WO2005040283A2 - Disperse azo dyestuffs - Google Patents

Disperse azo dyestuffs Download PDF

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Publication number
WO2005040283A2
WO2005040283A2 PCT/EP2004/011590 EP2004011590W WO2005040283A2 WO 2005040283 A2 WO2005040283 A2 WO 2005040283A2 EP 2004011590 W EP2004011590 W EP 2004011590W WO 2005040283 A2 WO2005040283 A2 WO 2005040283A2
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Prior art keywords
alkyl
hydrogen
formula
group
methyl
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PCT/EP2004/011590
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French (fr)
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WO2005040283A3 (en
Inventor
Nigel Hall
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dystar Textilfarben GmbH and Co Deutschland KG
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Dystar Textilfarben GmbH and Co Deutschland KG
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Application filed by Dystar Textilfarben GmbH and Co Deutschland KG filed Critical Dystar Textilfarben GmbH and Co Deutschland KG
Priority to BRPI0415469-0A priority Critical patent/BRPI0415469A/en
Priority to US10/575,599 priority patent/US7358345B2/en
Priority to KR1020067004769A priority patent/KR101141572B1/en
Priority to ES04790444.6T priority patent/ES2611945T3/en
Priority to JP2006536010A priority patent/JP2007509214A/en
Priority to CA002543056A priority patent/CA2543056A1/en
Priority to HK07100014.5A priority patent/HK1093351B/en
Priority to MXPA06002919A priority patent/MXPA06002919A/en
Priority to EP04790444.6A priority patent/EP1678259B1/en
Publication of WO2005040283A2 publication Critical patent/WO2005040283A2/en
Publication of WO2005040283A3 publication Critical patent/WO2005040283A3/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • 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
    • C09B29/0805—Amino benzenes free of acid groups
    • C09B29/0807—Amino benzenes free of acid groups characterised by the amino group
    • C09B29/0809—Amino benzenes free of acid groups characterised by the amino group substituted amino group
    • C09B29/0811—Amino benzenes free of acid groups characterised by the amino group substituted amino group further substituted alkylamino, alkenylamino, alkynylamino, cycloalkylamino aralkylamino or arylamino
    • C09B29/0815—Amino benzenes free of acid groups characterised by the amino group substituted amino group further substituted alkylamino, alkenylamino, alkynylamino, cycloalkylamino aralkylamino or arylamino substituted by -C(=O)-
    • C09B29/0816—Amino benzenes free of acid groups characterised by the amino group substituted amino group further substituted alkylamino, alkenylamino, alkynylamino, cycloalkylamino aralkylamino or arylamino substituted by -C(=O)- substituted by -COOR
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B29/00—Monoazo dyes prepared by diazotising and coupling
    • C09B29/0025—Monoazo dyes prepared by diazotising and coupling from diazotized amino heterocyclic compounds
    • 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
    • C09B31/00—Disazo and polyazo dyes of the type A->B->C, A->B->C->D, or the like, prepared by diazotising and coupling
    • C09B31/02—Disazo dyes
    • C09B31/04—Disazo dyes from a coupling component "C" containing a directive amino group
    • C09B31/043—Amino-benzenes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/92—Synthetic fiber dyeing
    • Y10S8/922—Polyester fiber

Definitions

  • the present invention relates to the field of disperse dyes.
  • Disperse dyestuffs containing cyanomethyl ester groups are known from literature and are described for example in GB 909,843, DE-A 2130992, GB 1 ,457,532, GB 1 ,536,429, FR-A 1 ,531 , 147, US 3,776,898, JP 551 61 857, GB 2, 1 04,088, EP 0 685 531 A1 and WO 95/20014.
  • the inventor of the present invention has surprisingly found that dyeings on polyester with very good wet fastness properties can be obtained if selected dyestuffs containing one cyanomethylester group as defined below are used.
  • the present invention claims dyestuffs of the formula I
  • T ⁇ T 2 and T 3 are, independently, hydrogen, halogen or nitro; T 4 is hydrogen, halogen, cyano or nitro; wherein at least one of T ⁇ T 2 , T 3 and T 4 is not hydrogen; or a group of the formula (lib)
  • T 5 is hydrogen or halogen; and T 6 is hydrogen -SO 2 CH 3 , -SCN or nitro; wherein at least one of T 5 and T 6 is not hydrogen; or a group of the formula (lie)
  • T 7 is nitro, -CHO or a group of the formula
  • T is -H, halogen, nitro and cyano; T 8 is hydrogen or halogen; and T 9 is nitro, cyano, -COCH 3 or -COOT 10 , wherein T 10 is (C,-C 4 )-alkyl; or a group of the formula (lie)
  • R 1 is hydrogen, (C C 4 )-alkyl or -NCOR 6 , where R 6 is (C,-C 4 )-alkyl or phenyl;
  • R 2 is unsubstituted (C,-C 6 )-alkyl, substituted (C C 6 )-alkyl, benzyl or phenylethyl;
  • R 3 is hydrogen or methyl;
  • R 4 is hydrogen or methyl;
  • R 5 is hydrogen, methyl or phenyl;
  • R 7 is hydrogen, chloro, methoxy or ethoxy; n is 0, 1 or 2; s is 0 or 1 ;
  • D is a group of the formula (lie), (lid), (lie) or (lla) wherein T 1 is not nitro if T 2 , T 3 and T 4 are hydrogen, - if T 2 and T 3 are hydrogen and T 4 is chlorine or cyano and if T 2 and T 4 are hydrogen and T 3 is chlorine; and
  • Alkyl groups standing for R 1 , R 6 or T 10 may be straight-chain or branched and are preferably methyl, ethyl, n-propyl, i-propyl or n-butyl. The same applies to alkyl groups standing for R 2 , which can in addition be pentyl or hexyl. Substituted alkyl groups standing for R 2 are preferably substituted by hydroxyl, (C C 4 )-alkoxy or halogen. Halogen standing for T ⁇ T 2 , T 3 , T 4 , T 5 or T 8 are preferably chlorine or bromine.
  • D derive from the following amines: 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2-chloro-4-nitroaniline, 4-chloro-2- nitroaniline, 2-bromo-4-nitroaniIine, 2,6-dichloro-4-nitroaniline, 2,6-dibromo-4- nitroaniline, 2-ch oro-6-bromo-4-nitroaniline, 2,5-dichloro-4-nitroaniline, 2-cyano- 4-nitroaniline, 2-cyano-6-bromo-4-nitroaniline, 2-cyano-6-ch!oro-4-nitroaniline, 2,4-dinitroaniIine, 2-chloro-4,6-dinitroaniIine, 2-bromo-4,6-dinitroaniline, 2,6- dicyano-4-nitroaniIine, 2-cyano-4,6-dinitroaniline, 2-amino-5-nitrothiazole, 2- amino-3,5-dinitrothiophene, 2-amino-3-ethoxycarbon
  • 10 D is a group of the formulae (Ha), (lib), (lie), (lid) or (lie); R 1 is (C C 4 )-alkyl; R 2 is unsubstituted (C C 6 )-alkyl, benzyl or phenylethyl; and n is 0, 1 or 2.
  • R 2 is unsubstituted (C C 6 )-alkyl, substituted (C C 6 )-alkyl, benzyl or phenylethyl; 25
  • R 2 is ethyl, benzyl or phenethyl.
  • Still other preferred disperse dyestuffs according to the present invention are of the general formula (lc)
  • D is a group of the formulae (lla), (lib), (lie), (ild) or (lie);
  • R 1 is hydrogen, (C r C 4 )-alkyl or -NCOR 6 , where R 6 is (C r C 4 )-alkyl or phenyl;
  • R 2 is unsubstituted (C r C 6 )-alkyl, substituted (C r C 6 )-alkyI, benzyl or phenylethyl;
  • R 3 is hydrogen and R is methyl or R 3 is methyl and R is hydrogen.
  • Still other preferred disperse dyestuffs according to the present invention are of the general formula (Id)
  • D is a group of the formulae (lla), (lib), (lie), (Ild) or (lie);
  • R 1 is hydrogen, (C r C 4 )-alkyl or -NCOR 6 , where R 6 is (C C 4 ) -alkyl or phenyl;
  • R 2 is unsubstituted (C C 6 )-alkyl, substituted (C C 6 ) -al yl, benzyl or phenylethyl;
  • R 5 is methyl or phenyl
  • Still other preferred disperse dyestuffs according to the present invention are of the general formula (le)
  • D is a group of the formulae (lla), (lib), (lie), (Ild) or (lie);
  • R 2 is unsubstituted (C C 6 )-alkyl, substituted (C r C 6 )-alkyl, benzyl or phenylethyl;
  • R 6 is (C r C 4 )-aIkyl or phenyl;
  • R 7 is chloro, methoxy or ethoxy; and n is 0, 1 or 2.
  • Still other preferred disperse dyestuffs according to the present invention are of the general formula (If)
  • R 2 is unsubstituted (C C 6 )-aikyl, substituted (C C 6 )-alkyl, benzyl or phenylethyl; R 8 is nitro; and n is 0, 1 or 2;
  • Still other preferred disperse dyestuffs according to the present invention are of the general formula (Ig)
  • D is a group of the formulae (lla), (Mb), (He), (lid) or (lie);
  • R 1 is hydrogen, (C C 4 )-alkyi or -NCOR 6 , where R 6 is (C r C 4 )-alkyi or phenyl;
  • R 2 is unsubstituted (C,-C 6 )-alkyl, substituted (C C 6 )-alkyl, benzyl or phenylethyl; and R 3 is hydrogen or methyl.
  • the compounds of the formula I may be obtained by usual methods for the preparation of azo compounds such as by diazbtisation of an amine of the formula III D-NH 2 (III) wherein D is defined as given above, and coupling onto a compound of the formula IV
  • R ⁇ R 2 , R 3 , R 4 , R 5 and R 7 are defined as given above.
  • the amine of the formula (III) may be diazotised in an acidic medium, such as acetic, propionic or hydrochloric acid using a nitrosating agent such as nitrosylsulphuric acid, sodium nitrite or methylnitrite at a temperature from -1 0°C to 1 0°C.
  • a nitrosating agent such as nitrosylsulphuric acid, sodium nitrite or methylnitrite at a temperature from -1 0°C to 1 0°C.
  • Coupling onto the compound of the formula (IV) may be achieved by adding the diazotised amine to the compound of the formula (IV) under conditions described in literature and known to the skilled persons.
  • the compounds of the formula (I) are useful for dyeing and printing of synthetic textile material particularly polyester textile materials and fibre blends thereof with for example cellulosic materials like cotton, to which they impart colours Y which have excellent wet fastness properties.
  • Dyeing of the fibre goods mentioned with the dyestuffs of the formula (I) can be carried out in a manner known per se, preferably from aqueous dispersions, if appropriate in the presence of carriers, at between 80 and 1 1 0°C, by the exhaust process or by the HT process in a dyeing autoclave at 1 1 0 to 1 40°C, and by the so-called thermofixing process, in which the goods are padded with the dye liquor and then fixed at about 1 80 to 230°C.
  • the fibre goods mentioned can as well be printed in a manner known pers e by a procedure in which the dyestuffs of the formula (I) are incorporated into a printing paste and the goods printed with the paste are treated , if appropriate in the presence of a carrier, with HT steam, pressurized steam or dry heat at temperatures between 180 and 230°C to fix the dyestuff.
  • the dyestuffs of the formula (I) should be present in the finest possible dispersion in the dye liquors and printing pastes employed in the above applications.
  • the fine dispersion of the dyestuffs is effected in a manner known per se by a procedure in which the dyestuff obtained during preparation is suspended ina liquid medium, preferably in water, together with dispersing agents and the mixture is exposed to the action of shearing forces, the particles originally present being comminuted mechanically to the extent that an optimum specific surface area is achieved and sedimentation of the dyestuff is as low as possible.
  • the particle size of the dyestuffs is in general between 0.5 and 5 m, preferably about 1 m.
  • the dispersing agents used can be nonionic or anionic.
  • Nononic dispersing agents are, for example, reaction products of alkylene oxides, such as, for example, ethylene oxide or propyiene oxide, with alkylatable compounds, such as for example fatty alcohols, fatty amines, fatty acids, phenols, alkylphenols and carboxylic acid amines.
  • alkylatable compounds such as for example fatty alcohols, fatty amines, fatty acids, phenols, alkylphenols and carboxylic acid amines.
  • Anionic dispersing agnets are, for example, lignin- sulphonates, alkyl- or alkylarylsulphonates or alkylaryl polyglycol ethersulphates.
  • the dyestuff formulations thus obtained should be The dyestuff and dispersing agent content is therefore limited in these cases.
  • the dispersions are brought to a dyestuff content of up to 50 per cent by weight and a dispersing agent content of up to 25 per cent by weight.
  • the dyestuff contents usually do not fall below 1 5 per cent by weight.
  • the dispersions can also comprise other auxiliaries, for example those which act as oxidizing agents or fungicidal agents. Such agents are well known in the art.
  • the dyestuff dispersion thus obtained can be used very advantageously for the preparation of printing pastes and dye liquors.
  • powder formulations are preferred. These powders comprise the dyestuff, dispersing agents and other auxiliaries, such as, for example, wetting agents, oxidizing agents, preservatives and dust removal agents.
  • a preferred preparation process for pulverulent dyestuff formulations comprises removing the liquid from the liquid dyestuff dispersions described above, for example by vacuum drying, freeze drying, by drying on roller dryers, but preferably by spray drying.
  • 2,6-dichloro-4-nitroaniline (6.2parts) was set stirring at 5°C with a mixture of acetic acid and propionic acid, 86:1 (40parts). Nitrosyl sulphuric acid 40% (1 1 .4parts) was added below 5°C and the mixture was stirred for 30 minutes. The diazo solution was added gradually to a stirred coupling mixture of N-ethyl, N-2(cyanomethoxycarbonylethyl)-aniline (8.3parts), methanol (50parts), water (300parts) and sulphamic acid O part).
  • 2-amino-6-nitrobenzothiazole (3.9parts) was set stirring at 5°C with a mixture of acetic acid and propionic acid, 86:14 (40parts). Nitrosyl sulrlhuric acid 40% (7.6parts) was added below 5°C and the mixture was stirred for 1 hour. The diazo solution was added gradually to a stirred coupling mixture of N-ethyl, N-(2-cyanomethoxycarbonylethyl)-m-toluidine (5.9parts), methanol (25parts), water (200parts) and sulphamic acid (0.5parts).
  • Example 80 were prepared by the procedure of Example 80 (see Table 3)
  • Example 1 4-(3,5-dinitrothiophen-yl-azo)-3-methyl-N-ethyl-N-(2-cyanomethoxycarbonylethyl) aniline
  • 2-amino-3,5-dinitrothiophene (3.1 parts) was set stirring at 5°C with a mixture of acetic acid and propionic acid, 86: 14 (50parts) .
  • Nitrosyl sulphuric acid 40% (5.7parts) was added below 5°C and the mixture was stirred for 30 mins.
  • the diazo solution was added gradually to a stirred coupling mixture of N-ethyl, N-(2-cyanomethoxycarbonyethyl)-m-toluidine (4.0parts), acetone (50parts), water (300parts) and sulphamic acid (O. ⁇ parts) .
  • Example 1 27 4-(5-nitrobenzisothiazol-yl-azo)-3-methyl-N-ethyl-N-(2- cyanomethoxycarbonyiethyl) aniline
  • Example 1 27 were prepared by the procedure of Example 1 27 (see Table 5)
  • 2-amino-5-nitrothiazole (2.9parts) was was set stirring at 5°C with a mixture of acetic acid and propionic acid, 86:14 (50parts). Nitrosyl sulphuric acid 40% (7.0parts) was added below 5°C and the mixture was stirred for 30 mins. The diazo solution was added gradually to a stirred coupling mixture of N-butyl, N-2(cyanomethoxycarbonylethyl)-aniline ( ⁇ .2parts), acetone ( ⁇ Oparts), water (200parts) and sulphamic acid (O. ⁇ parts).
  • Example 1 39 4 (2-chloro-4-nitrophenylazo)-3-acetylamino-N-ethyl-N-(2- cyanomethoxycarbonylethyD-aniline
  • 2-chloro-4-nitroaniline (3. ⁇ parts) was set stirring at ⁇ °C with a mixture of acetic acid and propionic acid, 86: 14 (40parts). Nitrosyl sulphuric acid 40% (7.0parts) was added below 5°C and the mixture was stirred for 30 minutes. The diazo solution was added gradually to a stirred coupling mixture of 3(N- ethyl, N-cyanomethoxycarbonylethyl)-amino-acetanilide (6.3parts), methanol (40parts), water (200parts) and sulphamic acid O part).
  • Example139 were prepared by the procedure of Example139 (see Table 7)
  • 2-cyano-4-nitroaniline (3.2part,s) was set stirring at ⁇ °C with a mixture of acetic acid and propionic acid, 86:14s( ⁇ 0parts). Nitrosyl sulphuric acid 40% (7.6parts) was added below ⁇ °C and the mixture was stirred for 30 minutes. The diazo solution was added gradually to a stirred coupling mixture of N-ethyl, N-(4-cyanomethoxycarbonylbutyl)-m-toluidine ( ⁇ .Oparts), methanol ( ⁇ Oparts), water (200parts) and sulphamic acid part).
  • Example 1 69 4-(2-cyano-4-nitrophenylazo)-3-methyl-N-ethyl-N-(2-(1 -cyanoethoxy) carbonylethyD-aniline
  • 2-cyano-4-nitroaniline (2.1 parts) was set stirring at 5°C with a mixture of acetic acid and propionic acid, 86: 1 4 (40parts). Nitrosyl sulphuric acid 40% (4.9parts) was added below 5°C and the mixture was stirred for 30 minutes. The diazo solution was added gradually to a stirred coupling mixture of N-ethyl, N-(2-(1 -cyanoethoxy)carbonylethyl)-m-toluidine (3.7parts), acetone ( ⁇ Oparts), water (300parts) and sulphamic acid O part).
  • Example169 were prepared by the procedure of Example169 (see Table 9)
  • 2-chloro-4-nitr ⁇ a;hiline (parts) was set stirring at 5°C with a mixture of acetic acid and propionic acid, 86:14 (40parts). Nitrosyl sulphuric acid 40% (4.9parts) was added below ⁇ °C and the mixture was stirred for 30 minutes. The diazo solution was added gradually to a stirred coupling mixture of N-ethyl, N-2-(cyanomethoxycarbonylpropyl)-aniline (parts), acetone ( ⁇ Oparts), water (300parts) and sulphamic acid O part).
  • Example194 were prepared by the procedure of Example194 (see Table 10)
  • Example 21 3 4-(4-nitrophenylazo)-N-ethyl-N-(2-( 1 -cyanoethoxy) carbonylpropyD-aniline
  • 4-nitroaniline (2.0parts) was set stirring at ⁇ °C with a mixture of acetic acid and propionic acid, 86: 14 ( ⁇ Oparts). Nitrosyl sulphuric acid 40% ( ⁇ .7parts) was added below ⁇ °C and the mixture was stirred for 30 minutes. The diazo solution was added gradually to a stirred coupling mixture of N-ethyl, N-(2-(1 -cyanoethoxy)carbonylpropyl)-aniline (4.7parts), acetone ( ⁇ Oparts), water (200parts) and sulphamic acid O part) .
  • 2-cyano-4-nitroaniline (3.1 parts) was set stirring at 5°C with a mixture of acetic acid and propionic acid, 86: 1 4 (40parts). Nitrosyl sulphuric acid 40% (6.6parts) was added below 5°C and the mixture was stirred for 30 minutes. The diazo solution was added gradually to a stirred coupling mixture of N-ethyl, N-0 -cyanomethoxycarbonylethyl)-m-toluidine (4.1 parts), methanol (40parts), water (200parts) and sulphamic acid O part).

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  • Organic Chemistry (AREA)
  • Coloring (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Thiazole And Isothizaole Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)
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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention claims dyestuffs of formula (I), wherein D, R<1> to R<7> and n are defined as given in claim 1, a process for their preparation and their use.

Description

DYSTAR TEXTILFARBEN GMBH & CO. DEUTSCHLAND KG 2003/C 004 Dr. My
Description
Disperse Azo Dyestuffs
The present invention relates to the field of disperse dyes.
Disperse dyestuffs containing cyanomethyl ester groups are known from literature and are described for example in GB 909,843, DE-A 2130992, GB 1 ,457,532, GB 1 ,536,429, FR-A 1 ,531 , 147, US 3,776,898, JP 551 61 857, GB 2, 1 04,088, EP 0 685 531 A1 and WO 95/20014.
The inventor of the present invention has surprisingly found that dyeings on polyester with very good wet fastness properties can be obtained if selected dyestuffs containing one cyanomethylester group as defined below are used.
The present invention claims dyestuffs of the formula I
Figure imgf000002_0001
wherein
D is a group of the formula (Ha)
Figure imgf000002_0002
wherein T\ T2 and T3 are, independently, hydrogen, halogen or nitro; T4 is hydrogen, halogen, cyano or nitro; wherein at least one of T\ T2, T3 and T4 is not hydrogen; or a group of the formula (lib)
Figure imgf000003_0001
wherein T5 is hydrogen or halogen; and T6 is hydrogen -SO2CH3, -SCN or nitro; wherein at least one of T5 and T6 is not hydrogen; or a group of the formula (lie)
Figure imgf000003_0002
or a group of the formula (lid)
Figure imgf000003_0003
wherein T7 is nitro, -CHO or a group of the formula
Figure imgf000003_0004
T is -H, halogen, nitro and cyano; T8 is hydrogen or halogen; and T9 is nitro, cyano, -COCH3 or -COOT10, wherein T10 is (C,-C4)-alkyl; or a group of the formula (lie)
Figure imgf000003_0005
R1 is hydrogen, (C C4)-alkyl or -NCOR6, where R6 is (C,-C4)-alkyl or phenyl;
R2 is unsubstituted (C,-C6)-alkyl, substituted (C C6)-alkyl, benzyl or phenylethyl; R3 is hydrogen or methyl; R4 is hydrogen or methyl; R5 is hydrogen, methyl or phenyl; R7 is hydrogen, chloro, methoxy or ethoxy; n is 0, 1 or 2; s is 0 or 1 ;
with the proviso that in the case R1, R3, R4, R5 and R7 are hydrogen and n = 0
D is a group of the formula (lie), (lid), (lie) or (lla) wherein T1 is not nitro if T2, T3 and T4 are hydrogen, - if T2 and T3 are hydrogen and T4 is chlorine or cyano and if T2 and T4 are hydrogen and T3 is chlorine; and
with the further proviso that
R2 is unsubstituted (C C6)-alkyl if R1 is methyl, R3, R4, R5 and R7 are hydrogen and n = 0.
Alkyl groups standing for R1, R6 or T10 may be straight-chain or branched and are preferably methyl, ethyl, n-propyl, i-propyl or n-butyl. The same applies to alkyl groups standing for R2, which can in addition be pentyl or hexyl. Substituted alkyl groups standing for R2 are preferably substituted by hydroxyl, (C C4)-alkoxy or halogen. Halogen standing for T\ T2, T3, T4, T5 or T8 are preferably chlorine or bromine.
Preferred examples for D derive from the following amines: 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2-chloro-4-nitroaniline, 4-chloro-2- nitroaniline, 2-bromo-4-nitroaniIine, 2,6-dichloro-4-nitroaniline, 2,6-dibromo-4- nitroaniline, 2-ch oro-6-bromo-4-nitroaniline, 2,5-dichloro-4-nitroaniline, 2-cyano- 4-nitroaniline, 2-cyano-6-bromo-4-nitroaniline, 2-cyano-6-ch!oro-4-nitroaniline, 2,4-dinitroaniIine, 2-chloro-4,6-dinitroaniIine, 2-bromo-4,6-dinitroaniline, 2,6- dicyano-4-nitroaniIine, 2-cyano-4,6-dinitroaniline, 2-amino-5-nitrothiazole, 2- amino-3,5-dinitrothiophene, 2-amino-3-ethoxycarbonyl-5-nitrothiophene, 2- amino-3-acetyl-5-nitrothiophene, 2-amino-3-cyano-5-nitrothiophene, 2-amino-3- cyano-4-chloro-5-formylthiophene, 7-amino-5-nitrobenzoisothiazole, 2-amino-6- nitrobenzothiazole, 2-amino-6-methylsulphonylbenzothiazole; 2-amino-6- thiocyanatobenzothiazole, 2-amino-5,6-dichlorobenzothiazole and 2-amino-6,7- dichlorobenzothiazole (mixture). 5 Preferred disperse dyestuffs according to the present invention are of the general formula (la)
Figure imgf000005_0001
wherein 10 D is a group of the formulae (Ha), (lib), (lie), (lid) or (lie); R1 is (C C4)-alkyl; R2 is unsubstituted (C C6)-alkyl, benzyl or phenylethyl; and n is 0, 1 or 2.
15 In especially preferred dyestuffs of formula (la) R1 is methyl, R2 is ethyl and n is 0.
Other preferred disperse dyestuffs according to the present invention are of the general formula (lb)
Figure imgf000005_0002
\} wherein T3 is bromo or chloro; and R2 is unsubstituted (C C6)-alkyl, substituted (C C6)-alkyl, benzyl or phenylethyl; 25 In especially preferred dyestuffs of formula (lb) R2 is ethyl, benzyl or phenethyl. Still other preferred disperse dyestuffs according to the present invention are of the general formula (lc)
Figure imgf000006_0001
wherein D is a group of the formulae (lla), (lib), (lie), (ild) or (lie);
R1 is hydrogen, (CrC4)-alkyl or -NCOR6, where R6 is (CrC4)-alkyl or phenyl;
R2 is unsubstituted (CrC6)-alkyl, substituted (CrC6)-alkyI, benzyl or phenylethyl; and
R3 is hydrogen and R is methyl or R3 is methyl and R is hydrogen.
Still other preferred disperse dyestuffs according to the present invention are of the general formula (Id)
Figure imgf000006_0002
wherein D is a group of the formulae (lla), (lib), (lie), (Ild) or (lie);
R1 is hydrogen, (CrC4)-alkyl or -NCOR6, where R6 is (C C4) -alkyl or phenyl;
R2 is unsubstituted (C C6)-alkyl, substituted (C C6) -al yl, benzyl or phenylethyl; and
R5 is methyl or phenyl;
Still other preferred disperse dyestuffs according to the present invention are of the general formula (le)
Figure imgf000006_0003
wherein
D is a group of the formulae (lla), (lib), (lie), (Ild) or (lie);
R2 is unsubstituted (C C6)-alkyl, substituted (CrC6)-alkyl, benzyl or phenylethyl; R6 is (CrC4)-aIkyl or phenyl;
R7 is chloro, methoxy or ethoxy; and n is 0, 1 or 2.
Still other preferred disperse dyestuffs according to the present invention are of the general formula (If)
Figure imgf000007_0001
wherein
R2 is unsubstituted (C C6)-aikyl, substituted (C C6)-alkyl, benzyl or phenylethyl; R8 is nitro; and n is 0, 1 or 2;
Still other preferred disperse dyestuffs according to the present invention are of the general formula (Ig)
Figure imgf000007_0002
wherein
D is a group of the formulae (lla), (Mb), (He), (lid) or (lie);
R1 is hydrogen, (C C4)-alkyi or -NCOR6, where R6 is (CrC4)-alkyi or phenyl;
R2 is unsubstituted (C,-C6)-alkyl, substituted (C C6)-alkyl, benzyl or phenylethyl; and R3 is hydrogen or methyl. The compounds of the formula I may be obtained by usual methods for the preparation of azo compounds such as by diazbtisation of an amine of the formula III D-NH2 (III) wherein D is defined as given above, and coupling onto a compound of the formula IV
Figure imgf000008_0001
wherein R\ R2, R3, R4, R5 and R7 are defined as given above.
Typically the amine of the formula (III) may be diazotised in an acidic medium, such as acetic, propionic or hydrochloric acid using a nitrosating agent such as nitrosylsulphuric acid, sodium nitrite or methylnitrite at a temperature from -1 0°C to 1 0°C. Coupling onto the compound of the formula (IV) may be achieved by adding the diazotised amine to the compound of the formula (IV) under conditions described in literature and known to the skilled persons.
After coupling the compound of the formula (I) may be recovered from the reaction mixture by any convenient means such as filtration. The compounds of the formulae (III) and (IV) are known and can be obtained by methods described in literature or known to the skilled person.
The compounds of the formula (I) are useful for dyeing and printing of synthetic textile material particularly polyester textile materials and fibre blends thereof with for example cellulosic materials like cotton, to which they impart colours Y which have excellent wet fastness properties.
Dyeing of the fibre goods mentioned with the dyestuffs of the formula (I) can be carried out in a manner known per se, preferably from aqueous dispersions, if appropriate in the presence of carriers, at between 80 and 1 1 0°C, by the exhaust process or by the HT process in a dyeing autoclave at 1 1 0 to 1 40°C, and by the so-called thermofixing process, in which the goods are padded with the dye liquor and then fixed at about 1 80 to 230°C.
The fibre goods mentioned can as well be printed in a manner known pers e by a procedure in which the dyestuffs of the formula (I) are incorporated into a printing paste and the goods printed with the paste are treated , if appropriate in the presence of a carrier, with HT steam, pressurized steam or dry heat at temperatures between 180 and 230°C to fix the dyestuff.
The dyestuffs of the formula (I) should be present in the finest possible dispersion in the dye liquors and printing pastes employed in the above applications.
The fine dispersion of the dyestuffs is effected in a manner known per se by a procedure in which the dyestuff obtained during preparation is suspended ina liquid medium, preferably in water, together with dispersing agents and the mixture is exposed to the action of shearing forces, the particles originally present being comminuted mechanically to the extent that an optimum specific surface area is achieved and sedimentation of the dyestuff is as low as possible. The particle size of the dyestuffs is in general between 0.5 and 5 m, preferably about 1 m. The dispersing agents used can be nonionic or anionic. Nononic dispersing agents are, for example, reaction products of alkylene oxides, such as, for example, ethylene oxide or propyiene oxide, with alkylatable compounds, such as for example fatty alcohols, fatty amines, fatty acids, phenols, alkylphenols and carboxylic acid amines. Anionic dispersing agnets are, for example, lignin- sulphonates, alkyl- or alkylarylsulphonates or alkylaryl polyglycol ethersulphates. For most methods of use, the dyestuff formulations thus obtained should be The dyestuff and dispersing agent content is therefore limited in these
Figure imgf000009_0001
cases. In general, the dispersions are brought to a dyestuff content of up to 50 per cent by weight and a dispersing agent content of up to 25 per cent by weight. For economic reasons, the dyestuff contents usually do not fall below 1 5 per cent by weight. The dispersions can also comprise other auxiliaries, for example those which act as oxidizing agents or fungicidal agents. Such agents are well known in the art. The dyestuff dispersion thus obtained can be used very advantageously for the preparation of printing pastes and dye liquors.
For certain fields of use, powder formulations are preferred. These powders comprise the dyestuff, dispersing agents and other auxiliaries, such as, for example, wetting agents, oxidizing agents, preservatives and dust removal agents.
A preferred preparation process for pulverulent dyestuff formulations comprises removing the liquid from the liquid dyestuff dispersions described above, for example by vacuum drying, freeze drying, by drying on roller dryers, but preferably by spray drying.
Example 1
4-(4-nitrophenylazo)-3-methyl-N-ethyI-N-(2-cyanomethoxy- carbonylethyl) aniline
Figure imgf000010_0001
4-nitroaniline (4.1 parts) was set stirring at 5°C with a mixture of acetic acid and propionic acid, 86: 1 4 (50parts). Nitrosyl sulphuric acid 40% (1 1 .4parts) was added below 5°C and the mixture was stirred for 30 minutes. The diazo solution obtained was added gradually to a stirred coupling mixture of N-ethyl, N-(2-cyanomethoxycarbonylethyi)-m-toluidine (7.3parts), methanol (50parts), water (200parts) and sulphamic acid O part). After two hours the product was isolated by filtration, washed with cold water and dried to yield, 4- (4-nitrophenylazo)-3-methyl-N-ethyl-N-(2-cyanomethoxycarbonylethyl) aniline (6.5parts) λmax = 486nm (acetone) When applied to polyester materials from aqueous dispersion, red shades ,.§yjth excellent wet and light fastness properties were seen.
The following examples of dyes of formula (laa):
Figure imgf000011_0001
were prepared by the procedure of Example 1 (see Table 1 )
Table 1
Figure imgf000011_0002
Figure imgf000012_0001
Figure imgf000013_0001
Example 65 4-(2,6-dichloro-4-nitrophenylazo)-N-ethyl-N-(2-cyanomethoxy- carbonylethyl) aniline
Figure imgf000014_0001
2,6-dichloro-4-nitroaniline (6.2parts) was set stirring at 5°C with a mixture of acetic acid and propionic acid, 86:1 (40parts). Nitrosyl sulphuric acid 40% (1 1 .4parts) was added below 5°C and the mixture was stirred for 30 minutes. The diazo solution was added gradually to a stirred coupling mixture of N-ethyl, N-2(cyanomethoxycarbonylethyl)-aniline (8.3parts), methanol (50parts), water (300parts) and sulphamic acid O part). After one hour the product was isolated by filtration, washed with cold water and dried to yield, 4-(2,6-dichloro-4- nitrophenylazo)-N-ethyl-N-(2-cyanomethoxycarbonylethyl) aniline (9.5parts) λmax = 432nm (acetone)
When applied to polyester materials from aqueous dispersion, yellow brown shades with excellent wet and light fastness properties were seen.
The following examples of dyes of Formula (Iba)
Figure imgf000014_0002
were prepared by the procedure of Example 65 (see Table 2)
Table 2
Figure imgf000014_0003
Figure imgf000015_0002
Example 80 4-(6-nitrobenzothiazol-yl-azo)-3-methyl-N-ethyl-N-(2-cyanomethoxycarbonylethyl) aniline
Figure imgf000015_0001
2-amino-6-nitrobenzothiazole (3.9parts) was set stirring at 5°C with a mixture of acetic acid and propionic acid, 86:14 (40parts). Nitrosyl sulrlhuric acid 40% (7.6parts) was added below 5°C and the mixture was stirred for 1 hour. The diazo solution was added gradually to a stirred coupling mixture of N-ethyl, N-(2-cyanomethoxycarbonylethyl)-m-toluidine (5.9parts), methanol (25parts), water (200parts) and sulphamic acid (0.5parts). After one hour the product was isolated by filtration, washed with cold water and dried to yield, 4-(6-nitrobenzothiazol-yl-azo)-3-methyl-N-ethyl-N-(2-cyanomethoxycarbonyl ethyl) aniline (2.4parts) λmax = 545nm (acetone)
When applied to polyester materials from aqueous dispersion, rubine shades with excellent wet and light fastness properties were seen.
The following examples of dyes of Formula (lab):
Figure imgf000017_0001
were prepared by the procedure of Example 80 (see Table 3)
Table 3
Figure imgf000017_0002
Figure imgf000018_0002
Example 1 07 4-(3,5-dinitrothiophen-yl-azo)-3-methyl-N-ethyl-N-(2-cyanomethoxycarbonylethyl) aniline
Figure imgf000018_0001
2-amino-3,5-dinitrothiophene (3.1 parts) was set stirring at 5°C with a mixture of acetic acid and propionic acid, 86: 14 (50parts) . Nitrosyl sulphuric acid 40% (5.7parts) was added below 5°C and the mixture was stirred for 30 mins. The diazo solution was added gradually to a stirred coupling mixture of N-ethyl, N-(2-cyanomethoxycarbonyethyl)-m-toluidine (4.0parts), acetone (50parts), water (300parts) and sulphamic acid (O.δparts) . After one hour the product was isolated by filtration, washed with cold water and dried to yield, 4-(3,5- dinitrothiophen-yl-azo)-3-methyl-N-ethyl-N-(2-cyanomethoxycarbonyl- ethyl) aniline (3.0parts) λmax = 640nm (acetone) When applied to polyester materials from aqueous dispersion, blue shades with excellent wet and light fastness properties were seen.
The following examples of dyes of Formula (lac):
Figure imgf000019_0001
were prepared by the procedure of Example 107 (see Table 4)
Table 4
Figure imgf000019_0002
Figure imgf000020_0002
Example 1 27 4-(5-nitrobenzisothiazol-yl-azo)-3-methyl-N-ethyl-N-(2- cyanomethoxycarbonyiethyl) aniline
Figure imgf000020_0001
7-amino-5-nitrobenzoisothiazole (2.9parts) was added to a mixture of sulphuric acid 98% (1 5parts) and phosphoric acid (4parts) stirring at room temperature. The mixture was heated to 55°C and was stirred at that temperature for 30mins. Nitrosyl sulphuric acid 40% (6.1 parts) was added below 5°C and the mixture was stirred for 2hrs. The diazo solution was added gradually to a stirred coupling mixture of N-ethyl, N-(2-cyanomethoxycarbonylethyl)-m-toluidine (4.8parts), acetone (50parts), water O OOparts) and sulphamic acid (O.δparts). Sodium acetate was added to increase the pH to 4.0 and the mixture was stirred for 1 hour. The product was isolated by filtration, washed with cold water apd dried to yield, 4-(5- nitrobenzisothiazol-yl-azo)-3-methyl-N-ethyl-N -f -cyanomethoxycarbonylethyl) aniline (2.4parts) λmax = 601 nm (acetone) When applied to polyester materials from aqueous dispersion, blue shades with excellent wet and light fastness properties were seen. The following examples of dyes of Formula (lad)
Figure imgf000021_0001
were prepared by the procedure of Example 1 27 (see Table 5)
Table 5
Figure imgf000021_0003
Example 134
4-(5-nitrothiazol-yl-azo)-N-butyl-N-(2-cyanomethoxy- carbonylethyl) aniline
Figure imgf000021_0002
2-amino-5-nitrothiazole (2.9parts) was was set stirring at 5°C with a mixture of acetic acid and propionic acid, 86:14 (50parts). Nitrosyl sulphuric acid 40% (7.0parts) was added below 5°C and the mixture was stirred for 30 mins. The diazo solution was added gradually to a stirred coupling mixture of N-butyl, N-2(cyanomethoxycarbonylethyl)-aniline (δ.2parts), acetone (δOparts), water (200parts) and sulphamic acid (O.δparts). After one hour the product was isolated by filtration, washed with cold water and dried to yield, 4-(δ- nitrothiazol-yl-azo)-N-butyl-N-(2-cyanomethoxycarbonylethyl) aniline (2.9parts) λmax = 671 nm (acetone)
When applied to polyester materials from aqueous dispersion, blue shades with excellent wet and light fastness properties were seen.
The following examples of dyes of Formula (lae)
Figure imgf000022_0001
were prepared by the procedure of Example 134 (see Table 6)
Table 6
Figure imgf000022_0003
Example 1 39 4 (2-chloro-4-nitrophenylazo)-3-acetylamino-N-ethyl-N-(2- cyanomethoxycarbonylethyD-aniline
Figure imgf000022_0002
2-chloro-4-nitroaniline (3.δparts) was set stirring at δ°C with a mixture of acetic acid and propionic acid, 86: 14 (40parts). Nitrosyl sulphuric acid 40% (7.0parts) was added below 5°C and the mixture was stirred for 30 minutes. The diazo solution was added gradually to a stirred coupling mixture of 3(N- ethyl, N-cyanomethoxycarbonylethyl)-amino-acetanilide (6.3parts), methanol (40parts), water (200parts) and sulphamic acid O part). After two hours the product was isolated by filtration, washed with cold water and dried to yield, 4- (2-chloro-4-nitrophenylazo)-3-acetylamino-N-ethyl-N-(2-cyanomethoxy- carbonylethyD-aniline (4.1 parts) λmax = 52δnm (acetone) When applied to polyester materials from aqueous dispersion, rubine shades with excellent wet and light fastness properties were seen.
The following examples of dyes of formula (lea):
Figure imgf000023_0001
were prepared by the procedure of Example139 (see Table 7)
Table 7
Figure imgf000023_0002
Figure imgf000024_0001
Figure imgf000025_0002
Example 1 67 4-(2-cyano-4-nitrophenylazo)-3-methyl-N-ethyl-N-(4- cyanomethoxycarbonylbutyD-aniline
Figure imgf000025_0001
2-cyano-4-nitroaniline (3.2part,s) was set stirring at δ°C with a mixture of acetic acid and propionic acid, 86:14s(δ0parts). Nitrosyl sulphuric acid 40% (7.6parts) was added below δ°C and the mixture was stirred for 30 minutes. The diazo solution was added gradually to a stirred coupling mixture of N-ethyl, N-(4-cyanomethoxycarbonylbutyl)-m-toluidine (δ.Oparts), methanol (δOparts), water (200parts) and sulphamic acid part). After two hours the product was isolated by filtration, washed with cold water and dried to yield, 4-(2-cyano-4- nitrophenylazo)-3-methyl-N-ethyl-N-(4-cyanomethoxycarbonyl butyD-aniline. (δ.3parts) λmax = 648nm (acetone) When applied to polyester materials from aqueous dispersion, rubine shades with excellent wet and light fastness properties were seen.
The following examples of dyes of Formula (laf)
Figure imgf000026_0001
were prepared by the procedure of Example167 (see Table 8) Table 8
Figure imgf000026_0002
Figure imgf000027_0002
Example 1 69 4-(2-cyano-4-nitrophenylazo)-3-methyl-N-ethyl-N-(2-(1 -cyanoethoxy) carbonylethyD-aniline
Figure imgf000027_0001
2-cyano-4-nitroaniline (2.1 parts) was set stirring at 5°C with a mixture of acetic acid and propionic acid, 86: 1 4 (40parts). Nitrosyl sulphuric acid 40% (4.9parts) was added below 5°C and the mixture was stirred for 30 minutes. The diazo solution was added gradually to a stirred coupling mixture of N-ethyl, N-(2-(1 -cyanoethoxy)carbonylethyl)-m-toluidine (3.7parts), acetone (δOparts), water (300parts) and sulphamic acid O part). After two hours the product was isolated by filtration, washed with cold water and dried to yield, 4-(2-cyano-4- nitrophenylazo)-3-methyl-N-ethyl-N-(2-(1 -cyanoethoxy) carbonylethyD-aniline (3.5parts) λmax = 534nm (acetone) When applied to polyester materials from aqueous dispersion, rubine shades with excellent wet and light fastness properties were seen.
The following examples of dyes of Formula (Ida
Figure imgf000028_0001
were prepared by the procedure of Example169 (see Table 9)
Table 9
Figure imgf000028_0002
Figure imgf000029_0001
Figure imgf000030_0002
Example 194 4-(2-chloro-4-nitrophenylazo)-N-ethyl-N-(2-cyanomethoxy carbonylpropyD-aniline
Figure imgf000030_0001
2-chloro-4-nitrόa;hiline (parts) was set stirring at 5°C with a mixture of acetic acid and propionic acid, 86:14 (40parts). Nitrosyl sulphuric acid 40% (4.9parts) was added below δ°C and the mixture was stirred for 30 minutes. The diazo solution was added gradually to a stirred coupling mixture of N-ethyl, N-2-(cyanomethoxycarbonylpropyl)-aniline (parts), acetone (δOparts), water (300parts) and sulphamic acid O part). After two hours the product was isolated by filtration, washed with cold water and dried to yield, 4-(2-chloro-4- nitrophenylazo)-N-ethyl-N-(2-cyanomethoxycarbonylpropyl)-aniline (3.δparts) λmax = 634nm (acetone) When applied to polyester materials from aqueous dispersion, red shades with excellent wet and light fastness properties were seen.
The following examples of dyes of Formula (lea)
Figure imgf000031_0001
were prepared by the procedure of Example194 (see Table 10)
Tablel O
Figure imgf000031_0002
Figure imgf000032_0001
Example 21 3 4-(4-nitrophenylazo)-N-ethyl-N-(2-( 1 -cyanoethoxy) carbonylpropyD-aniline
Figure imgf000033_0001
4-nitroaniline (2.0parts) was set stirring at δ°C with a mixture of acetic acid and propionic acid, 86: 14 (δOparts). Nitrosyl sulphuric acid 40% (δ.7parts) was added below δ°C and the mixture was stirred for 30 minutes. The diazo solution was added gradually to a stirred coupling mixture of N-ethyl, N-(2-(1 -cyanoethoxy)carbonylpropyl)-aniline (4.7parts), acetone (δOparts), water (200parts) and sulphamic acid O part) . After two hours the product was isolated by filtration, washed with cold water and dried to yield, 4-(4-nitrophenylazo)-N- ethyl-N-(2-(1 -cyanoethoxy)carbonylpropyl)-aniline (2.9parts) λmax = 473nm (acetone) When applied to polyester materials from aqueous dispersion, scarlet shades with excellent wet and light fastness properties were seen.
The following examples of dyes of Formula (Ih):
Figure imgf000033_0002
were prepared by the procedure of Example 21 3 (see Table 1 X Table 1 1
Figure imgf000033_0003
Figure imgf000034_0001
Example 226
4-(2-cyano-4-nitrophenylazo)-N-ethyl-N-(1 -cyanomethoxy carbonylethyl)-m- toluidine
Figure imgf000035_0001
2-cyano-4-nitroaniline (3.1 parts) was set stirring at 5°C with a mixture of acetic acid and propionic acid, 86: 1 4 (40parts). Nitrosyl sulphuric acid 40% (6.6parts) was added below 5°C and the mixture was stirred for 30 minutes. The diazo solution was added gradually to a stirred coupling mixture of N-ethyl, N-0 -cyanomethoxycarbonylethyl)-m-toluidine (4.1 parts), methanol (40parts), water (200parts) and sulphamic acid O part). After two hours the product was isolated by filtration, washed with cold water and dried to yield, 4-(2-cyano-4- nitrophenylazo)-N-ethyl-N-(1 -cyanomethoxycarbonylethyl)-m-toluidine (3.9parts) λmax = 61 0nm (acetone) When applied to polyester materials from aqueous dispersion, red shades with excellent wet and light fastness properties were seen.

Claims

Patent Claims
1 . Dyestuff of the formula I
Figure imgf000036_0001
wherein D is a group of the formula (lla)
Figure imgf000036_0002
wherein T1 , T2 and T3 are, independently, hydrogen, halogen or nitro; T4 is hydrogen, halogen, cyano or nitro; wherein at least one of T\ T2, T3 and T4 is not hydrogen; or a group of the formula (lib)
Figure imgf000036_0003
wherein T5 is hydrogen or halogen; and T6 is hydrogen -SO2CH3, -SCN or nitro; wherein at least one of T5 and T6 is not hydrogen; or a group of the formula (lie)
Figure imgf000036_0004
or a group of the formula (Ild)
Figure imgf000037_0001
wherein T7 is nitro, -CHO or a group of the formula
Figure imgf000037_0002
wherein T10 is -H, halogen, nitro and cyano; T8 is hydrogen or halogen; and T9 is nitro, cyano, -COCH3 or -COOT10, wherein T10 is (CrC4)-alkyl; or a group of the formula (lie)
Figure imgf000037_0003
R1 s hydrogen, (CrC4)-alkyl or -NCOR6, where R6 is (C C4)-alkyl or phenyl; R2 s unsubstituted (C,-C6)-alkyl, substituted (C1-C6)-alkyl, benzyl or phenylethyl;
R3 s hydrogen or methyl; R4 s hydrogen or methyl; R5 s hydrogen, methyl or phenyl; R7 s hydrogen, chloro, methoxy or ethoxy; n is 0, 1 or 2; s is 0 or 1 ;
with the proviso that in the case R1, R3, R4, R5 and R7 are hydrogen and n = 0
D is a group of the formula (He), (Ild), (He) or (lla) wherein T1 is not nitro if T2, !•? and T4 are hydrogen, if T2 anU T3 are hydrogen and T4 is chlorine or cyano and if T2 and T4 are hydrogen and T3 is chlorine; and
with the further proviso that
R2 is unsubstituted (CrC6)-alkyl if R1 is methyl, R3, R4, R5 and R7 are hydrogen and n = 0.
2. Dyestuff according to claim 1 of the formula (la)
Figure imgf000038_0001
wherein
D is a group of the formulae (lla), (lib), (He), (Ild) or (We); R1 is (C rC4) -alkyl ;
R2 is unsubstituted (C,-C6)-alkyl, benzyl or phenylethyl; and n is 0, 1 or 2.
3. Dyestuff according to claim 1 of the formula (lb)
Figure imgf000038_0002
wherein T3 is bromo or chloro; and
R2 is unsubstituted (C,-C6)-alkyl, substituted (C,-C6)-alkyl, benzyl or phenylethyl;
4. Dyestuff according to claiml of the formula (lc)
Figure imgf000038_0003
wherein
D is a group of the formulae (lla), (lib), (lie), (Ild) or (We);
R1 is hydrogen, (CrC4)-alkyl or -NCOR6, where R6 is (CrC4)-alkyl or phenyl;
R2 is unsubstituted (C.,-Cβ)-alkyl, substituted (C^CeJ-alkyl, benzyl or phenylethyl; and R3 is hydrogen and R4 is methyl or R3 is methyl and R is hydrogen. δ. Dyestuff according to claiml of the formula (Id)
Figure imgf000039_0001
wherein
D is a group of the formulae (Ha), (lib), (He), (Ild) or (lie); R1 is hydrogen, (CrC4)-alkyl or -NCOR6, where R6 is (CrC4)-alkyl or phenyl; R2 is unsubstituted (C,-C6)-alkyl, substituted (C,-C6)-alkyl, benzyl or phenylethyl; and R5 is methyl or phenyl;
6. Dyestuff according to claim l of the formula (le)
Figure imgf000039_0002
wherein D is a group of the formulae (lla), (lib), (lie), (Ild) or (We);
R2 is unsubstituted (CrC6)-alkyl, substituted (C C6)-alkyl, benzyl or phenylethyl;
R6 is (CrC4)-alkyl or phenyl;
R7 is chloro, methoxy or ethoxy; and n is 0, 1 or 2.
7. Dyestuff according to claiml of the formula (If)
Figure imgf000039_0003
wherein R2 is unsubstituted (CrC6)-alkyl, substituted (CrC6)-alkyl, benzyl or phenylethyl; R8 is nitro; and n is 0, 1 or 2;
8. Dyestuff according to claiml of the formula (Ig)
Figure imgf000040_0001
wherein
D is a group of the formulae (lla), (lib), (He), (Ild) or (We); R1 is hydrogen, (C C4)-alkyl or -NCOR6, where R6 is (C C4)-alkyl or phenyl; R2 is unsubstituted (C,-C6)-alkyl, substituted (C^C^-alky!, benzyl or phenylethyl; and R3 is hydrogen or methyl.
9. Process for the preparation of a dyestuff as claimed in one or more of claims 1 to 8, which comprises diazotisation of an amine of the formula III D-NH2 (III) wherein D is defined as given in the preceding claims, and coupling onto a compound of the formula IV
Figure imgf000040_0002
wherein R1, R2, R3, R4, R5 and R7 are defined as given in the preceding claims.
1 0. The use of a dyestuff as claimed in one or more of claims 1 to 8 for dyeing and printing of synthetic textile material and fibre blends thereof.
PCT/EP2004/011590 2003-10-21 2004-10-15 Disperse azo dyestuffs Ceased WO2005040283A2 (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
BRPI0415469-0A BRPI0415469A (en) 2003-10-21 2004-10-15 dispersed azo dyes
US10/575,599 US7358345B2 (en) 2003-10-21 2004-10-15 Disperse azo dyestuffs
KR1020067004769A KR101141572B1 (en) 2003-10-21 2004-10-15 Disperse azo dyestuffs
ES04790444.6T ES2611945T3 (en) 2003-10-21 2004-10-15 Azo dyes dispersed
JP2006536010A JP2007509214A (en) 2003-10-21 2004-10-15 Disperse azo dye
CA002543056A CA2543056A1 (en) 2003-10-21 2004-10-15 Disperse azo dyestuffs
HK07100014.5A HK1093351B (en) 2003-10-21 2004-10-15 Disperse azo dyestuffs
MXPA06002919A MXPA06002919A (en) 2003-10-21 2004-10-15 Disperse azo dyestuffs.
EP04790444.6A EP1678259B1 (en) 2003-10-21 2004-10-15 Disperse azo dyestuffs

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GBGB0324584.2A GB0324584D0 (en) 2003-10-21 2003-10-21 Disperse azo dyestuffs
GB0324584.2 2003-10-21

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WO2005040283A2 true WO2005040283A2 (en) 2005-05-06
WO2005040283A3 WO2005040283A3 (en) 2005-06-30

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EP (1) EP1678259B1 (en)
JP (1) JP2007509214A (en)
KR (1) KR101141572B1 (en)
CN (1) CN100439450C (en)
BR (1) BRPI0415469A (en)
CA (1) CA2543056A1 (en)
ES (1) ES2611945T3 (en)
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008074719A1 (en) * 2006-12-21 2008-06-26 Dystar Textilfarben Gmbh & Co Deutschland Kg Disperse dyes mixtures
US7682408B2 (en) 2006-03-08 2010-03-23 Dy Star Textilfarben GmbH & Co. Disperse azo dyestuffs
US7833291B2 (en) 2007-01-23 2010-11-16 Dystar Textilfarben Gmbh & Co. Deutschland Kg Dispersion dye, the production and use thereof
CN103450707A (en) * 2013-09-07 2013-12-18 张家港市杨舍丝印工艺厂 Dye composition (black) and preparation method thereof
EP2995653A1 (en) 2014-09-15 2016-03-16 DyStar Colours Distribution GmbH High wet-fast disperse dyes and mixtures thereof
EP3715424A1 (en) 2019-03-27 2020-09-30 DyStar Colours Distribution GmbH High wet fast disperse dye mixtures of n-[4-(5-thiocyanato-2,4-dinitro-phenylazo)-phenyl]-amine derivatives and n-[4-(4-nitro-phenylazo)-phenyl]-amine derivatives
EP3715423A1 (en) 2019-03-27 2020-09-30 DyStar Colours Distribution GmbH High wet fast disperse dye mixtures of n-[4-(5-fluoro-2,4-dinitro-phenylazo)-phenyl]-amine derivatives and n-[4-(4-nitro-phenylazo)-phenyl]-amine derivatives
EP3922681A1 (en) 2018-06-25 2021-12-15 Basf Se Red pigment composition for color filter

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011077462A2 (en) * 2009-12-23 2011-06-30 Colourtex Industries Limited Disperse dyes
PH12012501294A1 (en) * 2009-12-23 2019-07-10 Colourtex Industries Ltd Disperse azo dyes
ES2800314T3 (en) * 2011-06-03 2020-12-29 Procter & Gamble Method for the care of clothes with dyes
MX2015013169A (en) * 2013-03-15 2015-12-15 3M Innovative Properties Co Benzothiazol-2-ylazo-phenyl compound as dye, compositions including the dye, and method of determining degree of cure of such compositions.

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB909843A (en) * 1959-02-10 1962-11-07 Ici Ltd New monoazo dyestuffs containing ester groups
US3097198A (en) * 1959-02-10 1963-07-09 Ici Ltd Azo dyestuffs
FR1531147A (en) 1966-07-15 1968-06-28 Ici Ltd Water-insoluble azo dyes and method of manufacturing said dyes
GB1176797A (en) 1966-07-15 1970-01-07 Ici Ltd Water-insoluble Monoazo Dyestuffs
US3776898A (en) 1970-04-23 1973-12-04 Gaf Corp Azo dyestuffs containing as the terminal coupling component a pyrrolidonoaniline
CA921464A (en) * 1970-06-22 1973-02-20 Imperial Chemical Industries Limited Monoazo dyestuffs
GB1321902A (en) 1970-06-22 1973-07-04 Ici Ltd Monoazo dyestuffs
GB1351381A (en) 1971-01-11 1974-04-24 Ici Ltd Disperse azo dyestuffs
US4119624A (en) * 1972-06-08 1978-10-10 Imperial Chemical Industries Limited Disperse monoazo dyestuffs
GB1457532A (en) 1973-09-26 1976-12-01 Ici Ltd Disperse monoazo dyestuffs
GB1536429A (en) 1975-03-25 1978-12-20 Ici Ltd Disperse monoazo dyestuffs
DE2811167C2 (en) 1978-03-15 1985-10-10 Hoechst Ag, 6230 Frankfurt Process for the production of real pad dyeings and prints on cellulose fiber materials and their mixtures with polyester fibers
GB2011483B (en) 1977-12-29 1982-08-18 Hoechst Ag Process for preparing fast dyeings and prints on cellulosic fibre materials and mixtures thereof with synthetic fibres
JPS55161857A (en) 1979-06-05 1980-12-16 Nippon Kayaku Co Ltd Water-insoluble azo compound, production thereof and dyeing and printing method using same
GB2104088B (en) 1981-07-14 1985-06-26 Yorkshire Chemicals Ltd Blue monoazo disperse dyes
RU2068429C1 (en) * 1993-04-09 1996-10-27 Московское научно-производственное объединение "НИОПИК" Process for preparing cyanogroups containing azo dyes
GB9400972D0 (en) 1994-01-19 1994-03-16 Zeneca Ltd Process
DE4419622A1 (en) 1994-06-03 1995-12-07 Cassella Ag Monoazo dyes, their production and use
GB9806810D0 (en) 1998-03-31 1998-05-27 Zeneca Ltd Compositions
AU2846099A (en) 1998-03-31 1999-10-18 Avecia Limited 1,3,4-thiadiazolylazo dyes and ink compositions containing the same

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7682408B2 (en) 2006-03-08 2010-03-23 Dy Star Textilfarben GmbH & Co. Disperse azo dyestuffs
WO2008074719A1 (en) * 2006-12-21 2008-06-26 Dystar Textilfarben Gmbh & Co Deutschland Kg Disperse dyes mixtures
US8226758B2 (en) 2006-12-21 2012-07-24 Dystar Colours Deutschland Gmbh Disperse dyes mixtures
US7833291B2 (en) 2007-01-23 2010-11-16 Dystar Textilfarben Gmbh & Co. Deutschland Kg Dispersion dye, the production and use thereof
CN103450707A (en) * 2013-09-07 2013-12-18 张家港市杨舍丝印工艺厂 Dye composition (black) and preparation method thereof
US10301474B2 (en) 2014-09-15 2019-05-28 Dystar Colours Distribution Gmbh High wet fast disperse dyes and mixtures thereof
EP2995653A1 (en) 2014-09-15 2016-03-16 DyStar Colours Distribution GmbH High wet-fast disperse dyes and mixtures thereof
EP3922681A1 (en) 2018-06-25 2021-12-15 Basf Se Red pigment composition for color filter
EP3715424A1 (en) 2019-03-27 2020-09-30 DyStar Colours Distribution GmbH High wet fast disperse dye mixtures of n-[4-(5-thiocyanato-2,4-dinitro-phenylazo)-phenyl]-amine derivatives and n-[4-(4-nitro-phenylazo)-phenyl]-amine derivatives
EP3715423A1 (en) 2019-03-27 2020-09-30 DyStar Colours Distribution GmbH High wet fast disperse dye mixtures of n-[4-(5-fluoro-2,4-dinitro-phenylazo)-phenyl]-amine derivatives and n-[4-(4-nitro-phenylazo)-phenyl]-amine derivatives
WO2020193159A1 (en) 2019-03-27 2020-10-01 Dystar Colours Distribution Gmbh High wet fast disperse dye mixtures of n-[4-(5-fluoro-2,4-dinitro-phenylazo)-phenyl]-amine derivatives and n-[4-(4-nitro-phenylazo)-phenyl]-amine derivatives
WO2020193160A1 (en) 2019-03-27 2020-10-01 Dystar Colours Distribution Gmbh High wet fast disperse dye mixtures of n-[4-(5-thiocyanato-2,4-dinitro-phenylazo)-phenyl]-amine derivatives and n-[4-(4-nitro-phenylazo)-phenyl]-amine derivatives
US11479672B2 (en) 2019-03-27 2022-10-25 Dystar Colours Distribution Gmbh High wet fast disperse dye mixtures of N-[4-(5-thiocyanato-2,4-dinitro-phenylazo)-phenyl]-amine derivatives and N-[4-(4-nitro-phenylazo)-phenyl]-amine derivatives
US11560480B2 (en) 2019-03-27 2023-01-24 Dystar Colours Distribution Gmbh High wet fast disperse dye mixtures of N-[4-(5-fluoro-2,4-dinitro-phenylazo)-phenyl]-amine derivatives and N-[4-(4-nitro-phenylazo)-phenyl]-amine derivatives

Also Published As

Publication number Publication date
RU2006116739A (en) 2007-11-27
EP1678259B1 (en) 2016-08-17
JP2007509214A (en) 2007-04-12
US7358345B2 (en) 2008-04-15
ES2611945T3 (en) 2017-05-11
TW200523322A (en) 2005-07-16
KR20060123719A (en) 2006-12-04
US20070050928A1 (en) 2007-03-08
GB0324584D0 (en) 2003-11-26
TWI408176B (en) 2013-09-11
BRPI0415469A (en) 2006-12-19
EP1678259A2 (en) 2006-07-12
MXPA06002919A (en) 2006-05-31
CN1871306A (en) 2006-11-29
RU2376334C2 (en) 2009-12-20
HK1093351A1 (en) 2007-03-02
PT1678259T (en) 2016-11-21
CN100439450C (en) 2008-12-03
CA2543056A1 (en) 2005-05-06
WO2005040283A3 (en) 2005-06-30
KR101141572B1 (en) 2012-05-03

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