CA2142251A1 - Water-soluble azo compounds, preparation thereof, and use thereof as dyes - Google Patents
Water-soluble azo compounds, preparation thereof, and use thereof as dyesInfo
- Publication number
- CA2142251A1 CA2142251A1 CA002142251A CA2142251A CA2142251A1 CA 2142251 A1 CA2142251 A1 CA 2142251A1 CA 002142251 A CA002142251 A CA 002142251A CA 2142251 A CA2142251 A CA 2142251A CA 2142251 A1 CA2142251 A1 CA 2142251A1
- Authority
- CA
- Canada
- Prior art keywords
- carbon atoms
- formula
- sulfo
- alkyl
- carboxy
- 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.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/48—Two nitrogen atoms
- C07D251/50—Two nitrogen atoms with a halogen atom attached to the third ring carbon atom
-
- 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
- C09B62/02—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring
- C09B62/04—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring to a triazine ring
- C09B62/08—Azo dyes
- C09B62/085—Monoazo dyes
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/38—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes
- D06P1/382—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using reactive dyes reactive group directly attached to heterocyclic group
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/02—Material containing basic nitrogen
- D06P3/04—Material containing basic nitrogen containing amide groups
- D06P3/24—Polyamides; Polyurethanes
- D06P3/248—Polyamides; Polyurethanes using reactive dyes
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/58—Material containing hydroxyl groups
- D06P3/60—Natural or regenerated cellulose
- D06P3/66—Natural or regenerated cellulose using reactive dyes
- D06P3/663—Natural or regenerated cellulose using reactive dyes reactive group directly attached to heterocyclic group
Abstract
Described are monoazo compounds which have dye properties and are capable of dyeing hydroxy - and/or carboxamido-containing material, in particular fiber material, such as cellulose fibers, for example cotton, wool and nylon, in strong fast shades. These monoazo compounds are based on 1-sulfo-6-carboxy-2-aminonaphthalene as diazo compon-ent and on a customary amino-containing coupling compon-ent to whose amino group is attached, as a fiber-reactive radical, a 2-halo-s-triazin-6-yl radical whose 4-position is substituted by the radical of an N-heterocycle or by an amino group which may be substituted by substituted or unsubstituted alkyl and phenyl radicals.
Description
~1 4225 t HOECHST AKll~SELLSCHAFT HOE 94/F 033 Dr.ST
DESCRIPTION
Water-soluble azo compounds, preparation thereof, and use thereof as dyes The present invention relates to the field of the fiber-reactive azo dyes.
Fiber-reactive azo dyes with 2-A inonAphthalenedisulfonic acids as diazo component are known in large numbers, for example from Japanese Patent Application Publications Sho-59-133 261 and Sho-60-23 453 and from European Patent Application Publications Nos. 0 128 034, 0 239 847 and 0 292 955. Further~ore, European Patent Application Publication No. 0 502 893 and PCT Patent Application Publications WO 91/09913 (U.S. Patent 5 268 458) and WO 91/09914 (U.S. Patent 5 310 886) describe fiber-reactive azo dyes having 1-sulfo-6-carboxy-2-amino-naphthalene as diazo component. The increasing expec-tations of the quality, the economics and the brilliance of the dyeings have made it necessary to develop novel azo dyes which have improved properties in these respects and, what is more, have simple application properties.
The present invention now provides novel azo compounds which conform to the formula (1) SO~U R~ N~N /R1 MOOC N = N--K--N--~NJ--N~ ( 1 ) 21~225~
where M is hydrogen or a salt-forming metal, in particular an alkali metal, such as sodium, potassium or lithium;
5 K is the bivalent radical, being free of the group of the formula --N(R)-, of a water-soluble coupling component containing said amino group;
R is hydrogen or alkyl of 1 to 4 carbon atoms, such as methyl or ethyl, or is alkyl of 1 to 4 carbon atoms,-for example ethyl, which is substituted by sulfo, carboxy , sulfato, phosphato, hydroxy , methoxy, ethoxy, phenyl, monosulfophenyl or disulfophenyl, and preferably is hydrogen;
G is halogen, such as fluorine or chlorine, preferably fluorine;
Rl is hydrogen or alkyl of 1 to 4 carbon atoms, such as ethyl or methyl, or is alkyl of 1 to 4 carbon atoms which is substituted by sulfo, carboxy , phosphato, sulfato, hydroxy , cyano, phenyl or sulfophenyl, or is phenyll or is phenyl substituted by sulfo, carboxy , alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, chlorine and/or nitro;
R2 is hydrogen or alkyl of 1 to 4 carbon atoms, such as ethyl or methyl, or alkyl of 1 to 4 carbon atoms which is substituted by sulfo, carboxy , phosphato, sulfato, hydroxy , cyano, phenyl or sulfophenyl, or is phenyl unsubstituted or substituted by 1, 2 or 3 substituents selected from the group of the follow-ing substituents: 2 alkyl groups of 1 to 4 carbon atoms, such as ethyl and in particular methyl, 2 alkoxy groups of 1 to 4 carbon atoms, such as ethoxy and methoxy, 1 bromine atom, 2 chlorine atoms, 3 sulfo groups, 2 carboxy groups, 1 nitro group, 1 alkylsulfonyl group of 1 to 4 carbon atoms unsubstituted or substituted by hydroxy (for example ~-hydroxyethylsulfonyl), 1 alkylamino group of 1 to 4 carbon atoms and 1 alkylamino group of 1 to 4 carbon atoms unsubstituted or substituted in the alkyl radical by hydroxy , sulfato, sulfo, phosphato, Al kAnoyloxy 21~225i of 2 to 5 carbon atoms or by carboxy -substituted alkanoylamido of 1 to 4 carbon atoms in the alkylene radical, such as succinamido, or R2 is monosulfo-naphthyl, disulfonaphthyl or trisulfonaphthyl, or R1 and R2 form together with the nitrogen atom a hetero-cyclic radical made up of an alkylene group of 3 to 8 carbon atoms, preferably 4 to 6 carbon atoms, or of a further hetero group, such as an -NH- or -O-group, and two alkylene groups of 1 to 4 carbon atoms, for example N-piperidino, N-piperazino or N-morpholino.
Substituted alkylamino groups as substituents in a phenyl radical of R2 are for example ~-sulfatoethylamino and ~-succinamidoethylamino.
Preferably -K-N(R)- is a radical of the formula (2a), (2b) or (2c) HO NH HOV--NH--( 2 ~ ) ( S 03M )m ( S 0~ )m R
{~ N--( 2 C ) ( S3~ )m where M and R are each as defined above, m is 1 or 2, and V is a direct, covalent bond or a radical of the formula -NH-CO-phenylene, -NH-CO-NH-phenylene, -N(CH3)-CO-phenylene, -N(CH3)-CO-NH-phenylene or -NH-phenylene;
in the formula (2a) in the case of m being 2,one of the sulfo groups is preferably disposed meta to the hydroxy group and the other is preferably disposed para or meta to the amino groupJ and in the formulae (2b) and (2c) the free bond which leads to the azo group is preferably disposed on the naph-thalene nucleus in a position ortho to the hydroxy group, the hydroxy group is preferably attached to the naphthalene nucleus in the 8-position, one sulfo group i6 preferably attached to the naphthalene nucleus in the 6-position, the group -V-NH- or -N(R)- is preferably attached to the naphthalene nucleus in the 2- or 3-position and in the case of m being 2 the second sulfo group is preferably attached to the naphthalene nucleus in the 3-position and particularly preferably in the 4-position.
Hereinbefore and hereinafter, "sulfo", "carboxy ", "sulfato" and "phosphato" include not only the acid form of the groups but also their salt form. Accordingly, sulfo groups are groups conforming to the formula -SO3M, carboxy groups are groups conforming to the formula -COOM, phosphato groups are groups conforming to the formula -OPO3M2 and sulfato groups are groups conforming to the formula -OSO3M, where M has in each case the abovementioned meaning.
30 In the formulae (2b) and (2c), the hydroxy group and the free bond are attached ortho to each other to the same aromatic nucleus. Preferably the hydroxy group is attached to the naphthalene radical in the ~-position.
Preference is further given to compounds of the formula (1) in which -NRlR2 is an above-defined heterocyclic radical, preferably N-morpholino.
Preferred azo compounds of the formula (1) are further those in which -R-N(R)- is a radical of the formula (3a) or (3b) HO NH--Z HO
~ ( 3 c ) ~N H--Z
UO,S SO,I~ IJO,S (SO3~),o where M is as defined above, Z is a radical of the formula (3A) G
N
~`N~N~ (3A) where G, R1 and R2 have the meanings mentioned above, in particular the preferred meanings, and p is zero or 1 (if zero, this group being hydrogen); 0 in the formula (3a) one of the sulfo groups is disposed meta or para relative to the -NH-Z group and in the formula (3b) the -NH-Z group i8 attached to the 8-hydroxynaphthalene radical in the 2-, 3- or 4-posi-tion, preferably in the 2- or 3-position, and in the case of p being equal to 1 this sulfo group is attached to the 8-hydroxynaphthalene radical in the 3- or 4-position, preferably in the 4-position.
Particular preference is given to compounds of the formulae (lA), (lB), (lC' and (lD) 21~2251 ~ N = N ~N H~N H ~ R
( S O ~ ~ ) p ( 1 A ) SO,~,I HO N~N/(CH2)c\
~ N = N ~ I~N \ X
IIOOC ~03S ( CH2)~
( S s ~
N~N R 3 SO3~ HO NHJ~N~NH~R~
N = N ~
~IOOC \103S SO,I~/ ( I C ) G
N~N /( CH2 ) o~
SO3~ HO NHI~N~N X
N= N$~ (CH2)b ~lOOC ~OsS SO3~ ( 1 D) where M, G and p have the meanings mentioned above, in particu-lar the preferred ^An;ng8, a iB 1, 2 or 3, preferably 2, b iB 1, 2 or 3, preferably 2, X is oxygen or -NH-, R3 is hydrogen, ~ulfo, carboxy , alkyl of 1 to 4 carbon atoms, such as ethyl and in particular methyl, alkoxy of 1 to 4 carbon atoms, such as ethoxy and in particular methoxy, or hydroxy , and R4 is hydrogen, sulfo, carboxy , alkyl of 1 to 4 carbon atoms, such as ethyl and in particular methyl, or alkoxy of 1 to 4 carbon atoms, such as ethoxy and in particular methoxy;
21~22~1 in the formulae (lA) and (lB) the triazinylamino radical is attached to the 8-hydroxynaphthalene radical in the 2- or 3-position and in the case of p being equal to 2 this sulfo group i8 attached to the 8-hydroxynaphthalene radical in the 3- or 4-position, preferably in the 4-position.
The present invention further provides processes for preparing the azo compounds of the formula (1) according to the present invention, which comprise coupling the diazonium compound of an amine of the formula (4) S o 3 M
~NH2 ( 4 ) M O O C
where M i~ as defined above, with a compound of the formula (5) G
I N l N / R (5) where K, R, G, Rl and R2 are each as defined above, or reacting a compound of the formula (6) ~3~ N= N--K--N--~1 ( 6 ) I/OOC
where M, K and R are each as defined above, with a compound of the formula (7) 21~2251 NlN ~R1 G ~N~L N ~ ( 7 ) where G, R1 and R2 are each as defined above, or reacting a compound of the formula (8) G
S o3~ I N~N
~ N=N--K--N--~ ~G ( 8 ) llOOC
where M, K, R and G are each as defined above, with an amino compound of the formula HNR1R2 where R1 and R2 are each as defined above.
The diazotization and coupling reactions of the process according to the present invention are carried out in a conventional manner, for instance the diazotization generally at a temperature between -5C and +15C and at a pH below 2 by means of a strong acid and sodium nitrite in a preferably aqueous mediumland the coupling reaction generally at a temperature between 0 and 30C and at a pH
between 1 and 4.5 in the case of an amino-contA;n;ng coupling component and at a pH between 3 and 7.5 in the case of a hydroxy -contA;n;ng coupling component, prefer-ably in aqueous medium.
The condensation reaction of an amino starting compound of the formula (6) with a compound of the formula (7) is effected in the usual manner of reacting an amino com-pound with a triazine compound containing a reactivehalogen atom, for instance in an organic or preferably aqueous-organic medium, particularly preferably in an 21q2251 aqueous medium, in the presence of an acid-binding agent, as of an alkali metal or alkaline earth metal carbonate, an alkali metal or alkaline earth metal bicarbonate or hydroxide or alkali metal acetate, the alkali metals and alkaline earth metals preferably being sodium, potassium or calcium, or of a tertiary amine, for example pyridine, triethylamine or quinoline. If these condensation reac-tions are carried out in an organic or agueous-organic medium, the organic solvent (proportion) is acetone, dioxane or dimethylformamide. More particularly, this condensation reaction takes place at a temperature between -10C and +60C, preferably between 30 and 45C, and at a pH between 2 and 7, preferably between 2 and 4.5. The reaction with a compound (7) where G is fluorine is particularly preferably carried out at a pH between 3 and 5 and at a temperature between 0C and 30C.
The condensation reaction of a halotriazinylamino com-pound of the formula (8) with an amino compound conform-ing to the formula HNRlR2 is likewise carried out analogously to known procedures for such reactions between halotriazinylamino compounds and amines, for instance in the above-indicated reaction media using an acid-binding agent. Generally this reaction takes place at a temperature between 0C and 80C and at a pH between 2 and 8, but in the case of starting compounds where Hal is a chlorine atom the reaction is preferably carried out at a temperature between 50 and 70C and at a pH between 2 and 4 and in the case of starting compounds where Hal is a fluorine atom preferably at a temperature between 0C and 10C and at a pH between 6 and 8.
Starting compounds of the formula H-R-N(R)-H are for example l-amino-3,6- or -4,6-disulfo-8-naphthol, 7-amino-3-sulfo-1-naphthol, 6-amino-3-sulfo-1-naphthol, 6-amino-3,5-disulfo-1-naphthol, 2-amino-4-acetyl~m;nohenzene-1-sulfonic acid, 2-amino-8-naphthol-6-sulfonic acid, 6-methylamino-3-sulfo-1-naphthol, 6-(4'-aminophenyl)-amino-3-sulfo-1-naphthol and 1-amino-2,4-disulfo-8-naphthol .
Starting compounds conforming to the formula HNRlR2 are for example 2-sulfoaniline, 3-sulfoaniline, 4-sulfoanil-ine, 2,4-disulfoaniline, 2,5-disulfoaniline, 5-sulfo-2-methoxyaniline, 4-sulfo-2-methoxyaniline, 5-sulfo-2-methylaniline, 4-sulfo-2-methylaniline, 3-sulfo-4-methoxyaniline, 4-sulfo-2-methoxy-5-methylaniline, 4-sulfo-2,5-dimethoxyaniline, 5-sulfo-2,4-dimethoxyaniline, 4-sulfo-5-methoxy-2-methylaniline, 5-sulfo-2-chloro-aniline, 3-sulfo-4-chloro-2-methylaniline, 4-sulfo-5-chloro-2-methoxyaniline, 5- or 6-sulfo-2-amino-naphthalene, 6,8-disulfo-2 -Am; non~ph thalene, 3,6,8-trisulfo-2-aminonaphthalene, 8-sulfo-2-aminonaphthalene, 4,6,8-trisulfo-2 -~m; no~Aphthalene, 1,5- orl,6-disulfo-2-Am;no~Aphthalene, 4~8-disulfo-2-a-m;nonAphthalene~ 6,7-disulfo-2-aminonaphthalene, 5,7-disulfo-2-amino-naphthalene, 5- or 6-sulfo-1-aminonaphthalene, 7-sulfo-1-aminonaphthalene, 1-sulfo-2-aminonaphthalene, 3,6- or 4,6- or 4,8-disulfo-1-aminonaphthalene, ~-sulfoethyl-amine, ~-hydroxyethylamine, N-methyl-N-(~-sulfatoethyl)-amine, N-methyl-N-ethylamine, dimethylamine, diethyl-amine, ~-carboxyethylamine, 4-sulfobenzylamine, 4-sulfo-penethylamine, benzylamine, 2-methylaniline, aniline, 4-chloroaniline, N-ethylaniline, N-methylaniline, ammonia, morpholine, piperidine and piperazine.
The separation and isolation of the compounds of the formula (1) according to the present invention - herein-after called compounds (1) - from the aqueous synthesis solutions can be effected by generally known methods for water-soluble compounds, for instance by precipitating from the reaction medium by means of an electrolyte, for example sodium chloride or potassium chloride, or else by evaporating the reaction solution itself, for example by spray drying.
If the last-mentioned form of isolation is chosen, it is 21422~
frequently advisable, prior to the evaporation, to remove any sulfate present in the solutions by precipitation as calcium sulfate and separation by filtration.
The compounds (1) have fiber-reactive properties and very useful dye properties. They can therefore be used for dyeing (including printing) hydroxy -containing and/or carboxamido-containing materials. For this purpose it is also possible to use the as-synthesized solutions of the compounds (1) directly in dyeing in the form of a liquid preparation, with or without prior addition of a buffer substance and with or without prior concentrating.
The present invention therefore also provides for the use of the compounds (1) for dyeing (including printing) hydroxy_ and/or carboxamido-contAi n; ng materials or processes for their application to these substrates.
Preferably the materials are employed in the form of fiber materials, in particular in the form of textile fibers, such as yarns, for example in the form of hanks or packages, and fabrics. This can be done analogously to known procedures.
Hydroxy -containing materials are those of natural or synthetic origin, for example cellulose fiber materials or their regenerated products and polyvinyl alcohols.
Cellulose fiber materials are preferably cotton but also vegetable fibers thereof, such as linen, hemp, jute and ramie fibers; regenerated cellulose fibers are for example staple viscose and filament viscose rayon.
Carboxamido-containing materials are for example 6yn-thetic and natural polyamides and polyurethanes, in particular in the form of fibers, for example wool and other animal hairs, silk, leather, nylon-6,6, nylon-6, nylon-11 and nylon-4.
The compounds (1) can be applied to and fixed on the substrate6 mentioned, in particular the fiber materials 21~22~1 mentioned, in accordance with the use provided by the present invention by the techniques known for water-soluble, fiber-reactive dyes, for example by applying the compound (1) to the substrate in dissolved form or incorporating it therein and fixing it thereon or therein by the action of heat or by the action of an alkaline agent or by both measures. Such dyeing and fixing methods are numerously described in the literature (for example in European Patent Application Publication No. 0 181 585). The compounds (1) are notable for high degrees of exhaustion and fixation. Especially in the exhaust processes they yield even at from 40 to 80C
dyeings of high color strength with a high degree of fixation.
The dyeings of the present invention, in particular on cellulose fiber materials, have good light fastness properties not only in the dry state of the dyeing but also in the wet state, moistened for example with a perspiration solution, and also good wet fastness prop-erties, for example good wash fastness properties at 60to 95C, even in the presence of perborates, acid and alkaline fulling, cross-dyeing and perspiration fastness properties, good acid and alkaline perspiration fastness properties, a high ste~m;ng resistance, good acid, water and seawater fastness properties, further good pleating fastness, hot press fastness and rub fastness. They similarly have good acid fading resistance when stored in the moist, dyed state with acetic acid still present.
The Examples which follow serve to illustrate the inven-30 tion. The part~ and percentages are by weight, unless otherwise stated. Parts by weight relate to parts by volume as kilogram to the liter.
The compounds described in the Examples by means of a formula are indicated in the form of the free acid;
generally they are prepared and isolated in the form of their alkali metal salts, such as lithium, sodium or 21~2~5~
potassium salts, and used for dyeing in the form of their salts.
Similarly, the starting compounds and components men-tioned in the Examples which follow, especially in the Table Examples, in the form of the free acid can be used in the synthesis a~ ~uch or in the form of their salt~, preferably alkali metal salts.
The absorption maxima (AmaX) in the visible region report-ed for the compounds of the present invention were determined on their alkali metal salts in aqueous sol-ution. In the Table Examples the AmaX values are given in brackets in the hue column; the reported wavelength i6 given in nm.
Example 1 31.9 parts of 1-amino-3,6-disulfo-8-naphthol are con-densed with 16 part~ of cyanuric fluoride in 200 parts of water and 100 parts of ice at a pH of 7.5 and at a temperature between 0C and 10C. Thereafter a solution of 8.7 parts of morpholine in 200 parts of water is added and the second condensation reaction is carried out at a pH of 8.5. A solution of the diazonium salt of 27 parts of 1-sulfo-6-carboxy-2-aminonaphthalene in about 450 parts of water, conventionally diazotized with sodium nitrite in a hydrochloric acid medium, is added to the resulting solution of the coupling component, a pH of 5 to 6 is set, and the coupling reaction is carried out within that pH range at a temperature of about 20C.
The novel azo compound of the formula (written in the form of the free acid) 21~ 5t N~r ~CH2-CH2\
S O ~ H H O N H J~`N~ N ~ ~
)~3~ N = N ~ 2 2 HOOC HO~S SO,H
(~lrnaX = 545 nm) is salted out with sodium chloride and isolated in the form of the sodium salt. It has very good fiber-reactive dye properties. The customary application techniques for fiber-reactive dyes give strong dyeings and prints in fast, bluish red shades of high brilliance.
Examples 2 to 25 Further novel dyes conforming to a formula (A) G
so3~ N l N /R~
~IOOC N N K ~N~ \ (A) where M is as defined above, are written in the ~able ~xamples which follow by means of the formula (A) and the symbols indicated in the Table. They can be prepared according to the present invention, for example analog-ously to the above Example 1, and likewise have very good fiber-reactive dye properties. The customary application and fixing techniques in the art for fiber-reactive dyes produce in particular on cellulose fiber materials the strong fast hue indicated for each Table Example.
2~4~51 ~x. -K-NH- G -NRlR2 Hue 2 8-hydroxy-3,6-fluorinepiperazinored (546) disulfonaphth-7-yl-l-ylamino 3 dittofluorine piperidino red (541) 4 dittofluorine 2-methyl- red (525) phenyl-amino dittofluorine 3-sulfo- red (515) phenyl-amino 6 8-hydroxy-4,6- fluorine phenyl- red (510) disulfonaphth-7- amino yl-l-ylamino 7 dittofluorine 3-sulfo- red phenyl-amino 8 8-11YdLOXY-6-8U1- fluorine morpholino orange fonaphth-7-yl-2- (483) ylamino 9 dittofluorine 3-sulfo- orange phenyl- (480) amino dittofluorine N-methyl- orange phenyl-amino 11 8-hydroxy-6-sul- fluorine morpholino scarlet fonaphth-7-yl-3- (490) ylamino 12 dittofluorine 3-sulfo- scarlet phenyl- (492) amino 13 dittofluorine N-methyl- scarlet phenyl- (495) amino 14 dittofluorine N-ethyl- scarlet phenyl- (495) amino 15 8-hydroxy-4-sul- fluorine 3-sulfo- orange fonaphth-7-yl-1- phenyl-ylamino amino 16 ditto chlorine ditto orange 17 8-hydroxy-6-sul- chlorine 2,5-disul- scarlet fonaphth-7-yl-3-fophenyl-ylamino amino 1~ dittochlorine 3-sulfo- scarlet phenyl- (493) amino 19 8-hydroxy-6-sul- chlorine 2,5-disul- orange fonaphth-7-yl-2- fophenyl-ylamino amino 21422~1 Ex. -R-NH- G -NRlR2 ~ue 8-l-ydloxy-3,6-chlorine N-methyl- red di 8ul fonaphth-7- phenyl-yl-l-ylamino amino 21 dittochlorine 2-methyl- red phenyl-amino 22 ditto chlorine 3-sulfo- red (546) phenyl-amino 23 8-hydroxy-4,6-chlorine N-methyl- red disulfonaphth-7-phenyl-yl-l-ylamino amino 24 ditto chlorine 4- 8ul fo- red (520) phenyl-amino dittochlorine morpholino red
DESCRIPTION
Water-soluble azo compounds, preparation thereof, and use thereof as dyes The present invention relates to the field of the fiber-reactive azo dyes.
Fiber-reactive azo dyes with 2-A inonAphthalenedisulfonic acids as diazo component are known in large numbers, for example from Japanese Patent Application Publications Sho-59-133 261 and Sho-60-23 453 and from European Patent Application Publications Nos. 0 128 034, 0 239 847 and 0 292 955. Further~ore, European Patent Application Publication No. 0 502 893 and PCT Patent Application Publications WO 91/09913 (U.S. Patent 5 268 458) and WO 91/09914 (U.S. Patent 5 310 886) describe fiber-reactive azo dyes having 1-sulfo-6-carboxy-2-amino-naphthalene as diazo component. The increasing expec-tations of the quality, the economics and the brilliance of the dyeings have made it necessary to develop novel azo dyes which have improved properties in these respects and, what is more, have simple application properties.
The present invention now provides novel azo compounds which conform to the formula (1) SO~U R~ N~N /R1 MOOC N = N--K--N--~NJ--N~ ( 1 ) 21~225~
where M is hydrogen or a salt-forming metal, in particular an alkali metal, such as sodium, potassium or lithium;
5 K is the bivalent radical, being free of the group of the formula --N(R)-, of a water-soluble coupling component containing said amino group;
R is hydrogen or alkyl of 1 to 4 carbon atoms, such as methyl or ethyl, or is alkyl of 1 to 4 carbon atoms,-for example ethyl, which is substituted by sulfo, carboxy , sulfato, phosphato, hydroxy , methoxy, ethoxy, phenyl, monosulfophenyl or disulfophenyl, and preferably is hydrogen;
G is halogen, such as fluorine or chlorine, preferably fluorine;
Rl is hydrogen or alkyl of 1 to 4 carbon atoms, such as ethyl or methyl, or is alkyl of 1 to 4 carbon atoms which is substituted by sulfo, carboxy , phosphato, sulfato, hydroxy , cyano, phenyl or sulfophenyl, or is phenyll or is phenyl substituted by sulfo, carboxy , alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, chlorine and/or nitro;
R2 is hydrogen or alkyl of 1 to 4 carbon atoms, such as ethyl or methyl, or alkyl of 1 to 4 carbon atoms which is substituted by sulfo, carboxy , phosphato, sulfato, hydroxy , cyano, phenyl or sulfophenyl, or is phenyl unsubstituted or substituted by 1, 2 or 3 substituents selected from the group of the follow-ing substituents: 2 alkyl groups of 1 to 4 carbon atoms, such as ethyl and in particular methyl, 2 alkoxy groups of 1 to 4 carbon atoms, such as ethoxy and methoxy, 1 bromine atom, 2 chlorine atoms, 3 sulfo groups, 2 carboxy groups, 1 nitro group, 1 alkylsulfonyl group of 1 to 4 carbon atoms unsubstituted or substituted by hydroxy (for example ~-hydroxyethylsulfonyl), 1 alkylamino group of 1 to 4 carbon atoms and 1 alkylamino group of 1 to 4 carbon atoms unsubstituted or substituted in the alkyl radical by hydroxy , sulfato, sulfo, phosphato, Al kAnoyloxy 21~225i of 2 to 5 carbon atoms or by carboxy -substituted alkanoylamido of 1 to 4 carbon atoms in the alkylene radical, such as succinamido, or R2 is monosulfo-naphthyl, disulfonaphthyl or trisulfonaphthyl, or R1 and R2 form together with the nitrogen atom a hetero-cyclic radical made up of an alkylene group of 3 to 8 carbon atoms, preferably 4 to 6 carbon atoms, or of a further hetero group, such as an -NH- or -O-group, and two alkylene groups of 1 to 4 carbon atoms, for example N-piperidino, N-piperazino or N-morpholino.
Substituted alkylamino groups as substituents in a phenyl radical of R2 are for example ~-sulfatoethylamino and ~-succinamidoethylamino.
Preferably -K-N(R)- is a radical of the formula (2a), (2b) or (2c) HO NH HOV--NH--( 2 ~ ) ( S 03M )m ( S 0~ )m R
{~ N--( 2 C ) ( S3~ )m where M and R are each as defined above, m is 1 or 2, and V is a direct, covalent bond or a radical of the formula -NH-CO-phenylene, -NH-CO-NH-phenylene, -N(CH3)-CO-phenylene, -N(CH3)-CO-NH-phenylene or -NH-phenylene;
in the formula (2a) in the case of m being 2,one of the sulfo groups is preferably disposed meta to the hydroxy group and the other is preferably disposed para or meta to the amino groupJ and in the formulae (2b) and (2c) the free bond which leads to the azo group is preferably disposed on the naph-thalene nucleus in a position ortho to the hydroxy group, the hydroxy group is preferably attached to the naphthalene nucleus in the 8-position, one sulfo group i6 preferably attached to the naphthalene nucleus in the 6-position, the group -V-NH- or -N(R)- is preferably attached to the naphthalene nucleus in the 2- or 3-position and in the case of m being 2 the second sulfo group is preferably attached to the naphthalene nucleus in the 3-position and particularly preferably in the 4-position.
Hereinbefore and hereinafter, "sulfo", "carboxy ", "sulfato" and "phosphato" include not only the acid form of the groups but also their salt form. Accordingly, sulfo groups are groups conforming to the formula -SO3M, carboxy groups are groups conforming to the formula -COOM, phosphato groups are groups conforming to the formula -OPO3M2 and sulfato groups are groups conforming to the formula -OSO3M, where M has in each case the abovementioned meaning.
30 In the formulae (2b) and (2c), the hydroxy group and the free bond are attached ortho to each other to the same aromatic nucleus. Preferably the hydroxy group is attached to the naphthalene radical in the ~-position.
Preference is further given to compounds of the formula (1) in which -NRlR2 is an above-defined heterocyclic radical, preferably N-morpholino.
Preferred azo compounds of the formula (1) are further those in which -R-N(R)- is a radical of the formula (3a) or (3b) HO NH--Z HO
~ ( 3 c ) ~N H--Z
UO,S SO,I~ IJO,S (SO3~),o where M is as defined above, Z is a radical of the formula (3A) G
N
~`N~N~ (3A) where G, R1 and R2 have the meanings mentioned above, in particular the preferred meanings, and p is zero or 1 (if zero, this group being hydrogen); 0 in the formula (3a) one of the sulfo groups is disposed meta or para relative to the -NH-Z group and in the formula (3b) the -NH-Z group i8 attached to the 8-hydroxynaphthalene radical in the 2-, 3- or 4-posi-tion, preferably in the 2- or 3-position, and in the case of p being equal to 1 this sulfo group is attached to the 8-hydroxynaphthalene radical in the 3- or 4-position, preferably in the 4-position.
Particular preference is given to compounds of the formulae (lA), (lB), (lC' and (lD) 21~2251 ~ N = N ~N H~N H ~ R
( S O ~ ~ ) p ( 1 A ) SO,~,I HO N~N/(CH2)c\
~ N = N ~ I~N \ X
IIOOC ~03S ( CH2)~
( S s ~
N~N R 3 SO3~ HO NHJ~N~NH~R~
N = N ~
~IOOC \103S SO,I~/ ( I C ) G
N~N /( CH2 ) o~
SO3~ HO NHI~N~N X
N= N$~ (CH2)b ~lOOC ~OsS SO3~ ( 1 D) where M, G and p have the meanings mentioned above, in particu-lar the preferred ^An;ng8, a iB 1, 2 or 3, preferably 2, b iB 1, 2 or 3, preferably 2, X is oxygen or -NH-, R3 is hydrogen, ~ulfo, carboxy , alkyl of 1 to 4 carbon atoms, such as ethyl and in particular methyl, alkoxy of 1 to 4 carbon atoms, such as ethoxy and in particular methoxy, or hydroxy , and R4 is hydrogen, sulfo, carboxy , alkyl of 1 to 4 carbon atoms, such as ethyl and in particular methyl, or alkoxy of 1 to 4 carbon atoms, such as ethoxy and in particular methoxy;
21~22~1 in the formulae (lA) and (lB) the triazinylamino radical is attached to the 8-hydroxynaphthalene radical in the 2- or 3-position and in the case of p being equal to 2 this sulfo group i8 attached to the 8-hydroxynaphthalene radical in the 3- or 4-position, preferably in the 4-position.
The present invention further provides processes for preparing the azo compounds of the formula (1) according to the present invention, which comprise coupling the diazonium compound of an amine of the formula (4) S o 3 M
~NH2 ( 4 ) M O O C
where M i~ as defined above, with a compound of the formula (5) G
I N l N / R (5) where K, R, G, Rl and R2 are each as defined above, or reacting a compound of the formula (6) ~3~ N= N--K--N--~1 ( 6 ) I/OOC
where M, K and R are each as defined above, with a compound of the formula (7) 21~2251 NlN ~R1 G ~N~L N ~ ( 7 ) where G, R1 and R2 are each as defined above, or reacting a compound of the formula (8) G
S o3~ I N~N
~ N=N--K--N--~ ~G ( 8 ) llOOC
where M, K, R and G are each as defined above, with an amino compound of the formula HNR1R2 where R1 and R2 are each as defined above.
The diazotization and coupling reactions of the process according to the present invention are carried out in a conventional manner, for instance the diazotization generally at a temperature between -5C and +15C and at a pH below 2 by means of a strong acid and sodium nitrite in a preferably aqueous mediumland the coupling reaction generally at a temperature between 0 and 30C and at a pH
between 1 and 4.5 in the case of an amino-contA;n;ng coupling component and at a pH between 3 and 7.5 in the case of a hydroxy -contA;n;ng coupling component, prefer-ably in aqueous medium.
The condensation reaction of an amino starting compound of the formula (6) with a compound of the formula (7) is effected in the usual manner of reacting an amino com-pound with a triazine compound containing a reactivehalogen atom, for instance in an organic or preferably aqueous-organic medium, particularly preferably in an 21q2251 aqueous medium, in the presence of an acid-binding agent, as of an alkali metal or alkaline earth metal carbonate, an alkali metal or alkaline earth metal bicarbonate or hydroxide or alkali metal acetate, the alkali metals and alkaline earth metals preferably being sodium, potassium or calcium, or of a tertiary amine, for example pyridine, triethylamine or quinoline. If these condensation reac-tions are carried out in an organic or agueous-organic medium, the organic solvent (proportion) is acetone, dioxane or dimethylformamide. More particularly, this condensation reaction takes place at a temperature between -10C and +60C, preferably between 30 and 45C, and at a pH between 2 and 7, preferably between 2 and 4.5. The reaction with a compound (7) where G is fluorine is particularly preferably carried out at a pH between 3 and 5 and at a temperature between 0C and 30C.
The condensation reaction of a halotriazinylamino com-pound of the formula (8) with an amino compound conform-ing to the formula HNRlR2 is likewise carried out analogously to known procedures for such reactions between halotriazinylamino compounds and amines, for instance in the above-indicated reaction media using an acid-binding agent. Generally this reaction takes place at a temperature between 0C and 80C and at a pH between 2 and 8, but in the case of starting compounds where Hal is a chlorine atom the reaction is preferably carried out at a temperature between 50 and 70C and at a pH between 2 and 4 and in the case of starting compounds where Hal is a fluorine atom preferably at a temperature between 0C and 10C and at a pH between 6 and 8.
Starting compounds of the formula H-R-N(R)-H are for example l-amino-3,6- or -4,6-disulfo-8-naphthol, 7-amino-3-sulfo-1-naphthol, 6-amino-3-sulfo-1-naphthol, 6-amino-3,5-disulfo-1-naphthol, 2-amino-4-acetyl~m;nohenzene-1-sulfonic acid, 2-amino-8-naphthol-6-sulfonic acid, 6-methylamino-3-sulfo-1-naphthol, 6-(4'-aminophenyl)-amino-3-sulfo-1-naphthol and 1-amino-2,4-disulfo-8-naphthol .
Starting compounds conforming to the formula HNRlR2 are for example 2-sulfoaniline, 3-sulfoaniline, 4-sulfoanil-ine, 2,4-disulfoaniline, 2,5-disulfoaniline, 5-sulfo-2-methoxyaniline, 4-sulfo-2-methoxyaniline, 5-sulfo-2-methylaniline, 4-sulfo-2-methylaniline, 3-sulfo-4-methoxyaniline, 4-sulfo-2-methoxy-5-methylaniline, 4-sulfo-2,5-dimethoxyaniline, 5-sulfo-2,4-dimethoxyaniline, 4-sulfo-5-methoxy-2-methylaniline, 5-sulfo-2-chloro-aniline, 3-sulfo-4-chloro-2-methylaniline, 4-sulfo-5-chloro-2-methoxyaniline, 5- or 6-sulfo-2-amino-naphthalene, 6,8-disulfo-2 -Am; non~ph thalene, 3,6,8-trisulfo-2-aminonaphthalene, 8-sulfo-2-aminonaphthalene, 4,6,8-trisulfo-2 -~m; no~Aphthalene, 1,5- orl,6-disulfo-2-Am;no~Aphthalene, 4~8-disulfo-2-a-m;nonAphthalene~ 6,7-disulfo-2-aminonaphthalene, 5,7-disulfo-2-amino-naphthalene, 5- or 6-sulfo-1-aminonaphthalene, 7-sulfo-1-aminonaphthalene, 1-sulfo-2-aminonaphthalene, 3,6- or 4,6- or 4,8-disulfo-1-aminonaphthalene, ~-sulfoethyl-amine, ~-hydroxyethylamine, N-methyl-N-(~-sulfatoethyl)-amine, N-methyl-N-ethylamine, dimethylamine, diethyl-amine, ~-carboxyethylamine, 4-sulfobenzylamine, 4-sulfo-penethylamine, benzylamine, 2-methylaniline, aniline, 4-chloroaniline, N-ethylaniline, N-methylaniline, ammonia, morpholine, piperidine and piperazine.
The separation and isolation of the compounds of the formula (1) according to the present invention - herein-after called compounds (1) - from the aqueous synthesis solutions can be effected by generally known methods for water-soluble compounds, for instance by precipitating from the reaction medium by means of an electrolyte, for example sodium chloride or potassium chloride, or else by evaporating the reaction solution itself, for example by spray drying.
If the last-mentioned form of isolation is chosen, it is 21422~
frequently advisable, prior to the evaporation, to remove any sulfate present in the solutions by precipitation as calcium sulfate and separation by filtration.
The compounds (1) have fiber-reactive properties and very useful dye properties. They can therefore be used for dyeing (including printing) hydroxy -containing and/or carboxamido-containing materials. For this purpose it is also possible to use the as-synthesized solutions of the compounds (1) directly in dyeing in the form of a liquid preparation, with or without prior addition of a buffer substance and with or without prior concentrating.
The present invention therefore also provides for the use of the compounds (1) for dyeing (including printing) hydroxy_ and/or carboxamido-contAi n; ng materials or processes for their application to these substrates.
Preferably the materials are employed in the form of fiber materials, in particular in the form of textile fibers, such as yarns, for example in the form of hanks or packages, and fabrics. This can be done analogously to known procedures.
Hydroxy -containing materials are those of natural or synthetic origin, for example cellulose fiber materials or their regenerated products and polyvinyl alcohols.
Cellulose fiber materials are preferably cotton but also vegetable fibers thereof, such as linen, hemp, jute and ramie fibers; regenerated cellulose fibers are for example staple viscose and filament viscose rayon.
Carboxamido-containing materials are for example 6yn-thetic and natural polyamides and polyurethanes, in particular in the form of fibers, for example wool and other animal hairs, silk, leather, nylon-6,6, nylon-6, nylon-11 and nylon-4.
The compounds (1) can be applied to and fixed on the substrate6 mentioned, in particular the fiber materials 21~22~1 mentioned, in accordance with the use provided by the present invention by the techniques known for water-soluble, fiber-reactive dyes, for example by applying the compound (1) to the substrate in dissolved form or incorporating it therein and fixing it thereon or therein by the action of heat or by the action of an alkaline agent or by both measures. Such dyeing and fixing methods are numerously described in the literature (for example in European Patent Application Publication No. 0 181 585). The compounds (1) are notable for high degrees of exhaustion and fixation. Especially in the exhaust processes they yield even at from 40 to 80C
dyeings of high color strength with a high degree of fixation.
The dyeings of the present invention, in particular on cellulose fiber materials, have good light fastness properties not only in the dry state of the dyeing but also in the wet state, moistened for example with a perspiration solution, and also good wet fastness prop-erties, for example good wash fastness properties at 60to 95C, even in the presence of perborates, acid and alkaline fulling, cross-dyeing and perspiration fastness properties, good acid and alkaline perspiration fastness properties, a high ste~m;ng resistance, good acid, water and seawater fastness properties, further good pleating fastness, hot press fastness and rub fastness. They similarly have good acid fading resistance when stored in the moist, dyed state with acetic acid still present.
The Examples which follow serve to illustrate the inven-30 tion. The part~ and percentages are by weight, unless otherwise stated. Parts by weight relate to parts by volume as kilogram to the liter.
The compounds described in the Examples by means of a formula are indicated in the form of the free acid;
generally they are prepared and isolated in the form of their alkali metal salts, such as lithium, sodium or 21~2~5~
potassium salts, and used for dyeing in the form of their salts.
Similarly, the starting compounds and components men-tioned in the Examples which follow, especially in the Table Examples, in the form of the free acid can be used in the synthesis a~ ~uch or in the form of their salt~, preferably alkali metal salts.
The absorption maxima (AmaX) in the visible region report-ed for the compounds of the present invention were determined on their alkali metal salts in aqueous sol-ution. In the Table Examples the AmaX values are given in brackets in the hue column; the reported wavelength i6 given in nm.
Example 1 31.9 parts of 1-amino-3,6-disulfo-8-naphthol are con-densed with 16 part~ of cyanuric fluoride in 200 parts of water and 100 parts of ice at a pH of 7.5 and at a temperature between 0C and 10C. Thereafter a solution of 8.7 parts of morpholine in 200 parts of water is added and the second condensation reaction is carried out at a pH of 8.5. A solution of the diazonium salt of 27 parts of 1-sulfo-6-carboxy-2-aminonaphthalene in about 450 parts of water, conventionally diazotized with sodium nitrite in a hydrochloric acid medium, is added to the resulting solution of the coupling component, a pH of 5 to 6 is set, and the coupling reaction is carried out within that pH range at a temperature of about 20C.
The novel azo compound of the formula (written in the form of the free acid) 21~ 5t N~r ~CH2-CH2\
S O ~ H H O N H J~`N~ N ~ ~
)~3~ N = N ~ 2 2 HOOC HO~S SO,H
(~lrnaX = 545 nm) is salted out with sodium chloride and isolated in the form of the sodium salt. It has very good fiber-reactive dye properties. The customary application techniques for fiber-reactive dyes give strong dyeings and prints in fast, bluish red shades of high brilliance.
Examples 2 to 25 Further novel dyes conforming to a formula (A) G
so3~ N l N /R~
~IOOC N N K ~N~ \ (A) where M is as defined above, are written in the ~able ~xamples which follow by means of the formula (A) and the symbols indicated in the Table. They can be prepared according to the present invention, for example analog-ously to the above Example 1, and likewise have very good fiber-reactive dye properties. The customary application and fixing techniques in the art for fiber-reactive dyes produce in particular on cellulose fiber materials the strong fast hue indicated for each Table Example.
2~4~51 ~x. -K-NH- G -NRlR2 Hue 2 8-hydroxy-3,6-fluorinepiperazinored (546) disulfonaphth-7-yl-l-ylamino 3 dittofluorine piperidino red (541) 4 dittofluorine 2-methyl- red (525) phenyl-amino dittofluorine 3-sulfo- red (515) phenyl-amino 6 8-hydroxy-4,6- fluorine phenyl- red (510) disulfonaphth-7- amino yl-l-ylamino 7 dittofluorine 3-sulfo- red phenyl-amino 8 8-11YdLOXY-6-8U1- fluorine morpholino orange fonaphth-7-yl-2- (483) ylamino 9 dittofluorine 3-sulfo- orange phenyl- (480) amino dittofluorine N-methyl- orange phenyl-amino 11 8-hydroxy-6-sul- fluorine morpholino scarlet fonaphth-7-yl-3- (490) ylamino 12 dittofluorine 3-sulfo- scarlet phenyl- (492) amino 13 dittofluorine N-methyl- scarlet phenyl- (495) amino 14 dittofluorine N-ethyl- scarlet phenyl- (495) amino 15 8-hydroxy-4-sul- fluorine 3-sulfo- orange fonaphth-7-yl-1- phenyl-ylamino amino 16 ditto chlorine ditto orange 17 8-hydroxy-6-sul- chlorine 2,5-disul- scarlet fonaphth-7-yl-3-fophenyl-ylamino amino 1~ dittochlorine 3-sulfo- scarlet phenyl- (493) amino 19 8-hydroxy-6-sul- chlorine 2,5-disul- orange fonaphth-7-yl-2- fophenyl-ylamino amino 21422~1 Ex. -R-NH- G -NRlR2 ~ue 8-l-ydloxy-3,6-chlorine N-methyl- red di 8ul fonaphth-7- phenyl-yl-l-ylamino amino 21 dittochlorine 2-methyl- red phenyl-amino 22 ditto chlorine 3-sulfo- red (546) phenyl-amino 23 8-hydroxy-4,6-chlorine N-methyl- red disulfonaphth-7-phenyl-yl-l-ylamino amino 24 ditto chlorine 4- 8ul fo- red (520) phenyl-amino dittochlorine morpholino red
Claims (16)
1. An azo compound of the formula (1) (1) where M is hydrogen or a salt-forming metal;
K is the bivalent radical, being free of the group -N(R°)-, of a water-soluble coupling component containing said amino group;
R° is hydrogen or alkyl of 1 to 4 carbon atoms or alkyl of 1 to 4 carbon atoms, which is sub-stituted by sulfo, carboxy , sulfato, phosphato, hydroxy , methoxy, ethoxy, phenyl, monosulfophenyl or disulfophenyl;
G is halogen;
R1 is hydrogen or alkyl of 1 to 4 carbon atoms or is alkyl of 1 to 4 carbon atoms which is substituted by sulfo, carboxy , phosphato, sulfato, hydroxy , cyano, phenyl or sulfophenyl, or is phenyl or phenyl substituted by sulfo, carboxy , alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, chlorine and/or nitro;
R2 is hydrogen or alkyl of 1 to 4 carbon atoms or alkyl of 1 to 4 carbon atoms which is substituted by sulfo, carboxy , phosphato, sulfato, hydroxy , cyano, phenyl or sulfophenyl, or is phenyl or phenyl substituted by 1, 2 or 3 substituents selected from the group of the following sub-stituents: 2 alkyl groups of 1 to 4 carbon atoms,
K is the bivalent radical, being free of the group -N(R°)-, of a water-soluble coupling component containing said amino group;
R° is hydrogen or alkyl of 1 to 4 carbon atoms or alkyl of 1 to 4 carbon atoms, which is sub-stituted by sulfo, carboxy , sulfato, phosphato, hydroxy , methoxy, ethoxy, phenyl, monosulfophenyl or disulfophenyl;
G is halogen;
R1 is hydrogen or alkyl of 1 to 4 carbon atoms or is alkyl of 1 to 4 carbon atoms which is substituted by sulfo, carboxy , phosphato, sulfato, hydroxy , cyano, phenyl or sulfophenyl, or is phenyl or phenyl substituted by sulfo, carboxy , alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, chlorine and/or nitro;
R2 is hydrogen or alkyl of 1 to 4 carbon atoms or alkyl of 1 to 4 carbon atoms which is substituted by sulfo, carboxy , phosphato, sulfato, hydroxy , cyano, phenyl or sulfophenyl, or is phenyl or phenyl substituted by 1, 2 or 3 substituents selected from the group of the following sub-stituents: 2 alkyl groups of 1 to 4 carbon atoms,
2 alkoxy groups of 1 to 4 carbon atoms, 1 bromine atom, 2 chlorine atoms, 3 sulfo groups, 2 carboxy groups, 1 nitro group, 1 alkylsulfonyl group of 1 to 4 carbon atoms unsubstituted or substi-tuted by hydroxy , 1 alkylamino group of 1 to 4 carbon atoms and 1 alkylamino group of 1 to 4 carbon atoms unsubstituted or substituted in the alkyl radical by hydroxy , sulfato, sulfo, phos-phato, alkanoyloxy of 2 to 5 carbon atoms or by carboxy-substituted alkanoylamido of 1 to 4 carbon atoms in the alkylene radical, or R2 is monosulfonaphthyl, disulfonaphthyl or trisulfo-naphthyl, or R1 and R2 form together with the nitrogen atom a heterocyclic radical made up of an alkylene group of 3 to 8 carbon atoms or of a further hetero group and two alkylene groups of 1 to 4 carbon atoms.
2. An azo compound as claimed in claim 1 wherein -K-N(R°)- is a radical of the formula (2a), (2b) or (2c) (2a) (2b) (2c) where M and R° are each as defined in claim 1, m is 1 or 2, and V is a direct, covalent bond or a radical of the formula -NH-CO-phenylene, -NH-CO-NH-phenylene, -N(CH3)-CO-phenylene, -N(CH3)-CO-NH-phenylene or -NH-phenylene.
2. An azo compound as claimed in claim 1 wherein -K-N(R°)- is a radical of the formula (2a), (2b) or (2c) (2a) (2b) (2c) where M and R° are each as defined in claim 1, m is 1 or 2, and V is a direct, covalent bond or a radical of the formula -NH-CO-phenylene, -NH-CO-NH-phenylene, -N(CH3)-CO-phenylene, -N(CH3)-CO-NH-phenylene or -NH-phenylene.
3. An azo compound as claimed in claim 1 wherein -K-N(R°)- is a radical of the formula (3a) or (3b) (3a) (3b) where M is as defined in claim 1, Z° is a radical of the formula (3A) (3A) where G, R1 and R2 are each as defined in claim 1, and p is zero or 1 (if zero, this group being hydrogen).
4. An azo compound as claimed in claim 1 conforming to the formula (1A) (1A) where M and G are each as defined in claim 1, p is zero or 1 (if zero, this group being hydrogen), R3 is hydrogen, sulfo, carboxy , alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms or hydroxy , and R4 is hydrogen, sulfo, carboxy , alkyl of 1 to 4 carbon atoms or alkoxy of 1 to 4 carbon atoms.
5. An azo compound as claimed in claim 1 of the formula (1B) (1B) where M and G are each as defined in claim 1, p is zero or 1 (if zero, this group being hydro-gen), a is 1, 2 or 3, b is 1, 2 or 3, and X is oxygen or -NH-.
6. An azo compound as claimed in claim 1 of the formula (1C) (1C) where M and G are each as defined in claim 1, R3 is hydrogen, sulfo, carboxy , alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms or hydroxy , and R4 is hydrogen, sulfo, carboxy , alkyl of 1 to 4 carbon atoms or alkoxy of 1 to 4 carbon atoms.
7. An azo compound as claimed in claim 1 of the formula (1D) (1D) where M and G are each as defined in claim 1, R3 is hydrogen, sulfo, carboxy , alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms or hydroxy , and R4 is hydrogen, sulfo, carboxy , alkyl of 1 to 4 carbon atoms or alkoxy of 1 to 4 carbon atoms.
8. An azo compound as claimed in claim 5 or 7 wherein a is 2, b is 2 and X is oxygen.
9. An azo compound as claimed in at least one of claims 1 to 3 wherein R° is hydrogen.
10. An azo compound as claimed in at least one of claims 1 to 9 wherein G is chlorine.
11. An azo compound as claimed in at least one of claims 1 to 9 wherein G is fluorine.
12. An azo compound as claimed in at least one of claims 1 to 3 and 9 to 11 wherein -NR1R2 is morpholino.
13. An azo compound as claimed in claim 1 of the formula where M is as defined in claim 1.
14. A process for preparing an azo compound of the formula (1) of claim 1, which comprises coupling the diazonium compound of an amine of the formula (4) (4) where M is as defined in claim 1, with a compound of the formula (5) (5) where K, R°, G, R1 and R2 are each as defined in claim 1, or reacting a compound of the formula (6) (6) where M, K and R° are each as defined in claim 1, with a compound of the formula (7) (7) where G, R1 and R2 are each as defined in claim 1, or reacting a compound of the formula (8) (8) where M, K, R° and G are each as defined in claim 1, with an amino compound of the formula HNR1R2 where R1 and R2 are each as defined in claim 1.
15. The use of a dye of claim 1 or of a dye prepared as claimed in claim 14 for dyeing (including printing) hydroxy - and/or carboxamido-containing material, in particular fiber material.
16. A process for dyeing (including printing) hydroxy -and/or carboxamido-containing material, in particu-lar fiber material, by applying a dye to the material and fixing the dye on the material by means of heat or with the aid of an alkaline agent or by means of both measures, which comprises using a dye as claimed in claim 1 or as prepared according to claim 14.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4404341A DE4404341A1 (en) | 1994-02-11 | 1994-02-11 | Water-soluble azo compounds, processes for their preparation and their use as dyes |
| DEP4404341.4 | 1994-02-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2142251A1 true CA2142251A1 (en) | 1995-08-12 |
Family
ID=6510019
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002142251A Abandoned CA2142251A1 (en) | 1994-02-11 | 1995-02-10 | Water-soluble azo compounds, preparation thereof, and use thereof as dyes |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0668327A1 (en) |
| JP (1) | JPH07304980A (en) |
| KR (1) | KR950032487A (en) |
| CN (1) | CN1109899A (en) |
| BR (1) | BR9500490A (en) |
| CA (1) | CA2142251A1 (en) |
| CZ (1) | CZ35895A3 (en) |
| DE (1) | DE4404341A1 (en) |
| PL (1) | PL307202A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19611636A1 (en) * | 1996-03-25 | 1997-10-02 | Dystar Textilfarben Gmbh & Co | Water-soluble fibre-reactive azo dyes containing triazine group |
| US7235645B2 (en) | 2004-07-23 | 2007-06-26 | L'oreal, S.A. | Cationic azo monomers or symmetric dimers, preparation thereof, compositions comprising same and process for dyeing keratin fibers |
| FR2873369B1 (en) * | 2004-07-23 | 2006-09-22 | Oreal | MONOMERS OR CATIONIC AZOTIC SYMMETRICAL DIMERS, PREPARATION THEREOF, COMPOSITIONS COMPRISING SAME, AND METHOD FOR COLORING KERATINIC FIBERS |
| CN104559320A (en) * | 2014-04-28 | 2015-04-29 | 无锡润新染料有限公司 | Composite active brilliant orange dye composition |
| CN106009769A (en) * | 2016-05-17 | 2016-10-12 | 黄山普米特新材料有限公司 | Reactive orange and synthesis method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB954631A (en) * | 1959-10-20 | 1964-04-08 | Ici Ltd | New monoazo dyestuffs |
| CH449143A (en) * | 1961-03-08 | 1967-12-31 | Ciba Geigy | Process for the preparation of new monoazo dyes |
| DE3943286A1 (en) * | 1989-12-29 | 1991-07-04 | Hoechst Ag | AZO COMPOUNDS, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS A DYE |
| DE4206040A1 (en) * | 1992-02-27 | 1993-09-02 | Bayer Ag | NEW REACTIVE COLORS |
-
1994
- 1994-02-11 DE DE4404341A patent/DE4404341A1/en not_active Withdrawn
-
1995
- 1995-01-26 EP EP95101053A patent/EP0668327A1/en not_active Withdrawn
- 1995-02-09 CN CN95101653A patent/CN1109899A/en active Pending
- 1995-02-10 CZ CZ95358A patent/CZ35895A3/en unknown
- 1995-02-10 PL PL95307202A patent/PL307202A1/en unknown
- 1995-02-10 BR BR9500490A patent/BR9500490A/en not_active Application Discontinuation
- 1995-02-10 KR KR1019950002442A patent/KR950032487A/en not_active Application Discontinuation
- 1995-02-10 JP JP7023221A patent/JPH07304980A/en not_active Withdrawn
- 1995-02-10 CA CA002142251A patent/CA2142251A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| KR950032487A (en) | 1995-12-20 |
| CZ35895A3 (en) | 1995-11-15 |
| CN1109899A (en) | 1995-10-11 |
| JPH07304980A (en) | 1995-11-21 |
| EP0668327A1 (en) | 1995-08-23 |
| DE4404341A1 (en) | 1995-08-17 |
| BR9500490A (en) | 1995-09-26 |
| PL307202A1 (en) | 1995-08-21 |
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