CN104487630A

CN104487630A - Reactive dyes and their metal complexes, process for the production thereof and their use

Info

Publication number: CN104487630A
Application number: CN201380032387.2A
Authority: CN
Inventors: 瓦捷拉维鲁·希华慕鲁甘; 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: 2015-04-01
Also published as: MX2014015534A; KR20150032668A; AU2013279555A1; JP2015525280A; WO2013189816A1; EP2904142A1

Abstract

The present invention refers to dyes of the formula (I) and mixtures thereof, in which n, A, B 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

REACTIVE DYES and metal complex thereof, and preparation method and application

The present invention relates to REACTIVE DYES and metal complex technical field thereof, described REACTIVE DYES and metal complex thereof are used for containing hydroxyl, amino, and the dyeing of the material of formamido group and stamp.

Based on being that prior art is known containing two of at least one anchor and the metal complex REACTIVE DYES of polyazo group, and can to use in different application as colouring agent, see DE3514969, DE3515407, US5319074, US3450689, US3462409, US3457251, US3457252, GB1279283, GB1553474, WO2003104335, US5527886, DE3519551 and US4939243.

Comprising hydroxyl, amino, and/or in the dyeing of formamido group material and the background technology of stamp, known dye has many technological deficiencies, such as low fixation power, medium moisture-proof and fast light level.Therefore, be necessary to develop the new reactive dyes with superior technical performance.

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 excellent moisture-proof and light resistance, excellent ecological performance, and can realize tone miscellaneous, comprise darkviolet, dark brown, navy blue and black.

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

Wherein

N is integer 0 or 1;

K is the group of coupling heterocyclic moiety as described below;

When n is 1, A is the group of intermediate structure part as described below; When n is 0, A has the implication of B;

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

M is hydrogen, lithium, sodium, potassium, ammonium or list, two, three or four-(C ₁-C ₄)-alkylammonium, the alkaline-earth metal of an equivalent, or monovalence organic cation;

K is the coupled structures part shown in general formula (K1) ~ (K3) below;

Wherein,

R ¹and R ⁴, be independently separately, hydrogen, alkyl, cycloalkyl, trifluoromethyl; Alkoxyl, cyano group, carbamoyl, alkoxy carbonyl, COOM, amino; Hydroxyl, monocycle alkyl-amino; Monoalkyl-amino; Two (ring) alkyl-amino; Dialkyl-7-amino; Single aryl-amino; Diaryl-amino; Monocycle alkyl list arylamino; Monoalkyl list arylamino; Alkylthio group; Arylthio;

Or be

By the alkyl that one or more substituting group replaces, described substituting group is selected from the group be made up of following groups: hydroxyl, cycloalkyl, heteroaryl, Heterocyclylalkyl, aryl, aryloxy group, alkoxyl, alkylthio group, arylthio, halogen, cyano group, COOM, alkoxy carbonyl, acyloxy, carbamoyl, nitro, amino, acylamino-, aromatic carbonyl is amino, alkyl sulfonyl-amino, arlysulfonylamino, urea groups, alkyl urea groups and phenyl urea groups;

R ², R ⁵and R ¹¹, be independently separately, cyano group, carbamoyl, alkoxy carbonyl, trifluoromethyl, carbonyl trifluoromethyl, halogen, methyl sulphonyl Huo – SO ₃m;

R ³, R ⁶~ R ⁹and R ¹², respective is independently hydrogen, alkyl, thiazolinyl, cycloalkyl, trifluoromethyl, aryl, heteroaryl, Heterocyclylalkyl, carbamoyl, N-monocycle alkyl-carbamoyl, N-monoalkyl-amino formoxyl, N, N-bicyclic alkyl-carbamoyl, N, N-dialkyl-carbamoyl radicals, the mono-aryl-carbamoyl of N-, N, N-diaryl-carbamoyl, the single aryl-amino-carbonyl of N-monocycle alkyl-N-, the single aryl-amino-carbonyl of N-monoalkyl-N-, amino-sulfonyl, N-monocycle alkyl-amino-sulfonyl, N-monoalkyl-amino sulfonyl, N, N-bicyclic alkyl amino sulfonyl, N, N-dialkyl-7-amino sulfonyl, the mono-aryl-amino sulfonyl of N-, N, N-diaryl-amino-sulfonyl, the single n-aryl sulfonyl of N-monocycle alkyl-N-, the single aryl-amino sulfonyl of N-monoalkyl-N-, amino, N-acylamino-, N-thio acylamino, urea groups, alkyl urea groups, phenyl urea groups, N-alkyl monosubstituted amino, N, N-dialkyl-7-amino, N-arylamino, N, N-ammonia diaryl base, N-alkyl-N-aryl-amino, N-monocycloalkylamino, N, N-bicyclic alkyl amino, N-alkyl-N-cycloalkyl-amino, N-aryl-N-cycloalkyl-amino, N-heteroaryl amino, N-heterocyclalkylamino or hydroxyalkyl Sulfonylalkyl,

Or be

By the alkyl that one or more hetero atom interrupts as oxygen or sulphur;

Or be

By the alkyl that one or more substituting group replaces, described substituting group is selected from the group be made up of following groups: hydroxyl, aryl, cycloalkyl, alkoxyl, thio alkoxy, amino, N-monoalkyl-amino, N, N-dialkyl amido, 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-monocycle alkyl-amino, N, the mono-aryl of N--monocycle alkyl-amino, N-acylamino-, N-alkylsulfonyl-amino, urea groups, alkyl urea groups, phenyl urea groups, halogen, cyano group, COOM, nitro, acyl group, Thioacyl, alkyl sulphonyl, aroyl, trifluoromethyl, heteroaryl, Heterocyclylalkyl, alkoxy carbonyl, alkoxy carbonyl, acyloxy, aryl acyloxy, carbamoyl, N-monocycle alkyl-carbamoyl, N-monoalkyl-amino formoxyl, N, N-bicyclic alkyl-carbamoyl, N, N-dialkyl-carbamoyl radicals, the mono-aryl-carbamoyl of N-, N, N-diaryl-carbamoyl, 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 sulfonyl, N, N-bicyclic alkyl-amino-sulfonyl, N, N-dialkyl-7-amino sulfonyl, the mono-n-aryl sulfonyl of N-, N, N-diaryl-amino-sulfonyl, the single n-aryl sulfonyl of N-monocycle alkyl-N-, the single n-aryl sulfonyl of N-monoalkyl-N-or-SO ₃m,

Or Bei – SO ₂the alkyl or aryl that X replaces; Wherein

X is vinyl or Ji Tuan – CH ₂cH ₂-Y, wherein Y is the group can left away in the basic conditions, and it can leave molecule in the basic conditions to obtain vinyl sulfone functional group.

The example of this type of group is OSO ₃m, SSO ₃m, OCOCH ₃, OPO ₃m and halogen;

And

R ¹⁰hydroxyl or amino;

And

Wherein, in general formula K2, tie point and R ⁵can be positioned at and there is substituent R ⁶and R ⁷the ortho position of amino or contraposition, namely when tie point is positioned at, there is substituent R ⁶and R ⁷the ortho position of amino time, R ⁵be positioned at its contraposition, vice versa.

Or

K is the coupled structures part shown in following general formula (K4) ~ (K6);

Wherein

T is the active anchor shown in general formula (T1) ~ (T3);

Wherein

R ²⁴and R ²⁵, separately independent be halogen or

R ²⁶~ R ³⁰respective is independently halogen;

Or R ²⁴~ R ³⁰, be independently selected from the group shown in one of general formula (1a) ~ (1c) separately and replace;

Wherein

R ³¹, R ³², R ³³⁹and R ³⁴⁰, be independently, hydrogen, alkyl, phenyl or the phenyl be substituted with a substituent that described substituting group is selected from one of following: alkyl, alkoxyl, halogen ， Huo – SO separately ₃m, thiazolinyl, cycloalkyl, trifluoromethyl, aryl, heteroaryl, Heterocyclylalkyl, carbamoyl, N-monocycle alkyl-carbamoyl, N-monoalkyl-amino formoxyl, N, N-bicyclic alkyl-carbamoyl, N, N-dialkyl-carbamoyl radicals, the mono-aryl-carbamoyl of N-, N, N-diaryl-carbamoyl, the single aryl-amino-carbonyl of N-monocycle alkyl-N-, the single aryl-amino-carbonyl of N-monoalkyl-N-, amino-sulfonyl, N-monocycle alkyl-amino-sulfonyl, N-monoalkyl-amino sulfonyl, N, N-bicyclic alkyl amino sulfonyl, N, N-dialkyl-7-amino sulfonyl, the mono-aryl-amino sulfonyl of N-, N, N-diaryl-amino-sulfonyl, the single n-aryl sulfonyl of N-monocycle alkyl-N-, the single aryl-amino sulfonyl of N-monoalkyl-N-, amino, N-acylamino-, N-thio acylamino, urea groups, alkyl urea groups, phenyl urea groups, N-alkyl monosubstituted amino, N, N-dialkyl-7-amino, N-arylamino, N, N-ammonia diaryl base, N-alkyl-N-aryl-amino, N-monocycloalkylamino, N, N-bicyclic alkyl amino, N-alkyl-N-cycloalkyl-amino, N-aryl-N-cycloalkyl-amino, N-heteroaryl amino, N-heterocyclalkylamino or hydroxyalkyl Sulfonylalkyl,

Or

By the alkyl that one or more hetero atom interrupts as oxygen or sulphur;

Or

R ³³, R ³⁴and R ³³⁸, be independently separately, hydrogen, alkyl, alkoxyl, halogen, trifluoromethyl, cyano group, nitro, ester group, carbamoyl, SO ₃m or-SO ₂x;

Wherein M is hydrogen, sodium, potassium, lithium or ammonium;

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

P is the integer of 1 ~ 5

R ¹³and R ¹⁵, be independently separately, hydrogen, alkyl, cycloalkyl, trifluoromethyl; Alkoxyl, cyano group, carbamoyl, alkoxy carbonyl, COOM, amino; Hydroxyl, monocycle alkyl-amino; Monoalkyl-amino; Two (ring) alkyl-amino; Dialkyl-7-amino; Single aryl-amino; Diaryl-amino; Monocycle alkyl list arylamino; Monoalkyl list arylamino; Alkylthio group; Arylthio;

Or be

By the alkyl that one or more substituting group replaces, described substituting group is selected from the group be made up of following groups: hydroxyl, cycloalkyl, heteroaryl, Heterocyclylalkyl, aryl, aryloxy group, alkoxyl, alkylthio group, arylthio, halogen, cyano group, COOM, alkoxy carbonyl, acyloxy, carbamoyl, nitro, amino, acylamino-, aromatic carbonyl is amino, alkyl sulfonyl-amino, arlysulfonylamino, urea groups, alkyl urea groups or phenyl urea groups;

R ¹², R ¹⁶and R ²², be independently separately, cyano group, carbamoyl, alkoxy carbonyl, trifluoromethyl, carbonyl trifluoromethyl, halogen, methyl sulphonyl Huo – SO ₃m;

R ¹⁴, R ¹⁷~ R ²⁰and R ²³, be independently separately, hydrogen, alkyl, thiazolinyl, cycloalkyl, trifluoromethyl, aryl, heteroaryl, Heterocyclylalkyl, carbamoyl, N-monocycle alkyl-carbamoyl, N-monoalkyl-amino formoxyl, N, N-bicyclic alkyl-carbamoyl, N, N-dialkyl-carbamoyl radicals, the mono-aryl-carbamoyl of N-, N, N-diaryl-carbamoyl, the single aryl-amino-carbonyl of N-monocycle alkyl-N-, the single aryl-amino-carbonyl of N-monoalkyl-N-, amino-sulfonyl, N-monocycle alkyl-amino-sulfonyl, N-monoalkyl-amino sulfonyl, N, N-bicyclic alkyl amino sulfonyl, N, N-dialkyl-7-amino sulfonyl, the mono-aryl-amino sulfonyl of N-, N, N-diaryl-amino-sulfonyl, the single n-aryl sulfonyl of N-monocycle alkyl-N-, the single aryl-amino sulfonyl of N-monoalkyl-N-, amino, N-acylamino-, N-thio acylamino, urea groups, alkyl urea groups, phenyl urea groups, N-alkyl monosubstituted amino, N, N-dialkyl-7-amino, N-arylamino, N, N-ammonia diaryl base, N-alkyl-N-aryl-amino, N-monocycloalkylamino, N, N-bicyclic alkyl amino, N-alkyl-N-cycloalkyl-amino, N-aryl-N-cycloalkyl-amino, N-heteroaryl amino, N-heterocyclalkylamino or hydroxyalkyl Sulfonylalkyl,

Or be

By the alkyl that one or more hetero atom interrupts as oxygen or sulphur;

Or be

By the alkyl that one or more substituting group replaces, described substituting group is selected from the group be made up of following groups: hydroxyl, aryl, cycloalkyl, alkoxyl, thio alkoxy, amino, N-monoalkyl-amino, N, N-dialkyl amido, 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-monocycle alkyl-amino, N, the mono-aryl of N--monocycle alkyl-amino, N-acylamino-, N-alkylsulfonyl-amino, urea groups, alkyl urea groups, phenyl urea groups, halogen, cyano group, COOM, nitro, acyl group, Thioacyl, alkyl sulphonyl, aroyl, trifluoromethyl, heteroaryl, Heterocyclylalkyl, alkoxy carbonyl, alkoxy carbonyl, acyloxy, aryl acyloxy, carbamoyl, N-monocycle alkyl-carbamoyl, N-monoalkyl-amino formoxyl, N, N-bicyclic alkyl-carbamoyl, N, N-dialkyl-carbamoyl radicals, the mono-aryl-carbamoyl of N-, N, N-diaryl-carbamoyl, 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 sulfonyl, N, N-bicyclic alkyl-amino-sulfonyl, N, N-dialkyl-7-amino sulfonyl, the mono-n-aryl sulfonyl of N-, N, N-diaryl-amino-sulfonyl, the single n-aryl sulfonyl of N-monocycle alkyl-N-, the single n-aryl sulfonyl of N-monoalkyl-N-or SO ₃m,

R ²¹hydroxyl or amino;

And

Wherein, in general formula K5, tie point and R ¹⁶can be positioned at and there is substituent R ¹⁷and R ¹⁸the ortho position of amino or contraposition, namely when tie point is positioned at, there is substituent R ¹⁷and R ¹⁸the ortho position of amino time, R ¹⁶be positioned at its contraposition, vice versa.

A is phenylene or naphthylene intermediate structure part, and has general formula (A1) or the structure shown in (A2);

R ³⁴¹~ R ³⁴⁸, be independently separately, hydrogen, alkyl, by the alkyl chain of one or two heteroatom interruptions, alkoxyl, halogen, trifluoromethyl; Cycloalkyl; Heterocyclylalkyl; Cyano group; Nitro; Acyloxy; Alkyl-carbonyl, acylamino-; Aroylamino, cinnamoyl is amino, alkyl sulfonyl-amino; Alkylthio group; Alkyl sulphonyl, alkoxy carbonyl, carbamoyl, amino-sulfonyl, urea groups, alkyl urea groups, SO ₃m, COOM;

Or be

Or

By the alkyl that one or more hetero atom interrupts as oxygen or sulphur;

Or be

Or

Group shown in formula (2a) ~ (2c)

Wherein R ³⁴⁹and R ³⁵⁰, be independently that hydrogen, alkyl, by SO separately ₃the alkyl that M replaces, by the alkyl chain of one or two heteroatom interruptions, or T;

Wherein T has implication same as described above;

U Shi – O-,-S-Huo – N (R ³²⁹)-;

R ³²³, R ³²⁷and R ³²⁹, be independently that hydrogen, alkyl, by SO separately ₃the alkyl that M replaces, by the alkyl chain of one or two heteroatom interruptions;

R ³²⁴, R ³²⁵, R ³²⁶and R ³²⁸, be independently separately, hydrogen, alkyl or the alkyl chain by one or two heteroatom interruptions;

R is the integer of 0 ~ 6;

S is the integer of 1 ~ 6;

* refers to the tie point with A1 or A2

* * refers to the tie point with T

T has implication as above;

B is diazonium structure division, and the structure shown in one of general formula (B1) or (B2);

Wherein

R ³⁵~ R ⁴⁰and R ³⁵¹, be independently separately, hydrogen or alkyl, alkoxyl, halogen, cyano group ,-SO ₃m, trifluoromethyl, nitro, ester group, NHC (O) R ⁴¹, CONH ₂, S (O) ₂r ⁴²， – SO ₂x or by the monobasic amino of T or general formula (E1) ~ (E3);

Wherein

V Shi – O-,-S-Huo – N (R ³⁵²)-

R ⁴³, R ⁴⁷and R ³⁵², be independently that hydrogen, alkyl, by SO separately ₃the alkyl that M replaces, by the alkyl chain of one or two heteroatom interruptions;

R ⁴⁴, R ⁴⁵, R ⁴⁶and R ⁴⁸, be independently separately, hydrogen, alkyl or the alkyl chain by one or two heteroatom interruptions; R ³³⁰~ R ³³³, be independently separately, hydrogen or alkyl, alkoxyl, halogen, cyano group ,-SO ₃m, trifluoromethyl, nitro, ester group, NHC (O) R ³³⁴, CONH ₂, S (O) ₂r ³³⁵or the group shown in formula (3a);

R ³³⁶and R ³³⁷, be independently separately, hydrogen, alkyl, thiazolinyl, cycloalkyl, trifluoromethyl, aryl, heteroaryl, Heterocyclylalkyl, carbamoyl, N-monocycle alkyl-carbamoyl, N-monoalkyl-amino formoxyl, N, N-bicyclic alkyl-carbamoyl, N, N-dialkyl-carbamoyl radicals, the mono-aryl-carbamoyl of N-, N, N-diaryl-carbamoyl, the single aryl-amino-carbonyl of N-monocycle alkyl-N-, the single aryl-amino-carbonyl of N-monoalkyl-N-, amino-sulfonyl, N-monocycle alkyl-amino-sulfonyl, N-monoalkyl-amino sulfonyl, N, N-bicyclic alkyl amino sulfonyl, N, N-dialkyl-7-amino sulfonyl, the mono-aryl-amino sulfonyl of N-, N, N-diaryl-amino-sulfonyl, the single n-aryl sulfonyl of N-monocycle alkyl-N-, the single aryl-amino sulfonyl of N-monoalkyl-N-, amino, N-acylamino-, N-thio acylamino, urea groups, alkyl urea groups, phenyl urea groups, N-alkyl monosubstituted amino, N, N-dialkyl-7-amino, N-arylamino, N, N-ammonia diaryl base, N-alkyl-N-aryl-amino, N-monocycloalkylamino, N, N-bicyclic alkyl amino, N-alkyl-N-cycloalkyl-amino, N-aryl-N-cycloalkyl-amino, N-heteroaryl amino, N-heterocyclalkylamino or hydroxyalkyl Sulfonylalkyl, or be

By the alkyl that one or more hetero atom interrupts as oxygen or sulphur; Or be

By the alkyl that one or more substituting group replaces, described substituting group is selected from the group be made up of following groups: hydroxyl, aryl, cycloalkyl, alkoxyl, thio alkoxy, amino, N-monoalkyl-amino, N, N-dialkyl amido, 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-monocycle alkyl-amino, N, the mono-aryl of N--monocycle alkyl-amino, N-acylamino-, N-alkylsulfonyl-amino, urea groups, alkyl urea groups, phenyl urea groups, halogen, cyano group, COOM, nitro, acyl group, Thioacyl, alkyl sulphonyl, aroyl, trifluoromethyl, heteroaryl, Heterocyclylalkyl, alkoxy carbonyl, alkoxy carbonyl, acyloxy, aryl acyloxy, carbamoyl, N-monocycle alkyl-carbamoyl, N-monoalkyl-amino formoxyl, N, N-bicyclic alkyl-carbamoyl, N, N-dialkyl-carbamoyl radicals, the mono-aryl-carbamoyl of N-, N, N-diaryl-carbamoyl, 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 sulfonyl, N, N-bicyclic alkyl-amino-sulfonyl, N, N-dialkyl-7-amino sulfonyl, the mono-n-aryl sulfonyl of N-, N, N-diaryl-amino-sulfonyl, the single n-aryl sulfonyl of N-monocycle alkyl-N-, the single n-aryl sulfonyl of N-monoalkyl-N-or SO ₃m, or by the alkyl that one or more hetero atom interrupts as oxygen or sulphur,

Or comprise there is free valency group to connect active anchor T;

R ⁴¹, R ⁴², R ³³⁴and R ³³⁵, be independently separately, hydrogen, alkyl or the alkyl by hydroxyl or halogen substiuted;

C is the integer of 0 ~ 6;

D is the integer of 1 ~ 6;

* * * refers to the tie point with B1 and B2;

* * * * refers to the tie point with T;

* * * * * refers to the tie point with E3;

T with X is identical with above-mentioned defined;

Preferred hydrogen, lithium, sodium, potassium, ammonium, or the alkaline-earth metal of an equivalent, particularly preferably hydrogen, sodium, potassium, or lithium.

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

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

Occur that alkyl in this application can be straight chain or side chain, 1 ~ 12 C-atom can be had, such as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, isobutyl group, n-pentyl, isopentyl, n-hexyl, 2-ethylhexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, n-undecane base and dodecyl, preferable methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, isobutyl group, n-pentyl, isopentyl, n-hexyl, 2-ethylhexyl, particularly preferably methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, n-pentyl, isopentyl, n-hexyl, with 2-ethylhexyl.Same logic is suitable for alkoxyl, and described Alkoxy is as methoxyl group and ethyoxyl.

Cycloalkyl is (C ₃-C ₈)-cycloalkyl, preferably (C ₄-C ₈)-cycloalkyl, particularly preferably cyclopentyl and cyclohexyl.According to aim of the present invention, term cycloalkyl comprises substituted cycloalkyl and unsaturated cycloalkyl.This type of group cyclopentene base.Preferred substituting group is alkyl, cycloalkyl, Heterocyclylalkyl, hydroxyalkyl, halogen, hydroxyl, alkoxyl, alkylthio group, acyl group, nitro, cyano group ,-SO ₃m ,-COOM, amino; alkyl monosubstituted amino, dialkyl amido, single (hydroxyalkyl) is amino; two (hydroxyalkyl) is amino; monoalkyl-mono-(hydroxyalkyl) is amino, carbamoyl, amino-sulfonyl; acylamino-; urea groups, aminosulfonylamino, alkoxy carbonyl or acyloxy.Particularly preferred substituting group is alkyl, hydroxyalkyl, halogen, hydroxyl, alkoxyl, acyl group, nitro, cyano group ,-SO3M ,-COOM, amino, alkyl monosubstituted amino, dialkyl amido, carbamoyl, amino-sulfonyl, urea groups or acylamino-.

Thiazolinyl can be straight chain or side chain, such as vinyl and allyl.According to aim of the present invention, term thiazolinyl also comprises alkynyl, such as acetenyl and propargyl.

The preferred pyrrolidines of Heterocyclylalkyl, piperidines, morpholine or piperazine, oxolane, imidazoles, triazole.

Occur that aryl is in this application phenyl or naphthyl.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, alkylthio group, acyl group, nitro, cyano group ,-SO ₃m ,-COOM, amino; alkyl monosubstituted amino, dialkyl amido, single (hydroxyalkyl) is amino; two (hydroxyalkyl) is amino; monoalkyl-mono-(hydroxyalkyl) is amino, carbamoyl, amino-sulfonyl; acylamino-; urea groups, aminosulfonylamino, alkoxy carbonyl or acyloxy.Particularly preferred substituting group is alkyl, hydroxyalkyl, halogen, hydroxyl, alkoxyl, acyl group, nitro, cyano group ,-SO ₃m ,-COOM, amino, alkyl monosubstituted amino, dialkyl amido, carbamoyl, amino-sulfonyl, urea groups or acylamino-.

Halogen is fluorine, chlorine, bromine or iodine, preferred fluorine, chlorine or bromine, particularly preferably chlorine and bromine.

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

Wherein

R ⁴⁹, R ⁵⁸, R ⁶⁶, R ⁷⁴, R ⁷⁸and R ⁸⁵, be independently separately, hydrogen, alkyl, cycloalkyl, trifluoromethyl; Alkoxyl, cyano group, carbamoyl, alkoxy carbonyl, COOM, amino; Hydroxyl, monocycle alkyl-amino; Monoalkyl-amino; Two (ring) alkyl-amino; Dialkyl-7-amino; Single aryl-amino; Diaryl-amino; Monocycle alkyl list arylamino; Monoalkyl list arylamino; Alkylthio group; Arylthio;

Or be

R ⁵⁰, R ⁵⁴, R ⁵⁹, R ⁶⁷, R ⁷⁵and R ⁷⁹, be independently separately, cyano group, carbamoyl, alkoxy carbonyl, trifluoromethyl, carbonyl trifluoromethyl, halogen, methyl sulphonyl Huo – SO ₃m;

R ⁵¹, R ⁵⁵, R ⁶⁰and R ⁶⁸, be independently separately, hydrogen, alkyl, thiazolinyl, cycloalkyl, trifluoromethyl, aryl, heteroaryl, Heterocyclylalkyl, carbamoyl, N-monocycle alkyl-carbamoyl, N-monoalkyl-amino formoxyl, N, N-bicyclic alkyl-carbamoyl, N, N-dialkyl-carbamoyl radicals, the mono-aryl-carbamoyl of N-, N, N-diaryl-carbamoyl, the single aryl-amino-carbonyl of N-monocycle alkyl-N-, the single aryl-amino-carbonyl of N-monoalkyl-N-, amino-sulfonyl, N-monocycle alkyl-amino-sulfonyl, N-monoalkyl-amino sulfonyl, N, N-bicyclic alkyl amino sulfonyl, N, N-dialkyl-7-amino sulfonyl, the mono-aryl-amino sulfonyl of N-, N, N-diaryl-amino-sulfonyl, the single n-aryl sulfonyl of N-monocycle alkyl-N-, the single aryl-amino sulfonyl of N-monoalkyl-N-, amino, N-acylamino-, N-thio acylamino, urea groups, alkyl urea groups, phenyl urea groups, N-alkyl monosubstituted amino, N, N-dialkyl-7-amino, N-arylamino, N, N-ammonia diaryl base, N-alkyl-N-aryl-amino, N-monocycloalkylamino, N, N-bicyclic alkyl amino, N-alkyl-N-cycloalkyl-amino, N-aryl-N-cycloalkyl-amino, N-heteroaryl amino, N-heterocyclalkylamino or hydroxyalkyl Sulfonylalkyl,

Or be

By the alkyl that one or more hetero atom interrupts as oxygen or sulphur;

Or be

R ⁵², R ⁵³, R ⁵⁶, R ⁵⁷, R ⁶⁴, R ⁶⁵, R ⁷², R ⁷³, R ⁷⁶, R ⁷⁷, R ⁸³and R ⁸⁴, be independently separately, hydrogen or alkyl, alkoxyl, halogen, cyano group ,-SO ₃m, trifluoromethyl, nitro, ester group, NHC (O) R ⁸⁶, CONH ₂, S (O) ₂r ⁸⁷huo – SO ₂x;

R ⁸⁶and R ⁸⁷, be independently separately, hydrogen, alkyl or the alkyl by hydroxyl or halogen substiuted;

R ⁶¹~ R ⁶³, R ⁶⁹~ R ⁷¹and R ⁸⁰~ R ⁸², be independently separately, hydrogen, alkyl, substituted alkyl, by the alkyl chain of one or two heteroatom interruptions, alkoxyl, substituted alkoxy, halogen, trifluoromethyl; Cycloalkyl; Heterocyclylalkyl; Cyano group; Nitro; Acyloxy; Alkyl-carbonyl, acylamino-; Aromatic acylamino, cinnamoyl is amino, alkyl sulfonyl-amino; Alkylthio group; Alkyl sulphonyl, alkoxy carbonyl, carbamoyl, amino-sulfonyl, urea groups, alkyl urea groups, SO ₃m, COOM; Or the group shown in formula (2a) ~ (2c) defined as above-mentioned;

In the particularly preferred dyestuff of the present invention,

R ⁴⁹, R ⁵⁸, R ⁶⁶, R ⁷⁴, R ⁷⁸and R ⁸⁵for hydrogen or (C ₁-C ₄)-alkyl or aryl;

R ⁵⁰, R ⁵⁴, R ⁵⁹, R ⁶⁷, R ⁷⁵and R ⁷⁹for cyano group, carbamido group, alkoxy carbonyl, carbonyl, sulfonymethyl ,-SO ₃m or-COOM;

R ⁵¹, R ⁵⁵, R ⁶⁰and R ⁶⁸for alkyl or aryl; By the aryl that more than one substituting group replaces, described substituting group is selected from alkyl, alkoxyl, Lu Su Huo – SO ₃m;

R ⁶¹~ R ⁶³, R ⁶⁹~ R ⁷¹and R ⁸⁰~ R ⁸², be independently separately, hydrogen, (C ₁-C ₄)-alkyl, (C ₁-C ₄)-alkoxyl, hydroxyl, carbamido group, Lu Su Huo – SO ₃m, or the group shown in contained (2a) ~ (2c);

R ⁸⁶and R ⁸⁷, be independently separately, hydrogen, alkyl or the alkyl be optionally substituted by a hydroxyl group;

R ⁸⁸and R ⁸⁹, be independently that hydrogen, alkyl, by SO separately ₃the alkyl that M replaces;

T, X and M are identical with above-mentioned defined.

The present invention further preferred dyestuff is formula (Ig) and the dyestuff shown in (Ih) and composition thereof;

Wherein

R ⁹⁰and R ⁹⁴, be independently separately, hydrogen, alkyl, cycloalkyl, trifluoromethyl; Alkoxyl, cyano group, carbamoyl, alkoxy carbonyl, COOM, amino; Hydroxyl, monocycle alkyl-amino; Monoalkyl-amino; Two (ring) alkyl-amino; Dialkyl-7-amino; Single aryl-amino; Diaryl-amino; Monocycle alkyl list arylamino; Monoalkyl list arylamino; Alkylthio group; Arylthio;

Or be

R ⁹¹and R ⁹⁵, be independently separately, cyano group, carbamoyl, alkoxy carbonyl, trifluoromethyl, carbonyl trifluoromethyl, halogen, methyl sulphonyl Huo – SO ₃m;

D ¹and D ², be independently separately, hydrogen, alkyl, thiazolinyl, cycloalkyl, trifluoromethyl, aryl, heteroaryl, Heterocyclylalkyl, carbamoyl, N-monocycle alkyl-carbamoyl, N-monoalkyl-amino formoxyl, N, N-bicyclic alkyl-carbamoyl, N, N-dialkyl-carbamoyl radicals, the mono-aryl-carbamoyl of N-, N, N-diaryl-carbamoyl, the single aryl-amino-carbonyl of N-monocycle alkyl-N-, the single aryl-amino-carbonyl of N-monoalkyl-N-, amino-sulfonyl, N-monocycle alkyl-amino-sulfonyl, N-monoalkyl-amino sulfonyl, N, N-bicyclic alkyl amino sulfonyl, N, N-dialkyl-7-amino sulfonyl, the mono-aryl-amino sulfonyl of N-, N, N-diaryl-amino-sulfonyl, the single n-aryl sulfonyl of N-monocycle alkyl-N-, the single aryl-amino sulfonyl of N-monoalkyl-N-, amino, N-acylamino-, N-thio acylamino, urea groups, alkyl urea groups, phenyl urea groups, N-alkyl monosubstituted amino, N, N-dialkyl-7-amino, N-arylamino, N, N-ammonia diaryl base, N-alkyl-N-aryl-amino, N-monocycloalkylamino, N, N-bicyclic alkyl amino, N-alkyl-N-cycloalkyl-amino, N-aryl-N-cycloalkyl-amino, N-heteroaryl amino, N-heterocyclalkylamino or hydroxyalkyl Sulfonylalkyl,

Or be

By the alkyl that one or more hetero atom interrupts as oxygen or sulphur;

Or be

R ⁹², R ⁹³, R ⁹⁹and R ¹⁰⁰, be independently separately, hydrogen or alkyl, alkoxyl, halogen, cyano group ,-SO ₃m, trifluoromethyl, nitro, ester group, NHC (O) R ¹⁰¹, CONH ₂, S (O) ₂r ¹⁰²huo – SO ₂x;

R ¹⁰¹and R ¹⁰², be independently separately, hydrogen, alkyl or the alkyl by hydroxyl or halogen substiuted;

R ⁹⁶~ R ⁹⁸, be independently separately, hydrogen, alkyl, substituted alkyl, by the alkyl chain of one or two heteroatom interruptions, alkoxyl, substituted alkoxy, halogen, trifluoromethyl; Cycloalkyl; Heterocyclylalkyl; Cyano group; Nitro; Acyloxy; Alkyl-carbonyl, acylamino-; Aromatic acylamino, cinnamoyl is amino, alkyl sulfonyl-amino; Alkylthio group; Alkyl sulphonyl, alkoxy carbonyl, carbamoyl, amino-sulfonyl, urea groups, alkyl urea groups, SO ₃m, COOM; Or the group shown in formula (2a) ~ (2c) defined as above-mentioned;

In addition, D ¹and D ²comprise a free valency part to connect active anchor T;

T with M is identical with above-mentioned defined;

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

R ⁹⁰and R ⁹⁴, be independently separately, hydrogen or (C ₁-C ₄)-alkyl or aryl;

R ⁹¹and R ⁹⁵, independent is separately cyano group, carbamido group, alkoxy carbonyl, carbonyl, sulfonymethyl ,-SO ₃m or-COOM;

D ¹and D ², be independently separately, alkyl or aryl; By the alkyl or aryl that more than one substituting group replaces, described substituting group is selected from alkyl, alkoxyl, Lu Su Huo – SO ₃m, amino, N-alkyl amino;

R ⁹⁶~ R ⁹⁸, be independently separately, hydrogen, (C ₁-C ₄)-alkyl, (C ₁-C ₄)-alkoxyl, hydroxyl, carbamido group, Lu Su Huo – SO ₃m, or the group shown in contained (2a) ~ (2c);

R ¹⁰¹and R ¹⁰², be independently separately, hydrogen, alkyl or the alkyl be optionally substituted by a hydroxyl group;

T, X and M are identical with above-mentioned defined.

The present invention further preferred dyestuff is formula (Ii) and the dyestuff shown in (Il) and composition thereof;

Wherein

R ¹⁰⁵, R ¹¹⁰, R ¹¹⁵and R ¹²³, be independently separately, hydrogen, alkyl, cycloalkyl, trifluoromethyl; Alkoxyl, cyano group, carbamoyl, alkoxy carbonyl, COOM, amino; Hydroxyl, monocycle alkyl-amino; Monoalkyl-amino; Two (ring) alkyl-amino; Dialkyl-7-amino; Single aryl-amino; Diaryl-amino; Monocycle alkyl list arylamino; Monoalkyl list arylamino; Alkylthio group; Arylthio;

Or be

R ¹⁰⁶, R ¹¹¹, R ¹¹⁶and R ¹²⁴, be independently separately, cyano group, carbamoyl, alkoxy carbonyl, trifluoromethyl, carbonyl trifluoromethyl, halogen, methyl sulphonyl Huo – SO ₃m;

R ¹⁰⁷, R ¹¹², R ¹¹⁷and R ¹²⁵, be independently separately, hydrogen, alkyl, thiazolinyl, cycloalkyl, trifluoromethyl, aryl, heteroaryl, Heterocyclylalkyl, carbamoyl, N-monocycle alkyl-carbamoyl, N-monoalkyl-amino formoxyl, N, N-bicyclic alkyl-carbamoyl, N, N-dialkyl-carbamoyl radicals, the mono-aryl-carbamoyl of N-, N, N-diaryl-carbamoyl, the single aryl-amino-carbonyl of N-monocycle alkyl-N-, the single aryl-amino-carbonyl of N-monoalkyl-N-, amino-sulfonyl, N-monocycle alkyl-amino-sulfonyl, N-monoalkyl-amino sulfonyl, N, N-bicyclic alkyl amino sulfonyl, N, N-dialkyl-7-amino sulfonyl, the mono-aryl-amino sulfonyl of N-, N, N-diaryl-amino-sulfonyl, the single n-aryl sulfonyl of N-monocycle alkyl-N-, the single aryl-amino sulfonyl of N-monoalkyl-N-, amino, N-acylamino-, N-thio acylamino, urea groups, alkyl urea groups, phenyl urea groups, N-alkyl monosubstituted amino, N, N-dialkyl-7-amino, N-arylamino, N, N-ammonia diaryl base, N-alkyl-N-aryl-amino, N-monocycloalkylamino, N, N-bicyclic alkyl amino, N-alkyl-N-cycloalkyl-amino, N-aryl-N-cycloalkyl-amino, N-heteroaryl amino, N-heterocyclalkylamino or hydroxyalkyl Sulfonylalkyl,

Or be

By the alkyl that one or more hetero atom interrupts as oxygen or sulphur;

Or be

R ¹⁰⁸, R ¹⁰⁹, R ¹¹³, R ¹¹⁴, R ¹²¹, R ¹²², R ¹²⁹and R ¹³⁰, be independently separately, hydrogen or alkyl, alkoxyl, halogen, cyano group ,-SO ₃m, trifluoromethyl, nitro, ester group, NHC (O) R ¹³¹, CONH ₂, S (O) ₂r ¹³²huo – SO ₂x;

R ¹³¹and R ¹³², be independently separately, hydrogen, alkyl or the alkyl by hydroxyl or halogen substiuted;

R ¹¹⁸~ R ¹²⁰and R ¹²⁶~ R ¹²⁸, be independently separately, hydrogen, alkyl, substituted alkyl, by the alkyl chain of one or two heteroatom interruptions, alkoxyl, substituted alkoxy, halogen, trifluoromethyl; Cycloalkyl; Heterocyclylalkyl; Cyano group; Nitro; Acyloxy; Alkyl-carbonyl, acylamino-; Aromatic acylamino, cinnamoyl is amino, alkyl sulfonyl-amino; Alkylthio group; Alkyl sulphonyl, alkoxy carbonyl, carbamoyl, amino-sulfonyl, urea groups, alkyl urea groups, SO ₃m, COOM; Or the group shown in contained (2a) ~ (2c);

E ⁴~ E ⁷, be independently separately, the group shown in general formula (E1) ~ (E3);

In the particularly preferred dyestuff of the present invention,

R ¹⁰⁵, R ¹¹⁰, R ¹¹⁵and R ¹²³, be independently separately, hydrogen or (C ₁-C ₄)-alkyl or aryl;

R ¹⁰⁶, R ¹¹¹, R ¹¹⁶and R ¹²⁴, be independently separately, cyano group, carbamido group, alkoxy carbonyl, carbonyl, sulfonymethyl ,-SO ₃m or-COOM;

R ¹⁰⁷, R ¹¹², R ¹¹⁷and R ¹²⁵, be independently separately, alkyl or aryl; By the aryl that more than one substituting group replaces, described substituting group is selected from alkyl, alkoxyl, Lu Su Huo – SO ₃m;

R ¹¹⁸~ R ¹²⁰and R ¹²⁶~ R ¹²⁸, be independently separately, hydrogen, (C ₁-C ₄)-alkyl, (C ₁-C ₄)-alkoxyl, hydroxyl, carbamido group, Lu Su Huo – SO ₃m or the group shown in contained (2a) ~ (2c);

R ¹⁰⁸, R ¹⁰⁹, R ¹¹³, R ¹¹⁴, R ¹²¹, R ¹²², R ¹²⁹and R ¹³⁰, be independently separately, hydrogen or alkyl, alkoxyl, halogen ,-SO ₃m Huo – SO ₂x;

R ¹³¹and R ¹³², be independently separately, hydrogen, alkyl or the alkyl be optionally substituted by a hydroxyl group;

R ¹³³and R ¹³⁴, be independently that hydrogen, alkyl, by SO separately ₃the alkyl that M replaces;

T, X and M are identical with above-mentioned defined.

The present invention further preferred dyestuff is dyestuff shown in formula (Im) ~ (Ip) and composition thereof;

Wherein

R ¹³⁵, R ¹³⁹, R ¹⁴³and R ¹⁵⁰, be independently separately, hydrogen, alkyl, cycloalkyl, trifluoromethyl; Alkoxyl, cyano group, carbamoyl, alkoxy carbonyl, COOM, amino; Hydroxyl, monocycle alkyl-amino; Monoalkyl-amino; Two (ring) alkyl-amino; Dialkyl-7-amino; Single aryl-amino; Diaryl-amino; Monocycle alkyl list arylamino; Monoalkyl list arylamino; Alkylthio group; Arylthio;

Or be

R ¹³⁶, R ¹⁴⁰, R ¹⁴⁴and R ¹⁵¹, be independently separately, cyano group, carbamoyl, alkoxy carbonyl, trifluoromethyl, carbonyl trifluoromethyl, halogen, methyl sulphonyl Huo – SO ₃m;

D ³, D ⁴, D ⁵and D ⁶, be independently separately, hydrogen, alkyl, thiazolinyl, cycloalkyl, trifluoromethyl, aryl, heteroaryl, Heterocyclylalkyl, carbamoyl, N-monocycle alkyl-carbamoyl, N-monoalkyl-amino formoxyl, N, N-bicyclic alkyl-carbamoyl, N, N-dialkyl-carbamoyl radicals, the mono-aryl-carbamoyl of N-, N, N-diaryl-carbamoyl, the single aryl-amino-carbonyl of N-monocycle alkyl-N-, the single aryl-amino-carbonyl of N-monoalkyl-N-, amino-sulfonyl, N-monocycle alkyl-amino-sulfonyl, N-monoalkyl-amino sulfonyl, N, N-bicyclic alkyl amino sulfonyl, N, N-dialkyl-7-amino sulfonyl, the mono-aryl-amino sulfonyl of N-, N, N-diaryl-amino-sulfonyl, the single n-aryl sulfonyl of N-monocycle alkyl-N-, the single aryl-amino sulfonyl of N-monoalkyl-N-, amino, N-acylamino-, N-thio acylamino, urea groups, alkyl urea groups, phenyl urea groups, N-alkyl monosubstituted amino, N, N-dialkyl-7-amino, N-arylamino, N, N-ammonia diaryl base, N-alkyl-N-aryl-amino, N-monocycloalkylamino, N, N-bicyclic alkyl amino, N-alkyl-N-cycloalkyl-amino, N-aryl-N-cycloalkyl-amino, N-heteroaryl amino, N-heterocyclalkylamino or hydroxyalkyl Sulfonylalkyl,

Or

By the alkyl that one or more hetero atom interrupts as oxygen or sulphur;

Or

R ¹³⁷, R ¹³⁸, R ¹⁴¹, R ¹⁴², R ¹⁴⁸, R ¹⁴⁹, R ¹⁵⁵and R ¹⁵⁶, be independently separately, hydrogen or alkyl, alkoxyl, halogen, cyano group ,-SO ₃m, trifluoromethyl, nitro, ester group, NHC (O) R ¹⁵⁷, CONH ₂, S (O) ₂r ¹⁵⁸huo – SO ₂x;

R ¹⁵⁷and R ¹⁵⁸, be independently separately, hydrogen, alkyl or the alkyl by hydroxyl or halogen substiuted;

R ¹⁴⁵, R ¹⁴⁶, R ¹⁴⁷, R ¹⁵², R ¹⁵³and R ¹⁵⁴, be independently separately, hydrogen, alkyl, substituted alkyl, by the alkyl chain of one or two heteroatom interruptions, alkoxyl, substituted alkoxy, halogen, trifluoromethyl; Cycloalkyl; Heterocyclylalkyl; Cyano group; Nitro; Acyloxy; Alkyl-carbonyl, acylamino-; Aromatic acylamino, cinnamoyl is amino, alkyl sulfonyl-amino; Alkylthio group; Alkyl sulphonyl, alkoxy carbonyl, carbamoyl, amino-sulfonyl, urea groups, alkyl urea groups, SO ₃m, COOM; Or the group comprised as shown in above-mentioned formula (2a) ~ (2c) defined;

E ⁸~ E ¹¹, be independently separately, the group shown in general formula (E1) ~ (E3) defined as above-mentioned;

T, X and M are identical with above-mentioned defined.

In the dyestuff shown in particularly preferred formula (Im) ~ (Ip),

R ¹³⁵, R ¹³⁹, R ¹⁴³and R ¹⁵⁰, be independently separately, hydrogen or (C ₁-C ₄)-alkyl or aryl;

R ¹³⁶, R ¹⁴⁰, R ¹⁴⁴and R ¹⁵¹, be independently separately, cyano group, carbamido group, alkoxy carbonyl, carbonyl, sulfonymethyl ,-SO ₃m or-COOM;

D ³, D ⁴, D ⁵and D ⁶, be independently separately, alkyl or aryl; By the alkyl or aryl that more than one substituting group replaces, described substituting group is selected from alkyl, alkoxyl, Lu Su Huo – SO ₃m, amino, N-alkyl amino; Or by amino that T replaces;

R ¹³⁷, R ¹³⁸, R ¹⁴¹, R ¹⁴², R ¹⁴⁸, R ¹⁴⁹, R ¹⁵⁵and R ¹⁵⁶, be independently separately, hydrogen or alkyl, alkoxyl, halogen ,-SO ₃m Huo – SO ₂x;

R ¹⁴⁵~ R ¹⁴⁷and R ¹⁵²~ R ¹⁵⁴, be independently separately, hydrogen, (C ₁-C ₄)-alkyl, (C ₁-C ₄)-alkoxyl, hydroxyl, carbamido group, Lu Su Huo – SO ₃m or the group shown in contained (2a) ~ (2c);

E ⁸~ E ¹¹, be independently separately, the group shown in general formula (E1) ~ (E3);

T, X and M are identical with above-mentioned defined.

The present invention further preferred dyestuff is dyestuff shown in formula (Iq) ~ (It) and composition thereof;

Wherein

R ¹⁶¹, R ¹⁶⁸, R ¹⁷⁵and R ¹⁸⁵, be independently separately, alkyl, cyano group, carbamoyl, alkoxy carbonyl, trifluoromethyl, carbonyl trifluoromethyl, halogen, methyl sulphonyl Huo – SO ₃m;

R ¹⁶², R ¹⁶⁹, R ¹⁷⁶and R ¹⁸⁶be independently separately, hydroxyl or amino;

R ¹⁶³~ R ¹⁶⁵, R ¹⁷⁰~ R ¹⁷², R ¹⁷⁷~ R ¹⁷⁹and R ¹⁸⁷~ R ¹⁸⁹, be independently separately, hydrogen, alkyl, thiazolinyl, cycloalkyl, trifluoromethyl, aryl, heteroaryl, Heterocyclylalkyl, carbamoyl, N-monocycle alkyl-carbamoyl, N-monoalkyl-amino formoxyl, N, N-bicyclic alkyl-carbamoyl, N, N-dialkyl-carbamoyl radicals, the mono-aryl-carbamoyl of N-, N, N-diaryl-carbamoyl, the single aryl-amino-carbonyl of N-monocycle alkyl-N-, the single aryl-amino-carbonyl of N-monoalkyl-N-, amino-sulfonyl, N-monocycle alkyl-amino-sulfonyl, N-monoalkyl-amino sulfonyl, N, N-bicyclic alkyl amino sulfonyl, N, N-dialkyl-7-amino sulfonyl, the mono-aryl-amino sulfonyl of N-, N, N-diaryl-amino-sulfonyl, the single n-aryl sulfonyl of N-monocycle alkyl-N-, the single aryl-amino sulfonyl of N-monoalkyl-N-, amino, N-acylamino-, N-thio acylamino, urea groups, alkyl urea groups, phenyl urea groups, N-alkyl monosubstituted amino, N, N-dialkyl-7-amino, N-arylamino, N, N-ammonia diaryl base, N-alkyl-N-aryl-amino, N-monocycloalkylamino, N, N-bicyclic alkyl amino, N-alkyl-N-cycloalkyl-amino, N-aryl-N-cycloalkyl-amino, N-heteroaryl amino, N-heterocyclalkylamino or hydroxyalkyl Sulfonylalkyl,

Or be

By the alkyl that one or more hetero atom interrupts as oxygen or sulphur;

Or be

Or Bei – SO ₂the alkyl or aryl that X replaces; 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; Or

A free valency part is to connect active anchor T;

R ¹⁶⁶, R ¹⁶⁷, R ¹⁷³, R ¹⁷⁴, R ¹⁸³, R ¹⁸⁴, R ¹⁹³and R ¹⁹⁴, be independently separately, hydrogen or alkyl, alkoxyl, halogen, cyano group ,-SO ₃m, trifluoromethyl, nitro, ester group, NHC (O) R ¹⁹⁵, CONH ₂, S (O) ₂r ¹⁹⁶huo – SO ₂x;

R ¹⁹⁵and R ¹⁹⁶, be independently separately, hydrogen, alkyl or the alkyl by hydroxyl or halogen substiuted;

R ¹⁸⁰~ R ¹⁸²and R ¹⁹⁰~ R ¹⁹², be independently separately, hydrogen, alkyl, substituted alkyl, by the alkyl chain of one or two heteroatom interruptions, alkoxyl, substituted alkoxy, halogen, trifluoromethyl; Cycloalkyl; Heterocyclylalkyl; Cyano group; Nitro; Acyloxy; Alkyl-carbonyl, acylamino-; Aromatic acylamino, cinnamoyl is amino, alkyl sulfonyl-amino; Alkylthio group; Alkyl sulphonyl, alkoxy carbonyl, carbamoyl, amino-sulfonyl, urea groups, alkyl urea groups, SO ₃m, COOM; Or the group shown in contained (2a) ~ (2c);

X is identical with above-mentioned defined.

In the particularly preferred dyestuff of the present invention,

R ¹⁶¹, R ¹⁶⁸, R ¹⁷⁵and R ¹⁸⁵, be (C ₁-C ₄)-alkyl, cyano group, carbamido group, alkoxy carbonyl, carbonyl or sulfonymethyl;

R ¹⁶², R ¹⁶⁹, R ¹⁷⁶and R ¹⁸⁶for hydroxyl or amino;

R ¹⁶³~ R ¹⁶⁵, R ¹⁷⁰~ R ¹⁷², R ¹⁷⁷~ R ¹⁷⁹and R ¹⁸⁷~ R ¹⁸⁹, independent is separately hydrogen, (C ₁-C ₄)-alkyl, (C ₁-C ₄)-alkoxyl, halogen ,-SO ₃m Huo – SO ₂x or the free valency replaced with T;

R ¹⁶⁶, R ¹⁶⁷, R ¹⁷³, R ¹⁷⁴, R ¹⁸³, R ¹⁸⁴, R ¹⁹³and R ¹⁹⁴, be independently separately, hydrogen, (C ₁-C ₄)-alkyl, (C ₁-C ₄)-alkoxyl, Lu Su Huo – SO ₃m;

R ¹⁸⁰~ R ¹⁸²and R ¹⁹⁰~ R ¹⁹², be independently separately, hydrogen, (C ₁-C ₄)-alkyl, (C ₁-C ₄)-alkoxyl, hydroxyl, carbamido group, Lu Su Huo – SO ₃m or the group shown in contained (2a) ~ (2c);

T, X and M have implication same as described above.

The present invention further preferred dyestuff is dyestuff shown in formula (Iu) ~ (Ix) and composition thereof;

Wherein

R ¹⁹⁹, R ²⁰⁶, R ²¹³and R ²²³, be independently separately, alkyl, cyano group, carbamoyl, alkoxy carbonyl, trifluoromethyl, carbonyl trifluoromethyl, halogen, methyl sulphonyl Huo – SO ₃m;

R ²⁰⁰, R ²⁰⁷, R ²¹⁴and R ²²⁴, be independently separately, hydroxyl or amino;

R ²⁰¹~ R ²⁰³, R ²⁰⁸~ R ²¹⁰, R ²¹⁵~ R ²¹⁷and R ²²⁵~ R ²²⁷, be independently separately, hydrogen, alkyl, thiazolinyl, cycloalkyl, trifluoromethyl, aryl, heteroaryl, Heterocyclylalkyl, carbamoyl, N-monocycle alkyl-carbamoyl, N-monoalkyl-amino formoxyl, N, N-bicyclic alkyl-carbamoyl, N, N-dialkyl-carbamoyl radicals, the mono-aryl-carbamoyl of N-, N, N-diaryl-carbamoyl, the single aryl-amino-carbonyl of N-monocycle alkyl-N-, the single aryl-amino-carbonyl of N-monoalkyl-N-, amino-sulfonyl, N-monocycle alkyl-amino-sulfonyl, N-monoalkyl-amino sulfonyl, N, N-bicyclic alkyl amino sulfonyl, N, N-dialkyl-7-amino sulfonyl, the mono-aryl-amino sulfonyl of N-, N, N-diaryl-amino-sulfonyl, the single n-aryl sulfonyl of N-monocycle alkyl-N-, the single aryl-amino sulfonyl of N-monoalkyl-N-, amino, N-acylamino-, N-thio acylamino, urea groups, alkyl urea groups, phenyl urea groups, N-alkyl monosubstituted amino, N, N-dialkyl-7-amino, N-arylamino, N, N-ammonia diaryl base, N-alkyl-N-aryl-amino, N-monocycloalkylamino, N, N-bicyclic alkyl amino, N-alkyl-N-cycloalkyl-amino, N-aryl-N-cycloalkyl-amino, N-heteroaryl amino, N-heterocyclalkylamino or hydroxyalkyl Sulfonylalkyl,

Or be

By the alkyl that one or more hetero atom interrupts as oxygen or sulphur;

Or be

Or Bei – SO ₂the alkyl or aryl that X replaces; 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; Or comprise a free valency part to connect active anchor T;

R ²⁰⁴, R ²⁰⁵, R ²¹¹, R ²¹², R ²²¹, R ²²², R ²³¹and R ²³², be independently separately, hydrogen or alkyl, alkoxyl, halogen, cyano group ,-SO ₃m, trifluoromethyl, nitro, ester group, NHC (O) R ²³³, CONH ₂, S (O) ₂r ²³⁴huo – SO ₂x;

R ²³³and R ²³⁴, be independently separately, hydrogen, alkyl or the alkyl by hydroxyl or halogen substiuted;

R ²¹⁸~ R ²²⁰and R ²²⁸~ R ²³⁰, be independently separately, hydrogen, alkyl, substituted alkyl, by the alkyl chain of one or two heteroatom interruptions, alkoxyl, substituted alkoxy, halogen, trifluoromethyl; Cycloalkyl; Heterocyclylalkyl; Cyano group; Nitro; Acyloxy; Alkyl-carbonyl, acylamino-; Aromatic acylamino, cinnamoyl is amino, alkyl sulfonyl-amino; Alkylthio group; Alkyl sulphonyl, alkoxy carbonyl, carbamoyl, amino-sulfonyl, urea groups, alkyl urea groups, SO ₃m, COOM; Or the group shown in formula (2a) ~ (2c) defined as above-mentioned;

E ¹²~ E ¹⁵, be independently separately, the group shown in general formula (E1) ~ (E3);

T, X and M have implication same as described above.

In the particularly preferred dyestuff of the present invention,

R ¹⁹⁹, R ²⁰⁶, R ²¹³and R ²²³, independent is separately (C ₁-C ₄)-alkyl, cyano group, carbamido group, alkoxy carbonyl, carbonyl or sulfonymethyl;

R ²⁰¹~ R ²⁰³, R ²⁰⁸~ R ²¹⁰, R ²¹⁵~ R ²¹⁷and R ²²⁵~ R ²²⁷, be independently separately, hydrogen, (C ₁-C ₄)-alkyl, (C ₁-C ₄)-alkoxyl, halogen ,-SO ₃m Huo – SO ₂x or the free valency replaced with T;

R ²⁰⁴, R ²⁰⁵, R ²¹¹, R ²¹², R ²²¹, R ²²², R ²³¹and R ²³², be independently separately, hydrogen, (C ₁-C ₄)-alkyl, (C ₁-C ₄)-alkoxyl, Lu Su Huo – SO ₃m;

R ²¹⁸~ R ²²⁰and R ²²⁸~ R ²³⁰, be independently separately, hydrogen, (C ₁-C ₄)-alkyl, (C ₁-C ₄)-alkoxyl, hydroxyl, carbamido group, Lu Su Huo – SO ₃m or the group shown in contained (2a) ~ (2c);

T and X has implication same as described above.

The present invention further preferred dyestuff is dyestuff shown in formula (Iy) ~ (Iab) and composition thereof;

Wherein

R ²³⁷, R ²⁴⁵, R ²⁵³and R ²⁶⁴, be independently separately, hydrogen, alkyl, cycloalkyl, trifluoromethyl; Alkoxyl, cyano group, carbamoyl, alkoxy carbonyl, COOM, amino; Hydroxyl, monocycle alkyl-amino; Monoalkyl-amino; Two (ring) alkyl-amino; Dialkyl-7-amino; Single aryl-amino; Diaryl-amino; Monocycle alkyl list arylamino; Monoalkyl list arylamino; Alkylthio group; Arylthio;

Or be

R ²³⁸, R ²⁴⁶, R ²⁵⁴and R ²⁶⁵, be independently separately, cyano group, carbamoyl, alkoxy carbonyl, trifluoromethyl, carbonyl trifluoromethyl, halogen, methyl sulphonyl Huo – SO ₃m;

R ²³⁹~ R ²⁴², R ²⁴⁷~ R ²⁵⁰, R ²⁵⁵~ R ²⁵⁸and R ²⁶⁷~ R ²⁷⁰, be independently separately, hydrogen, alkyl, thiazolinyl, cycloalkyl, trifluoromethyl, aryl, heteroaryl, Heterocyclylalkyl, carbamoyl, N-monocycle alkyl-carbamoyl, N-monoalkyl-amino formoxyl, N, N-bicyclic alkyl-carbamoyl, N, N-dialkyl-carbamoyl radicals, the mono-aryl-carbamoyl of N-, N, N-diaryl-carbamoyl, the single aryl-amino-carbonyl of N-monocycle alkyl-N-, the single aryl-amino-carbonyl of N-monoalkyl-N-, amino-sulfonyl, N-monocycle alkyl-amino-sulfonyl, N-monoalkyl-amino sulfonyl, N, N-bicyclic alkyl amino sulfonyl, N, N-dialkyl-7-amino sulfonyl, the mono-aryl-amino sulfonyl of N-, N, N-diaryl-amino-sulfonyl, the single n-aryl sulfonyl of N-monocycle alkyl-N-, the single aryl-amino sulfonyl of N-monoalkyl-N-, amino, N-acylamino-, N-thio acylamino, urea groups, alkyl urea groups, phenyl urea groups, N-alkyl monosubstituted amino, N, N-dialkyl-7-amino, N-arylamino, N, N-ammonia diaryl base, N-alkyl-N-aryl-amino, N-monocycloalkylamino, N, N-bicyclic alkyl amino, N-alkyl-N-cycloalkyl-amino, N-aryl-N-cycloalkyl-amino, N-heteroaryl amino, N-heterocyclalkylamino or hydroxyalkyl Sulfonylalkyl,

Or be

By the alkyl that one or more hetero atom interrupts as oxygen or sulphur;

Or be

By the alkyl that one or more substituting group replaces, described substituting group is selected from the group be made up of following groups: hydroxyl, aryl, cycloalkyl, alkoxyl, thio alkoxy, amino, N-monoalkyl-amino, N, N-dialkyl amido, 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-monocycle alkyl-amino, N, the mono-aryl of N--monocycle alkyl-amino, N-acylamino-, N-alkylsulfonyl-amino, urea groups, alkyl urea groups, phenyl urea groups, halogen, cyano group, COOM, nitro, acyl group, Thioacyl, alkyl sulphonyl, aroyl, trifluoromethyl, heteroaryl, Heterocyclylalkyl, alkoxy carbonyl, alkoxy carbonyl, acyloxy, aryl acyloxy, carbamoyl, N-monocycle alkyl-carbamoyl, N-monoalkyl-amino formoxyl, N, N-bicyclic alkyl-carbamoyl, N, N-dialkyl-carbamoyl radicals, the mono-aryl-carbamoyl of N-, N, N-diaryl-carbamoyl, 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 sulfonyl, N, N-bicyclic alkyl-amino-sulfonyl, N, N-dialkyl-7-amino sulfonyl, the mono-n-aryl sulfonyl of N-, N, N-diaryl-amino-sulfonyl, the single n-aryl sulfonyl of N-monocycle alkyl-N-, the single n-aryl sulfonyl of N-monoalkyl-N-or-SO ₃m, or comprise the alkyl of a free valency part to connect active anchor T,

R ²⁴³, R ²⁴⁴, R ²⁵¹, R ²⁵², R ²⁶², R ²⁶³, R ²⁷⁴and R ²⁷⁵, be independently separately, hydrogen or alkyl, alkoxyl, halogen, cyano group ,-SO ₃m, trifluoromethyl, nitro, ester group, NHC (O) R ²⁷⁶, CONH ₂, S (O) ₂r ²⁷⁷huo – SO ₂x;

R ²⁷⁶and R ²⁷⁷, be independently separately, hydrogen, alkyl or the alkyl by hydroxyl or halogen substiuted;

R ²⁵⁹~ R ²⁶¹and R ²⁷¹~ R ²⁷³, be independently separately, hydrogen, alkyl, substituted alkyl, by the alkyl chain of one or two heteroatom interruptions, alkoxyl, substituted alkoxy, halogen, trifluoromethyl; Cycloalkyl; Heterocyclylalkyl; Cyano group; Nitro; Acyloxy; Alkyl-carbonyl, acylamino-; Aromatic acylamino, cinnamoyl is amino, alkyl sulfonyl-amino; Alkylthio group; Alkyl sulphonyl, alkoxy carbonyl, carbamoyl, amino-sulfonyl, urea groups, alkyl urea groups, SO ₃m, COOM; Or the group comprised as shown in above-mentioned formula (2a) ~ (2c) defined;

In the dyestuff shown in particularly preferred formula (Iy) ~ (Iab),

R ²³⁷, R ²⁴⁵, R ²⁵³and R ²⁶⁴for hydrogen or (C ₁-C ₄)-alkyl, aryl, (C ₁-C ₄)-alkoxyl;

R ²³⁸, R ²⁴⁶, R ²⁵⁴and R ²⁶⁵for (C ₁-C ₄)-alkyl, cyano group, carbamido group, alkoxy carbonyl, carbonyl or sulfonymethyl;

R ²³⁹~ R ²⁴², R ²⁴⁷~ R ²⁵⁰, R ²⁵⁵~ R ²⁵⁸and R ²⁶⁷~ R ²⁷⁰, be independently separately, hydrogen, (C ₁-C ₄)-alkyl, (C ₁-C ₆)-alkoxyl, aryl;

Huo person – alkyl-SO ₂x,

Or by the aryl that one or more substituting group replaces, described substituting group is selected from halogen ,-SO ₃m Huo – SO ₂x or the free valency replaced with T;

R ²⁴³, R ²⁴⁴, R ²⁵¹, R ²⁵², R ²⁶², R ²⁶³, R ²⁷⁴and R ²⁷⁵, independent is separately hydrogen, (C ₁-C ₄)-alkyl, (C ₁-C ₄)-alkoxyl, Lu Su Huo – SO ₃m;

R ²⁵⁹~ R ²⁶¹and R ²⁷¹~ R ²⁷³, be independently separately, hydrogen, (C ₁-C ₄)-alkyl, (C ₁-C ₄)-alkoxyl, hydroxyl, carbamido group, Lu Su Huo – SO ₃m or the group shown in contained (2a) ~ (2c);

T, X and M are identical with above-mentioned defined.

The present invention further preferred dyestuff is dyestuff shown in formula (Iac) ~ (Iaf) and composition thereof;

Wherein

R ²⁸⁰, R ²⁸⁸, R ²⁹⁶and R ³⁰⁷, be independently separately, hydrogen, alkyl, cycloalkyl, trifluoromethyl; Alkoxyl, cyano group, carbamoyl, alkoxy carbonyl, COOM, amino; Hydroxyl, monocycle alkyl-amino; Monoalkyl-amino; Two (ring) alkyl-amino; Dialkyl-7-amino; Single aryl-amino; Diaryl-amino; Monocycle alkyl list arylamino; Monoalkyl list arylamino; Alkylthio group; Arylthio;

Or be

R ²⁸¹, R ²⁸⁹, R ²⁹⁷and R ³⁰⁸, be independently separately, cyano group, carbamoyl, alkoxy carbonyl, trifluoromethyl, carbonyl trifluoromethyl, halogen, methyl sulphonyl Huo – SO ₃m;

R ²⁸²~ R ²⁸⁵, R ²⁹⁰~ R ²⁹³, R ²⁹⁸~ R ³⁰¹and R ³⁰⁹~ R ³¹², be independently separately, hydrogen, alkyl, thiazolinyl, cycloalkyl, trifluoromethyl, aryl, heteroaryl, Heterocyclylalkyl, carbamoyl, N-monocycle alkyl-carbamoyl, N-monoalkyl-amino formoxyl, N, N-bicyclic alkyl-carbamoyl, N, N-dialkyl-carbamoyl radicals, the mono-aryl-carbamoyl of N-, N, N-diaryl-carbamoyl, the single aryl-amino-carbonyl of N-monocycle alkyl-N-, the single aryl-amino-carbonyl of N-monoalkyl-N-, amino-sulfonyl, N-monocycle alkyl-amino-sulfonyl, N-monoalkyl-amino sulfonyl, N, N-bicyclic alkyl amino sulfonyl, N, N-dialkyl-7-amino sulfonyl, the mono-aryl-amino sulfonyl of N-, N, N-diaryl-amino-sulfonyl, the single n-aryl sulfonyl of N-monocycle alkyl-N-, the single aryl-amino sulfonyl of N-monoalkyl-N-, amino, N-acylamino-, N-thio acylamino, urea groups, alkyl urea groups, phenyl urea groups, N-alkyl monosubstituted amino, N, N-dialkyl-7-amino, N-arylamino, N, N-ammonia diaryl base, N-alkyl-N-aryl-amino, N-monocycloalkylamino, N, N-bicyclic alkyl amino, N-alkyl-N-cycloalkyl-amino, N-aryl-N-cycloalkyl-amino, N-heteroaryl amino, N-heterocyclalkylamino or hydroxyalkyl Sulfonylalkyl,

Or be

By the alkyl that one or more hetero atom interrupts as oxygen or sulphur;

Or be

R ²⁸⁶, R ²⁸⁷, R ²⁹⁴, R ²⁹⁵, R ³⁰⁵, R ³⁰⁶, R ³¹⁶and R ³¹⁷, be independently separately, hydrogen or alkyl, alkoxyl, halogen, cyano group ,-SO ₃m, trifluoromethyl, nitro, ester group, NHC (O) R ³¹⁸, CONH ₂, S (O) ₂r ³¹⁹huo – SO ₂x;

R ³¹⁸and R ³¹⁹, be independently separately, hydrogen, alkyl or the alkyl by hydroxyl or halogen substiuted;

R ³⁰²~ R ³⁰⁴and R ³¹³~ R ³¹⁵, be independently separately, hydrogen, alkyl, substituted alkyl, by the alkyl chain of one or two heteroatom interruptions, alkoxyl, substituted alkoxy, halogen, trifluoromethyl; Cycloalkyl; Heterocyclylalkyl; Cyano group; Nitro; Acyloxy; Alkyl-carbonyl, acylamino-; Aromatic acylamino, cinnamoyl is amino, alkyl sulfonyl-amino; Alkylthio group; Alkyl sulphonyl, alkoxy carbonyl, carbamoyl, amino-sulfonyl, urea groups, alkyl urea groups, SO ₃m, COOM; Or the group comprised as shown in above-mentioned formula (2a) ~ (2c) defined;

E ¹⁶~ E ¹⁹, be independently separately, the group shown in general formula (E1) ~ (E3);

T, X and M have the implication identical with above-mentioned definition.

In the particularly preferred dyestuff of the present invention,

R ²⁸⁰, R ²⁸⁸, R ²⁹⁶and R ³⁰⁷, be independently separately, hydrogen or (C ₁-C ₄)-alkyl, aryl, (C ₁-C ₄)-alkoxyl;

R ²⁸¹, R ²⁸⁹, R ²⁹⁷and R ³⁰⁸, be independently separately, (C ₁-C ₄)-alkyl, cyano group, carbamido group, alkoxy carbonyl, carbonyl or sulfonymethyl;

R ²⁸²~ R ²⁸⁵, R ²⁹⁰~ R ²⁹³, R ²⁹⁸~ R ³⁰¹and R ³⁰⁹~ R ³¹¹, be independently separately, hydrogen, (C ₁-C ₄)-alkyl, (C ₁-C ₆)-alkoxyl, aryl;

Huo person – alkyl-SO ₂x,

R ²⁸⁶, R ²⁸⁷, R ²⁹⁴, R ²⁹⁵, R ³⁰⁵, R ³⁰⁶, R ³¹⁶and R ³¹⁷, be independently separately, hydrogen, (C ₁-C ₄)-alkyl, (C ₁-C ₄)-alkoxyl, Lu Su Huo – SO ₃m;

R ³⁰²~ R ³⁰⁴and R ³¹³~ R ³¹⁵, be independently separately, hydrogen, (C ₁-C ₄)-alkyl, (C ₁-C ₄)-alkoxyl, hydroxyl, carbamido group, Lu Su Huo – SO ₃m or the group shown in contained (2a) ~ (2c);

T, X and M are identical with above-mentioned defined.

The preferred dyestuff example of the present invention corresponds to the dyestuff (table 1) of general formula (II) from 1 ~ 168.

Wherein

K ⁷be the group of heterocycle coupled structures part, and there is the implication identical with above-mentioned K;

A ³be the group of intermediate structure part, and there is the implication identical with above-mentioned A;

B ³be the group of diazonium structure division, and there is the implication identical with above-mentioned B;

M is hydrogen, sodium, potassium, lithium or ammonium;

Table 1

The present invention further preferred dyestuff example be correspond to general formula (III) from 169 ~ 336 dyestuff (table 2).

Wherein

K ⁸be the group of heterocycle coupled structures part, and there is the implication identical with above-mentioned K;

A ⁴be the group of intermediate structure part, and there is the implication identical with above-mentioned A;

B ⁴be the group of diazonium structure division, and there is the implication identical with above-mentioned B;

M is hydrogen, sodium, potassium, lithium or ammonium;

Table 2

Present invention also offers the preparation method of dyestuff shown in formula (I), the method comprises the diazotization of compound shown in formula (IV), and compound shown in the diazol of corresponding gained and formula K reacts to obtain the intermediate shown in general formula (V).

In a rear step, diazo component (B-NH ₂) by diazotization, and be coupled on intermediate V to obtain the bisazo thing shown in general formula (VI).

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

Further, dyestuff (VI) and (VIII) and mantoquita particularly copper sulphate react, to obtain copper complex dyestuff (Ⅸ) and (Ⅹ).

Wherein A, B and K have implication same as described above.

Formula (IV), B-NH ₂(VII) diazo-reaction of compound shown in, undertaken by diazotisation methods well known by persons skilled in the art, preferably in acid medium, use natrium nitrosum or nitrosylsulfuric acid, described acid medium adopts inorganic acid to compare example hydrochloric acid, sulfuric acid or phosphoric acid or their mixture, or organic acid such as acetic acid or propionic acid or their mixture.Inorganic acid and organic acid mixture also can advantageously use.

Through diazotizing formula (IV), B-NH ₂(VII) shown in, the coupling reaction of compound shown in compound and formula (K) and (V), is undertaken by known method equally.

The complexation reaction of dyestuff (VI) and (VIII) is undertaken by known method equally.

Compound shown in formula A, B and K is known and commercially available acquisition, or is synthesized by conventional chemical reaction method well known by persons skilled in the art.

Present invention also offers dyestuff of the present invention and comprise hydroxyl, amino, and/or the application in the dyeing of formamido group material or stamp, or comprise the dyeing of hydroxyl and/or formamido group material or the technique of stamp, wherein dyestuff is applied to material by conventional method and anchors on material, and described technology utilization is according to dyestuff of the present invention.

The material of hydroxyl can be natural or synthesis source.Such as cellulosic fibre material, preferably cotton, flax, hemp, jute and ramee, regenerated celulose fibre, as preferred short fiber viscose glue and long filament viscose glue, the cellulose fibre of chemical modification, as the cellulose fibre of amination, and polyvinyl alcohol.

Material containing formamido group is, such as synthesize with natural polyamide and polyurethane, as wool and other animal hair, silk, leather, nylon-6,6, nylon-6, nylon-11 and nylon-4.

Described hydroxyl and/or can present in a variety of forms containing the material of formamido group.Such as with the form of laminated structure, as paper and leather, in the form of a film, as nylon film, or with large block form, as being made up of polyamide and polyurethane, particularly in the form of fibers, as cellulose fibre.Described fiber preferably textile fiber, such as, with the form of woven fabric or yarn, or with the form of reeled yarn or wound bag.

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 multicomponent product mix.

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 performance with this type of dyestuff together.Technical performance comprises lifting force, fixing property and equalization.

Mentioned material can be applied to, particularly mentioned fibrous material, by the known application technology for water-soluble dye according to dyestuff of the present invention.This is applicable to simultaneously, dyeing and printing technology.

The dyeing that it is specially adapted on fibrous material is produced, and described fibrous material is made up of wool or other natural polyamide, or is made up of synthesizing polyamides and composition thereof and other fibrous material.Usually, material to be dyed is introduced in dye bath at temperature about 40 DEG C, stirs a period of time wherein, and then dye bath is adjusted to required faintly acid, preferred weak acetic acid, and pH value regulates and the dyeing of reality carries out at temperature between 60 ~ 98 DEG C.But dyeing also can be carried out under boiling condition or in airtight dyeing apparatus at up to the temperature of 106 DEG C.

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.For this reason, dyestuff of the present invention needs to be mixed with ink.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 other dyestuffs for digital printing.

For the ink of the present invention used in continuous-flow technique, by adding electrolyte, to arrange electrical conductivity be 0.5 ~ 25mS/m.The electrolyte be suitable for comprises such as lithium nitrate and potassium nitrate.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, isopropyl alcohol, n-butyl alcohol, the tert-butyl alcohol, amylalcohol, polyhydric alcohols as: 1, 2-ethylene glycol, 1, 2, 3-glycerol, butanediol, 1, 3-butanediol, 1, 4-butanediol, 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: polyethylene glycol, polypropylene glycol, there is the aklylene glycol of 1 ~ 8 alkylidene, such as: monoethylene glycol, diethylene glycol (DEG), triethylene glycol, tetraethylene glycol, thioglycol, thiodiglycol, butyltriglycol, hexylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, the low alkyl ether of polyalcohol, such as: glycol monoethyl 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, tetraethylene glycol 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, polyethylene glycol tridecyl ether, polyethylene glycol nonylphenyl ether, amine, such as: methylamine, ethamine, triethylamine, diethylamine, dimethylamine, trimethylamine, dibutyl amine, diethanol amine, triethanolamine, N-acetyl ethanonlamine, N-formyl monoethanolamine, ethylenediamine, urea derivative, such as: urea, thiocarbamide, N-MU, N, N '-ε dimethyl urea, ethylidene-urea, 1, 1, 3, 3-tetramethylurea, amide-type, such as: dimethyl formamide, dimethylacetylamide, acetamide, ketone or ketols, such as: acetone, DAA, cyclic ethers class, such as: oxolane, trimethylolethane, trimethylolpropane, butoxy ethanol, phenmethylol, butoxy ethanol, gamma-butyrolacton, epsilon-caprolactams, be sulfolane further, dimethylsulfolane, methyl sulfolane, 2, 4-dimethylsulfolane, dimethyl sulfone, butadiene sulfone, methyl-sulfoxide, dibutyl sulfoxide, N-cyclohexyl pyrrolidone, METHYLPYRROLIDONE, N-ethyl pyrrolidone, 2-Pyrrolidone, 1-(2-ethoxy)-2-Pyrrolidone, 1-(3-hydroxypropyl)-2-Pyrrolidone, 1, 3-dimethyl-2-imidazolidinone, 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-propoxyl group ethyoxyl) ethanol, pyridine, piperidines, 1, 3-dimethyl-2-imidazolidinone, butyrolactone, trimethyl propane, 1, 2-dimethoxy propane, dioxanes ethyl acetate, ethylenediamine tetra-acetic acid ethyl pentyl group ether, 1, 2-dimethoxy propane 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, polyurethane, sodium alginate, modified galactomannans, polyethers urea, polyurethane, nonionic cellulose ether.

As further additive, ink of the present invention can comprise surface reactive material 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 surface reactive material be suitable for comprises such as: all surfactants, 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 stamp of multiple pretreated material, and such as silk, leather, wool, polyamide fiber and polyurethane, and the cellulosic fibre material of any kind.BLENDED FABRIC, such as cotton, silk, the blend of wool and polyester fiber or polyamide fiber is same can stamp.

Different from traditional textile printing, in traditional textile printing, printing inks has contained all required chemicals, numeral or ink-jet printed in, auxiliary agent must be applied on fabric substrate in an independent pre-treatment step.

The preliminary treatment of textile substrate, such as cellulose and regenerated celulose fibre and silk and wool are before stamp, use aqueous alkali process.In addition, need thickener to prevent flowing when using printing inks, such as sodium alginate, the galactomannans of modified polyacrylate or height etherificate.

These pretreating reagents put on fabric substrate equably according to the suitable applicator of formula ratio, such as, use 2-or 3-roller pad, contactless spraying technology, foam coating method or use suitable ink-jet technology, and dry subsequently.

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

The synthesis step of dyestuff example 1

8.0 parts of 4-amino-5-hydroxyl naphthalene-2,7-disulfonic acid (a) are dissolved in 50 parts of water.With ice-salt mixture reactor vessel cooled to 0 ~ 5 DEG C.After 10 minutes, 7.5 part of 37% hydrochloric acid is added in reactant mixture.Reactant mixture stirs 1 ~ 2 hour.After completing, 0.2 part of sulfamic acid is added in reactant mixture.

8.7 parts of coupling components (b) are suspended in 50 parts of water.Regulate pH to 4.5.Add diazo component.Reactant mixture stirs 2 hours.After completing, by adding salt and filtering subsequently, obtain 16.1 parts of products (c).

8.6 part of 2,5-Dimethoxyphenyl-4 (2-sulfatoethyl) sulfonanilide (d) is suspended in 50 parts of water, and stirs 10 minutes.7.5 part of 37% hydrochloric acid is added in reactant mixture.With ice-salt mixture reactor vessel cooled to 0 ~ 5 DEG C.5.1 parts of sodium nitrite solutions are added in reactant mixture.Reactant mixture stirs 1 ~ 2 hour.

After completing, 0.2 part of sulfamic acid is added in reactant mixture.17.7 parts of couplets (c) are dissolved in 50 parts of water.In this solution, diazo component is dripped in 1 hour.Reactant mixture stirs 2 hours.After completing, by adding salt and filtering subsequently, obtain 26.3 parts of dyestuff examples 3.

Dissolve 13.16 parts of dyestuffs (e) in 50 parts of water, and regulate pH to micro-acid.Be added in 4.90 parts of copper sulphate and 8.26 parts of sodium acetate solution in reactant mixture.Reactant mixture is heated to 100 DEG C and keeps 1 hour.After completing, by adding salt and vacuum filtration subsequently, obtain 13.76 parts of dyestuff examples (1).

Dyeing Example 1

2 of gained parts of sodium chloride such as formula the dyestuff shown in (I) and 50 parts are dissolved in the water of 999 parts, add 5 parts of sodium carbonate and 1 part of dye leveller.100 parts of woven cotton fabric are put in this dye bath.Dye bath temperature rises to 30 DEG C and keeps 30 minutes.Then, dye bath temperature rises to 60 DEG C, and keeps 60 minutes at 60 DEG C.Afterwards, first the fabric of dyeing uses water rinse.Then, the fabric of dyeing neutralizes containing 1 part of 60% second aqueous acid with 1000 parts, and keeps 30 ~ 40 minutes at calorifying 50 DEG C.The fabric of dyeing with water rinse, then boils with laundry detergent compositions and soaps 30 ~ 40 minutes at 70 DEG C, subsequently rinsing centrifugal drying in water again.

Dyeing Example 2

Dyestuff 1 part of formula (I) Suo Shi is dissolved in 2000 parts of water, is heated to 80 DEG C and keeps 20 minutes, and add 1 part of dye leveller.Then use acetic acid (60%) to regulate pH to 4.5,100 parts of wool fabrics are put into dye bath.Dye bath is heated to 40 DEG C and keeps 15 minutes.Temperature rises to 98 DEG C, and keeps 90 minutes at 98 DEG C.Then dye bath drops to 60 DEG C, is shifted out by fabric from dye bath.The fabric of dyeing washes with water and centrifugal drying.

Dyeing Example 3

Dyestuff 1 part of formula (I) Suo Shi is dissolved in 2000 parts of water, and adds 1 part of dye leveller (condensation product based on higher aliphatic amine and oxirane) and 6 parts of sodium acetates.Then acetic acid (80%) is used to regulate pH to 5.Dye bath is heated to 50 DEG C and keeps 10 minutes, then puts into 100 parts of woven polyamide fabrics.In 50 minutes, temperature is risen to 110 DEG C, then dye bath is cooled to 60 DEG C, and shifts out coloring material.Polyamide fabric hot water and cold water washing, soap and centrifugal drying.

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 rate 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 example (I), 20% sulfolane, 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 COLOR FASTNESS washing with hot water, then use warm water washing, then dry.

Claims

1. such as formula the compound shown in (I)

Wherein

N is integer 0 or 1;

K is the group of coupling heterocyclic moiety as described below;

When n is 1, A is the group of intermediate structure part as described below, and when n is 0, A has the implication of B;

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

M is hydrogen, sodium, potassium, lithium or ammonium;

K is the coupled structures part shown in following general formula (K1) ~ (K3);

Wherein,

Or be

By the alkyl that one or more hetero atom interrupts as oxygen or sulphur;

Or be

Or

Alkyl

Or

Bei – SO ₂the alkyl or aryl that X replaces; 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;

R ¹⁰hydroxyl or amino;

And

Wherein, in general formula K2, tie point and R ⁵can be positioned at and there is substituent R ⁶and R ⁷the ortho position of amino or contraposition, namely

When tie point is positioned at, there is substituent R ⁶and R ⁷the ortho position of amino time, R ⁵be positioned at its contraposition, vice versa.

Or K is the coupled structures part shown in following general formula (K4) ~ (K6);

Wherein

T is the active anchor shown in general formula (T1) ~ (T3);

Wherein

R ²⁴and R ²⁵, separately independent be halogen or

R ²⁶~ R ³⁰respective is independently halogen;

Wherein

Or be

By the alkyl that one or more hetero atom interrupts as oxygen or sulphur;

Or be

Wherein M is hydrogen, sodium, potassium, lithium or ammonium;

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;

P is the integer of 1 ~ 5

Or be

By the alkyl that one or more hetero atom interrupts as oxygen or sulphur;

Or be

R ²¹hydroxyl or amino;

And wherein, in general formula K5, tie point and R ¹⁶can be positioned at and there is substituent R ¹⁷and R ¹⁸the ortho position of amino or contraposition, namely when tie point is positioned at, there is substituent R ¹⁷and R ¹⁸the ortho position of amino time, R ¹⁶be positioned at its contraposition, vice versa.

Or be

Or

By the alkyl that one or more hetero atom interrupts as oxygen or sulphur;

Or be

Or the group shown in formula (2a) ~ (2c)

Wherein T has implication same as described above;

U Shi – O-,-S-Huo – N (R ³²⁹)-;

R is the integer of 0 ~ 6;

S is the integer of 1 ~ 6;

* refers to the tie point with A1 or A2

* * refers to the tie point with T

T has implication as above;

Wherein

V Shi – O-,-S-Huo – N (R ³⁵²)-

By the alkyl that one or more substituting group replaces, described substituting group is selected from the group be made up of following groups: hydroxyl, aryl, cycloalkyl, alkoxyl, thio alkoxy, amino, N-monoalkyl-amino, N, N-dialkyl amido, 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-monocycle alkyl-amino, N, the mono-aryl of N--monocycle alkyl-amino, N-acylamino-, N-alkylsulfonyl-amino, urea groups, alkyl urea groups, phenyl urea groups, halogen, cyano group, COOM, nitro, acyl group, Thioacyl, alkyl sulphonyl, aroyl, trifluoromethyl, heteroaryl, Heterocyclylalkyl, alkoxy carbonyl, alkoxy carbonyl, acyloxy, aryl acyloxy, carbamoyl, N-monocycle alkyl-carbamoyl, N-monoalkyl-amino formoxyl, N, N-bicyclic alkyl-carbamoyl, N, N-dialkyl-carbamoyl radicals, the mono-aryl-carbamoyl of N-, N, N-diaryl-carbamoyl, 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 sulfonyl, N, N-bicyclic alkyl-amino-sulfonyl, N, N-dialkyl-7-amino sulfonyl, the mono-n-aryl sulfonyl of N-, N, N-diaryl-amino-sulfonyl, the single n-aryl sulfonyl of N-monocycle alkyl-N-, the single n-aryl sulfonyl of N-monoalkyl-N-or SO ₃m, or comprise the alkyl of a free valency to connect active anchor T,

C is the integer of 0 ~ 6;

D is the integer of 1 ~ 6;

* * * refers to the tie point with B1 and B2;

* * * * refers to the tie point with T;

* * * * * refers to the tie point with E3;

T with X is identical with above-mentioned defined;

2. compound according to claim 1, has the structure shown in formula (Ia) ~ (If): be compound shown in formula (Ia) ~ (If) and composition thereof;

Wherein

Or be

By the alkyl that one or more hetero atom interrupts as oxygen or sulphur;

Or be

R ⁶¹~ R ⁶³, R ⁶⁹~ R ⁷¹and R ⁸⁰~ R ⁸², be independently separately, hydrogen, alkyl, substituted alkyl, by the alkyl chain of one or two heteroatom interruptions, alkoxyl, substituted alkoxy, halogen, trifluoromethyl; Cycloalkyl; Heterocyclylalkyl; Cyano group; Nitro; Acyloxy; Alkyl-carbonyl, acylamino-; Aromatic acylamino, cinnamoyl is amino, alkyl sulfonyl-amino; Alkylthio group; Alkyl sulphonyl, alkoxy carbonyl, carbamoyl, amino-sulfonyl, urea groups, alkyl urea groups, SO ₃m, COOM; Or the group shown in formula (2a) ~ (2c);

X with M is identical with claim 1.

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

Wherein

Or be

By the alkyl that one or more hetero atom interrupts as oxygen or sulphur;

Or be

R ⁹⁶~ R ⁹⁸, be independently separately, hydrogen, alkyl, substituted alkyl, by the alkyl chain of one or two heteroatom interruptions, alkoxyl, substituted alkoxy, halogen, trifluoromethyl; Cycloalkyl; Heterocyclylalkyl; Cyano group; Nitro; Acyloxy; Alkyl-carbonyl, acylamino-; Aromatic acylamino, cinnamoyl is amino, alkyl sulfonyl-amino; Alkylthio group; Alkyl sulphonyl, alkoxy carbonyl, carbamoyl, amino-sulfonyl, urea groups, alkyl urea groups, SO ₃m, COOM; Or the group shown in formula (2a) ~ (2c);

T, X and M with define in claim 1 identical.

4. compound according to claim 1, has the structure shown in one of formula (Ii) ~ (Il):

Wherein

Or be

By the alkyl that one or more hetero atom interrupts as oxygen or sulphur;

Or be

M with define in claim 1 identical.

5. compound according to claim 1, has the structure shown in one of formula (Im) ~ (Ip):

Wherein

Or be

Or

By the alkyl that one or more hetero atom interrupts as oxygen or sulphur;

Or

T, X and M with define in claim 1 identical.

6. compound according to claim 1, has the structure shown in one of formula (Iq) ~ (It):

Wherein

Or be

By the alkyl that one or more hetero atom interrupts as oxygen or sulphur;

Or be

Or

Bei – SO ₂the alkyl or aryl that X replaces; 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; Or a free valency part is to connect active anchor T;

X is identical with above-mentioned defined,

M and T as defined in claim 1.

7. compound according to claim 1, has the structure shown in one of formula (Iu) ~ (Ix):

Wherein

Or be

By the alkyl that one or more hetero atom interrupts as oxygen or sulphur;

Or be

Or Bei – SO ₂the alkyl or aryl that X replaces; Wherein

R ²¹⁸~ R ²²⁰and R ²²⁸~ R ²³⁰, be independently separately, hydrogen, alkyl, substituted alkyl, by the alkyl chain of one or two heteroatom interruptions, alkoxyl, substituted alkoxy, halogen, trifluoromethyl; Cycloalkyl; Heterocyclylalkyl; Cyano group; Nitro; Acyloxy; Alkyl-carbonyl, acylamino-; Aromatic acylamino, cinnamoyl is amino, alkyl sulfonyl-amino; Alkylthio group; Alkyl sulphonyl, alkoxy carbonyl, carbamoyl, amino-sulfonyl, urea groups, alkyl urea groups, SO ₃m, COOM; Or the group shown in formula (2a) ~ (2c);

T, X and M have with identical implication in claim 1.

8. such as formula the compound one of (Iy) ~ (Iab) Suo Shi:

Wherein

Or be

By the alkyl that one or more hetero atom interrupts as oxygen or sulphur;

Or be

R ²⁵⁹~ R ²⁶¹and R ²⁷¹~ R ²⁷³, be independently separately, hydrogen, alkyl, substituted alkyl, by the alkyl chain of one or two heteroatom interruptions, alkoxyl, substituted alkoxy, halogen, trifluoromethyl; Cycloalkyl; Heterocyclylalkyl; Cyano group; Nitro; Acyloxy; Alkyl-carbonyl, acylamino-; Aromatic acylamino, cinnamoyl is amino, alkyl sulfonyl-amino; Alkylthio group; Alkyl sulphonyl, alkoxy carbonyl, carbamoyl, amino-sulfonyl, urea groups, alkyl urea groups, SO ₃m, COOM; Or the radicals X shown in contained (2a) ~ (2c), M and T as defined in claim 1.

9. such as formula the compound one of (Iac) ~ (Iaf) Suo Shi:

Wherein

Or be

By the alkyl that one or more hetero atom interrupts as oxygen or sulphur;

Or be

By the alkyl that one or more substituting group replaces, described substituting group is selected from the group be made up of following groups: hydroxyl, aryl, cycloalkyl, alkoxyl, thio alkoxy, amino, N-monoalkyl-amino, N, N-dialkyl amido, 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-monocycle alkyl-amino, N, the mono-aryl of N--monocycle alkyl-amino, N-acylamino-, N-alkylsulfonyl-amino, urea groups, alkyl urea groups, phenyl urea groups, halogen, cyano group, COOM, nitro, acyl group, Thioacyl, alkyl sulphonyl, aroyl, trifluoromethyl, heteroaryl, Heterocyclylalkyl, alkoxy carbonyl, alkoxy carbonyl, acyloxy, aryl acyloxy, carbamoyl, N-monocycle alkyl-carbamoyl, N-monoalkyl-amino formoxyl, N, N-bicyclic alkyl-carbamoyl, N, N-dialkyl-carbamoyl radicals, the mono-aryl-carbamoyl of N-, N, N-diaryl-carbamoyl, 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 sulfonyl, N, N-bicyclic alkyl-amino-sulfonyl, N, N-dialkyl-7-amino sulfonyl, the mono-n-aryl sulfonyl of N-, N, N-diaryl-amino-sulfonyl, the single n-aryl sulfonyl of N-monocycle alkyl-N-, the single n-aryl sulfonyl of N-monoalkyl-N-or-SO ₃m, or a free valency part is to connect active anchor T,

R ³⁰²~ R ³⁰⁴and R ³¹³~ R ³¹⁵, be independently separately, hydrogen, alkyl, substituted alkyl, by the alkyl chain of one or two heteroatom interruptions, alkoxyl, substituted alkoxy, halogen, trifluoromethyl; Cycloalkyl; Heterocyclylalkyl; Cyano group; Nitro; Acyloxy; Alkyl-carbonyl, acylamino-; Aromatic acylamino, cinnamoyl is amino, alkyl sulfonyl-amino; Alkylthio group; Alkyl sulphonyl, alkoxy carbonyl, carbamoyl, amino-sulfonyl, urea groups, alkyl urea groups, SO ₃m, COOM; Or the group shown in contained (2a) ~ (2c);

T, X and M have and the identical implication defined in claim.

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

11. Chemical composition thats, comprise one or more compounds according to any one of claim 1 ~ 9.

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

13., such as formula the preparation method of compound (I) Suo Shi, comprise step:

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

B) by step a) in compound shown in the diazol of gained and formula K react, to obtain the intermediate shown in formula (V)

C) component (B-NH ₂) diazotization,

Cx1) step c) in diazotization selectivity of product be coupled to compound (A-NH ₂) on

Cx2) step cx1) diazotization of gained coupled product

D) in step c), by step c) gained diazotization product is coupled on intermediate V to obtain the bisazo product shown in general formula (VI)

Or by cx2) the diazotizing coupled product of gained is coupled to obtain the trisazo-product shown in general formula (VIII) on intermediate V,

E) steps d) formula (VI) or (VIII) shown in product and mantoquita react to obtain copper complex dyestuff, when (VI) participates in reaction, obtain copper complex dyestuff (IX), when (VIII) participates in reaction, obtain copper complex dyestuff (X):

14. compounds according to any one in claim 1 ~ 9, Chemical composition that according to claim 10 or 11 or the application of the aqueous solution according to claim 12 in stock-dye, described fiber is selected from by following fibrous group: string, seed fiber, cotton, kapok, the fiber of cocoanut shell; Bast fiber, flax, hemp, jute, bluish dogbane, ramie, rattan; Leaf fiber, sisal hemp, henequen, Basho fiber; Stalk fibre, bamboo fibre; From the fiber of animal, wool, silk, goat cashmere wool, alpaca fibre fiber, mohair, Angola's wool fibre and fur and leather substance; Artificial and fiber, cellulose fibre; Paper and tModified Cellulose Fibers, viscose rayon fibers, acetate 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, described fiber is selected from by following fibrous group: string, seed fiber, cotton, kapok, the fiber of cocoanut shell; Bast fiber, flax, hemp, jute, bluish dogbane, ramie, rattan; Leaf fiber, sisal hemp, henequen, Basho fiber; Stalk fibre, bamboo fibre; From the fiber of animal, wool, silk, goat cashmere wool, alpaca fibre fiber, mohair, Angola's wool fibre and fur and leather substance; Artificial, regeneration with the fiber reclaimed, cellulose fibre; Paper and tModified Cellulose Fibers, viscose rayon fibers, acetate and triacetate ester fiber and Lyocell fibers; And composite fibre materials, nylon material, nylon-6, nylon-6 .6 and aramid fiber.