CN104508052A

CN104508052A - Metal-free reactive dyes, process for the production thereof and their use

Info

Publication number: CN104508052A
Application number: CN201380032386.8A
Authority: CN
Inventors: 汉·袁; 小天·王; 亨奎·金; 罗克森纳·巴贝鲁
Original assignee: Dystar Textilfarben GmbH and Co Deutschland KG
Current assignee: Dystar Textilfarben GmbH and Co Deutschland KG
Priority date: 2012-06-18
Filing date: 2013-06-13
Publication date: 2015-04-08
Also published as: WO2013189814A1; EP2904051A1; MX2014015540A; JP2015523436A; KR20150033612A; AU2013279553A1

Abstract

Metal-free reactive dyes, a process for the production thereof and their use are provided. The present invention relates to reactive dyes of the formula (I), in which A, B, a and K are defined as given in claim, a process for preparing them, and their use for dyeing and printing hydroxyl-, amino-, and/or carboxamido-containing materials.

Description

Metal-free reactive dyestuffs, and its preparation method and application

The present invention relates to the technical field of reactive dyestuffs, described reactive dyestuffs are used for comprising hydroxyl, amino, and/or the dyeing of the material of formamido group and stamp.

Metal-free reactive dyestuffs are well known in the prior art, can be used as tinting material and use in different applications, see such as US20030172476.

But, comprising hydroxyl, in the amino and/or dyeing of formamido group material and the background technology of stamp, existing metal-free dyestuff has many technological deficiencies, such as photostabilization is not good, and particularly in the restriction that realization has in the shade of good overall fastness, described shade is as intense violet color, Vandyke brown, navy blue and black.

Surprisingly, have now found that the dyestuff shown in formula (I) as described below is compared with known dye, demonstrates very superior performance.These performances comprise for more dark-toned high lifting force and high fastness, as the light fastness on above-mentioned materials and blend thereof, and washable and fastness to rubbing.Most importantly, the dyestuff shown in formula (I) is metal-free, therefore has excellent ecological performance and provides the extraordinary dyeing of levelling degree.

The present invention relates to dyestuff shown in formula (I) and composition thereof

wherein,

A is the group of diazonium structure division as described below;

B is the group of intermediate structure part as described below;

K is the group of coupled structures part as described below;

A is the integer of 0 ~ 1;

Generally, the dyestuff shown in general formula (I) comprises at least one active anchor;

Further, the present invention relates to all types of tautomer of dyestuff and geometrical isomer shown in formula (I),

A is the group shown in general formula (1a)

wherein,

R ¹~ R ³be independently separately, hydrogen, halogen, alkyl; N-amido, alkoxyl group, thio alkoxy, hydroxyl; cyano group, nitro, alkoxy carbonyl, alkoxy carbonyl; acyl group, Thioacyl, aroyl, trifluoromethyl; acyloxy, aryl acyloxy, cycloalkyl, aryl; heteroaryl, Heterocyclylalkyl, N-cinnyl is amino, SO ₃m or COOM;

Or the alkyl for being replaced by one or more substituting group, described substituting group is selected from the group be made up of following groups: hydroxyl, aryl, cycloalkyl, alkoxyl group, thio alkoxy, N, N, N-trialkyl ammonium, N, N, N-triaryl ammonium, the single aryl ammonium of N, N-dialkyl group-N-, N, N-diaryl-N-monoalkyl-ammonium, N-amido, N-cinnyl is amino, halogen, cyano group, SO ₃m, COOM nitro, acyl group, Thioacyl, alkyl sulphonyl, aroyl, trifluoromethyl, heteroaryl, Heterocyclylalkyl, alkoxy carbonyl, alkoxy carbonyl, acyloxy, aryl acyloxy;

Or be that described substituting group is selected from the group be made up of following groups: hydroxyl, aryl, cycloalkyl by one or more heteroatoms as oxygen or sulphur interrupt and the alkyl replaced by one or more substituting group, alkoxyl group, thio alkoxy, N, N, N-trialkyl ammonium, N, N, N-triaryl ammonium, the single aryl ammonium of N, N-dialkyl group-N-, N, N-diaryl-N-monoalkyl ammonium, N-amido, N-cinnyl is amino, halogen, cyano group, SO ₃m, COOM, nitro, acyl group, Thioacyl, alkyl sulphonyl, aroyl, trifluoromethyl, heteroaryl, Heterocyclylalkyl, alkoxy carbonyl, alkoxy carbonyl, acyloxy, aryl acyloxy;

Or be SO ₂-X, wherein X is vinyl or Ji Tuan – CH ₂cH ₂-Y, and Y is the group can left away in the basic conditions, as OSO ₃m, SSO ₃m, OCOCH ₃, OPO ₃m or halogen;

Or be general formula (2a), (2b) or the group shown in (2c)

Wherein,

R ⁴and R ⁷, be independently separately, hydrogen, halogen, alkyl, N-amido, alkoxyl group, thio alkoxy; hydroxyl, cyano group, alkoxy carbonyl, alkoxy carbonyl, acyl group, Thioacyl, aroyl, trifluoromethyl; acyloxy, aryl acyloxy, cycloalkyl, aryl, heteroaryl, Heterocyclylalkyl, SO ₃m or COOM;

Or the alkyl for being replaced by one or more substituting group, described substituting group is selected from the group be made up of following groups: hydroxyl, aryl, cycloalkyl, alkoxyl group, thio alkoxy, N-amido, halogen, cyano group, SO ₃m, COOM, nitro, acyl group, Thioacyl, alkyl sulphonyl, aroyl, trifluoromethyl, heteroaryl, Heterocyclylalkyl, alkoxy carbonyl, alkoxy carbonyl, acyloxy or aryl acyloxy;

Or be that described substituting group is selected from the group be made up of following groups: hydroxyl, aryl, cycloalkyl, alkoxyl group, thio alkoxy, N-amido, halogen, cyano group, SO by one or more heteroatoms as oxygen or sulphur interrupt and the alkyl replaced by one or more substituting group ₃m, COOM, nitro, acyl group, Thioacyl, alkyl sulphonyl, aroyl, trifluoromethyl, heteroaryl, Heterocyclylalkyl, alkoxy carbonyl, alkoxy carbonyl, acyloxy or aryl acyloxy;

R ⁵, R ⁶, R ⁸and R ¹², be independently separately, hydrogen, alkyl or aryl;

R ⁹~ R ¹¹, be independently separately, hydrogen, halogen, alkyl, alkoxyl group or SO ₃m;

B is the integer of 0 ~ 6;

C is the integer of 1 ~ 6;

When b and c is independently the integer of>=2 separately, R ⁴and R ⁷can be different group separately, but all should in above-mentioned defined identical group range;

D is 0 or 1;

RG is general formula (3a), (3b) or the active anchor shown in (3c);

Wherein,

R ¹⁴~ R ¹⁹, independent is separately halogen;

In addition, R ¹⁴also can be the group shown in formula (8a)

Wherein,

R ⁹⁶hydrogen, halogen, alkyl, alkoxyl group, thio alkoxy, hydroxyl, cycloalkyl, aryl, heteroaryl, Heterocyclylalkyl, SO ₃m or COOM;

R ¹³be selected from the group shown in one of general formula (4a) or (4b);

Wherein,

R ²⁰, R ²³and R ⁹⁴, be independently separately, hydrogen, alkyl, cycloalkyl or aryl;

R ²¹, R ²²and R ⁹⁵, be independently separately, hydrogen, halogen, alkyl, N-amido, alkoxyl group, thio alkoxy; hydroxyl, cyano group, alkoxy carbonyl, alkoxy carbonyl, acyl group, Thioacyl, aroyl, amino-sulfonyl; trifluoromethyl, acyloxy, aryl acyloxy, cycloalkyl, aryl, heteroaryl, Heterocyclylalkyl, SO ₃m or COOM;

In addition, R ⁹⁴ke Yi Shi – CH ₂cH ₂-SO ₂-X, wherein X is vinyl or Ji Tuan – CH ₂cH ₂-Y, wherein Y is the group can left away in the basic conditions, as OSO ₃m, SSO ₃m, OCOCH ₃, OPO ₃m or halogen;

In addition, R ⁹⁵can be-SO ₂-X, wherein X is identical with above-mentioned defined.

B is the group shown in general formula (5a)

Wherein,

R ²⁴~ R ²⁶, be independently separately, hydrogen, halogen, alkyl; N-amido, alkoxyl group, thio alkoxy, hydroxyl; cyano group, nitro, alkoxy carbonyl, alkoxy carbonyl; acyl group, Thioacyl, aroyl, trifluoromethyl; acyloxy, aryl acyloxy, cycloalkyl, aryl; heteroaryl, Heterocyclylalkyl, N-cinnyl is amino, SO ₃m or COOM;

Or the alkyl for being replaced by one or more substituting group, described substituting group is selected from the group be made up of following groups: hydroxyl, aryl, cycloalkyl, alkoxyl group, thio alkoxy, N, N, N-trialkyl ammonium, N, N, N-triaryl ammonium, the single aryl ammonium of N, N-dialkyl group-N-, N, N-diaryl-N-monoalkyl-ammonium, N-amido, N-cinnyl is amino, halogen, cyano group, SO ₃m, COOM, nitro, acyl group, Thioacyl, alkyl sulphonyl, aroyl, trifluoromethyl, heteroaryl, Heterocyclylalkyl, alkoxy carbonyl, alkoxy carbonyl, acyloxy, aryl acyloxy;

Or be the group shown in general formula (2a) or (2b)

Wherein R ⁴~ R ⁸, b, c and RG are identical with above-mentioned defined,

K is general formula (6a) or the group shown in (6b)

Wherein,

D is the group as shown in above-mentioned the general formula (1a) defined;

R ²⁷~ R ²⁹, be independently separately, hydrogen, halogen, alkyl; N-amido, alkoxyl group, thio alkoxy, hydroxyl, cyano group; nitro, alkoxy carbonyl, alkoxy carbonyl, urea groups, alkyl urea groups; phenyl urea groups, amino-sulfonyl, acyl group, Thioacyl, aroyl; trifluoromethyl, acyloxy, aryl acyloxy, formamyl, cycloalkyl; aryl, heteroaryl, Heterocyclylalkyl, N-cinnyl is amino, SO ₃m or COOM;

Or the alkyl for being replaced by one or more substituting group, described substituting group is selected from the group be made up of following groups: hydroxyl, aryl, cycloalkyl, alkoxyl group, thio alkoxy, N, N, N-trialkyl ammonium, N, N, N-triaryl ammonium, N, the single aryl ammonium of N-dialkyl group-N-, N, N-diaryl-N-monoalkyl ammonium, N-amido, N-cinnyl is amino, N-alkylsulfonyl-amino, urea groups, alkyl urea groups, phenyl urea groups, halogen, cyano group, SO ₃m, COOM, nitro, acyl group, Thioacyl, alkyl sulphonyl, aroyl, trifluoromethyl, heteroaryl, Heterocyclylalkyl, alkoxy carbonyl, alkoxy carbonyl, acyloxy, aryl acyloxy, formamyl, N-monocycle alkyl-carbamoyl, N-monoalkyl-amino formyl radical, N, N-bicyclic alkyl-formamyl, N, N-dialkyl-carbamoyl radicals, the mono-aryl-carbamoyl of N-, N, N-diaryl-formamyl, the single aryl-amino-carbonyl of N-monocycle alkyl-N-, the single aryl-carbamoyl of N-monoalkyl-N-, amino-sulfonyl, N-monocycle alkyl-amino-sulfonyl, N-monoalkyl-amino alkylsulfonyl, N, N-bicyclic alkyl-amino-sulfonyl, N, N-dialkyl-7-amino alkylsulfonyl, the mono-aryl-amino alkylsulfonyl of N-, N, N-diaryl-amino-sulfonyl, the single n-aryl sulfonyl of N-monocycle alkyl-N-or the single n-aryl sulfonyl of N-monoalkyl-N-,

Or be that described substituting group is selected from the group be made up of following groups: hydroxyl, aryl, cycloalkyl, alkoxyl group by one or more heteroatoms as oxygen or sulphur interrupt and the alkyl replaced by one or more substituting group, thio alkoxy, N, N, N-trialkyl ammonium, N, N, N-triaryl ammonium, N, the single aryl ammonium of N-dialkyl group-N-, N, N-diaryl-N-monoalkyl ammonium, N-amido, N-cinnyl is amino, N-alkylsulfonyl-amino, urea groups, alkyl urea groups, phenyl urea groups, halogen, cyano group, SO ₃m, COOM, nitro, acyl group, Thioacyl, alkyl sulphonyl, aroyl, trifluoromethyl, heteroaryl, Heterocyclylalkyl, alkoxy carbonyl, alkoxy carbonyl, acyloxy, aryl acyloxy, formamyl, N-monocycle alkyl-carbamoyl, N-monoalkyl-amino formyl radical, N, N-bicyclic alkyl-formamyl, N, N-dialkyl-carbamoyl radicals, the mono-aryl-carbamoyl of N-, N, N-diaryl-formamyl, the single aryl-amino-carbonyl of N-monocycle alkyl-N-, the single aryl-carbamoyl of N-monoalkyl-N-, amino-sulfonyl, N-monocycle alkyl-amino-sulfonyl, N-monoalkyl-amino alkylsulfonyl, N, N-bicyclic alkyl-amino-sulfonyl, N, N-dialkyl-7-amino alkylsulfonyl, the mono-aryl-amino alkylsulfonyl of N-, N, N-diaryl-amino-sulfonyl, the single n-aryl sulfonyl of N-monocycle alkyl-N-or the single n-aryl sulfonyl of N-monoalkyl-N-,

R ³⁰, R ³¹, R ⁷³and R ⁷⁴, be independently separately, hydrogen, alkyl, acyl group, Thioacyl, aroyl, cycloalkyl, aryl, heteroaryl, Heterocyclylalkyl or cinnamoyl;

Or the alkyl for being replaced by one or more substituting group, described substituting group is selected from the group be made up of following groups: hydroxyl, aryl, cycloalkyl, alkoxyl group, thio alkoxy, amino, N-monoalkyl-amino, N, N-dialkyl-7-amino, the mono-aryl-amino of N-, N, N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycle alkyl-amino, N, N-bicyclic alkyl-amino, N-monoalkyl-N-monocycle alkyl-amino, the mono-aryl of N--N-monocycle alkyl-amino, N, N, N-trialkyl ammonium, N, N, N-triaryl ammonium, N, the single aryl ammonium of N-dialkyl group-N-, N, N-diaryl-N-monoalkyl ammonium, N-amido, N-cinnyl is amino, N-alkylsulfonyl-amino, urea groups, alkyl urea groups, phenyl urea groups, halogen, cyano group, SO ₃m, COOM, nitro, acyl group, Thioacyl, alkyl sulphonyl, aroyl, trifluoromethyl, heteroaryl, Heterocyclylalkyl, alkoxy carbonyl, alkoxy carbonyl, acyloxy, aryl acyloxy, formamyl, N-monocycle alkyl-carbamoyl, N-monoalkyl-amino formyl radical, N, N-bicyclic alkyl-formamyl, N, N-dialkyl-carbamoyl radicals, the mono-aryl-carbamoyl of N-, N, N-diaryl-formamyl, the single aryl-amino-carbonyl of N-monocycle alkyl-N-, the single aryl-carbamoyl of N-monoalkyl-N-, amino-sulfonyl, N-monocycle alkyl-amino-sulfonyl, N-monoalkyl-amino alkylsulfonyl, N, N-bicyclic alkyl-amino-sulfonyl, N, N-dialkyl-7-amino alkylsulfonyl, the mono-aryl-amino alkylsulfonyl of N-, N, N-diaryl-amino-sulfonyl, the single n-aryl sulfonyl of N-monocycle alkyl-N-or the single n-aryl sulfonyl of N-monoalkyl-N-,

Or be as oxygen or sulphur interrupt and the alkyl replaced by one or more substituting group by one or more heteroatoms, described substituting group is selected from the group be made up of following groups: hydroxyl, aryl, cycloalkyl, alkoxyl group, thio alkoxy, amino, N-monoalkyl-amino, N, N-dialkyl-7-amino, the mono-aryl-amino of N-, N, N-diaryl-amino, N-alkyl-N-aryl-amino, N-monocycle alkyl-amino, N, N-bicyclic alkyl-amino, N-monoalkyl-N-monocycle alkyl-amino, the mono-aryl of N--N-monocycle alkyl-amino, N, N, N-trialkyl ammonium, N, N, N-triaryl ammonium, N, the single aryl ammonium of N-dialkyl group-N-, N, N-diaryl-N-monoalkyl ammonium, N-amido, N-cinnyl is amino, N-alkylsulfonyl-amino, urea groups, alkyl urea groups, phenyl urea groups, halogen, cyano group, SO ₃m, COOM, nitro, acyl group, Thioacyl, alkyl sulphonyl, aroyl, trifluoromethyl, heteroaryl, Heterocyclylalkyl, alkoxy carbonyl, alkoxy carbonyl, acyloxy, aryl acyloxy, formamyl, N-monocycle alkyl-carbamoyl, N-monoalkyl-amino formyl radical, N, N-bicyclic alkyl-formamyl, N, N-dialkyl-carbamoyl radicals, the mono-aryl-carbamoyl of N-, N, N-diaryl-formamyl, the single aryl-amino-carbonyl of N-monocycle alkyl-N-, the single aryl-carbamoyl of N-monoalkyl-N-, amino-sulfonyl, N-monocycle alkyl-amino-sulfonyl, N-monoalkyl-amino alkylsulfonyl, N, N-bicyclic alkyl-amino-sulfonyl, N, N-dialkyl-7-amino alkylsulfonyl, the mono-aryl-amino alkylsulfonyl of N-, N, N-diaryl-amino-sulfonyl, the single n-aryl sulfonyl of N-monocycle alkyl-N-or the single n-aryl sulfonyl of N-monoalkyl-N-,

Or be active anchor RG, wherein RG is identical with above-mentioned defined;

Or be the group shown in general formula (7a)

Wherein,

RG is identical with above-mentioned defined;

R ³²hydrogen, halogen, alkyl, N-amido, alkoxyl group, thio alkoxy, hydroxyl, cyano group, alkoxy carbonyl, alkoxy carbonyl, acyl group, Thioacyl, aroyl, trifluoromethyl, acyloxy, aryl acyloxy, cycloalkyl, aryl, heteroaryl, Heterocyclylalkyl, SO ₃m or COOM;

R ³³hydrogen, alkyl or aryl;

E is the integer of 1 ~ 6; And when e>=2, according to above-mentioned defined group implication, R within the scope of this ³²it can be different groups.

The alkyl occurred in the application can be straight chain or side chain, and is (C ₁-C ₁₂)-alkyl, preferably (C ₁-C ₈)-alkyl, such as normal-butyl, isobutyl-, n-pentyl, isopentyl, n-hexyl, 2-ethylhexyl, sec-butyl, the tertiary butyl and methyl butyl.

Same logic is suitable for alkoxyl group and thio alkoxy, accordingly alkoxyl group preferably (C ₁-C ₈)-alkoxyl group, such as methoxyl group and oxyethyl group, thio alkoxy is (C preferably ₁-C ₈)-thio alkoxy, such as-SCH ₃or-SC ₂h ₅.

Cycloalkyl is (C preferably ₃-C ₈)-cycloalkyl, particularly preferably cyclopentyl and cyclohexyl.In order to the object of the application, term cycloalkyl comprises substituted cycloalkyl and unsaturated cycloalkyl.This type of cycloalkyl preferred is cyclopentyl.Preferred substituting group is alkyl, hydroxyalkyl, halogen, hydroxyl; alkoxyl group, acyl group, cyano group, nitro; amino, alkyl monosubstituted amino, dialkyl amido; single (hydroxyalkyl) is amino, and two (hydroxyalkyl) is amino, and monoalkyl-mono-(hydroxyalkyl) is amino; formamyl, amino-sulfonyl, amido; urea groups, aminosulfonylamino, alkoxy carbonyl and acyloxy.

The preferred phenyl or naphthyl of the aryl occurred in the application.Term phenyl and naphthyl comprise phenyl that is unsubstituted and that replace and naphthyl.Preferred substituting group is alkyl, cycloalkyl, Heterocyclylalkyl, hydroxyalkyl; halogen, hydroxyl, alkoxyl group, alkylthio; acyl group, nitro, cyano group, amino; alkyl monosubstituted amino, dialkyl amido, single (hydroxyalkyl) is amino, and two (hydroxyalkyl) is amino; monoalkyl-mono-(hydroxyalkyl) is amino, formamyl, amino-sulfonyl, amido; urea groups, aminosulfonylamino, alkoxy carbonyl and acyloxy.

The preferred pyridine of the heteroaryl occurred in the application, pyrimidine, pyridazine, pyrazine, pyrroles, imidazoles, pyrazoles, 1,2,4-thiadiazoles, 1,2,4-triazole, tetrazolium, thiophene, thiazole, isothiazole, benzothiazole, benzisothiazole, 1,3,4-thiadiazoles, furans, oxazole, benzoxazoles or isoxzzole.Term heteroaryl comprises above-mentioned group that is unsubstituted and replacement form.Preferred substituting group is alkyl, hydroxyalkyl, halogen, hydroxyl; alkoxyl group, alkylthio, acyl group, nitro; cyano group, amino, alkyl monosubstituted amino, dialkyl amido; single (hydroxyalkyl) is amino, and two (hydroxyalkyl) is amino, and monoalkyl-mono-(hydroxyalkyl) is amino; formamyl, amino-sulfonyl, amido; urea groups, aminosulfonylamino, alkoxy carbonyl and acyloxy.

Heterocyclylalkyl preferred tetramethyleneimine, piperidines, morpholine, tetrahydrofuran (THF) or piperazine.Term Heterocyclylalkyl comprises above-mentioned group that is unsubstituted and replacement form.Preferred substituting group is alkyl, hydroxyalkyl, halogen, hydroxyl; alkoxyl group, alkylthio, acyl group, nitro; cyano group, amino, alkyl monosubstituted amino, dialkyl amido; single (hydroxyalkyl) is amino, and two (hydroxyalkyl) is amino, and monoalkyl-mono-(hydroxyalkyl) is amino; formamyl, amino-sulfonyl, amido; amino carbonyl amino, aminosulfonylamino, alkoxy carbonyl and acyloxy.

Halogen preferred chlorine, bromine or fluorine.

The preferred hydrogen of M, lithium, sodium, potassium, ammonium or list, two, three or four (C ₁-C ₄)-alkylammonium, the alkaline-earth metal of monovalent equivalence, or monovalence organic cation.

The particularly preferred dyestuff of the present invention is dyestuff shown in formula (Ia) and composition thereof

Wherein,

R ³⁴~ R ³⁶, be independently separately, hydrogen, halogen, alkyl; N-amido, alkoxyl group, thio alkoxy, hydroxyl; cyano group, nitro, alkoxy carbonyl, alkoxy carbonyl; acyl group, Thioacyl, aroyl, trifluoromethyl; acyloxy, aryl acyloxy, cycloalkyl, aryl; heteroaryl, Heterocyclylalkyl, N-cinnyl is amino, SO ₃m or COOM;

Or the alkyl for being replaced by one or more substituting group, described substituting group is selected from the group be made up of following groups: hydroxyl, aryl, cycloalkyl; alkoxyl group, thio alkoxy, N, N; N-trialkyl ammonium, N, N, N-triaryl ammonium; the single aryl ammonium of N, N-dialkyl group-N-, N, N-diaryl-N-monoalkyl-ammonium; N-amido, N-cinnyl is amino, N-alkylsulfonyl-amino; halogen, cyano group, SO ₃m, COOM, nitro, acyl group, Thioacyl, alkyl sulphonyl, aroyl, trifluoromethyl, heteroaryl, Heterocyclylalkyl, alkoxy carbonyl, alkoxy carbonyl, acyloxy, aryl acyloxy;

Or be that described substituting group is selected from the group be made up of following groups: hydroxyl, aryl, cycloalkyl by one or more heteroatoms as oxygen or sulphur interrupt and the alkyl replaced by one or more substituting group; alkoxyl group, thio alkoxy, N, N; N-trialkyl ammonium, N, N, N-triaryl ammonium; the single aryl ammonium of N, N-dialkyl group-N-, N, N-diaryl-N-monoalkyl-ammonium; N-amido, N-cinnyl is amino, N-alkylsulfonyl-amino; halogen, cyano group, SO ₃m, COOM, nitro, acyl group, Thioacyl, alkyl sulphonyl, aroyl, trifluoromethyl, heteroaryl, Heterocyclylalkyl, alkoxy carbonyl, alkoxy carbonyl, acyloxy, aryl acyloxy;

Or for as above-mentioned the general formula (2a) defined, (2b) or the group shown in (2c);

R ³⁷and R ³⁸, be independently separately, hydrogen, alkyl, acyl group, Thioacyl, aroyl, cycloalkyl, aryl, heteroaryl, Heterocyclylalkyl or cinnamoyl;

Or be active anchor RG, wherein RG is identical with above-mentioned defined;

Or be the group as shown in above-mentioned the general formula (7a) defined.

In the dyestuff shown in particularly preferred general formula (Ia),

R ³⁴~ R ³⁶, independent is separately hydrogen, (C ₁-C ₄) alkyl, (C ₁-C ₄) alkoxyl group, halogen, acyl group or SO ₃m;

Or be SO ₂-X, wherein X is vinyl or Ji Tuan – CH ₂cH ₂-Y, and Y is the group can left away in the basic conditions, as OSO ₃m;

Huo Wei – NH-RG, wherein RG is identical with above-mentioned defined;

Huo Wei – (CH ₂) _f-NH-RG, wherein f is the integer of 1 ~ 3, and RG is identical with above-mentioned defined;

R ³⁷and R ³⁸, independent is separately hydrogen, alkyl, aryl, sulfonymethyl, acyl group or aroyl;

Or be active anchor RG, wherein RG is identical with above-mentioned defined;

Huo Wei – (CH ₂) _g-NH-RG, wherein g is the integer of 1 ~ 3, and RG is identical with above-mentioned defined.

The present invention further preferred dyestuff is dyestuff shown in general formula (Ib) and composition thereof

Wherein

R ³⁹~ R ⁴⁴, be independently separately, hydrogen, halogen, alkyl; N-amido, alkoxyl group, thio alkoxy, hydroxyl; cyano group, nitro, alkoxy carbonyl, alkoxy carbonyl; acyl group, Thioacyl, aroyl, trifluoromethyl; acyloxy, aryl acyloxy, cycloalkyl, aryl; heteroaryl, Heterocyclylalkyl, N-cinnyl is amino, SO ₃m or COOM;

Or be the group as shown in above-mentioned the general formula (2a) that defines or (2b);

In addition, R ³⁹~ R ⁴¹, can be independently the group as shown in above-mentioned the general formula (2c) defined separately;

R ⁴⁵and R ⁴⁶, independent is separately hydrogen, alkyl, acyl group, Thioacyl, aroyl, cycloalkyl, aryl, heteroaryl, Heterocyclylalkyl or cinnamoyl;

Or be active anchor RG, wherein RG is identical with above-mentioned defined;

Or be the group as shown in above-mentioned the general formula (7a) defined.

In the dyestuff shown in particularly preferred general formula (Ib),

R ³⁹~ R ⁴⁴, be independently separately, hydrogen, (C ₁-C ₄) alkyl, (C ₁-C ₄) alkoxyl group, halogen, acyl group or SO ₃m;

Huo Wei – NH-RG, wherein RG is identical with above-mentioned defined;

Huo Wei – (CH ₂) _h-NH-RG, wherein h is the integer of 1 ~ 3, and RG is identical with above-mentioned defined;

R ⁴⁵and R ⁴⁶, be independently separately, hydrogen, alkyl, aryl, sulfonymethyl, acyl group or aroyl;

Or be active anchor RG, wherein RG is identical with above-mentioned defined;

Huo Wei – (CH ₂) _i-NH-RG, wherein i is the integer of 1 ~ 3, and RG is identical with above-mentioned defined.

The present invention further preferred dyestuff is dyestuff shown in general formula (Ic) and composition thereof

Wherein,

J is 0 or 1;

R ⁴⁷~ R ⁴⁹, be independently separately, hydrogen, halogen, alkyl; N-amido, alkoxyl group, thio alkoxy, hydroxyl; cyano group, nitro, alkoxy carbonyl, alkoxy carbonyl; acyl group, Thioacyl, aroyl, trifluoromethyl; acyloxy, aryl acyloxy, cycloalkyl, aryl; heteroaryl, Heterocyclylalkyl, N-cinnyl is amino, SO ₃m or COOM;

R ⁵⁰and R ⁵¹, be independently separately, hydrogen, alkyl, acyl group, Thioacyl, aroyl, cycloalkyl, aryl, heteroaryl, Heterocyclylalkyl or cinnamoyl;

Or be active anchor RG, wherein RG is identical with above-mentioned defined;

Or be the group as shown in above-mentioned the general formula (7a) defined.

In the dyestuff shown in particularly preferred general formula (Ic),

R ⁴⁷~ R ⁴⁹, independent is separately hydrogen, (C ₁-C ₄) alkyl, (C ₁-C ₄) alkoxyl group, halogen, acyl or SO ₃m;

Huo Wei – NH-RG, wherein RG is identical with above-mentioned defined;

Huo Wei – (CH ₂) _k-NH-RG, wherein k is the integer of 1 ~ 3, and RG is identical with above-mentioned defined;

R ⁵⁰and R ⁵¹, independent is separately hydrogen, alkyl, aryl, sulfonymethyl, acyl group or aroyl;

Or be active anchor RG, wherein RG is identical with above-mentioned defined;

Huo Wei – (CH ₂) _m-NH-RG, wherein m is the integer of 1 ~ 3, and RG is identical with above-mentioned defined.

The present invention further preferred dyestuff is dyestuff shown in general formula (Id) and composition thereof:

Wherein,

N is 0 or 1

R ⁵²~ R ⁵⁷, be independently separately, hydrogen, halogen, alkyl; N-amido, alkoxyl group, thio alkoxy, hydroxyl; cyano group, nitro, alkoxy carbonyl, alkoxy carbonyl; acyl group, Thioacyl, aroyl, trifluoromethyl; acyloxy, aryl acyloxy, cycloalkyl, aryl; heteroaryl, Heterocyclylalkyl, N-cinnyl is amino, SO ₃m or COOM;

In addition, R ⁵²~ R ⁵⁴, can be independently the group as shown in above-mentioned the general formula (2c) defined separately;

R ⁵⁸and R ⁵⁹, independent is separately hydrogen, alkyl, acyl group, Thioacyl, aroyl, cycloalkyl, aryl, heteroaryl, Heterocyclylalkyl or cinnamoyl;

Or be active anchor RG, wherein RG is identical with above-mentioned defined;

Or be the group as shown in above-mentioned the general formula (7a) defined.

In the dyestuff shown in particularly preferred general formula (Id),

R ⁵²~ R ⁵⁷, be independently separately, hydrogen, (C ₁-C ₄) alkyl, (C ₁-C ₄) alkoxyl group, halogen, acyl group or SO ₃m;

Huo Wei – NH-RG, wherein RG is identical with above-mentioned defined;

Huo Wei – (CH ₂) _p-NH-RG, wherein p is the integer of 1 ~ 3, and RG is identical with above-mentioned defined;

R ⁵⁸and R ⁵⁹, be independently separately, hydrogen, alkyl, aryl, sulfonymethyl, acyl group or aroyl;

Or be active anchor RG, wherein RG is identical with above-mentioned defined;

Huo Wei – (CH ₂) _q-NH-RG, wherein q is the integer of 1 ~ 3, and RG is identical with above-mentioned defined.

The present invention further preferred dyestuff is dyestuff shown in general formula (Ie) and composition thereof:

Wherein,

R ⁶⁰, R ⁶¹and R ⁶², be independently separately, hydrogen, halogen, alkyl; N-amido, alkoxyl group, thio alkoxy, hydroxyl; cyano group, nitro, alkoxy carbonyl, alkoxy carbonyl; acyl group, Thioacyl, aroyl, trifluoromethyl; acyloxy, aryl acyloxy, cycloalkyl, aryl; heteroaryl, Heterocyclylalkyl, N-cinnyl is amino, SO ₃m or COOM;

R ⁶³and R ⁶⁴, independent is separately hydrogen, alkyl, acyl group, Thioacyl, aroyl, cycloalkyl, aryl, heteroaryl, Heterocyclylalkyl or cinnamoyl;

Or be active anchor RG, wherein RG is identical with above-mentioned defined;

Or be the group as shown in above-mentioned the general formula (7a) defined.

In the dyestuff shown in particularly preferred general formula (Ie),

R ⁶⁰~ R ⁶², be independently separately, hydrogen, (C ₁-C ₄) alkyl, (C ₁-C ₄) alkoxyl group, halogen, acyl group or SO ₃m;

Huo Wei – NH-RG, wherein RG is identical with above-mentioned defined;

Huo Wei – (CH ₂) _r-NH-RG, wherein r is the integer of 1 ~ 3, and RG is identical with above-mentioned defined;

R ⁶³and R ⁶⁴, be independently separately, hydrogen, alkyl, aryl, sulfonymethyl, acyl group or aroyl;

Or be active anchor RG, wherein RG is identical with above-mentioned defined;

Huo Wei – (CH ₂) _s-NH-RG, wherein s is the integer of 1 ~ 3, and RG is identical with above-mentioned defined.

The present invention further preferred dyestuff is dyestuff shown in general formula (If) and composition thereof:

Wherein,

R ⁶⁵~ R ⁷⁰, be independently separately, hydrogen, halogen, alkyl; N-amido, alkoxyl group, thio alkoxy, hydroxyl; cyano group, nitro, alkoxy carbonyl, alkoxy carbonyl; acyl group, Thioacyl, aroyl, trifluoromethyl; acyloxy, aryl acyloxy, cycloalkyl, aryl; heteroaryl, Heterocyclylalkyl, N-cinnyl is amino, SO ₃m or COOM;

In addition, R ⁶⁵~ R ⁶⁷, can be independently the group as shown in above-mentioned the general formula (2c) defined separately;

R ⁷¹and R ⁷², be independently separately, hydrogen, alkyl, acyl group, Thioacyl, aroyl, cycloalkyl, aryl, heteroaryl, Heterocyclylalkyl or cinnamoyl;

Or be active anchor RG, wherein RG is identical with above-mentioned defined;

Or be the group as shown in above-mentioned the general formula (7a) defined.

In the dyestuff shown in particularly preferred general formula (If),

R ⁶⁵~ R ⁷⁰, be independently separately, hydrogen, (C ₁-C ₄) alkyl, (C ₁-C ₄) alkoxyl group, halogen, acyl group or SO ₃m;

Huo Wei – NH-RG, wherein RG is identical with above-mentioned defined;

Huo Wei – (CH ₂) _t-NH-RG, wherein t is the integer of 1 ~ 3, and RG is identical with above-mentioned defined;

R ⁷¹and R ⁷², be independently separately, hydrogen, alkyl, aryl, sulfonymethyl, acyl group or aroyl;

Or be active anchor RG, wherein RG is identical with above-mentioned defined;

Huo Wei – (CH ₂) _u-NH-RG, wherein u is the integer of 1 ~ 3, and RG is identical with above-mentioned defined.

The present invention further preferred dyestuff is dyestuff shown in general formula (Ig) and composition thereof:

Wherein,

R ⁷⁵~ R ⁸⁰, be independently separately, hydrogen, halogen, alkyl; N-amido, alkoxyl group, thio alkoxy, hydroxyl; cyano group, nitro, alkoxy carbonyl, alkoxy carbonyl; acyl group, Thioacyl, aroyl, trifluoromethyl; acyloxy, aryl acyloxy, cycloalkyl, aryl; heteroaryl, Heterocyclylalkyl, N-cinnyl is amino, SO ₃m or COOM;

R ⁸¹and R ⁸², be independently separately, hydrogen, alkyl, acyl group, Thioacyl, aroyl, cycloalkyl, aryl, heteroaryl, Heterocyclylalkyl or cinnamoyl;

Or be active anchor RG, wherein RG is identical with above-mentioned defined;

Or be the group as shown in above-mentioned the general formula (7a) defined.

In the dyestuff shown in particularly preferred general formula (Ig),

R ⁷⁵~ R ⁸⁰, be independently separately, hydrogen, (C ₁-C ₄) alkyl, (C ₁-C ₄) alkoxyl group, halogen, acyl group or SO ₃m;

Huo Wei – NH-RG, wherein RG is identical with above-mentioned defined;

Huo Wei – (CH ₂) _v-NH-RG, wherein v is the integer of 1 ~ 3, and RG is identical with above-mentioned defined;

R ⁸¹and R ⁸², be independently separately, hydrogen, alkyl, aryl, sulfonymethyl, acyl group or aroyl;

Or be active anchor RG, wherein RG is identical with above-mentioned defined;

Huo Wei – (CH ₂) _w-NH-RG, wherein w is the integer of 1 ~ 3, and RG is identical with above-mentioned defined.

The present invention further preferred dyestuff is dyestuff shown in general formula (Ih) and composition thereof:

Wherein,

R ⁸³~ R ⁹¹, be independently separately, hydrogen, halogen, alkyl; N-amido, alkoxyl group, thio alkoxy, hydroxyl; cyano group, nitro, alkoxy carbonyl, alkoxy carbonyl; acyl group, Thioacyl, aroyl, trifluoromethyl; acyloxy, aryl acyloxy, cycloalkyl, aryl; heteroaryl, Heterocyclylalkyl, N-cinnyl is amino, SO ₃m or COOM;

In addition, R ⁸³, R ⁸⁴, R ⁸⁵, R ⁸⁹, R ⁹⁰and R ⁹¹, can be independently the group as shown in above-mentioned the general formula (2c) defined separately;

R ⁹²and R ⁹³, be independently separately, hydrogen, alkyl, acyl group, Thioacyl, aroyl, cycloalkyl, aryl, heteroaryl, Heterocyclylalkyl or cinnamoyl;

Or be active anchor RG, wherein RG is identical with above-mentioned defined;

Or be the group as shown in above-mentioned the general formula (7a) defined.

In the dyestuff shown in particularly preferred general formula (Ih),

R ⁸³~ R ⁹¹, be independently separately, hydrogen, (C ₁-C ₄) alkyl, (C ₁-C ₄) alkoxyl group, halogen, acyl group or SO ₃m;

Huo Wei – NH-RG, wherein RG is identical with above-mentioned defined;

Huo Wei – (CH ₂) _x-NH-RG, wherein x is the integer of 1 ~ 3, and RG is identical with above-mentioned defined;

R ⁹²and R ⁹³, be independently separately, hydrogen, alkyl, aryl, sulfonymethyl, acyl group or aroyl;

Or be active anchor RG, wherein RG is identical with above-mentioned defined;

Huo Wei – (CH ₂) _y-NH-RG, wherein y is the integer of 1 ~ 3, and RG is identical with above-mentioned defined.

The example of dyestuff shown in preferred formula (Ia) ~ (Ih) is Compound I listed in table 1 below ¹~ I ¹⁴⁰, and there is the structure shown in general formula (I ').

* refers to when a is 1, other tie points of B.

Present invention also offers the preparation method of dyestuff shown in formula (I).Described method comprises

Shown in formula (II), the diazotization of compound, reacts the compound shown in the diazonium salt of corresponding gained and formula K to obtain the intermediate shown in general formula (III).

In further step, diazo component (A-NH ₂) by diazotization, and be coupled in intermediate III to obtain the azoic dyestuff product shown in general formula (IV).

In addition, diazo component (A-NH ₂) by diazotization, and compound (B-NH can be coupled to ₂) on to obtain intermediate (V).Further, intermediate (V) by diazotization, and is coupled on compound (III) to obtain the trisazo dye product shown in general formula (VI).

Described diazotization reaction, under normal circumstances, implement by diazotization means well known by persons skilled in the art, preferably pass through to use Sodium Nitrite or nitrosyl-sulfuric acid in acidic medium, described acidic medium uses mineral acid example hydrochloric acid, sulfuric acid or phosphoric acid or their mixture, or organic acid is as acetic acid or propionic acid or their mixture.Mineral acid and organic acid mixture also can be advantageously used.

Described linked reaction is generally implemented by currently known methods.

Formula A-NH ₂, B-NH ₂, the compound shown in K is known and commercially available, or synthesizes by conventional chemical reaction method well known by persons skilled in the art.

Final product also optionally can carry out vinylation reaction.For example, by vinylation reactive group as β-sulfatoethylsulfonyl changes into the form of its vinyl.Such reaction is well known by persons skilled in the art.This type of reaction usually in neutrality in alkaline medium, in temperature such as 20 ~ 80 DEG C, pH carries out under the condition of such as 7 ~ 14.

Dyestuff shown in formula (I) is fiber-reactive, comprises fiber-reactive functional group.Fiber-reactive functional group refer to can with the hydroxyl of cellulose materials, amino in wool and silk, carboxyl, the group of hydroxyl and thiol group reaction, or can with the amino of synthesizing polyamides and the carboxyl reaction that may contain thereof to form the group of covalent chemical bond.

Dyestuff of the present invention, by being used in the large metering method described in reactive dyestuff field, is applicable to natural, produces regeneration, modification or synthesis comprise hydroxyl, hydroxyl, and/or the filamentary material of formamido group and the dyeing of blend thereof and stamp.Therefore, present invention also offers a kind of for above-mentioned filamentary material and the dyeing of blend thereof and the method for stamp, wherein used according to dyestuff of the present invention or dye mixture.

The example of natural fiber material as above is vegetable fibre, such as seed hair, i.e. cotton, kapok, coir fibre; Phloem fiber, i.e. cotton, flax, hemp, jute, bluish dogbane, ramie, rattan; Leaf fibres, i.e. sisal hemp, henequen, banana fiber; Stalk fibre, i.e. bamboo fibers; From the fiber of animal, as wool, silk, cashmere wool, Aloysia gratissima alpaca fiber, mohair, Angola's hair fibre and fur and leather substance.

That produce is cellulosic fibre with Example fibers that is that produce regeneration, if paper fiber and tModified Cellulose Fibers are as viscose rayon fibers, and acetic ester and triacetate fiber and Lyocell fibers.

The example of composite fibre materials as above is nylon material, as nylon-6, and nylon-6 .6 and aramid fiber.

The above-mentioned base material carrying out dyeing can be various forms of, is such as but not limited to yarn, woven fabric, becomes ring braided fabric or carpet.

Dyestuff of the present invention and salt thereof or mixture can be used as single dye product and use in dyeing or printing technology, or in dyeing or stamp composition, it can be a part for two/tri-or polycomponent mixing prod.

Dyestuff of the present invention and salt thereof or mixture and other known and/or commercially available dyestuff highly compatibles, and they can use to obtain the same good particular shade of color of technical feature with this type of dyestuff together.Technical feature comprises lifting force, fixing property and equalization.

Water-soluble very good due to dyestuff according to the present invention, they can also advantageously use in the continuous dyeing process of routine.

Dyestuff of the present invention can also be used for digital printing technique, particularly digital textile printing.The water color ink comprising dyestuff of the present invention for digital printing forms a part for present subject matter equally.

Based on the gross weight of ink, in ink of the present invention, the preferred 0.1wt% ~ 50wt% of the content of dyestuff of the present invention, is more preferably 1wt% ~ 30wt%, most preferably 1wt% ~ 15wt%.

Described ink, and dyestuff of the present invention possibility, if needed, comprise further dyestuff for digital printing.

For the ink of the present invention used in continuous flow technique, by adding ionogen, to arrange specific conductivity be 0.5 ~ 25mS/m.The ionogen be suitable for comprises such as lithium nitrate and saltpetre.Ink of the present invention can comprise the organic solvent based on total amount 1wt% ~ 50wt%, preferred 5wt% ~ 30wt%.The organic solvent such as alcohols be applicable to, as methyl alcohol, ethanol, 1-propyl alcohol, Virahol, n-butyl alcohol, the trimethyl carbinol, amylalcohol, polyhydric alcohols as: 1, 2-ethylene glycol, 1, 2, 3-glycerol, butyleneglycol, 1, 3-butyleneglycol, 1, 4-butyleneglycol, 1, 2-propylene glycol, 2, ammediol, pentanediol, 1, 4-pentanediol, 1, 5-pentanediol, hexylene glycol, D, L-1, 2-hexylene glycol, 1, 6-hexylene glycol, 1, 2, 6-hexanetriol, 1, 2-ethohexadiol, polyalkylene glycols, such as: polyoxyethylene glycol, polypropylene glycol, there is the aklylene glycol of 1 ~ 8 alkylidene group, such as: monoethylene glycol, glycol ether, triglycol, Tetraglycol 99, thioglycol, thiodiglycol, butyltriglycol, hexylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, the low alkyl oxide of polyvalent alcohol, such as: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diglycol monotertiary hexyl ether, triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, Tripropylene glycol monomethyl Ether, Tetraglycol 99 monobutyl ether, tetraethylene glycol dimethyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol monobutyl ether, tripropylene glycol isopropyl ether, polyalkylene glycol ethers class, such as: poly glycol monomethyl ether, Polypropylene Glycol Glycerin Ether, polyoxyethylene glycol tridecyl ether, polyethylene glycol nonylphenyl ether, amine, such as: methylamine, ethamine, triethylamine, diethylamine, dimethylamine, Trimethylamine 99, dibutylamine, diethanolamine, trolamine, N-acetyl ethanolamine, N-formyl thanomin, quadrol, urea derivatives, such as: urea, thiocarbamide, N-MU, N, N'-ε dimethyl urea, ethylidene-urea, 1, 1, 3, 3-tetramethyl-urea, amides, such as: dimethyl formamide, N,N-DIMETHYLACETAMIDE, ethanamide, ketone or ketols, such as: acetone, diacetone alcohol, cyclic ethers class, such as: tetrahydrofuran (THF), trimethylolethane, TriMethylolPropane(TMP), butoxy ethanol, phenylcarbinol, butoxy ethanol, gamma-butyrolactone, ε-caprolactam, be tetramethylene sulfone further, dimethylsulfolane, methyl sulfolane, 2, 4-dimethylsulfolane, dimethyl sulfone, butadiene sulfone, methyl-sulphoxide, dibutyl sulfoxide, N-cyclohexyl pyrrolidone, METHYLPYRROLIDONE, N-ethyl pyrrolidone, 2-Pyrrolidone, 1-(2-hydroxyethyl)-2-Pyrrolidone, 1-(3-hydroxypropyl)-2-Pyrrolidone, 1, 3-dimethyl-2-imidazolidone, 1, 3-dimethyl-2-imidazolinone, 1, 3-dimethoxy-methyl imidazolidine, 2-(2-methoxy ethoxy) ethanol, 2-(2-ethoxy ethoxy) ethanol, 2-(2-Butoxyethoxy) ethanol, 2-(2-propoxy-oxyethyl group) ethanol, pyridine, piperidines, 1, 3-dimethyl-2-imidazolidone, butyrolactone, trimethyl propane, 1, 2-Propanal dimethyl acetal, dioxan ethyl acetate, ethylenediamine tetraacetic acid (EDTA) ethyl pentyl group ether, 1, 2-Propanal dimethyl acetal and trimethyl propane.

Ink of the present invention can comprise conventional additive further, such as viscosity modifier with adjusting viscosity at 20 ~ 50 DEG C in the scope of 1.5 ~ 40.0mPas.Preferred ink has the viscosity of 1.5 ~ 20mPas, and particularly preferably ink has the viscosity of 1.5 ~ 15mPas.

The viscosity modifier be suitable for comprises rheologic additive, such as: Polyvinylcaprolactame, and polyvinylpyrrolidone and their copolymer polyether polyol, associative thickener, polyureas, urethane, sodium alginate, modified galactomannans, polyethers urea, urethane, nonionic cellulose ether.

As further additive, ink of the present invention can comprise surfactant with reconciliation statement surface tension for 20 ~ 65mN/m, and a kind of function if necessary as technique used (heat or piezo technology) uses.The surfactant be suitable for comprises such as all tensio-active agents, preferred nonionic surfactants, butyldiglycol and 1,2-hexylene glycol.

Ink of the present invention can comprise conventional additive further, the material of such as Antifungi and bacterial growth, and its content is 0.01wt% ~ 1wt% based on the gross weight of ink.

Described ink is prepared by the usual manner each component mixed in water.

Ink of the present invention is specially adapted to ink-jet printed technique, for the material of stamp polytype material, particularly wool and tynex.

The following examples are for illustration of the present invention.Except as otherwise noted, number and per-cent are all by weight.The relation that relation between parts by weight and volume parts is kilogram and rises.

Embodiment 1

I) 6.2 parts of sulfuric acid lists-[2-(2-phenyl amino-ethylsulfonyl)-ethyl] ester is suspended in 70 parts of water.Add 14 parts of sodium bicarbonates.With ice, reaction vessel is cooled to 0 ~ 5 DEG C.Add 3.8 parts of cyanuric chlorides.Reaction is temperature 0 ~ 5 DEG C, and pH stirs 3h under the condition of 4 ~ 4.5.Afterwards, add 4.8 parts of 7-amino-4-hydroxy naphthalene-2-sulfonic acids, and regulate pH to 6 ~ 6.5 with 15% soda solution.Reaction stirs 2h under envrionment temperature and pH6 ~ 6.5 condition.Products therefrom (a) is directly used in next step without separation.

Ii) 6.7 parts of 4-amino-5-hydroxyl naphthalene-2,7-disulfonic acid are added in 70 parts of water.PH to 5 ~ 6 are regulated with 15% soda solution.With ice, reaction vessel is cooled to 0 ~ 5 DEG C.4.3mL 5M sodium nitrite solution is added in reaction mixture.After stirring 10min, add 20.7 part of 37% hydrochloric acid.Reaction stirs 0.5h at 0 ~ 5 DEG C, then adds 0.2 part of thionamic acid.

The solution of above-mentioned products therefrom (a) is ice-cooling to 0 ~ 5 DEG C.Diazonium salt is slowly added in this conjugate solution, keeps pH to be 5 ~ 6.5 simultaneously.Stirring reaction until complete, to obtain intermediate (b).

Iii) 5.9 parts of { 2-[(4-aminophenyl) alkylsulfonyl] oxyethyl group } sulfonic acid are suspended in 50 parts of water.Reaction vessel is ice-cooling to 0 ~ 5 DEG C.6.2 part of 37% hydrochloric acid is added in reaction mixture.After stirring 10min, add 4.3mL 5M sodium nitrite solution.Reaction stirs 1h at 0 ~ 5 DEG C, then adds 0.2 part of thionamic acid.

Diazonium salt is slowly added in the solution of (b) of above-mentioned synthesis, keeps pH to be 5 ~ 6.5 simultaneously.Stirring reaction is until complete.Product Precipitation, collecting by filtration is also dry, obtains 21.8 parts of black solid dyestuff I ⁵⁶.

By analogy, all formula (I ¹-1 ²⁸⁰) shown in dyestuff all can according to described in embodiment 1 method synthesis.

Dyeing Example 1

By 3 parts of dyestuff I of the present invention ⁵⁶be dissolved in 2000 parts of water, and add 1 part of dye leveller (condensation product based on higher aliphatic amine and oxyethane).Then acetic acid (60%) is used to regulate pH to 3.8 ~ 4.2.100 parts of wool fabrics are put in dye bath.In 30 minutes, temperature is risen to 40 DEG C, keep 15 minutes at this temperature, then in 58 minutes, rise to 98 DEG C, dye 90 minutes at such a temperature.Be cooled to 90 DEG C subsequently and the material of dyeing is shifted out.Wool fabric hot water and cold water washing, alkaline purification, then centrifugal and dry.

Dyeing Example 2

By 2 parts of dyestuff I of the present invention ⁵⁶be dissolved in 1000 parts of water with 60 parts of sodium-chlor, and add 12 parts of sodium carbonate and 0.5 part of wetting agent.The cotton fabric of 100 parts of bleachings is put in this dye bath.With the gradient of 0.5 DEG C/min, dye bath temperature is risen to 30 DEG C, and keep 30 minutes at this temperature, then in 30 minutes, rise to 60 DEG C, continue maintenance 60 minutes at this temperature.First coloring material uses tap water 5 minutes afterwards.Coloring material at 50 DEG C with in the acetic acid of 60% concentration and 30 ~ 40 minutes.The tap water of material boiling 30 ~ 40 minutes, last flushing also drying in 20 minutes at 40 ~ 50 DEG C subsequently.

Dyeing Example 3

By 1 part of dyestuff I of the present invention ⁵⁶be dissolved in 2000 parts of water, and add 1 part of dye leveller (condensation product based on higher aliphatic amine and oxyethane) and 6 parts of sodium acetates.Then acetic acid (80%) is used to regulate pH to 4.5.Dye bath is heated to 50 DEG C and keeps 10 minutes, then puts into 100 parts of polyamide fabric.In 50 minutes, temperature is risen to 110 DEG C, then carry out dyeing 60 minutes at this temperature.Be cooled to 60 DEG C subsequently and shift out coloring material.Polyamide fabric hot water and cold water washing, soap, then centrifugal and dry.

Dyeing Example 4

The textile fabric be made up of mercerized cotton is with containing 35g/L calcium carbonate sodium, and the liquor of 100g/L urea and 150g/L low viscosity sodium alginate solution (6%) pads, then dry.Liquor utilization ratio is 70%.Pass through the ink jet-print head use ink jet printing of drop (bubble inkjet) as required through this pretreated textiles, described water color ink comprises 2% dyestuff I of the present invention ⁵⁶, 20% tetramethylene sulfone, the water of 0.01%Mergal K9N and 77.99%.Printing is fully dry.Saturated steam mode fixation 8 minutes are used at 102 DEG C.Then Printing is carried out heat flush, at 95 DEG C, carry out colour fastness washing, warm water washing with hot water, then dry.

Claims

1. compound shown in formula (I) and composition thereof

Wherein,

A is the group of diazonium structure division as described below;

B is the group of intermediate structure part as described below;

K is the group of coupled structures part as described below;

A is 0 or 1 integer;

The present invention relates to all types of tautomer of dyestuff and geometrical isomer shown in formula (I).

A is the group shown in general formula (1a)

Wherein,

R ¹~ R ³, be independently separately, hydrogen, halogen, alkyl; N-amido, alkoxyl group, thio alkoxy, hydroxyl; cyano group, nitro, alkoxy carbonyl, alkoxy carbonyl; acyl group, Thioacyl, aroyl, trifluoromethyl; acyloxy, aryl acyloxy, cycloalkyl, aryl; heteroaryl, Heterocyclylalkyl, N-cinnyl is amino, SO ₃m or COOM;

Or be general formula (2a), (2b) or the group shown in (2c)

Wherein,

B is the integer of 0 ~ 6;

C is the integer of 1 ~ 6;

D is 0 or 1;

RG is general formula (3a), (3b) or the active anchor shown in (3c);

Wherein,

R ¹⁴~ R ¹⁹, independent is separately halogen;

In addition, R ¹⁴it can be the group shown in formula (8a)

Wherein,

R ¹³be selected from the group shown in one of general formula (4a) or (4b);

Wherein,

B is the group shown in general formula (5a)

Wherein,

Or be the group shown in general formula (2a) or (2b)

Wherein R ⁴~ R ⁸, b, c and RG are identical with above-mentioned defined.

K is general formula (6a) or the group shown in (6b)

Wherein,

D is the group as shown in above-mentioned the general formula (1a) defined;

Or be active anchor RG, wherein RG is identical with above-mentioned defined;

Or be the group shown in general formula (7a)

Wherein,

RG is identical with above-mentioned defined;

R ³³hydrogen, alkyl or aryl;

2. compound according to claim 1, has the structure shown in formula (Ia):

Wherein,

Or be general formula (2a) as defined in claim 1, (2b) or the group shown in (2c);

Or be active anchor RG, wherein RG with define in claim 1 identical;

Or be the such as group shown in general formula (7a) as defined in claim 1.

3. compound according to claim 1, has the structure shown in formula (Ib):

Wherein

Or be the group shown in general formula (2a) as defined in claim 1 or (2b);

In addition, R ³⁹~ R ⁴¹, can be independently the group shown in general formula (2c) as defined in claim 1 separately;

Or be active anchor RG, wherein RG with define in claim 1 identical;

Or be the group shown in general formula (7a) as defined in claim 1.

4. compound according to claim 1, has the structure shown in formula (Ic):

Wherein,

J is 0 or 1;

Or be active anchor RG, wherein RG with define in claim 1 identical;

Or be the group shown in general formula (7a) as defined in claim 1.

5. compound according to claim 1, has the structure shown in formula (Id):

Wherein,

N is 0 or 1

Or be the group shown in general formula (2a) as defined in claim 1 or (2b);

In addition, R ⁵²~ R ⁵⁴, can be independently the group shown in general formula (2c) as defined in claim 1 separately;

Or be active anchor RG, wherein RG with define in claim 1 identical;

Or be the group shown in general formula (7a) as defined in claim 1.

6. compound according to claim 1, has the structure shown in formula (Ie):

Wherein,

Or be active anchor RG, wherein RG with define in claim 1 identical;

Or be the group shown in general formula (7a) as defined in claim 1.

7. compound according to claim 1, has the structure shown in formula (If):

Wherein,

Or be the group shown in general formula (2a) as defined in claim 1 or (2b);

Or be active anchor RG, wherein RG with define in claim 1 identical;

Or be the group shown in general formula (7a) as defined in claim 1.

8. compound according to claim 1, has the structure shown in formula (Ig):

Wherein,

Or be active anchor RG, wherein RG with define in claim 1 identical;

Or be the group shown in general formula (7a) as defined in claim 1.

9. compound according to claim 1, has the structure shown in formula (Ih):

Wherein,

Or be that described substituting group is selected from the group be made up of following groups: hydroxyl, aryl, cycloalkyl by one or more heteroatoms as oxygen or sulphur interrupt and the alkyl replaced by one or more substituting group; alkoxyl group, thio alkoxy, N, N; N-trialkyl ammonium, N, N, N-triaryl ammonium; the single aryl ammonium of N, N-dialkyl group-N-, N, N-diaryl-N-monoalkyl ammonium; N-amido, N-cinnyl is amino, N-alkylsulfonyl-amino; halogen, cyano group, SO ₃m, COOM, nitro, acyl group, Thioacyl, alkyl sulphonyl, aroyl, trifluoromethyl, heteroaryl, Heterocyclylalkyl, alkoxy carbonyl, alkoxy carbonyl, acyloxy, aryl acyloxy;

Or be the group shown in general formula (2a) as defined in claim 1 or (2b);

In addition, R ⁸³, R ⁸⁴, R ⁸⁵, R ⁸⁹, R ⁹⁰and R ⁹¹, can be independently the group shown in general formula (2c) as defined in claim 1 separately;

Or be active anchor RG, wherein RG with define in claim 1 identical;

Or be the group shown in general formula (7a) as defined in claim 1.

10. chemical composition, is made up of two or more compounds according to any one in claim 1 ~ 9.

11. chemical compositions, comprise one or more compounds according to any one in claim 1 ~ 9.

12. aqueous solution for dyeing, comprise one or more compounds according to any one in claim 1 ~ 9.

The method of 13. preparation compound according to claim 1, comprises the steps:

A) diazotization of compound shown in formula (II),

B) step a) compound shown in gained diazonium salt and formula K react, to obtain the intermediate shown in formula (III)

C) reactant (A-NH ₂) diazotization,

Cx1) optionally by step c) gained diazotization product is coupled to compound (B-NH ₂) on

Cx2) by step cx1) gained coupled product diazotization

D) in step c), by step c) gained diazotization product is coupled in intermediate III, to obtain the tetrazo product shown in general formula (IV)

or by cx2) the diazotizing coupled product of gained is coupled to obtain the trisazo-product shown in general formula (VI) in intermediate III,

14. compounds according to any one in claim 1 ~ 9, chemical composition according to claim 10 or 11 or the application of the aqueous solution according to claim 12 in fiber and the dyeing of fiber blend thing, described fiber is selected from by following fibrous group: vegetable fibre, seed hair, cotton, organic cotton, kapok, the fiber of Exocarpium cocois (Cocos nucifera L); Phloem fiber, flax, hemp, jute, bluish dogbane, ramie, rattan; Leaf fiber, sisal hemp, henequen, Basho fiber; Stalk fibre, bamboo fibers; From the fiber of animal, wool, including organic wool, silk, cashmere wool, Aloysia gratissima alpaca fiber, mohair, Angola's hair fibre and fur and leather substance; Artificial, regeneration with the fiber reclaimed, cellulosic fibre; Paper fiber, tModified Cellulose Fibers, viscose rayon fibers, acetic ester and triacetate fiber and Lyocell fibers; And composite fibre materials, nylon material, nylon-6, nylon 6.6 and aramid fiber.

The fiber of 15. compounds according to any one in claim 1 to 9 combined with form that is chemical and/or physics containing one or more and the blend comprising described fiber, described fiber is selected from by following fibrous group: vegetable fibre, seed hair, cotton, organic cotton, kapok, the fiber of Exocarpium cocois (Cocos nucifera L); Phloem fiber, flax, hemp, jute, bluish dogbane, ramie, rattan; Leaf fiber, sisal hemp, henequen, Basho fiber; Stalk fibre, bamboo fibers; From the fiber of animal, wool, including organic wool, silk, cashmere wool, Aloysia gratissima alpaca fiber, mohair, Angola's hair fibre and fur and leather substance; Artificial, regeneration with the fiber reclaimed, cellulosic fibre; Paper fiber, tModified Cellulose Fibers, viscose rayon fibers, acetic ester and triacetate ester fiber and Lyocell fibers; And composite fibre materials, nylon material, nylon-6, nylon-6 .6 and aramid fiber.