of the aforesaid salts.
The present invention also provides a process for the preparation of the dyestuffs of formula ~1) or of their salts, which comprises diazotizing an aromatic amine of the formula (2~
~-C~2-CH2-o2s ~NR~
. . . . . . ...
or a salt thereo~ prefexably an alkali metal or alkalin~
earth metal salt, in which R3 and R4 have the aforesaid mean-ing and W stands for the hydroxy or sulfato group, and coupl-ing it with a coupling component of the formula (3) , . . .. , ., ., . ., .. .., ., .. ., .. _ . _ _ ... . .. .
lE~< ' ~ 2 CH~-CM2-W
or a salt thereof, pre~erably an alkali met~l or alkaline earth metal salt, in which ~1' R2 and W have the aforesaid meaning, and, in the case o~ the preparation o~ a dyestuff o~ the formula (4) , .. , .. . , . . , . .. .. . , ; . ......
~ N=N ~ R ~ ~~
! CH2-2S ~ \ ~4 IlH2 R4 l2 CH2-CH2-w W
- . - : - -', . ' ~ .
.
:. , 7~
in which R1, R2, R3 and R4 have the aforesaid meaning and one or ~oth radicals W represent hydroxy, transforming this dyestuff of formula (4) into its ~ulfuric acid semi-ester compound of formula (1) or its salts by means of a sulfa-tization agent.
The acid compounds of formula (1) are transformed in-to their salts or vice versa by methods known to the expert, for example by neutralization or acidification with a strong inorganic acid, for example sulfuric acid.
Suitable diazo components of formula (2) for preparing the dyestuffs of the invention are especially 4-B-sulfatoethylsulfonyl-aniline, 3-~-sulfatoethylsulfonyl-aniline,
2-bromo~4-3-sulfatoethylsulfonyl-aniline, 2-chloro-4-~-sulfatoethylsulfonyl-aniline, 2-chloro-5-~-sulfatoethylsulfonyl-aniline, 2-bromo-5-~-sulfatoethylsulfonyl-aniline, 2,6-dichloro-4-B-sulfatoethylsulfonyl-aniline, 2,6-dibromo 4-~-sulfatoethy~sulfonyl-aniline, 2,5-dichloro-4-B-sulfatoethylsulfonyl-aniline, 2-methyl-~-B-sulfatoethylsulfonyl-aniline, 2 methoxy-5-B-sulfatoethylsulfonyl-aniline, 2-methoxy-4~B-sulfatoekhylsulfonyl-aniline, 2-methyl-6-chloro-4~B-sulfatoethylsulfonyl-aniline, 2,6-dimethyl-4-~sulfatoethylsulfonyl-aniline, 2,6-dimethyl-3-~-sulfatoethylsulfonyl-aniline, 2,5-dimethoxy-4-~-sulfatoethylsulfonyl-aniline, 2 methoxy 5-methyl-4 -B-sulfatoethylsulfonyl-aniline, ; 29 2-nitro-4-B-sulfatoethylsulfonyl-aniline, HOE 76/F ~75 a762~
4-nitro-2-~-sulfatoethylsulfonyl-a~iline, or the B-hydroxyethylsulfonyl derivatives thereof.
- The compounds of formula (2) containing a B-sulfato-ethylsulfonyl group can be prepared from the corresponding B-hydroxyethylsulfonyl-anilines by esterification, for ex-ample with water-containing or concentrated sulfuric acid or with amidosulfonic acid, for example by adding the cor-responding B-hydroxyethylsulfonyl anilines to an equimole-cular amount of 60 % sulfuric acid and subsequently heating in a manner analo~ous to the process descri~ed in German Patent 1,150,163, or by dissol~ing the ~ hydroxyethylsul-fonyl anilines in an excess of concentrated sulfuric acid or 100 % sulfuric acid (monohy~rate) at room temperature (i.e. at about 10 - 25 C~ or by reactiny with amidosulfo-nic acid in the presence of pyridlne or a pyridine base ina manner analogous to the esterification process described in German Patent 1,443,877. In the process of the invention the ~-sulfatoethylsulfonyl anilines prepared in this manner can be used directly in the form of the reaction mixture ; 20 obtained in the esterification, i.e. whithout isolation.
Suitable coupli~ components of formula ~3~ for pre-paring the dyestuffs of the invention are especially the following compounds.
N-B-sulfatoethyl-aniline, N-B-sulfatoethyl-N-ethyl-aniline, N-~-sulfatoethyl-N-methyl-aniline, N-~-sulfat~ethyi-N-n-butyl-aniline, N-~-sulfatoethyl-N-ethyl-3-methyl-aniline, N-B-sulfatoethyl-~-ethyl-3-chloro-aniline, N-~-sulfatoethyl-N-B-hydroxyethyl-3-~hloro-aniline, N,N-di-~-sulfa~oethyl-29 aniline, N,N-di-B-sulfatoethyl-3-chloro-aniline, N-B-sulfato-.
.. ~ . .. .
,. :
. ,, . , . .. ~ - -. . ~ . .
7~
ethyl~N-2-bromallyl-aniline, N~ sulfatoethyl~N-2-chloroal-lyl-aniline, N-~-sulfa~oethyl-N-benæyl-aniline, ~-~-sulfato-ethyl-N-B-carbonamidoethyl-aniline, N-B-sulfatoethyl-N-B-carboxyethyl-aniline, N-B-sulfatoethyl-N-~-carbethoxyethyl-aniline, N-e-sulfatoethyl-N-~-cyanethyl-aniline, N-~-sulfato-ethyl-N-~-acetoxyethyl-aniline, N-~-sulfatoethyl-N-B-cyan-ethyl--3-methyl-aniline, N-~-sulfatoethyl-N-~-hydroxyethyl-aniline, or the ~-hydroxyethyl derivatives thereof.
The coupling components of formula (3) containing a B-sulfatoethylamino group can be prepared, for example by the methods described by K.H. S~unders, J.Chem.Soc. (London) 121, 2667 - 2675 (1922). Alternatively, they can be obtain-ed by esterification of their B-hydroxyethyl-aniline deri-vatives, for example by reacting same with sulfuric acid, for instance 100 % sulfuric acid in the presence of chloro-sulfonic acid or with sulfuric acid containing sulfur tri-oxide (oleum)~ The coupling components oE formula (3) esteri-fied in this manner can als~ be used in the process of the invention directly in the form of the reaction mixture xe-sulting from the esterification, i.e. in non-isolated form, In the process of the invention the aromatic amines of formula (2) can be diazotized by generally known methods.
; In further processing reaction components carring the group of the formula ~SO2-CH2-CH2-OSO3H should not be subjected to strong alkaline conditions. Compounds of this type as well as compounds carrying the B-hydroxyethylsulfonyl group are preferably coupled at a pH in the range o~ from l to 7 and at a temperature of rom ~5 to ~25 C.
29 The dyestuffs of formula (1~ prepared by the process of .- .- ... . . ~ .
.. . , : .
.
: ' ~76~Z E 76/F 275 the invention can be isolated from the reaction solution by salting out with an electrolyte, for example sodium chloride or potassium chloride, advantageously after having adjusted the reaction mixture to a pH of from 3.5 to 7Ø They are then filtered off and dried. Alternatively, the dyestuffs of formula (1) obtained according to the invention can be isolated by concentration by evaporation or by spray-dry-ing. When the reaction solution contains large amounts of sulfate ions, it is recommended to precipitate same in th~
form of sparingly soluble salts prior to spray-drying, for example by the addition of calcium carbonate. It is also possible directly to use for dyeing the dyestuff solutions obtained after the synthesis, optionally after adclition of buffer substances.
When the coupling is carried out with diazo and/or coupl-ing components of formula (2) ox ~3) in which W represents hydroxy and the intermediate dyestuff of formula (4) is o~-tained, this dyestuff (41, which i~ only sparingly soluble in the aqueous medium in most cases, can be isolated direct-ly by filtration, optionally after ha~ing adjusted a pH of from 3.5 to 7Ø If precipitation of this dyestuff is not complete, it can be completed by the addition of electro-lyte. After drying, the isolated dy~stuffs o~ formula (4~
are trans~ormed into the sulfuric acid semi-ester dyestuffs of formula (1). The esterification can be carried out in a manner analogous to the process of K.H. Saunders mention-ed above, for exam~le by reacting the compound~ of formula (41 with h~ghly concentr~ted sulfuric acid in excess, for example of 80 to 100 % strength, or with chlorosulfonic acid ... . . , ... , ~ :
. : . . .: :
.: ., . ', : ' :
' ,' ': - - . , - , ~ . :
., , . ' .. . .
~7~;2~
in a non polar organic solvent. other esterification - methods suitable for transforming the dyestuffs o~ formu-la (4) into dyestuffs of formula (1) use amidosulfonic acid as sulfatization agent in the presence of pyridine or pyridine bases, or sulfur trioxide or chlorosulfonic acid in an aprotic polar organic solvent, for example N-methyl-pyrrolidone, dimethyl formamide or sulfolane (tetramethylenesulfone).
The dyestuffs of formula (1) obtained after the esteri-fication can be isolated as follows:
When the esterification has been carried out in an excess of sulfuric acid, the esterification mixture is preferably diluted with ice, the excess sulfuric acid is precipitated by adding a calcium compound, for example calcium carbona-te, the dyestuff solution is separated and the dyestuff isisolated from the filtrate obtained by salting out or spray-drying, -In the case of the esterification in a non-polar oxganic solvent immiscible with watar with one of the aforesaid esterification agents,for example chlorosulfonic acid, water or ice are added, the mixtuxe is optionally neutraliz-ed, th~ organic phase is separated and the dyestuff is iso-; lated from the aqueous phase in the manner described above3-With the esterification with amidosulfonic acid in pyridine or a pyridine base, the esterification mixture is fixst di~tilled in vacuo to recover the major proportion of the __ pyridine or pyridine base. Further amounts of the pyridine or pyridine base can then be separated in dilute form by 29 adding water and effecting another distillation. -. g _ .
, ,, ,', ' ~ ~
, , , When the esterification is carried out in a polar, aprotic,organic solvent immiscible with water using sulfur trioxide or chloroculfonic acid, the dyestuff can be precipitated by adding methanol and filtered off with suction after neutrali-zation with an alkaline agent, for example finely ground so-dium carbonate, or the esterification mixture is diluted with water, neutralized, the organic phase is extracted with methy-lene chloride and the dyestuff is isolated from its aqueous solution by spray-drying or salting out. -The dyestuffs described in Example 1, 2 and 3 are espe-cially preferred.
It is another object of the present invention to use the dyestuffs of formula (1) for dyeiny and printing cellu-lose fibers and natural or synthetic polyamide fiber materials.
Still another object of this invention is to provide a pro-cess for dyeing and printing cellulose fiber material-and natural or synthetic polyamide fiber materials by applying a dyestuff of formula (1) on said fiber material and fixing it thereon. Cellulose fiber materials are preferably cotton and regenerated cellulose; for example ~iscose rayon, flax~
hemp and jute. Suitable polyamide fiber materials are espe-cially wool and hairs of other animals as well as silk. Pre-ferred synthetic polyamides are especially polyamide 6,6, po-lyamide 6, polyamide 1~ and polyamide 4.
The no~el dyestuffs of formula (~ are especially sui-table as reactive dyes~ they can be fixed fast on the afore-said substrata by t-he method known for reactive dyes. On cellulose fibers they yield by the exhaust process in a long 2g bath with the use of various alkali additives dyeings of a ". ' ' . ' ' .
~., .
, ,: '. , ~
~76~2 very good dyestuff yield Excellent color yields (tinc-torial strengths) are also obtained by padding cellulose fibers by known padding processes wherein the dyestuff is fixed by means of an applied alkali while dwelling the so treated material at room temperature or by subsequent steam-ing or with dry heat. For printing, the usual One-Phase process are suitable wherein a printing paste containing an acid binding or alkali-yielding agent, for example so-dium bicarbonate, sodium carbonate or sodium trichloroace-tate, is applied on the material with subsequent fixationOf the dyestuff by steaming, for example at ~0~ to 103 C, as well as the two~phase processes are suitable wherein a neutral or weakly acid printing paste is printed on the fiber material which is passed thereafter through a hot ~5 alkaline bath containing an electrolyte, or which is cross-padded by an alkaline, electrol~te-containin~ pad-ding liquor and the dyestuff is then fixed by steaming or under the action of dry heat. ~ith these processes intense prints with sharp out-lines and a clear white background 2Q are obtained. The quality of the prints is practically not influenced by Yarying ~ixation conditions-and,therefore, the constancy of the shades is satisfactory.
The dyeing and prints obtained with the dyestuffs OI
formula (1) on cellulose fiber materials are distinguished by outstanding fastness properties. In this connection the most important properties o~ manufacture and use should be stressed, especially fastness to light, fastness to wet processing such as fastness to washing at 60 and 95~ C, 29 fastness to acid and alkaline milling, fastness to water ~nd , ~ . '' ~ ', .
.
HOE ~
~7~iZ;~
sea water, fastness to acid cross-dyeing, fastness to alka-line and acid perspiration and fastness to pleating, hot pressing (ironing) and rubbing. Moreover, the dischargeabi-lity to white af the dyeings is very good.
Natural as well as synthetic polyamide fiber materials are preferably dyed with the novel dyestuffs of formula (1) in an acid, aqueous dye bath or liquor. The desired pH ofthe dye bath or liquor is preferably adjusted with acetic acid or acetic acid and ammonium acetate or sodium acetate. To obtain dyeings having a good levelness or to improve the evelness of the dyeings it proved advantageous to add the usual levelling agents, for example compounds on the basis of a reaction product o~ a fatty amine, for example stearyl amine, with an alkylene oxide, such as ethylene oxide, and/or a reaction product of cyanuric chloride with approximately the three-fold molar amount of an aminobenzene-sulfonic acid and/or an aminonaphthalene-sulfonic acid. The material is dyed in usual manner at a temperature of from 60 to 100 C, preferably by the exhaust process~ more espe~ -2Q cially at the boiling temperature of the dye bath or in a pressure dyeing machine at a temperature of from about 110 to 120 C.
The ~ollowing examples illustrate the invention~ the parts being by weight unless otherwise stated, and the rela-tion of parts by weight to parts by ~olume bein~ the same asthat o the kilogram to the liter.
E X A M P L E ~:
.~ . ...___. _ _ ~2~4 Parts o~ 4-~-sulfatoethylsulfonyl--aniline were added 2~ while stirring to ~,200 parts by volume or water, ~43 parts , 1~7~
of 31 ~ hydrochloric acid were added and the mixture cooled to 0 - 5 C. At said temperature 80 parts by volume of an aqueous 5N sodium nitrite solution were slowly dropped in.
Stirring was continued for 15 minutes, whereupon the excess nitrous acid was destroyed with a small amount of amidosul-fonic acid. Coupling to obtain the azo dye was performed at a pH of about 1.8 to 2~0 by adding a solution of 98 parts of N-B sulfatoethyl-N-ethyl-aniline in 400 parts by volume of water, which solution had been neutralized by about 40 parts of sodiu~ bicarbonate. When the coupling was complete the pH was adjusted to 5.5 by adding about 65 parts of sodium bi-carbonate, and the dyestuff was precipitated by adding potas-sium chloride in an amount of 15 %, calculated on the ~l~me of the solution, filtered off whith suction and dried at 60 C in vacuo. An orange-red dyestuff powder was obtained with which clear reddish orange dyeings and prints could ~e produced on cotton by the fixation methods as usual for reac-tive dyes. In the form of the free acid the dyestuff had the following formula N -N - ~ / 2 CH3 ~H2-O S 2 2 OSO3H
fH2 Os03H
E X A M P L E 2:
112.4 Parts of 4-~-sulfatoethylsulfonyl~aniline were di-azotized as described in Example 1 and then coupled, instead : .
:
.
~7$%~
of the coupling component used in Example 1, with a solu-- tion of 150 parts of N,N-di-~-sulfatoethyl-3-chloroaniline in 400 paxts by volume of water; the solution containing the coupling component had a pH of 6.5 to 7.0 adjusted with sodium bic~rbonate. After salting out with potassium chlo-ride (in an amount of 25 %, calculated on the volume of the dyestuff solution obtained), filtering with suction and dry-ing, a brownish powder was obtained with which reddish-yel-low dyeings and prints were produced on cotton by the known fixation process for reactive dyes.
In the form of the free acid the dyestuff had the follow-ing formula ....
S ~ ~=N ~ / C~l2 C~2 OSO3~
CH2-C~ -OSG3H
IH~-O2S Cl 2 E X A M P I E 3:
59~3 Parts of N,N-di-~-hydroxyethyl-3-chloroaniline were introduced at 25 to 28 C over a period of about 25 mi-nutes into 49 parts of 100 % sulfuric acid. 43.8 Parts of chlorosulfonic acid were then added dropwise ~at 70 to 75 C
over a period of several hours. Next, the esterification mixture obtained was cautiously poured onto 200 parts of ice and the pH of the solution obtained was adjusted to 1 by adding 63 parts of sodium bicarbonate.
- 70.3 Parts of 4-B-sulfatoethylsulfonyl-aniline were ~76Z~ HOE 76/F 275 suspended in 350 par-ts by volume of water and 150 parts of ice and dissolvedfneutralized by adding about 15 parts of sodium carbonatej 43.5 parts of a 40 % aqueous solution of sodium nitrite were added to it at O to 5 C. For diazoti-zation this solution obtained was slowly added which stirringto a mixture of 375 parts of ice and 70.5 parts of 31 % hy-drochloric acid. After one houx, the excess of nitrous acid was decomposed with a small amount of amidosulfonic acid~
the coupling solution described above was added and a pH of 1.9 to 2.0 was adjusted. After a stirring time of several hours, the pH was adjusted to 5.5 to 6.0 by adding sodium bicarbonate, the dyestuff precipitated by adding 440 parts of potassium chloride, filtered off with suction and drie~.
A yellow-brown dyestuff powder was obtained with which red-dish-yellow dyeings and prints were produced on cotton by the known fixation process usual for reactive dyes.
The dyestuff represented a mixture of the following two dyestuffs in a molar proportion of about 35:65.
- - .. ...... . ... ... . . . .
N=N - ~ CH2-CH2-OH (ca. 35 ~) 2-c~2-2s Cl CH2-CH2-OS03H
CH2-CH2-Os03H
N=N ~ (ca. 65 %) ~ CH -CH -050 H
CH2-CH2-02S Cl 2 2 3 - ~5 -7~i~2 E X A M P L E 4:
144 Parts of 4-B-sulfatoe~hylsulfonyl-2-bromoaniline were dissolved in 400 parts by volume of water with the addi-tion of 46 parts of sodium bicarbonate and 82 parts by volume of an aqueous 5N sodium nitrite solution were added. The re-action mixture was cooled to O to 5 C snd poured onto a mix-ture of ~00 parts of ice and 143 parts by volume of 31 % hy-drochloric acid, whereby the diazonium compound formed pre-cipitated. Stirring of the mixture was continued for 15 minutes at O to 5 C, and the excess of nitrous acid was de-composed with a small amount of amidosulfonic acid. For coup-ling a solution of 98 parts of N-~-sulfatoethyl-N-ethyl aniline and 40 parts of sodium bicarbonate in 400 parts by volume of water was added to the diazonium solution obtained. Coupling was continued at a pH of 1.8 to 2.0 while stirring for some hours until completed. By adding 65 parts of sodium bicarbo-nate a pH of 5.0 to 5.5 was adjusted; the dyestuf was salted out by adding potassium chloride (in an amount of 15 %, cal-culated on the volume of the dyestuff solution), filtered off with suction and dried at 60 C in vacuo. The product was ground. A red dyestuff powder was obtained with wich scarlet dyeings and prints were obtained on a cotton fabric by the known ixing methods usual for reactive dyes.
In the form of the free acid the dyestuff had the o~low-ing constitution -~ N N ~ ~ 2 3 F~2-o S CH2-C~2-CH~
OS03~
-E X A M P L E 5:
140 Parts of 4-~sulfatoethylsulfonyl-2,6-dichloroanili-ne were diazotlzed by the indirect method as described in Ex-ample 4. The subsequent coupling was effected with a solu-tion of 86.8 parts of N~B-sulfatoethyl-aniline and 40 parts of sodium bicarbonate in 400 parts by volume of water. The azo dye obtained in this manner was isolated in analogous manner as in the preceding examples. In the form of the free acid it had the following formula Cl 2l5 = ~ N~l_C~2-CH2-OSO3H
~H2 ' CH2-OS03H
Yellowish-orange dyeings and prints were pxoduced therewi~h on cotton fa~ric under the known fixing conditions usual for re-active dyes.
E X A M P L E S 6:
2041 Parts of 4~B-hyroxyethylsulfonyl-aniline were intro duced into a mixture of 3Q parts of concentrated hydrochloric acid and 300 parts by volume of water, the mixture was cooled to 0 to 5 C and diazoti~ed at said temperatur2 with 20 parts by ~olume of aqueous 5N sodium nitrite solution. Stirring of the mixture uas continued for 60 minutes and the exces~ of ni-trous acid decomposed with amidosulfonic acid. For coupling a solution of 13.7 parts of N-B-hydroxyethyl-aniline in 30 parts : .
' .: , HOE 76/F 27~
7~2 by volume of glacial acetic acid was added, while the pH of the coupllng mixture was adjusted to and maintained at 1.8 to 2.0 by the addition of sodium bicarbonate. The coupling mixture was stirred for some hours at 10 to 18 C, the preci-pitated dyestu~f filtered of f with suction, washed with alittle 5 ~ sodium sulfate solution and dried at 60 C.
The dry product was introduced into 250 parts of 100 %
sulfuric acid and the mixture was stirred for 4 hours at 50 to 70 C. After cooling, the esterification mixture was cau-tiously poured onto 1,400 parts of ice, the excess sulfuricacid was precipitated in the form of calcium sulfate by slow-ly adding 235 parts of calcium carbonate in portions, the hot reaction mixture was filtered off with suction and the preci-pitate washed with hot water. The dyestuff solution obtained as filtrate was spray-dried.
The dyestuff isolated in this manner yielded on cotton orange dyeings and prints under the fixing conditions known and usual for reactive dyes. In the form of the free acid it had t~e formula ... , .. ~, .. . , . . , , .. , ~ .. . ... . .. ... ...
=N ~ H~CH2-CH2-O~O3H
fH2 2 .
E X A M P L E S 7 to 35:
The dyestuffs listed in the fol1Owing table were prepared - according ~o the processes of the instant invention, especially in a way a~ described, or analoyously thereto, in the aore-said examples. They yielded likewise on cotton fast dyeings ~762~2 and prints in the shades indicated in the table.
Exam le formula of dyestuff shade on cotton P
7 1 3S C~l2C~I2 02S ~ N==N- ~ N < orange 8 H35-CII2C~I2-2S- ~ N==N- ~ C2~15 orange Br H
4-nitro-2-~-sulfatoethylsulfonyl-a~iline, or the B-hydroxyethylsulfonyl derivatives thereof.
- The compounds of formula (2) containing a B-sulfato-ethylsulfonyl group can be prepared from the corresponding B-hydroxyethylsulfonyl-anilines by esterification, for ex-ample with water-containing or concentrated sulfuric acid or with amidosulfonic acid, for example by adding the cor-responding B-hydroxyethylsulfonyl anilines to an equimole-cular amount of 60 % sulfuric acid and subsequently heating in a manner analo~ous to the process descri~ed in German Patent 1,150,163, or by dissol~ing the ~ hydroxyethylsul-fonyl anilines in an excess of concentrated sulfuric acid or 100 % sulfuric acid (monohy~rate) at room temperature (i.e. at about 10 - 25 C~ or by reactiny with amidosulfo-nic acid in the presence of pyridlne or a pyridine base ina manner analogous to the esterification process described in German Patent 1,443,877. In the process of the invention the ~-sulfatoethylsulfonyl anilines prepared in this manner can be used directly in the form of the reaction mixture ; 20 obtained in the esterification, i.e. whithout isolation.
Suitable coupli~ components of formula ~3~ for pre-paring the dyestuffs of the invention are especially the following compounds.
N-B-sulfatoethyl-aniline, N-B-sulfatoethyl-N-ethyl-aniline, N-~-sulfatoethyl-N-methyl-aniline, N-~-sulfat~ethyi-N-n-butyl-aniline, N-~-sulfatoethyl-N-ethyl-3-methyl-aniline, N-B-sulfatoethyl-~-ethyl-3-chloro-aniline, N-~-sulfatoethyl-N-B-hydroxyethyl-3-~hloro-aniline, N,N-di-~-sulfa~oethyl-29 aniline, N,N-di-B-sulfatoethyl-3-chloro-aniline, N-B-sulfato-.
.. ~ . .. .
,. :
. ,, . , . .. ~ - -. . ~ . .
7~
ethyl~N-2-bromallyl-aniline, N~ sulfatoethyl~N-2-chloroal-lyl-aniline, N-~-sulfa~oethyl-N-benæyl-aniline, ~-~-sulfato-ethyl-N-B-carbonamidoethyl-aniline, N-B-sulfatoethyl-N-B-carboxyethyl-aniline, N-B-sulfatoethyl-N-~-carbethoxyethyl-aniline, N-e-sulfatoethyl-N-~-cyanethyl-aniline, N-~-sulfato-ethyl-N-~-acetoxyethyl-aniline, N-~-sulfatoethyl-N-B-cyan-ethyl--3-methyl-aniline, N-~-sulfatoethyl-N-~-hydroxyethyl-aniline, or the ~-hydroxyethyl derivatives thereof.
The coupling components of formula (3) containing a B-sulfatoethylamino group can be prepared, for example by the methods described by K.H. S~unders, J.Chem.Soc. (London) 121, 2667 - 2675 (1922). Alternatively, they can be obtain-ed by esterification of their B-hydroxyethyl-aniline deri-vatives, for example by reacting same with sulfuric acid, for instance 100 % sulfuric acid in the presence of chloro-sulfonic acid or with sulfuric acid containing sulfur tri-oxide (oleum)~ The coupling components oE formula (3) esteri-fied in this manner can als~ be used in the process of the invention directly in the form of the reaction mixture xe-sulting from the esterification, i.e. in non-isolated form, In the process of the invention the aromatic amines of formula (2) can be diazotized by generally known methods.
; In further processing reaction components carring the group of the formula ~SO2-CH2-CH2-OSO3H should not be subjected to strong alkaline conditions. Compounds of this type as well as compounds carrying the B-hydroxyethylsulfonyl group are preferably coupled at a pH in the range o~ from l to 7 and at a temperature of rom ~5 to ~25 C.
29 The dyestuffs of formula (1~ prepared by the process of .- .- ... . . ~ .
.. . , : .
.
: ' ~76~Z E 76/F 275 the invention can be isolated from the reaction solution by salting out with an electrolyte, for example sodium chloride or potassium chloride, advantageously after having adjusted the reaction mixture to a pH of from 3.5 to 7Ø They are then filtered off and dried. Alternatively, the dyestuffs of formula (1) obtained according to the invention can be isolated by concentration by evaporation or by spray-dry-ing. When the reaction solution contains large amounts of sulfate ions, it is recommended to precipitate same in th~
form of sparingly soluble salts prior to spray-drying, for example by the addition of calcium carbonate. It is also possible directly to use for dyeing the dyestuff solutions obtained after the synthesis, optionally after adclition of buffer substances.
When the coupling is carried out with diazo and/or coupl-ing components of formula (2) ox ~3) in which W represents hydroxy and the intermediate dyestuff of formula (4) is o~-tained, this dyestuff (41, which i~ only sparingly soluble in the aqueous medium in most cases, can be isolated direct-ly by filtration, optionally after ha~ing adjusted a pH of from 3.5 to 7Ø If precipitation of this dyestuff is not complete, it can be completed by the addition of electro-lyte. After drying, the isolated dy~stuffs o~ formula (4~
are trans~ormed into the sulfuric acid semi-ester dyestuffs of formula (1). The esterification can be carried out in a manner analogous to the process of K.H. Saunders mention-ed above, for exam~le by reacting the compound~ of formula (41 with h~ghly concentr~ted sulfuric acid in excess, for example of 80 to 100 % strength, or with chlorosulfonic acid ... . . , ... , ~ :
. : . . .: :
.: ., . ', : ' :
' ,' ': - - . , - , ~ . :
., , . ' .. . .
~7~;2~
in a non polar organic solvent. other esterification - methods suitable for transforming the dyestuffs o~ formu-la (4) into dyestuffs of formula (1) use amidosulfonic acid as sulfatization agent in the presence of pyridine or pyridine bases, or sulfur trioxide or chlorosulfonic acid in an aprotic polar organic solvent, for example N-methyl-pyrrolidone, dimethyl formamide or sulfolane (tetramethylenesulfone).
The dyestuffs of formula (1) obtained after the esteri-fication can be isolated as follows:
When the esterification has been carried out in an excess of sulfuric acid, the esterification mixture is preferably diluted with ice, the excess sulfuric acid is precipitated by adding a calcium compound, for example calcium carbona-te, the dyestuff solution is separated and the dyestuff isisolated from the filtrate obtained by salting out or spray-drying, -In the case of the esterification in a non-polar oxganic solvent immiscible with watar with one of the aforesaid esterification agents,for example chlorosulfonic acid, water or ice are added, the mixtuxe is optionally neutraliz-ed, th~ organic phase is separated and the dyestuff is iso-; lated from the aqueous phase in the manner described above3-With the esterification with amidosulfonic acid in pyridine or a pyridine base, the esterification mixture is fixst di~tilled in vacuo to recover the major proportion of the __ pyridine or pyridine base. Further amounts of the pyridine or pyridine base can then be separated in dilute form by 29 adding water and effecting another distillation. -. g _ .
, ,, ,', ' ~ ~
, , , When the esterification is carried out in a polar, aprotic,organic solvent immiscible with water using sulfur trioxide or chloroculfonic acid, the dyestuff can be precipitated by adding methanol and filtered off with suction after neutrali-zation with an alkaline agent, for example finely ground so-dium carbonate, or the esterification mixture is diluted with water, neutralized, the organic phase is extracted with methy-lene chloride and the dyestuff is isolated from its aqueous solution by spray-drying or salting out. -The dyestuffs described in Example 1, 2 and 3 are espe-cially preferred.
It is another object of the present invention to use the dyestuffs of formula (1) for dyeiny and printing cellu-lose fibers and natural or synthetic polyamide fiber materials.
Still another object of this invention is to provide a pro-cess for dyeing and printing cellulose fiber material-and natural or synthetic polyamide fiber materials by applying a dyestuff of formula (1) on said fiber material and fixing it thereon. Cellulose fiber materials are preferably cotton and regenerated cellulose; for example ~iscose rayon, flax~
hemp and jute. Suitable polyamide fiber materials are espe-cially wool and hairs of other animals as well as silk. Pre-ferred synthetic polyamides are especially polyamide 6,6, po-lyamide 6, polyamide 1~ and polyamide 4.
The no~el dyestuffs of formula (~ are especially sui-table as reactive dyes~ they can be fixed fast on the afore-said substrata by t-he method known for reactive dyes. On cellulose fibers they yield by the exhaust process in a long 2g bath with the use of various alkali additives dyeings of a ". ' ' . ' ' .
~., .
, ,: '. , ~
~76~2 very good dyestuff yield Excellent color yields (tinc-torial strengths) are also obtained by padding cellulose fibers by known padding processes wherein the dyestuff is fixed by means of an applied alkali while dwelling the so treated material at room temperature or by subsequent steam-ing or with dry heat. For printing, the usual One-Phase process are suitable wherein a printing paste containing an acid binding or alkali-yielding agent, for example so-dium bicarbonate, sodium carbonate or sodium trichloroace-tate, is applied on the material with subsequent fixationOf the dyestuff by steaming, for example at ~0~ to 103 C, as well as the two~phase processes are suitable wherein a neutral or weakly acid printing paste is printed on the fiber material which is passed thereafter through a hot ~5 alkaline bath containing an electrolyte, or which is cross-padded by an alkaline, electrol~te-containin~ pad-ding liquor and the dyestuff is then fixed by steaming or under the action of dry heat. ~ith these processes intense prints with sharp out-lines and a clear white background 2Q are obtained. The quality of the prints is practically not influenced by Yarying ~ixation conditions-and,therefore, the constancy of the shades is satisfactory.
The dyeing and prints obtained with the dyestuffs OI
formula (1) on cellulose fiber materials are distinguished by outstanding fastness properties. In this connection the most important properties o~ manufacture and use should be stressed, especially fastness to light, fastness to wet processing such as fastness to washing at 60 and 95~ C, 29 fastness to acid and alkaline milling, fastness to water ~nd , ~ . '' ~ ', .
.
HOE ~
~7~iZ;~
sea water, fastness to acid cross-dyeing, fastness to alka-line and acid perspiration and fastness to pleating, hot pressing (ironing) and rubbing. Moreover, the dischargeabi-lity to white af the dyeings is very good.
Natural as well as synthetic polyamide fiber materials are preferably dyed with the novel dyestuffs of formula (1) in an acid, aqueous dye bath or liquor. The desired pH ofthe dye bath or liquor is preferably adjusted with acetic acid or acetic acid and ammonium acetate or sodium acetate. To obtain dyeings having a good levelness or to improve the evelness of the dyeings it proved advantageous to add the usual levelling agents, for example compounds on the basis of a reaction product o~ a fatty amine, for example stearyl amine, with an alkylene oxide, such as ethylene oxide, and/or a reaction product of cyanuric chloride with approximately the three-fold molar amount of an aminobenzene-sulfonic acid and/or an aminonaphthalene-sulfonic acid. The material is dyed in usual manner at a temperature of from 60 to 100 C, preferably by the exhaust process~ more espe~ -2Q cially at the boiling temperature of the dye bath or in a pressure dyeing machine at a temperature of from about 110 to 120 C.
The ~ollowing examples illustrate the invention~ the parts being by weight unless otherwise stated, and the rela-tion of parts by weight to parts by ~olume bein~ the same asthat o the kilogram to the liter.
E X A M P L E ~:
.~ . ...___. _ _ ~2~4 Parts o~ 4-~-sulfatoethylsulfonyl--aniline were added 2~ while stirring to ~,200 parts by volume or water, ~43 parts , 1~7~
of 31 ~ hydrochloric acid were added and the mixture cooled to 0 - 5 C. At said temperature 80 parts by volume of an aqueous 5N sodium nitrite solution were slowly dropped in.
Stirring was continued for 15 minutes, whereupon the excess nitrous acid was destroyed with a small amount of amidosul-fonic acid. Coupling to obtain the azo dye was performed at a pH of about 1.8 to 2~0 by adding a solution of 98 parts of N-B sulfatoethyl-N-ethyl-aniline in 400 parts by volume of water, which solution had been neutralized by about 40 parts of sodiu~ bicarbonate. When the coupling was complete the pH was adjusted to 5.5 by adding about 65 parts of sodium bi-carbonate, and the dyestuff was precipitated by adding potas-sium chloride in an amount of 15 %, calculated on the ~l~me of the solution, filtered off whith suction and dried at 60 C in vacuo. An orange-red dyestuff powder was obtained with which clear reddish orange dyeings and prints could ~e produced on cotton by the fixation methods as usual for reac-tive dyes. In the form of the free acid the dyestuff had the following formula N -N - ~ / 2 CH3 ~H2-O S 2 2 OSO3H
fH2 Os03H
E X A M P L E 2:
112.4 Parts of 4-~-sulfatoethylsulfonyl~aniline were di-azotized as described in Example 1 and then coupled, instead : .
:
.
~7$%~
of the coupling component used in Example 1, with a solu-- tion of 150 parts of N,N-di-~-sulfatoethyl-3-chloroaniline in 400 paxts by volume of water; the solution containing the coupling component had a pH of 6.5 to 7.0 adjusted with sodium bic~rbonate. After salting out with potassium chlo-ride (in an amount of 25 %, calculated on the volume of the dyestuff solution obtained), filtering with suction and dry-ing, a brownish powder was obtained with which reddish-yel-low dyeings and prints were produced on cotton by the known fixation process for reactive dyes.
In the form of the free acid the dyestuff had the follow-ing formula ....
S ~ ~=N ~ / C~l2 C~2 OSO3~
CH2-C~ -OSG3H
IH~-O2S Cl 2 E X A M P I E 3:
59~3 Parts of N,N-di-~-hydroxyethyl-3-chloroaniline were introduced at 25 to 28 C over a period of about 25 mi-nutes into 49 parts of 100 % sulfuric acid. 43.8 Parts of chlorosulfonic acid were then added dropwise ~at 70 to 75 C
over a period of several hours. Next, the esterification mixture obtained was cautiously poured onto 200 parts of ice and the pH of the solution obtained was adjusted to 1 by adding 63 parts of sodium bicarbonate.
- 70.3 Parts of 4-B-sulfatoethylsulfonyl-aniline were ~76Z~ HOE 76/F 275 suspended in 350 par-ts by volume of water and 150 parts of ice and dissolvedfneutralized by adding about 15 parts of sodium carbonatej 43.5 parts of a 40 % aqueous solution of sodium nitrite were added to it at O to 5 C. For diazoti-zation this solution obtained was slowly added which stirringto a mixture of 375 parts of ice and 70.5 parts of 31 % hy-drochloric acid. After one houx, the excess of nitrous acid was decomposed with a small amount of amidosulfonic acid~
the coupling solution described above was added and a pH of 1.9 to 2.0 was adjusted. After a stirring time of several hours, the pH was adjusted to 5.5 to 6.0 by adding sodium bicarbonate, the dyestuff precipitated by adding 440 parts of potassium chloride, filtered off with suction and drie~.
A yellow-brown dyestuff powder was obtained with which red-dish-yellow dyeings and prints were produced on cotton by the known fixation process usual for reactive dyes.
The dyestuff represented a mixture of the following two dyestuffs in a molar proportion of about 35:65.
- - .. ...... . ... ... . . . .
N=N - ~ CH2-CH2-OH (ca. 35 ~) 2-c~2-2s Cl CH2-CH2-OS03H
CH2-CH2-Os03H
N=N ~ (ca. 65 %) ~ CH -CH -050 H
CH2-CH2-02S Cl 2 2 3 - ~5 -7~i~2 E X A M P L E 4:
144 Parts of 4-B-sulfatoe~hylsulfonyl-2-bromoaniline were dissolved in 400 parts by volume of water with the addi-tion of 46 parts of sodium bicarbonate and 82 parts by volume of an aqueous 5N sodium nitrite solution were added. The re-action mixture was cooled to O to 5 C snd poured onto a mix-ture of ~00 parts of ice and 143 parts by volume of 31 % hy-drochloric acid, whereby the diazonium compound formed pre-cipitated. Stirring of the mixture was continued for 15 minutes at O to 5 C, and the excess of nitrous acid was de-composed with a small amount of amidosulfonic acid. For coup-ling a solution of 98 parts of N-~-sulfatoethyl-N-ethyl aniline and 40 parts of sodium bicarbonate in 400 parts by volume of water was added to the diazonium solution obtained. Coupling was continued at a pH of 1.8 to 2.0 while stirring for some hours until completed. By adding 65 parts of sodium bicarbo-nate a pH of 5.0 to 5.5 was adjusted; the dyestuf was salted out by adding potassium chloride (in an amount of 15 %, cal-culated on the volume of the dyestuff solution), filtered off with suction and dried at 60 C in vacuo. The product was ground. A red dyestuff powder was obtained with wich scarlet dyeings and prints were obtained on a cotton fabric by the known ixing methods usual for reactive dyes.
In the form of the free acid the dyestuff had the o~low-ing constitution -~ N N ~ ~ 2 3 F~2-o S CH2-C~2-CH~
OS03~
-E X A M P L E 5:
140 Parts of 4-~sulfatoethylsulfonyl-2,6-dichloroanili-ne were diazotlzed by the indirect method as described in Ex-ample 4. The subsequent coupling was effected with a solu-tion of 86.8 parts of N~B-sulfatoethyl-aniline and 40 parts of sodium bicarbonate in 400 parts by volume of water. The azo dye obtained in this manner was isolated in analogous manner as in the preceding examples. In the form of the free acid it had the following formula Cl 2l5 = ~ N~l_C~2-CH2-OSO3H
~H2 ' CH2-OS03H
Yellowish-orange dyeings and prints were pxoduced therewi~h on cotton fa~ric under the known fixing conditions usual for re-active dyes.
E X A M P L E S 6:
2041 Parts of 4~B-hyroxyethylsulfonyl-aniline were intro duced into a mixture of 3Q parts of concentrated hydrochloric acid and 300 parts by volume of water, the mixture was cooled to 0 to 5 C and diazoti~ed at said temperatur2 with 20 parts by ~olume of aqueous 5N sodium nitrite solution. Stirring of the mixture uas continued for 60 minutes and the exces~ of ni-trous acid decomposed with amidosulfonic acid. For coupling a solution of 13.7 parts of N-B-hydroxyethyl-aniline in 30 parts : .
' .: , HOE 76/F 27~
7~2 by volume of glacial acetic acid was added, while the pH of the coupllng mixture was adjusted to and maintained at 1.8 to 2.0 by the addition of sodium bicarbonate. The coupling mixture was stirred for some hours at 10 to 18 C, the preci-pitated dyestu~f filtered of f with suction, washed with alittle 5 ~ sodium sulfate solution and dried at 60 C.
The dry product was introduced into 250 parts of 100 %
sulfuric acid and the mixture was stirred for 4 hours at 50 to 70 C. After cooling, the esterification mixture was cau-tiously poured onto 1,400 parts of ice, the excess sulfuricacid was precipitated in the form of calcium sulfate by slow-ly adding 235 parts of calcium carbonate in portions, the hot reaction mixture was filtered off with suction and the preci-pitate washed with hot water. The dyestuff solution obtained as filtrate was spray-dried.
The dyestuff isolated in this manner yielded on cotton orange dyeings and prints under the fixing conditions known and usual for reactive dyes. In the form of the free acid it had t~e formula ... , .. ~, .. . , . . , , .. , ~ .. . ... . .. ... ...
=N ~ H~CH2-CH2-O~O3H
fH2 2 .
E X A M P L E S 7 to 35:
The dyestuffs listed in the fol1Owing table were prepared - according ~o the processes of the instant invention, especially in a way a~ described, or analoyously thereto, in the aore-said examples. They yielded likewise on cotton fast dyeings ~762~2 and prints in the shades indicated in the table.
Exam le formula of dyestuff shade on cotton P
7 1 3S C~l2C~I2 02S ~ N==N- ~ N < orange 8 H35-CII2C~I2-2S- ~ N==N- ~ C2~15 orange Br H
3 2 2 2 ~ N==N- ~ N < orange 0 N- ~ N-=N- ~ N bluish red 11 H03SO-CH2CH2-02S- ~ N==N- ~ N \ red Cl CH2CH2COOH
12 H03SO-CH2CH2-02S- ~ N==N- ~ N / orange 13 HO SO-CH2CH2-02S- ~ N^~ N < orange 14 H3S-C~2CH2-2S- ~ N==N- ~ N / orange ~ , ... .
-, : , . - ' :
, ~7~
Example formula of dyestuff shade on cotton ~CH2CH2CONH2 HO3SO-CH2CH2-O2S- ~ N==N- ~ N \ orange Cll2CH2OSO3H
16 3 2 2 2 ~ N==N- ~ N \ orange CH2C~120S3~1 17 3SO CH2CH2 2 ~N N ~N / orange Br CH2 -1=CH2 18 HO3SO-CH2CH2-O2S- ~ N==N- ~ N \ orange Cl ~CH2 -C=CH2 19 HO3SO-CH2CH2-O2S- ~ N==N- ~ N \ orange HO3SO-CH2CH2-O2S- ~ N==N- ~ N / orange 21 ~ N =N ~ N orange :~ Ho3so-cH2cH2-so2 2 2 3 22 HO3SO-cH2cu2-~2 ~ ~ \ C~l CH253H dd sh _ 20 -7~
Example formula o:E dyestuff shade on cotton 23 ~ ~ yellowish 3 2 2 2 \ CH2C~I20SO3H orange 24 ~ N==N- ~ -N \ orange HO3SO-c~l2-cH2-so2 CH2CH2 S 3 HO3SO-CH2cH2-02s- ~ N==N- ~ -N ~ reddish OCH3 2 2 3 orange 26 ~ N-==N- ~ N orange CEI CH OSO H
Cl / CH3 27 HO3SO CH2CH2 2 ~ ~ \ orange 28H3S-CH2CH2 2S- ~ N==N- ~ -N~/ orange 29 ~ ~ ~ orange ~ OCH3 / 2 2 2 3 30H3S-CH2CH2-2S~ ~ N==N- ~ -N \ orange Br CH -CH
31~ -N==N~ ~ -N / orange CH CH OSO H
- Ho3so-cH2-cH2-so2 2 2 3 -~ - 21 -, ' :. ~ ' ~976~:
F.xample formula of dyestuff shade on cotton 32 11~5-C~12CH2 2 ~ ~ < Cll CH 0503H orange 33 ~13S-cH2cH2-2s- ~ N==N- ~ N \ orange Cl 2 2 3 34 H03SO CH2CH2 02S ~ N N ~ N \ orange 3 2 2 2 ~ N==N- ~ N / orange .
Cl CH2CH2S3H
' . , ' '
12 H03SO-CH2CH2-02S- ~ N==N- ~ N / orange 13 HO SO-CH2CH2-02S- ~ N^~ N < orange 14 H3S-C~2CH2-2S- ~ N==N- ~ N / orange ~ , ... .
-, : , . - ' :
, ~7~
Example formula of dyestuff shade on cotton ~CH2CH2CONH2 HO3SO-CH2CH2-O2S- ~ N==N- ~ N \ orange Cll2CH2OSO3H
16 3 2 2 2 ~ N==N- ~ N \ orange CH2C~120S3~1 17 3SO CH2CH2 2 ~N N ~N / orange Br CH2 -1=CH2 18 HO3SO-CH2CH2-O2S- ~ N==N- ~ N \ orange Cl ~CH2 -C=CH2 19 HO3SO-CH2CH2-O2S- ~ N==N- ~ N \ orange HO3SO-CH2CH2-O2S- ~ N==N- ~ N / orange 21 ~ N =N ~ N orange :~ Ho3so-cH2cH2-so2 2 2 3 22 HO3SO-cH2cu2-~2 ~ ~ \ C~l CH253H dd sh _ 20 -7~
Example formula o:E dyestuff shade on cotton 23 ~ ~ yellowish 3 2 2 2 \ CH2C~I20SO3H orange 24 ~ N==N- ~ -N \ orange HO3SO-c~l2-cH2-so2 CH2CH2 S 3 HO3SO-CH2cH2-02s- ~ N==N- ~ -N ~ reddish OCH3 2 2 3 orange 26 ~ N-==N- ~ N orange CEI CH OSO H
Cl / CH3 27 HO3SO CH2CH2 2 ~ ~ \ orange 28H3S-CH2CH2 2S- ~ N==N- ~ -N~/ orange 29 ~ ~ ~ orange ~ OCH3 / 2 2 2 3 30H3S-CH2CH2-2S~ ~ N==N- ~ -N \ orange Br CH -CH
31~ -N==N~ ~ -N / orange CH CH OSO H
- Ho3so-cH2-cH2-so2 2 2 3 -~ - 21 -, ' :. ~ ' ~976~:
F.xample formula of dyestuff shade on cotton 32 11~5-C~12CH2 2 ~ ~ < Cll CH 0503H orange 33 ~13S-cH2cH2-2s- ~ N==N- ~ N \ orange Cl 2 2 3 34 H03SO CH2CH2 02S ~ N N ~ N \ orange 3 2 2 2 ~ N==N- ~ N / orange .
Cl CH2CH2S3H
' . , ' '
Claims (6)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A water soluble dyestuff having, in the form of the free acid, the formula (1) (1) in which R1 is hydrogen, alkyl having from 1 to 4 carbon atoms, benzyl, benzyl substituted in the benzene nucleus by methyl and/or chlorine, or is hydroxyalkyl having from 2 to 4 carbon atoms or hydroxyalkyl having from 2 to 4 carbon atoms and esterified with an inorganic or organic acid, cyanoalkyl having from 2 to 4 carbon atoms in the alkyl moiety, carboxy, carbonamido or carbalkoxyalkylene each having from 1 to 4 carbon atoms in the alkyl or alkylene moiety, halogenoalkyl having 2 or 3 carbon atoms, or halogenoalkenyl having 2 or 3 carbon atoms, R2 is hydrogen, methyl, ethyl or halogen, R3 is hydrogen, halogen, methyl, ethyl, methoxy, ethoxy or nitro, R4 is hydrogen, halogen, methyl, ethyl, methoxy, ethoxy or nitro, and a salt thereof.
2. Process for the preparation of the dyestuffs of formula (1) as defined in claim 1, or of their salts, which comprises diazotizing an aromatic amine of the formula (2) (2) or a salt thereof, in which R3 and R4 have the meaning of claim 1 and W stands for the hydroxy or sulfato group, and coupling with a coupling component of the formula (3) (3) or a salt thereof, in which R1 and R2 have the meaning of claim 1, and W has the meaning of claim 2, and, in the case of the preparation of a dyestuff of the formula (4) (4) in which R1, R2, R3 and R4 have the meaning specified in claim 1 and one or both radicals W represent hydroxy, transforming the dyestuff of formula (4) or its salt by means of a sulfatization agent.
3. A process for colouring, dyeing or printing a fiber material made of cellulose fibers, natural or synthetic polyamide fibers or of mixtures thereof, which comprises applying the dyestuff of formula (1) defined in claim 1, on said material and fixing it by the action of an alkaline agent, optionally by the additional action of steam or heat.
4. A dyestuff according to claim 1, having in form of the free acid, the formula wherein R1, R2, R3, R4 are defined as in claim 1.
5. A dyestuff according to claim 4, wherein R3 and R4 each is hydrogen.
6. A dyestuff according to claim 4, wherein R2, R3, R4 each is hydrogen and R1 is ethyl.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP2653478.1 | 1976-11-25 | ||
| DE2653478A DE2653478C3 (en) | 1976-11-25 | 1976-11-25 | Water-soluble dyes, processes for their production and their use for dyeing and printing cellulose and polyamide fiber materials |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1097622A true CA1097622A (en) | 1981-03-17 |
Family
ID=5993912
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA291,703A Expired CA1097622A (en) | 1976-11-25 | 1977-11-24 | Water-soluble dyestuffs, process for preparing them and their use for dyeing and printing cellulose and polyamide fiber materials |
Country Status (13)
| Country | Link |
|---|---|
| JP (1) | JPS6035948B2 (en) |
| AR (1) | AR224998A1 (en) |
| BE (1) | BE861220A (en) |
| BR (1) | BR7707806A (en) |
| CA (1) | CA1097622A (en) |
| CH (1) | CH627774A5 (en) |
| CS (1) | CS192597B2 (en) |
| DE (1) | DE2653478C3 (en) |
| FR (1) | FR2372210A1 (en) |
| GB (1) | GB1561944A (en) |
| IN (1) | IN146167B (en) |
| IT (1) | IT1088896B (en) |
| MX (1) | MX148757A (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2951061A1 (en) * | 1979-12-19 | 1981-07-02 | Hoechst Ag, 6230 Frankfurt | WATER-SOLUBLE AZO COMPOUNDS AND THEIR COPPER COMPLEXES, METHODS FOR THEIR PRODUCTION AND THEIR USE AS DYES |
| DE3139657A1 (en) * | 1980-11-06 | 1982-06-16 | Hoechst Ag, 6000 Frankfurt | WATER-SOLUBLE DISAZO COMPOUNDS, METHOD FOR THEIR PRODUCTION AND THEIR USE AS DYES |
| DE3113001A1 (en) * | 1980-11-06 | 1982-06-09 | Hoechst Ag, 6000 Frankfurt | WATER-SOLUBLE MONOAZO COMPOUNDS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS DYES |
| IN156477B (en) * | 1980-11-06 | 1985-08-10 | Hoechst Ag | |
| DE3537260A1 (en) * | 1985-10-12 | 1987-04-16 | Hoechst Ag | MIXTURES OF WATER-SOLUBLE REACTIVE DYES |
| DE3643386A1 (en) * | 1986-12-19 | 1988-06-23 | Hoechst Ag | AZO COMPOUNDS CONTAINING CYAN GROUPS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS DYES |
| US6464734B1 (en) | 2000-03-13 | 2002-10-15 | Dystar Textilfarben Gmbh & Co. Deutschland Kg | Deep black dye mixtures of fiber-reactive azo dyes |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB779781A (en) * | 1952-06-09 | 1957-07-24 | Hoechst Ag | Water insoluble dyestuffs and a process for producing fast dyeings and prints therewith |
-
1976
- 1976-11-25 DE DE2653478A patent/DE2653478C3/en not_active Expired
-
1977
- 1977-11-18 IN IN1623/CAL/77A patent/IN146167B/en unknown
- 1977-11-22 CH CH1425977A patent/CH627774A5/en not_active IP Right Cessation
- 1977-11-23 IT IT29963/77A patent/IT1088896B/en active
- 1977-11-23 CS CS777744A patent/CS192597B2/en unknown
- 1977-11-23 AR AR270084A patent/AR224998A1/en active
- 1977-11-24 MX MX171445A patent/MX148757A/en unknown
- 1977-11-24 BR BR7707806A patent/BR7707806A/en unknown
- 1977-11-24 JP JP52140082A patent/JPS6035948B2/en not_active Expired
- 1977-11-24 GB GB48956/77A patent/GB1561944A/en not_active Expired
- 1977-11-24 CA CA291,703A patent/CA1097622A/en not_active Expired
- 1977-11-25 BE BE182942A patent/BE861220A/en not_active IP Right Cessation
- 1977-11-25 FR FR7735491A patent/FR2372210A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| DE2653478A1 (en) | 1978-10-19 |
| IT1088896B (en) | 1985-06-10 |
| DE2653478B2 (en) | 1979-06-28 |
| JPS6035948B2 (en) | 1985-08-17 |
| DE2653478C3 (en) | 1980-03-06 |
| CS192597B2 (en) | 1979-08-31 |
| MX148757A (en) | 1983-06-14 |
| GB1561944A (en) | 1980-03-05 |
| JPS5367725A (en) | 1978-06-16 |
| BR7707806A (en) | 1978-06-13 |
| IN146167B (en) | 1979-03-10 |
| CH627774A5 (en) | 1982-01-29 |
| AR224998A1 (en) | 1982-02-15 |
| FR2372210A1 (en) | 1978-06-23 |
| BE861220A (en) | 1978-05-25 |
| FR2372210B1 (en) | 1984-05-25 |
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| MKEX | Expiry |