阅读说明：本技术 一种噻唑杂环偶氮型活性染料及其制备方法 (Thiazole heterocyclic azo type reactive dye and preparation method thereof ) 是由 单斌 孟德泉 马继平 于 2021-07-10 设计创作，主要内容包括：本发明涉及染料技术领域,特别涉及一种噻唑杂环偶氮型活性染料及其制备方法。本发明将分子中含噻唑杂环结构的弱碱性芳胺作为重氮组份引入水溶性的活性染料结构中,制得偶氮型活性染料,制备方法为：三聚氯氰或三聚氟氰与氨基萘酚磺酸进行缩合反应,得到缩合产物；含噻唑杂环结构的弱碱性芳胺的重氮化反应；重氮化反应产物与缩合产物的偶合反应。本发明在不同酸碱环境中会呈现出蓝色到红色或红色到蓝色的颜色变化,具有较好的酸碱变色性能,灵敏度高,变色可逆,无需借助任何光学器件,直接通过肉眼观察就可以快速检测出溶液的pH值的噻唑杂环偶氮型活性染料,为偶氮型活性染料的合成及应用提供了新的途径。(The invention relates to the technical field of dyes, in particular to a thiazole heterocyclic azo type reactive dye and a preparation method thereof. The invention introduces alkalescent arylamine containing thiazole heterocyclic structure in molecule as diazo component into water-soluble reactive dye structure to prepare azo type reactive dye, the preparation method comprises: carrying out condensation reaction on cyanuric chloride or cyanuric fluoride and amino naphthol sulfonic acid to obtain a condensation product; diazotization reaction of alkalescent arylamine containing thiazole heterocyclic structure; coupling reaction of the diazotised reaction product with the condensation product. The thiazole heterocyclic azo type active dye can show color change from blue to red or from red to blue in different acid-base environments, has better acid-base color change performance, high sensitivity and reversible color change, can quickly detect the pH value of a solution by direct visual observation without any optical device, and provides a new way for the synthesis and application of the azo type active dye.)

1. A reactive dye of thiazole azo type, characterized in that the reactive dye of thiazole azo type has the general formula (i):

wherein the content of the first and second substances,

x is selected from-Cl and-F;

a is selected from formula (II-a);

R₁is selected from-H, -CH₃；

R₂Is selected from-NH₂、-NHCH₃、-NHCH₂CH₃、-NHCH₂COOH、-NHCH(CH₃)COOH、-OH、-OCH₃、-OCH₂CH₃Or formula (II-b);

in the formula (II-a),

n is 1 or 2;

in the formula (II-b),

R₃selected from-H, carboxyl, sulfonic group, methyl, methoxy, nitro, nitrile group, amino, -Cl or-Br;

R₄selected from-H, carboxyl, sulfonic group, methyl, methoxy, nitro, nitrile group, amino, -Cl, -Br, -CH₂COOH、-COCH₂Cl、-COCH₂CH₂Cl、-NHCOCH₂Cl、-NHCOCH₂CH₂Cl、-NHCOCH＝CH₂、-NHCOC(Br)＝CH₂、-NHCH₂CH(OH)CH₂Cl、-NHSO₂CH＝CH₂、-N(CH₃)SO₂CH₂CH₂M、-SO₂CH＝CH、-SO₂CH₂CH₂M、-SO₂CH₂CH₂OSO₃M、-SO₂NHCH₂CH₂M or-SO₂N(CH₃)CH₂CH₂M; wherein M is selected from-Cl, -F or-OSO₃R₅；R₅Is selected from-H, -Na or-K.

2. A reactive dye of the thiazolylazaazo type according to claim 1, wherein in formula (I), a is selected from one of the following groups:

an H acid residue having the formula:

j acid residue of the formula:

a gamma acid residue having the formula:

a K acid residue of the formula:

a chicago acid residue having the formula:

3. a process for the preparation of reactive dyes of the thiazoleazaazo type according to any one of claims 1 to 2, characterized in that:

1) condensation reaction

Cyanuric chloride or cyanuric fluoride and amino naphthol sulfonic acid carry out a condensation reaction to obtain a condensation product; adding the first condensation product into the corresponding second condensation raw material to carry out second condensation reaction;

2) diazotization reaction

Under the condition of an ice salt bath, gradually adding sodium nitrite solid into concentrated sulfuric acid, stirring, heating until the sodium nitrite solid is completely dissolved, cooling to 0-5 ℃, gradually adding alkalescent arylamine containing a thiazole heterocyclic structure, stirring for reaction, and after the reaction is finished, adding a small amount of sulfamic acid to remove excessive nitrous acid to obtain alkalescent arylamine diazonium salt containing the thiazole heterocyclic structure;

3) coupling reaction

Gradually dripping the weakly alkaline arylamine diazonium salt containing the thiazole heterocyclic structure obtained in the step 2) into the condensation product obtained in the step 1), controlling the pH value and carrying out reaction, and adding Na after the reaction is finished₂HPO₄-NaH₂PO₄Adding potassium acetate or sodium acetate solid into the pH buffer, stirring, standing, filtering, washing with appropriate amount of ethanol for 3 times, air drying the filter cake to obtain a crude product, re-dissolving the crude product, adjusting pH, and re-salting out to obtain the blue dye.

4. A process for the preparation of thiazolylazaazo-type reactive dyes according to claim 3, characterized in that:

the amino naphthol sulfonic acid in the step 1) is one of H acid, J acid, gamma acid, K acid or Chicago acid.

5. A process for the preparation of thiazolylazaazo-type reactive dyes according to claim 3, characterized in that: the weakly alkaline arylamine containing the thiazole heterocyclic structure in the step 2) is one of 2-amino-5-nitrothiazole and 2-amino-4-methyl-5-nitrothiazole.

6. A process for the preparation of thiazolylazaazo-type reactive dyes according to claim 3, characterized in that:

the first condensation reaction comprises the following steps: adding an aminonaphthol sulfonic acid solution into aqueous dispersion of cyanuric chloride or cyanuric fluoride, reacting under stirring at 0-5 ℃, and controlling the pH value of the solution to be 4-5 in the reaction process to obtain a condensation product;

the secondary condensation reaction comprises the following steps: and then adding unsubstituted or substituted aminobenzene or aliphatic amine into the primary condensation product, raising the temperature to 20-30 ℃, and controlling the pH value to be 5-6 for reaction to obtain a secondary condensation product.

7. The process for the preparation of thiazolylazaazo-type reactive dyes according to claim 6, characterized in that:

preferably, the molar ratio of the cyanuric chloride or the cyanuric fluoride to the amino naphthol sulfonic acid is 1.02: 1;

preferably, the molar ratio of the mono-condensation product to the unsubstituted or substituted aminobenzene or fatty amine is 1: 1.

8. The process for preparing thiazole heterocyclic azo type reactive dyes according to claim 3, wherein the diazotization reaction in step 2) is specifically: under the condition of an ice salt bath at the temperature of-5 to-10 ℃, gradually adding sodium nitrite solid into 11.0g of concentrated sulfuric acid, stirring, heating until the sodium nitrite solid is completely dissolved, cooling to 0 to 5 ℃, and gradually adding weakly alkaline arylamine containing a thiazole heterocyclic structure; stirring and reacting for 2-4 h, and after the reaction is finished, adding a small amount of sulfamic acid to remove excessive nitrous acid to obtain the weakly alkaline arylamine diazonium salt with the thiazole heterocyclic structure.

9. The preparation method of the thiazole heterocyclic azo type reactive dye according to claim 8, wherein the molar ratio of the sodium nitrite to the weakly basic arylamine containing the thiazole heterocyclic structure is 1.05: 1.

10. The process for preparing thiazolylazaazo-type reactive dyes according to claim 3, wherein the coupling reaction in step 3) is specifically: dropwise adding weakly alkaline arylamine diazonium salt containing thiazole heterocyclic structure into the condensation product obtained in the step 1), controlling the pH to be 1-2, reacting at 0-5 ℃, and adding 1% (w/v) of Na after the reaction is finished₂HPO₄-NaH₂PO₄Adding potassium acetate or sodium acetate solid in batches, detecting the salting-out condition of the dye by using a permeable ring, stirring, standing, performing suction filtration, washing by using a proper amount of ethanol for 3 times, drying a filter cake to obtain a crude product, re-dissolving the crude product, adjusting the pH value to 6.8-7.0, and re-salting out to obtain the blue dye to obtain the thiazole heterocyclic azo type reactive dye.

Technical Field

The invention relates to the technical field of dyes, in particular to a thiazole heterocyclic azo type reactive dye and a preparation method thereof.

Background

Among the classes of dyes, azo-type dyes are a very important class of dyes. Azo dyes are the most productive and useful varieties of dyes due to the readily available raw materials, simple synthetic methods, and high absorption coefficients. In the monoazo dye molecule, because azo bonds are easy to generate tautomerism of an azo-quinone hydrazone structure, a plurality of monoazo water-soluble dyes can present certain color difference in different acid and alkali environments and have acid and alkali discoloration effects of different degrees. Therefore, the study on the pH discoloration performance of azo structure dyes has become a hot research point in the dye field.

Researches show that the thiazole heterocycle-containing azo dye has bright color light, high color development intensity, good dark color effect and high light absorption performance, and is an important dye variety in disperse dyes. The thiazole heterocyclic intermediate containing the nitro has higher absorptivity due to the existence of sulfur or nitrogen atoms with slightly higher electronegativity in a five-membered heterocyclic structure, better electron transfer capability of a heterocyclic system and strong electron withdrawing action of the nitro. In water insoluble dyes such as disperse dyes and direct dyes, the weak basic arylamine is often used as a diazo component for synthesizing high-performance azo dyes. The alkalescent arylamine of the type is rarely applied to water-soluble reactive dyes with wide application.

Disclosure of Invention

Aiming at the defects in the prior art, the invention aims to solve the technical problem of providing a thiazole heterocyclic azo type reactive dye and a preparation method thereof, synthesizing the thiazole heterocyclic azo type reactive dye which has good acid-base color change performance, high sensitivity and reversible color change, can rapidly detect the pH value of a solution by direct visual observation without any optical device, and providing a new way for the synthesis and application of the azo type reactive dye.

The technical scheme adopted by the invention for realizing the purpose is as follows: a thiazole heterocyclic azo type reactive dye, which has a structure of general formula (i):

wherein the content of the first and second substances,

x is selected from-Cl and-F;

a is selected from formula (II-a);

R₁is selected from-H, -CH₃；

R₂Is selected from-NH₂、-NHCH₃、-NHCH₂CH₃、-NHCH₂COOH、-NHCH(CH₃)COOH、-OH、-OCH₃、-OCH₂CH₃Or formula (II-b);

in the formula (II-a),

n is 1 or 2;

in the formula (II-b),

R₃selected from-H, carboxyl, sulfonic group, methyl, methoxy, nitro, nitrile group, amino, -Cl or-Br;

R₄selected from-H, carboxyl, sulfonic group, methyl, methoxy, nitro, nitrile group, amino, -Cl, -Br, -CH₂COOH、-COCH₂Cl、-COCH₂CH₂Cl、-NHCOCH₂Cl、-NHCOCH₂CH₂Cl、-NHCOCH＝CH₂、-NHCOC(Br)＝CH₂、-NHCH₂CH(OH)CH₂Cl、-NHSO₂CH＝CH₂、-N(CH₃)SO₂CH₂CH₂M、-SO₂CH＝CH、-SO₂CH₂CH₂M、-SO₂CH₂CH₂OSO₃M、-SO₂NHCH₂CH₂M or-SO₂N(CH₃)CH₂CH₂M; wherein M is selected from-Cl, -F or-OSO₃R₅；R₅Is selected from-H, -Na or-K.

Further, in the formula (I), A is selected from one of the following groups:

an H acid residue having the formula:

j acid residue of the formula:

a gamma acid residue having the formula:

a K acid residue of the formula:

a chicago acid residue having the formula:

the invention also comprises a method for preparing the thiazole heterocyclic azo type reactive dye,

1) condensation reaction

Cyanuric chloride or cyanuric fluoride and amino naphthol sulfonic acid carry out a condensation reaction to obtain a condensation product; adding the first condensation product into the corresponding second condensation raw material to carry out second condensation reaction;

2) diazotization reaction

Under the condition of an ice salt bath, gradually adding sodium nitrite solid into concentrated sulfuric acid, stirring, heating until the sodium nitrite solid is completely dissolved, cooling to 0-5 ℃, gradually adding alkalescent arylamine containing a thiazole heterocyclic structure, stirring for reaction, and after the reaction is finished, adding a small amount of sulfamic acid to remove excessive nitrous acid to obtain alkalescent arylamine diazonium salt containing the thiazole heterocyclic structure;

3) coupling reaction

Gradually dripping the weakly alkaline arylamine diazonium salt containing the thiazole heterocyclic structure obtained in the step 2) into the condensation product obtained in the step 1), controlling the pH value and carrying out reaction, and adding Na after the reaction is finished₂HPO₄-NaH₂PO₄Adding potassium acetate or sodium acetate solid into the pH buffer, stirring, standing, filtering, washing with appropriate amount of ethanol for 3 times, air drying the filter cake to obtain crude product, dissolving the crude product again, adjusting pH, salting out again to obtain blue dye and thiazole impurityA reactive dye of the cyclic azo type.

Further, in the above-mentioned case,

the amino naphthol sulfonic acid in the step 1) is one of H acid, J acid, gamma acid, K acid or Chicago acid.

Further, the weakly basic arylamine containing the thiazole heterocyclic structure in the step 2) is one of 2-amino-5-nitrothiazole and 2-amino-4-methyl-5-nitrothiazole.

Further, in the above-mentioned case,

the first condensation reaction comprises the following steps: adding an aminonaphthol sulfonic acid solution into aqueous dispersion of cyanuric chloride or cyanuric fluoride, reacting under stirring at 0-5 ℃, and controlling the pH value of the solution to be 4-5 in the reaction process to obtain a condensation product;

the secondary condensation reaction comprises the following steps: and then adding unsubstituted or substituted aminobenzene or aliphatic amine into the primary condensation product, raising the temperature to 20-30 ℃, and controlling the pH value to be 5-6 for reaction to obtain a secondary condensation product.

Further, in the above-mentioned case,

the molar ratio of the cyanuric chloride or the cyanuric fluoride to the amino naphthol sulfonic acid is 1.02: 1;

the molar ratio of the primary condensation product to the unsubstituted or substituted aminobenzene or fatty amine is 1: 1.

Further, the diazotization reaction in the step 2) is specifically as follows: under the condition of an ice salt bath at the temperature of-5 to-10 ℃, gradually adding sodium nitrite solid into 11.0g of concentrated sulfuric acid, stirring, heating until the sodium nitrite solid is completely dissolved, cooling to 0 to 5 ℃, and gradually adding weakly alkaline arylamine containing a thiazole heterocyclic structure; stirring and reacting for 2-4 h, and after the reaction is finished, adding a small amount of sulfamic acid to remove excessive nitrous acid to obtain the weakly alkaline arylamine diazonium salt with the thiazole heterocyclic structure.

Further, the molar ratio of the sodium nitrite to the weakly basic arylamine containing the thiazole heterocyclic structure is 1.05: 1.

Further, the coupling reaction in the step 3) is specifically: dropwise adding weakly alkaline arylamine diazonium salt containing thiazole heterocyclic structure into the condensation product obtained in the step 1), controlling the pH to be 1-2, reacting at 0-5 ℃, and adding 1% (w/v) of Na after the reaction is finished₂HPO₄-NaH₂PO₄Adding potassium acetate or sodium acetate solid in batches, detecting the salting-out condition of the dye by using a permeable ring, stirring, standing, performing suction filtration, washing by using a proper amount of ethanol for 3 times, drying a filter cake to obtain a crude product, re-dissolving the crude product, adjusting the pH value to 6.8-7.0, and re-salting out to obtain the blue dye to obtain the thiazole heterocyclic azo type reactive dye.

The thiazole heterocyclic azo type reactive dye and the preparation method thereof have the beneficial effects that: the thiazole heterocyclic azo type active dye can show color change from blue to red or from red to blue in different acid-base environments, has good acid-base color change performance, high sensitivity and reversible color change, can quickly detect the pH value of a solution by direct visual observation without any optical device, and provides a new approach for synthesis and application of the azo type active dye.

Drawings

FIG. 1 is a graph showing UV-VIS absorption spectra of a blue Dye1 obtained in example 1 of the present invention under different pH conditions;

FIG. 2 is an infrared spectrum of blue Dye1 obtained in example 1 of the present invention.

A specific embodiment;

the invention is further explained in detail with reference to the drawings and the specific embodiments;

example 1

A thiazole heterocyclic azo type reactive dye has the following structure:

a preparation method of thiazole heterocyclic azo type reactive dye comprises the following steps:

diazotization reaction: placing 11.0g of concentrated sulfuric acid with the mass fraction of 98% in an ice salt bath at the temperature of-5 to-10 ℃ for cooling, gradually adding 0.73g of sodium nitrite solid, stirring, heating until the concentrated sulfuric acid is completely dissolved, enabling the solution to be clear and transparent, stopping heating and cooling, gradually adding 1.48g of 2-amino-5-nitrothiazole (0.01mol and 98%), stirring, continuing to react at the temperature of 0 to 5 ℃, detecting a reaction end point (a developing agent is ethyl acetate) by thin-layer chromatography (TLC), and adding a small amount of sulfamic acid to remove excessive nitrous acid after the reaction is finished;

condensation reaction of cyanuric chloride: taking 1.90g of cyanuric chloride (0.0103mol) and 20g of small ice blocks, mechanically stirring at 0-5 ℃ until the cyanuric chloride is milky, then adding an aqueous solution containing 4.0g (0.01mol, 85.6%) of H acid monosodium salt, adjusting the pH of the solution to be 4-5, and detecting by using an Ehrlich reagent to determine a reaction end point; after the reaction is finished, 2.81g of p- (beta-sulfatoethylsulfone) aniline (0.01mol) is added, the temperature is raised to 20-30 ℃, the pH value is controlled to be 5-6 by using a 10% sodium carbonate solution, after the reaction is carried out for 3-4 h, the reaction end point is detected by TLC (a developing agent is n-butyl alcohol, isopropanol, ethyl acetate and water, the ratio of n-butyl alcohol to isopropanol to ethyl acetate to water is 2:4:1:3, and v/v);

coupling reaction: gradually dripping the 2-amino-5-nitrothiazole diazonium salt into a cyanuric chloride condensation product, controlling the pH value to be 1-2, reacting at 0-5 ℃, and detecting the reaction condition by a ring penetration method. After the reaction is finished, adding a pH buffering agent of 1% (w/v), adding potassium acetate solid in batches, detecting the salting-out condition of the dye by using a permeable ring, stirring, standing, performing suction filtration, washing by using a proper amount of ethanol for 3 times, and drying a filter cake to obtain a crude product. And (3) re-dissolving the crude product, adjusting the pH value to 6.8-7.0, and re-salting out to obtain a blue Dye 1.

FIG. 1 is a diagram showing UV-VIS absorption spectra of a blue Dye1 at pH2,3,4,5,6,7,8,9, 10;

FIG. 2 is an infrared spectrum of blue Dye 1.

Example 2

A thiazole heterocyclic azo type reactive dye has the following structure:

a preparation method of thiazole heterocyclic azo type reactive dye comprises the following steps:

diazotization reaction: same preparation as in example 1;

condensation reaction of cyanuric chloride: taking 1.90g of cyanuric chloride (0.0103mol) and 20g of small ice blocks, mechanically stirring at 0-5 ℃ until the cyanuric chloride is milky, then adding an aqueous solution containing 4.0g (0.01mol, 85.6%) of H acid monosodium salt, adjusting the pH of the solution to be 4-5, and detecting by using an Ehrlich reagent to determine a reaction end point; after the reaction is finished, adding 2.81g of m- (beta-sulfuric ester ethyl sulfone) aniline (0.01mol), raising the temperature to 20-30 ℃, controlling the pH value to be 5-6 by using a 10% sodium carbonate solution, reacting for 3-4 h, and detecting the reaction end point by TLC (a developing agent is n-butyl alcohol, isopropanol, ethyl acetate and water, wherein the ratio of n-butyl alcohol to isopropanol to ethyl acetate to water is 2:4:1:3, and v/v);

coupling reaction: the preparation is the same as that of the embodiment 1, potassium acetate is added to precipitate dye after the reaction is finished, the dye is filtered, the crude product is re-dissolved, the pH value is adjusted to 6.8-7.0, and the blue solid is obtained by re-salting out.

Example 3

A thiazole heterocyclic azo type reactive dye has the following structure:

a preparation method of thiazole heterocyclic azo type reactive dye comprises the following steps:

diazotization reaction: same preparation as in example 1;

condensation reaction of cyanuric chloride: taking 1.90g of cyanuric chloride (0.0103mol) and 20g of small ice blocks, mechanically stirring at 0-5 ℃ until the cyanuric chloride is milky, then adding an aqueous solution containing 4.0g (0.01mol, 85.6%) of H acid monosodium salt, adjusting the pH of the solution to be 4-5, and detecting by using an Ehrlich reagent to determine a reaction end point; after the reaction is finished, 1.77g of o-aminobenzenesulfonic acid (0.01mol, 98%) is added, the temperature is raised to 20-30 ℃, the pH value is controlled to be 5-6 by using a 10% sodium carbonate solution, and after the reaction is carried out for 3-4 h, the reaction end point is detected by TLC (a developing agent is n-butyl alcohol, isopropanol, ethyl acetate, and water, wherein the ratio of water to n-butyl alcohol to isopropanol to ethyl acetate is 2:4:1:3, and v/v);

coupling reaction: the preparation is the same as that of the embodiment 1, potassium acetate is added to precipitate dye after the reaction is finished, the dye is filtered, the crude product is re-dissolved, the pH value is adjusted to 6.8-7.0, and the blue solid is obtained by re-salting out.

Example 4

A thiazole heterocyclic azo type reactive dye has the following structure:

a preparation method of thiazole heterocyclic azo type reactive dye comprises the following steps:

diazotization reaction: same preparation as in example 1;

condensation reaction of cyanuric chloride: taking 1.90g of cyanuric chloride (0.0103mol) and 20g of small ice blocks, mechanically stirring at 0-5 ℃ until the cyanuric chloride is milky, then adding an aqueous solution containing 4.0g (0.01mol, 85.6%) of H acid monosodium salt, adjusting the pH of the solution to be 4-5, and detecting by using an Ehrlich reagent to determine a reaction end point; after the reaction is finished, adding 1.75g of m-aminobenzene sulfonic acid (0.01mol, 99%), raising the temperature to 20-30 ℃, controlling the pH value to be 5-6 by using 10% sodium carbonate solution, reacting for 3-4 h, and detecting the reaction end point by TLC (a developing agent is n-butyl alcohol, isopropanol, ethyl acetate, water, 2:4:1:3, v/v);

coupling reaction: the preparation is the same as that of the embodiment 1, potassium acetate is added to precipitate dye after the reaction is finished, the dye is filtered, the crude product is re-dissolved, the pH value is adjusted to 6.8-7.0, and the blue solid is obtained by re-salting out.

Example 5

A thiazole heterocyclic azo type reactive dye has the following structure:

a preparation method of thiazole heterocyclic azo type reactive dye comprises the following steps:

diazotization reaction: same preparation as in example 1;

condensation reaction of cyanuric chloride: taking 1.90g of cyanuric chloride (0.0103mol) and 20g of small ice blocks, mechanically stirring at 0-5 ℃ until the cyanuric chloride is milky, then adding an aqueous solution containing 4.0g (0.01mol, 85.6%) of H acid monosodium salt, adjusting the pH of the solution to be 4-5, and detecting by using an Ehrlich reagent to determine a reaction end point; after the reaction is finished, adding 1.73g of sulfanilic acid (0.01mol, 99.8%), raising the temperature to 20-30 ℃, controlling the pH value to be 5-6 by using 10% sodium carbonate solution, reacting for 3-4 h, and detecting the reaction end point by TLC (a developing agent is n-butyl alcohol, isopropanol, ethyl acetate, water, 2:4:1:3, v/v);

coupling reaction: the preparation is the same as that of the embodiment 1, potassium acetate is added to precipitate dye after the reaction is finished, the dye is filtered, the crude product is re-dissolved, the pH value is adjusted to 6.8-7.0, and the blue solid is obtained by re-salting out.

Example 6

A thiazole heterocyclic azo type reactive dye has the following structure:

a preparation method of thiazole heterocyclic azo type reactive dye comprises the following steps:

diazotization reaction: same preparation as in example 1;

condensation reaction of cyanuric chloride: taking 1.90g of cyanuric chloride (0.0103mol) and 20g of small ice blocks, mechanically stirring at 0-5 ℃ until the cyanuric chloride is milky, then adding an aqueous solution containing 4.0g (0.01mol, 85.6%) of H acid monosodium salt, adjusting the pH of the solution to be 4-5, and detecting by using an Ehrlich reagent to determine a reaction end point; after the reaction is finished, adding 2.67g of aniline-2, 5-disulfonic acid (0.01mol, 92.0%), raising the temperature to 20-30 ℃, controlling the pH value to be 5-6 by using a 10% sodium carbonate solution, reacting for 3-4 h, and detecting the reaction end point by TLC (a developing agent is n-butyl alcohol, isopropanol, ethyl acetate and water in a ratio of 2:4:1:3, v/v);

coupling reaction: the preparation is the same as that of the embodiment 1, potassium acetate is added to precipitate dye after the reaction is finished, the dye is filtered, the crude product is re-dissolved, the pH value is adjusted to 6.8-7.0, and the blue solid is obtained by re-salting out.

Example 7

A thiazole heterocyclic azo type reactive dye has the following structure:

a preparation method of thiazole heterocyclic azo type reactive dye comprises the following steps:

diazotization reaction: same preparation as in example 1;

condensation reaction of cyanuric chloride: taking 1.90g of cyanuric chloride (0.0103mol) and 20g of small ice blocks, mechanically stirring at 0-5 ℃ until the cyanuric chloride is milky, then adding an aqueous solution containing 4.0g (0.01mol, 85.6%) of H acid monosodium salt, adjusting the pH of the solution to be 4-5, and detecting by using an Ehrlich reagent to determine a reaction end point; after the reaction is finished, adding 1.40g of p-aminobenzoic acid (0.01mol, 98%), raising the temperature to 20-30 ℃, controlling the pH value to be 5-6 by using 10% sodium carbonate solution, reacting for 3-4 h, and detecting the reaction end point by TLC (a developing agent is n-butyl alcohol, isopropanol, ethyl acetate and water in a ratio of 2:4:1:3, v/v);

coupling reaction: the preparation is the same as that of the embodiment 1, potassium acetate is added to precipitate dye after the reaction is finished, the dye is filtered, the crude product is re-dissolved, the pH value is adjusted to 6.8-7.0, and the blue solid is obtained by re-salting out.

Example 8

A thiazole heterocyclic azo type reactive dye has the following structure:

a preparation method of thiazole heterocyclic azo type reactive dye comprises the following steps:

diazotization reaction: same preparation as in example 1;

condensation reaction of cyanuric chloride: taking 1.90g of cyanuric chloride (0.0103mol) and 20g of small ice blocks, mechanically stirring at 0-5 ℃ until the cyanuric chloride is milky, then adding an aqueous solution containing 4.0g (0.01mol, 85.6%) of H acid monosodium salt, adjusting the pH of the solution to be 4-5, and detecting by using an Ehrlich reagent to determine a reaction end point; after the reaction is finished, 1.73g of 2-chloro-4-aminobenzoic acid (0.01mol, 99%) is added, the temperature is raised to 20-30 ℃, the pH value is controlled to be 5-6 by using 10% sodium carbonate solution, after the reaction is carried out for 3-4 h, the reaction end point is detected by TLC (a developing agent is n-butyl alcohol, isopropanol, ethyl acetate and water, the ratio of n-butyl alcohol to isopropanol to ethyl acetate to water is 2:4:1:3, v/v);

coupling reaction: the preparation is the same as that of the embodiment 1, potassium acetate is added to precipitate dye after the reaction is finished, the dye is filtered, the crude product is re-dissolved, the pH value is adjusted to 6.8-7.0, and the blue solid is obtained by re-salting out.

Example 9

A thiazole heterocyclic azo type reactive dye has the following structure:

a preparation method of thiazole heterocyclic azo type reactive dye comprises the following steps:

diazotization reaction: same preparation as in example 1;

condensation reaction of cyanuric chloride: taking 1.90g of cyanuric chloride (0.0103mol) and 20g of small ice blocks, mechanically stirring at 0-5 ℃ until the cyanuric chloride is milky, then adding an aqueous solution containing 4.0g (0.01mol, 85.6%) of H acid monosodium salt, adjusting the pH of the solution to be 4-5, and detecting by using an Ehrlich reagent to determine a reaction end point; after the reaction is finished, 2.21g of 2-amino-4-sulfobenzoic acid (0.01mol, 98%) is added, the temperature is raised to 20-30 ℃, the pH value is controlled to be 5-6 by 10% sodium carbonate solution, after the reaction is carried out for 3-4 h, the reaction end point is detected by TLC (a developing agent is n-butyl alcohol, isopropanol, ethyl acetate and water, the ratio of n-butyl alcohol to isopropanol to ethyl acetate to water is 2:4:1:3, v/v);

coupling reaction: the preparation is the same as that of the embodiment 1, potassium acetate is added to precipitate dye after the reaction is finished, the dye is filtered, the crude product is re-dissolved, the pH value is adjusted to 6.8-7.0, and the blue solid is obtained by re-salting out.

Example 10

A thiazole heterocyclic azo type reactive dye has the following structure:

a preparation method of thiazole heterocyclic azo type reactive dye comprises the following steps:

diazotization reaction: same preparation as in example 1;

condensation reaction of cyanuric chloride: taking 1.90g of cyanuric chloride (0.0103mol) and 20g of small ice blocks, mechanically stirring at 0-5 ℃ until the cyanuric chloride is milky, then adding an aqueous solution containing 4.0g (0.01mol, 85.6%) of H acid monosodium salt, adjusting the pH of the solution to be 4-5, and detecting by using an Ehrlich reagent to determine a reaction end point; after the reaction is finished, adding 0.93g of aniline (0.01mol), raising the temperature to 20-30 ℃, controlling the pH value to be 5-6 by using a 10% sodium carbonate solution, reacting for 3-4 h, and detecting the reaction end point by TLC (a developing agent is n-butyl alcohol, isopropanol, ethyl acetate and water, wherein the developing agent is 2:4:1:3, v/v);

coupling reaction: the preparation is the same as that of the embodiment 1, potassium acetate is added to precipitate dye after the reaction is finished, the dye is filtered, the crude product is re-dissolved, the pH value is adjusted to 6.8-7.0, and the blue solid is obtained by re-salting out.

Example 11

A thiazole heterocyclic azo type reactive dye has the following structure:

a preparation method of thiazole heterocyclic azo type reactive dye comprises the following steps:

diazotization reaction: same preparation as in example 1;

condensation reaction of cyanuric chloride: taking 1.90g of cyanuric chloride (0.0103mol) and 20g of small ice blocks, mechanically stirring at 0-5 ℃ until the cyanuric chloride is milky, then adding an aqueous solution containing 4.0g (0.01mol, 85.6%) of H acid monosodium salt, adjusting the pH of the solution to be 4-5, and detecting by using an Ehrlich reagent to determine a reaction end point; after the reaction is finished, adding 0.64g of ethylamine (0.01mol, 70%), raising the temperature to 20-30 ℃, controlling the pH value to be 5-6 by using a 10% sodium carbonate solution, reacting for 3-4 h, and detecting the reaction end point by TLC (a developing agent is n-butyl alcohol, isopropanol, ethyl acetate and water, wherein the developing agent is 2:4:1:3, v/v);

coupling reaction: the preparation is the same as that of the embodiment 1, potassium acetate is added to precipitate dye after the reaction is finished, the dye is filtered, the crude product is re-dissolved, the pH value is adjusted to 6.8-7.0, and the blue solid is obtained by re-salting out.

Example 12

A thiazole heterocyclic azo type reactive dye has the following structure:

a preparation method of thiazole heterocyclic azo type reactive dye comprises the following steps:

diazotization reaction: same preparation as in example 1;

condensation reaction of cyanuric chloride: taking 1.90g of cyanuric chloride (0.0103mol) and 20g of small ice blocks, mechanically stirring at 0-5 ℃ until the cyanuric chloride is milky, then adding an aqueous solution containing 4.0g (0.01mol, 85.6%) of H acid monosodium salt, adjusting the pH of the solution to be 4-5, and detecting by using an Ehrlich reagent to determine a reaction end point; after the reaction is finished, adding 0.75g of glycine (0.01mol), raising the temperature to 20-30 ℃, controlling the pH value to be 5-6 by using a 10% sodium carbonate solution, reacting for 3-4 h, and detecting the reaction end point by TLC (a developing agent is n-butyl alcohol, isopropanol, ethyl acetate and water, wherein the developing agent is 2:4:1:3, v/v);

coupling reaction: the preparation is the same as that of the embodiment 1, potassium acetate is added to precipitate dye after the reaction is finished, the dye is filtered, the crude product is re-dissolved, the pH value is adjusted to 6.8-7.0, and the blue solid is obtained by re-salting out.

Example 13

A thiazole heterocyclic azo type reactive dye has the following structure:

a preparation method of thiazole heterocyclic azo type reactive dye comprises the following steps:

diazotization reaction: same preparation as in example 1;

condensation reaction of the cyanuric fluoride: adding the dissolved substances into a beaker4.0g (0.01mol, 85.6%) of H acid, cooling to-5-0 ℃, gradually adding 1.39g (0.0103mol) of cyanuric fluoride under mechanical stirring, continuously adding crushed ice, strictly controlling the temperature below 0 ℃, and using Na with the mass fraction of 10% in the reaction process₂CO₃Controlling the pH value of the solution to be 4-5, and detecting by using an Ehrlich reagent to determine a reaction end point; after the reaction is finished, 2.81g of p- (beta-sulfuric ester ethyl sulfone) aniline (0.01mol) is added, the temperature is raised to 15-20 ℃, and 10% of Na is used₂CO₃Controlling the pH value of the solution to be 5-6, reacting for 3-4 h, and detecting a reaction end point by TLC (a developing agent is isobutanol, n-propanol, ethyl acetate and water, wherein the ratio of the developing agent to the water is 2:4:1:3, and v/v);

coupling reaction: the preparation is the same as that of the embodiment 1, potassium acetate is added to precipitate dye after the reaction is finished, the dye is filtered, the crude product is re-dissolved, the pH value is adjusted to 6.8-7.0, and the blue solid is obtained by re-salting out.

Example 14

A thiazole heterocyclic azo type reactive dye has the following structure:

a preparation method of thiazole heterocyclic azo type reactive dye comprises the following steps:

diazotization reaction: same preparation as in example 1;

condensation reaction of the cyanuric fluoride: adding 4.0g (0.01mol, 85.6%) of dissolved H acid into a beaker, cooling to-5-0 ℃, gradually adding 1.39g (0.0103mol) of cyanuric fluoride under mechanical stirring, continuously adding crushed ice, strictly controlling the temperature below 0 ℃, and using 10% of Na in mass fraction in the reaction process₂CO₃Controlling the pH value of the solution to be 4-5, and detecting by using an Ehrlich reagent to determine a reaction end point; after the reaction is finished, 2.81g of m- (beta-sulfuric ester ethyl sulfone) aniline (0.01mol) is added, the temperature is increased to 15-20 ℃, and 10% of Na is used₂CO₃Controlling the pH value of the solution to be 5-6, reacting for 3-4 h, and detecting a reaction end point by TLC (a developing agent is isobutanol, n-propanol, ethyl acetate and water, wherein the ratio of the developing agent to the water is 2:4:1:3, and v/v);

coupling reaction: the preparation is the same as that of the embodiment 1, potassium acetate is added to precipitate dye after the reaction is finished, the dye is filtered, the crude product is re-dissolved, the pH value is adjusted to 6.8-7.0, and the blue solid is obtained by re-salting out.

Example 15

A thiazole heterocyclic azo type reactive dye has the following structure:

a preparation method of thiazole heterocyclic azo type reactive dye comprises the following steps:

diazotization reaction: same preparation as in example 1;

condensation reaction of the cyanuric fluoride: adding 4.0g (0.01mol, 85.6%) of dissolved H acid into a beaker, cooling to-5-0 ℃, gradually adding 1.39g (0.0103mol) of cyanuric fluoride under mechanical stirring, continuously adding crushed ice, strictly controlling the temperature below 0 ℃, and using 10% of Na in mass fraction in the reaction process₂CO₃Controlling the pH value of the solution to be 4-5, and detecting by using an Ehrlich reagent to determine a reaction end point; after the reaction, 1.77g of o-aminobenzenesulfonic acid (0.01mol, 98%) is added, the temperature is raised to 15-20 ℃, and 10% of Na is used₂CO₃Controlling the pH value of the solution to be 5-6, reacting for 3-4 h, and detecting a reaction end point by TLC (a developing agent is isobutanol, n-propanol, ethyl acetate and water, wherein the ratio of the developing agent to the water is 2:4:1:3, and v/v);

coupling reaction: the preparation is the same as that of the embodiment 1, potassium acetate is added to precipitate dye after the reaction is finished, the dye is filtered, the crude product is re-dissolved, the pH value is adjusted to 6.8-7.0, and the blue solid is obtained by re-salting out.

Example 16

A thiazole heterocyclic azo type reactive dye has the following structure:

a preparation method of thiazole heterocyclic azo type reactive dye comprises the following steps:

diazotization reaction: same preparation as in example 1;

condensation reaction of the cyanuric fluoride: adding 4.0g (0.01mol, 85.6%) of dissolved H acid into a beaker, cooling to-5-0 ℃, gradually adding 1.39g (0.0103mol) of cyanuric fluoride under mechanical stirring, continuously adding crushed ice, strictly controlling the temperature below 0 ℃, and using 10% of Na in mass fraction in the reaction process₂CO₃Controlling the pH value of the solution to be 4-5, and detecting by using an Ehrlich reagent to determine a reaction end point; after the reaction is finished, 1.75g of m-aminobenzene sulfonic acid (0.01mol, 99%) is added, the temperature is raised to 15-20 ℃, and 10% of Na is used₂CO₃Controlling the pH value of the solution to be 5-6, reacting for 3-4 h, and detecting a reaction end point by TLC (a developing agent is isobutanol, n-propanol, ethyl acetate and water, wherein the ratio of the developing agent to the water is 2:4:1:3, and v/v);

coupling reaction: the preparation is the same as that of the embodiment 1, potassium acetate is added to precipitate dye after the reaction is finished, the dye is filtered, the crude product is re-dissolved, the pH value is adjusted to 6.8-7.0, and the blue solid is obtained by re-salting out.

Example 17

A thiazole heterocyclic azo type reactive dye has the following structure:

a preparation method of thiazole heterocyclic azo type reactive dye comprises the following steps:

diazotization reaction: same preparation as in example 1;

condensation reaction of the cyanuric fluoride: adding 4.0g (0.01mol, 85.6%) of dissolved H acid into a beaker, cooling to-5-0 ℃, gradually adding 1.39g (0.0103mol) of cyanuric fluoride under mechanical stirring, continuously adding crushed ice, strictly controlling the temperature below 0 ℃, and using 10% of Na in mass fraction in the reaction process₂CO₃Controlling the pH value of the solution to be 4-5, and detecting by using an Ehrlich reagent to determine a reaction end point; after the reaction is finished, 1.73g of sulfanilic acid (0.01mol, 99.8%) is added, the temperature is raised to 15-20 ℃, and 1 is used0% of Na₂CO₃Controlling the pH value of the solution to be 5-6, reacting for 3-4 h, and detecting a reaction end point by TLC (a developing agent is isobutanol, n-propanol, ethyl acetate and water, wherein the ratio of the developing agent to the water is 2:4:1:3, and v/v);

coupling reaction: the preparation is the same as that of the embodiment 1, potassium acetate is added to precipitate dye after the reaction is finished, the dye is filtered, the crude product is re-dissolved, the pH value is adjusted to 6.8-7.0, and the blue solid is obtained by re-salting out.

Example 18

A thiazole heterocyclic azo type reactive dye has the following structure:

a preparation method of thiazole heterocyclic azo type reactive dye comprises the following steps:

diazotization reaction: same preparation as in example 1;

condensation reaction of the cyanuric fluoride: adding 4.0g (0.01mol, 85.6%) of dissolved H acid into a beaker, cooling to-5-0 ℃, gradually adding 1.39g (0.0103mol) of cyanuric fluoride under mechanical stirring, continuously adding crushed ice, strictly controlling the temperature below 0 ℃, and using 10% of Na in mass fraction in the reaction process₂CO₃Controlling the pH value of the solution to be 4-5, and detecting by using an Ehrlich reagent to determine a reaction end point; after the reaction is finished, 2.67g of aniline-2, 5-disulfonic acid (0.01mol, 92.0%) is added, the temperature is raised to 15-20 ℃, and 10% of Na is used₂CO₃Controlling the pH value of the solution to be 5-6, reacting for 3-4 h, and detecting a reaction end point by TLC (a developing agent is isobutanol, n-propanol, ethyl acetate and water, wherein the ratio of the developing agent to the water is 2:4:1:3, and v/v);

coupling reaction: the preparation is the same as that of the embodiment 1, potassium acetate is added to precipitate dye after the reaction is finished, the dye is filtered, the crude product is re-dissolved, the pH value is adjusted to 6.8-7.0, and the blue solid is obtained by re-salting out.

Example 19

A thiazole heterocyclic azo type reactive dye has the following structure:

a preparation method of thiazole heterocyclic azo type reactive dye comprises the following steps:

diazotization reaction: same preparation as in example 1;

condensation reaction of the cyanuric fluoride: adding 4.0g (0.01mol, 85.6%) of dissolved H acid into a beaker, cooling to-5-0 ℃, gradually adding 1.39g (0.0103mol) of cyanuric fluoride under mechanical stirring, continuously adding crushed ice, strictly controlling the temperature below 0 ℃, and using 10% of Na in mass fraction in the reaction process₂CO₃Controlling the pH value of the solution to be 4-5, and detecting by using an Ehrlich reagent to determine a reaction end point; after the reaction is finished, 1.40g of p-aminobenzoic acid (0.01mol, 98%) is added, the temperature is raised to 15-20 ℃, and 10% of Na is used₂CO₃Controlling the pH value of the solution to be 5-6, reacting for 3-4 h, and detecting a reaction end point by TLC (a developing agent is isobutanol, n-propanol, ethyl acetate and water, wherein the ratio of the developing agent to the water is 2:4:1:3, and v/v);

coupling reaction: the preparation is the same as that of the embodiment 1, potassium acetate is added to precipitate dye after the reaction is finished, the dye is filtered, the crude product is re-dissolved, the pH value is adjusted to 6.8-7.0, and the blue solid is obtained by re-salting out.

Example 20

A thiazole heterocyclic azo type reactive dye has the following structure:

a preparation method of thiazole heterocyclic azo type reactive dye comprises the following steps:

diazotization reaction: same preparation as in example 1;

condensation reaction of the cyanuric fluoride: adding 4.0g (0.01mol, 85.6%) of dissolved H acid into a beaker, cooling to-5-0 ℃, gradually adding 1.39g (0.0103mol) of cyanuric fluoride under mechanical stirring, continuously adding crushed ice, strictly controlling the temperature below 0 ℃, and using 10% of Na in mass fraction in the reaction process₂CO₃Controlling the pH value of the solution to be 4-5, and detecting by using an Ehrlich reagent to determine a reaction end point; after the reaction, 1.73g of 2-chloro-4-aminobenzoic acid (0.01mol, 99%) was added, the temperature was raised to 15-20 ℃ and 10% Na was added₂CO₃Controlling the pH value of the solution to be 5-6, reacting for 3-4 h, and detecting a reaction end point by TLC (a developing agent is isobutanol, n-propanol, ethyl acetate and water, wherein the ratio of the developing agent to the water is 2:4:1:3, and v/v);

coupling reaction: the preparation is the same as that of the embodiment 1, potassium acetate is added to precipitate dye after the reaction is finished, the dye is filtered, the crude product is re-dissolved, the pH value is adjusted to 6.8-7.0, and the blue solid is obtained by re-salting out.

Example 21

A thiazole heterocyclic azo type reactive dye has the following structure:

a preparation method of thiazole heterocyclic azo type reactive dye comprises the following steps:

diazotization reaction: same preparation as in example 1;

condensation reaction of the cyanuric fluoride: adding 4.0g (0.01mol, 85.6%) of dissolved H acid into a beaker, cooling to-5-0 ℃, gradually adding 1.39g (0.0103mol) of cyanuric fluoride under mechanical stirring, continuously adding crushed ice, strictly controlling the temperature below 0 ℃, and using 10% of Na in mass fraction in the reaction process₂CO₃Controlling the pH value of the solution to be 4-5, and detecting by using an Ehrlich reagent to determine a reaction end point; after the reaction is finished, 2.21g of 2-amino-4-sulfobenzoic acid (0.01mol, 98%) is added, the temperature is raised to 15-20 ℃, and 10% of Na is used₂CO₃Controlling the pH value of the solution to be 5-6, reacting for 3-4 h, and detecting a reaction end point by TLC (a developing agent is isobutanol, n-propanol, ethyl acetate and water, wherein the ratio of the developing agent to the water is 2:4:1:3, and v/v);

coupling reaction: the preparation is the same as that of the embodiment 1, potassium acetate is added to precipitate dye after the reaction is finished, the dye is filtered, the crude product is re-dissolved, the pH value is adjusted to 6.8-7.0, and the blue solid is obtained by re-salting out.

Example 22

A thiazole heterocyclic azo type reactive dye has the following structure:

a preparation method of thiazole heterocyclic azo type reactive dye comprises the following steps:

diazotization reaction: same preparation as in example 1;

condensation reaction of the cyanuric fluoride: adding 4.0g (0.01mol, 85.6%) of dissolved H acid into a beaker, cooling to-5-0 ℃, gradually adding 1.39g (0.0103mol) of cyanuric fluoride under mechanical stirring, continuously adding crushed ice, strictly controlling the temperature below 0 ℃, and using 10% of Na in mass fraction in the reaction process₂CO₃Controlling the pH value of the solution to be 4-5, and detecting by using an Ehrlich reagent to determine a reaction end point; after the reaction is finished, 0.93g of aniline (0.01mol) is added, the temperature is raised to 15-20 ℃, and 10% of Na is used₂CO₃Controlling the pH value of the solution to be 5-6, reacting for 3-4 h, and detecting a reaction end point by TLC (a developing agent is isobutanol, n-propanol, ethyl acetate and water, wherein the ratio of the developing agent to the water is 2:4:1:3, and v/v);

coupling reaction: the preparation is the same as that of the embodiment 1, potassium acetate is added to precipitate dye after the reaction is finished, the dye is filtered, the crude product is re-dissolved, the pH value is adjusted to 6.8-7.0, and the blue solid is obtained by re-salting out.

Example 23

A thiazole heterocyclic azo type reactive dye has the following structure:

a preparation method of thiazole heterocyclic azo type reactive dye comprises the following steps:

diazotization reaction: same preparation as in example 1;

condensation reaction of the cyanuric fluoride: adding 4.0g (0.01mol, 85.6%) of dissolved H acid into a beaker, cooling to-5-0 ℃, and carrying out on-machine operationGradually adding 1.39g (0.0103mol) of cyanuric fluoride under mechanical stirring, continuously adding crushed ice, strictly controlling the temperature below 0 deg.C, and using 10% Na in mass fraction during the reaction process₂CO₃Controlling the pH value of the solution to be 4-5, and detecting by using an Ehrlich reagent to determine a reaction end point; after the reaction is finished, 0.64g of ethylamine (0.01mol, 70%) is added, the temperature is raised to 15-20 ℃, and 10% of Na is used₂CO₃Controlling the pH value of the solution to be 5-6, reacting for 3-4 h, and detecting a reaction end point by TLC (a developing agent is isobutanol, n-propanol, ethyl acetate and water, wherein the ratio of the developing agent to the water is 2:4:1:3, and v/v);

coupling reaction: the preparation is the same as that of the embodiment 1, potassium acetate is added to precipitate dye after the reaction is finished, the dye is filtered, the crude product is re-dissolved, the pH value is adjusted to 6.8-7.0, and the blue solid is obtained by re-salting out.

Example 24

A thiazole heterocyclic azo type reactive dye has the following structure:

a preparation method of thiazole heterocyclic azo type reactive dye comprises the following steps:

diazotization reaction: same preparation as in example 1;

condensation reaction of the cyanuric fluoride: adding 4.0g (0.01mol, 85.6%) of dissolved H acid into a beaker, cooling to-5-0 ℃, gradually adding 1.39g (0.0103mol) of cyanuric fluoride under mechanical stirring, continuously adding crushed ice, strictly controlling the temperature below 0 ℃, and using 10% of Na in mass fraction in the reaction process₂CO₃Controlling the pH value of the solution to be 4-5, and detecting by using an Ehrlich reagent to determine a reaction end point; after the reaction is finished, 0.75g of glycine (0.01mol) is added, the temperature is raised to 15-20 ℃, and 10% of Na is used₂CO₃Controlling the pH value of the solution to be 5-6, reacting for 3-4 h, and detecting a reaction end point by TLC (a developing agent is isobutanol, n-propanol, ethyl acetate and water, wherein the ratio of the developing agent to the water is 2:4:1:3, and v/v);

coupling reaction: the preparation is the same as that of the embodiment 1, potassium acetate is added to precipitate dye after the reaction is finished, the dye is filtered, the crude product is re-dissolved, the pH value is adjusted to 6.8-7.0, and the blue solid is obtained by re-salting out.

Examples 25 to 36

The thiazole heterocyclic azo type reactive dye has a specific structural formula shown in a table 1:

TABLE 1 structures of thiazole heterocyclic azo type reactive dyes synthesized in examples 25 to 36

A preparation method of thiazole heterocyclic azo type reactive dye comprises the following steps:

diazotization reaction: same preparation as in example 1;

condensation reaction of cyanuric chloride: 2.66g of J acid (0.01mol, 89.7%) was used in place of H acid in the preparation of the first condensate, the other reactants and reaction conditions were the same as in example 1, and the preparation of the second condensate was the same as in examples 1 to 12;

coupling reaction: the preparation is the same as that of the embodiment 1, potassium acetate is added to precipitate dye after the reaction is finished, the dye is filtered, the crude product is re-dissolved, the pH value is adjusted to 6.8-7.0, and the blue solid is obtained by re-salting out.

Examples 37 to 48

The thiazole heterocyclic azo type reactive dye has a specific structural formula shown in a table 2:

TABLE 2 structures of thiazole heterocyclic azo type reactive dyes synthesized in examples 37 to 48

A preparation method of thiazole heterocyclic azo type reactive dye comprises the following steps:

diazotization reaction: same preparation as in example 1;

condensation reaction of the cyanuric fluoride: 2.66g of J acid (0.01mol, 89.7%) was used in place of H acid in the preparation of the first condensate, the other reactants and reaction conditions were the same as in example 13, and the preparation of the second condensate was the same as in examples 13 to 24;

coupling reaction: the preparation is the same as that of the embodiment 1, potassium acetate is added to precipitate dye after the reaction is finished, the dye is filtered, the crude product is re-dissolved, the pH value is adjusted to 6.8-7.0, and the blue solid is obtained by re-salting out.

Examples 49 to 60

The thiazole heterocyclic azo type reactive dye has a specific structural formula shown in a table 3:

TABLE 3 structures of thiazole heterocyclic azo type reactive dyes synthesized in examples 49 to 60

A preparation method of thiazole heterocyclic azo type reactive dye comprises the following steps:

diazotization reaction: same preparation as in example 1;

condensation reaction of cyanuric chloride: 2.68g of gamma acid (0.01mol, 89%) was used in place of H acid in the first condensate preparation, the other reactants and reaction conditions were the same as in example 1, and the second condensate preparation was the same as in examples 1 to 12 above, respectively;

coupling reaction: the preparation is the same as that of the embodiment 1, potassium acetate is added to precipitate dye after the reaction is finished, the dye is filtered, the crude product is re-dissolved, the pH value is adjusted to 6.8-7.0, and the blue solid is obtained by re-salting out.

Examples 61 to 72

The thiazole heterocyclic azo type reactive dye has a specific structural formula shown in a table 4:

TABLE 4 structures of thiazole-heterocyclic azo type reactive dyes synthesized in examples 61 to 72

A preparation method of thiazole heterocyclic azo type reactive dye comprises the following steps:

diazotization reaction: same preparation as in example 1;

condensation reaction of the cyanuric fluoride: 2.68g of gamma acid (0.01mol, 89%) was used in place of H acid in the first condensate preparation, the other reactants and reaction conditions were the same as in example 13, and the second condensate preparation was the same as in examples 1 to 12 above, respectively;

coupling reaction: the preparation is the same as that of the embodiment 1, potassium acetate is added to precipitate dye after the reaction is finished, the dye is filtered, the crude product is re-dissolved, the pH value is adjusted to 6.8-7.0, and the blue solid is obtained by re-salting out.

Examples 73 to 84

The thiazole heterocyclic azo type reactive dye has a specific structural formula shown in a table 5:

TABLE 5 structures of thiazole heterocyclic azo type reactive dyes synthesized in examples 73 to 84

A preparation method of thiazole heterocyclic azo type reactive dye comprises the following steps:

diazotization reaction: same preparation as in example 1;

condensation reaction of cyanuric chloride: 4.0g of K acid (0.01mol, 85%) was used in place of H acid in the first condensate preparation, the other reactants and reaction conditions were the same as in example 1, and the second condensate preparation was the same as in examples 1 to 12 above, respectively;

coupling reaction: the preparation is the same as that of the embodiment 1, potassium acetate is added to precipitate dye after the reaction is finished, the dye is filtered, the crude product is re-dissolved, the pH value is adjusted to 6.8-7.0, and the blue solid is obtained by re-salting out.

Examples 85 to 96

The thiazole heterocyclic azo type reactive dye has a specific structural formula shown in a table 6:

TABLE 6 Structure of thiazole heterocyclic azo type reactive dye synthesized in examples 85 to 96

A preparation method of thiazole heterocyclic azo type reactive dye comprises the following steps:

diazotization reaction: same preparation as in example 1;

condensation reaction of the cyanuric fluoride: 4.0g of K acid (0.01mol, 85%) was used in place of H acid in the preparation of first condensate, the other reactants and reaction conditions were the same as in example 13, and the preparation of second condensate was the same as in examples 13 to 24;

coupling reaction: the preparation is the same as that of the embodiment 1, potassium acetate is added to precipitate dye after the reaction is finished, the dye is filtered, the crude product is re-dissolved, the pH value is adjusted to 6.8-7.0, and the blue solid is obtained by re-salting out.

Examples 97 to 108

The thiazole heterocyclic azo type reactive dye has a specific structural formula shown in a table 7:

TABLE 7 structures of thiazole heterocyclic azo type reactive dyes synthesized in examples 97 to 108

A preparation method of thiazole heterocyclic azo type reactive dye comprises the following steps:

diazotization reaction: same preparation as in example 1;

condensation reaction of cyanuric chloride: 4.0g of Chicago acid (0.01mol, 85%) was used in place of H acid in the first condensation preparation, the other reactants and reaction conditions were the same as in example 1, and the second condensation preparation was the same as in examples 1 to 12 above;

coupling reaction: the preparation is the same as that of the embodiment 1, potassium acetate is added to precipitate dye after the reaction is finished, the dye is filtered, the crude product is re-dissolved, the pH value is adjusted to 6.8-7.0, and the blue solid is obtained by re-salting out.

Examples 109 to 120

The thiazole heterocyclic azo type reactive dye has a specific structural formula shown in a table 8:

TABLE 8 structures of thiazole heterocyclic azo type reactive dyes synthesized in examples 109 to 120

A preparation method of thiazole heterocyclic azo type reactive dye comprises the following steps:

diazotization reaction: same preparation as in example 1;

condensation reaction of the cyanuric fluoride: 4.0g of Chicago acid (0.01mol, 85%) was used in place of H acid in the first condensation preparation, the other reactants and reaction conditions were the same as in example 13, and the second condensation preparation was the same as in examples 13 to 24;

coupling reaction: the preparation is the same as that of the embodiment 1, potassium acetate is added to precipitate dye after the reaction is finished, the dye is filtered, the crude product is re-dissolved, the pH value is adjusted to 6.8-7.0, and the blue solid is obtained by re-salting out.

Example 121

A thiazole heterocyclic azo type reactive dye, which has a structure of general formula (i):

wherein the content of the first and second substances,

x is selected from-Cl and-F;

a is selected from formula (II-a);

R₁is selected from-H, -CH₃；

R₂Is selected from-NH₂、-NHCH₃、-NHCH₂CH₃、-NHCH₂COOH、-NHCH(CH₃)COOH、-OH、-OCH₃、-OCH₂CH₃Or formula (II-b);

in the formula (II-a),

n is 1 or 2;

in the formula (II-b),

R₃selected from-H, carboxyl, sulfonic group, methyl, methoxy, nitro, nitrile group, amino, -Cl or-Br;

R₄selected from-H, carboxyl, sulfonic group, methyl, methoxy, nitro, nitrile group, amino, -Cl, -Br, -CH₂COOH、-COCH₂Cl、-COCH₂CH₂Cl、-NHCOCH₂Cl、-NHCOCH₂CH₂Cl、-NHCOCH＝CH₂、-NHCOC(Br)＝CH₂、-NHCH₂CH(OH)CH₂Cl、-NHSO₂CH＝CH₂、-N(CH₃)SO₂CH₂CH₂M、-SO₂CH＝CH、-SO₂CH₂CH₂M、-SO₂CH₂CH₂OSO₃M、-SO₂NHCH₂CH₂M or-SO₂N(CH₃)CH₂CH₂M; wherein M is selected from-Cl, -F or-OSO₃R₅；R₅Is selected from-H, -Na or-K.

In the formula (I), A is selected from one of the following groups:

an H acid residue having the formula:

j acid residue of the formula:

a gamma acid residue having the formula:

a K acid residue of the formula:

a chicago acid residue having the formula:

the invention also comprises a method for preparing the thiazole heterocyclic azo type reactive dye,

1) condensation reaction

Cyanuric chloride or cyanuric fluoride and amino naphthol sulfonic acid carry out a condensation reaction to obtain a condensation product; adding the first condensation product into the corresponding second condensation raw material to carry out second condensation reaction;

2) diazotization reaction

Under the condition of an ice salt bath, gradually adding sodium nitrite solid into concentrated sulfuric acid, stirring, heating until the sodium nitrite solid is completely dissolved, cooling to 0-5 ℃, gradually adding alkalescent arylamine containing a thiazole heterocyclic structure, stirring for reaction, and after the reaction is finished, adding a small amount of sulfamic acid to remove excessive nitrous acid to obtain alkalescent arylamine diazonium salt containing the thiazole heterocyclic structure;

3) coupling reaction

Gradually dripping the weakly alkaline arylamine diazonium salt containing the thiazole heterocyclic structure obtained in the step 2) into the condensation product obtained in the step 1), controlling the pH value and carrying out reaction, and adding Na after the reaction is finished₂HPO₄-NaH₂PO₄Adding potassium acetate or sodium acetate solid into the pH buffer, stirring, standing, filtering, washing with appropriate amount of ethanol for 3 times, air drying the filter cake to obtain a crude product, re-dissolving the crude product, adjusting pH, and re-salting out to obtain the blue dye.

The amino naphthol sulfonic acid in the step 1) is one of H acid, J acid, gamma acid, K acid or Chicago acid.

The weakly alkaline arylamine containing the thiazole heterocyclic structure in the step 2) is one of 2-amino-5-nitrothiazole and 2-amino-4-methyl-5-nitrothiazole.

The first condensation reaction comprises the following steps: adding an aminonaphthol sulfonic acid solution into aqueous dispersion of cyanuric chloride or cyanuric fluoride, reacting under stirring at 0-5 ℃, and controlling the pH value of the solution to be 4-5 in the reaction process to obtain a condensation product;

the secondary condensation reaction comprises the following steps: and then adding unsubstituted or substituted aminobenzene or aliphatic amine into the primary condensation product, raising the temperature to 20-30 ℃, and controlling the pH value to be 5-6 for reaction to obtain a secondary condensation product.

The molar ratio of the cyanuric chloride or the cyanuric fluoride to the amino naphthol sulfonic acid is 1.02: 1;

the molar ratio of the primary condensation product to the unsubstituted or substituted aminobenzene or fatty amine is 1: 1.

The diazotization reaction in the step 2) is specifically as follows: under the condition of an ice salt bath at the temperature of-5 to-10 ℃, gradually adding sodium nitrite solid into 11.0g of concentrated sulfuric acid, stirring, heating until the sodium nitrite solid is completely dissolved, cooling to 0 to 5 ℃, and gradually adding weakly alkaline arylamine containing a thiazole heterocyclic structure; stirring and reacting for 2-4 h, and after the reaction is finished, adding a small amount of sulfamic acid to remove excessive nitrous acid to obtain the weakly alkaline arylamine diazonium salt with the thiazole heterocyclic structure.

The molar ratio of the sodium nitrite to the weakly alkaline arylamine containing the thiazole heterocyclic structure is 1.05: 1.

The coupling reaction in the step 3) is specifically as follows: dropwise adding weakly alkaline arylamine diazonium salt containing thiazole heterocyclic structure into the condensation product obtained in the step 1), controlling the pH to be 1-2, reacting at 0-5 ℃, and adding 1% (w/v) of Na after the reaction is finished₂HPO₄-NaH₂PO₄Adding potassium acetate or sodium acetate solid in batches, detecting the salting-out condition of the dye by using a permeable ring, stirring, standing, performing suction filtration, washing by using a proper amount of ethanol for 3 times, drying a filter cake to obtain a crude product, re-dissolving the crude product, adjusting the pH value to 6.8-7.0, and re-salting out to obtain the blue dye to obtain the thiazole heterocyclic azo type reactive dye.

The dye has excellent acid-base color change performance and wide application prospect in pH value detection.

The experimental methods used in the above examples are all conventional methods unless otherwise specified.

The materials and reagents used in the above examples were commercially available or synthesized from commercially available raw materials, unless otherwise specified.

The above embodiments are only for illustrating the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention accordingly, and not to limit the protection scope of the present invention accordingly. All equivalent changes or modifications made in accordance with the spirit of the present disclosure are intended to be covered by the scope of the present disclosure.