阅读说明：本技术 一种苯并噻唑杂环偶氮型水溶性染料及其制备方法 (Benzothiazole heterocyclic azo type water-soluble 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,特别涉及一种苯并噻唑杂环偶氮型水溶性染料及其制备方法。将分子中含杂环结构的弱碱性芳胺作为重氮组份引入水溶性的酸性或活性染料结构中,使之成为酸碱变色染料。制备方法为：三聚氯氰、三聚氟氰、乙酸酐或苯甲酰氯与氨基萘酚磺酸进行缩合反应,得到缩合产物；2-氨基-6-硝基苯并噻唑的重氮化反应；重氮化反应产物与缩合产物的偶合反应。本发明提供的苯并噻唑杂环偶氮型水溶性染料具有优异的酸碱变色性能,合成工艺简单,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,具有灵敏度高,选择性好,快捷,可逆,肉眼可见等优点,具有广阔的应用前景。(The invention relates to the technical field of dyes, in particular to a benzothiazole heterocyclic azo type water-soluble dye and a preparation method thereof. The weak alkaline arylamine with heterocyclic structure in the molecule is used as diazo component and introduced into the structure of water-soluble acidic or active dye to make it become acid-base allochroic dye. The preparation method comprises the following steps: cyanuric chloride, cyanuric fluoride, acetic anhydride or benzoyl chloride and amino naphthol sulfonic acid are subjected to condensation reaction to obtain a condensation product; diazotization reaction of 2-amino-6-nitrobenzothiazole; coupling reaction of the diazotised reaction product with the condensation product. The benzothiazole heterocyclic azo type water-soluble dye provided by the invention has excellent acid-base color changing performance, is simple in synthesis process, can be used for rapidly detecting the pH value of a solution by direct visual observation without any optical device, has the advantages of high sensitivity, good selectivity, quickness, reversibility, visibility by naked eyes and the like, and has wide application prospect.)

1. A water-soluble dye of the benzothiazole heteroazoic type, characterized in that the water-soluble dye of the benzothiazole heteroazoic type has the general formula (i):

wherein the content of the first and second substances,

a is selected from-OCH₃-OPh or formula (II-a);

n is 1 or 2;

in the general formula (II-a),

x is selected from-Cl or-F;

y is selected from-Cl, -F, -NH₂、-NHCH₃、-NHCH₂CH₃、-NHCH₂COOH、-NHCH(CH₃)COOH、-OH、-OCH₃、-OCH₂CH₃Or general formula (II-b);

in the general formula (II-b),

R₁selected from-H, carboxyl, sulfonic group, methyl, methoxy, nitro, nitrile group, amino, -Cl or-Br;

R₂selected 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-OSO₃R₃，R₃Is selected from-H, -Na or-K.

2. The water-soluble benzothiazole azo dye according to claim 1, wherein the aminonaphthol sulfonic acid residue or the aminonaphthol disulfonic acid residue attached to a in formula (I) 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 water-soluble dyes of the benzothiazolylazo type according to any of claims 1 to 2, characterized in that:

1) condensation reaction

Cyanuric chloride, cyanuric fluoride, acetic anhydride or benzoyl chloride and amino naphthol sulfonic acid are subjected to condensation reaction to obtain a condensation product;

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 2-amino-6-nitrobenzothiazole, stirring for reaction, and after the reaction is finished, adding a small amount of sulfamic acid to remove excessive nitrous acid to obtain 2-amino-6-nitrobenzothiazole diazonium;

3) coupling reaction

Gradually dripping the 2-amino-6-nitrobenzothiazole diazonium salt obtained in the step 2) into the condensation product obtained in the step 1), controlling the pH value and carrying out reaction, adding a pH buffering agent after the reaction is finished, then adding potassium acetate or sodium acetate solid in several times, stirring, standing, carrying out suction filtration, drying a filter cake to obtain a crude product, regulating the pH value after the crude product is redissolved, and carrying out salting out again to obtain the benzothiazole heterocyclic azo type water-soluble dye.

4. The process for preparing a water-soluble dye of the benzothiazolylazo type according to claim 3, wherein: in the step 1), the condensation reaction of cyanuric chloride or cyanuric fluoride and amino naphthol sulfonic acid is a primary condensation reaction or a secondary condensation reaction;

preferably, the amino naphthol sulfonic acid is one of H acid, J acid, γ acid, K acid or chicago acid.

5. The process for preparing a water-soluble dye of the benzothiazolylazo type according to claim 4, wherein: the primary condensation reaction comprises the following steps: adding 10% of aminonaphthol sulfonic acid solution into cyanuric chloride or cyanuric fluoride solution, reacting under stirring at 0-5 ℃, controlling the pH value of the solution to be 4-5 in the reaction process, and detecting a first condensation reaction end point by using an Ehrlich reagent to obtain a first condensation product;

the secondary condensation reaction comprises the following steps: adding unsubstituted or substituted aminobenzene or aliphatic amine into the first condensation product, raising the temperature to 15-30 ℃, controlling the pH value to be 5-6, reacting, and detecting the end point of the second condensation reaction by thin-layer chromatography to obtain the second condensation product.

6. The process for preparing a water-soluble dye of the benzothiazolylazo type according to claim 5, wherein:

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.

7. The method for preparing benzothiazole heterocyclic azo type water-soluble dyes of claim 3, wherein in said step 1), said condensation reaction of acetic anhydride or benzoyl chloride and amino naphthol sulfonic acid is: dropwise adding acetic anhydride or benzoyl chloride into an aqueous solution of aminonaphthol sulfonic acid, heating to 60-80 ℃, stirring for reaction, and detecting by using an Ehrlich reagent to determine a reaction end point to obtain a condensation product of the acetic anhydride or benzoyl chloride and the aminonaphthol sulfonic acid.

8. The process for preparing a water-soluble dye of the benzothiazolylazo type according to claim 7, wherein:

the molar ratio of the acetic anhydride or the benzoyl chloride to the amino naphthol sulfonic acid is 2-3: 1;

preferably, the molar ratio of acetic anhydride or benzoyl chloride to aminonaphthol sulfonic acid is 2.5: 1.

9. The method for preparing a benzothiazole heterocyclic azo type water-soluble dye according to claim 3, wherein said 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 the temperature of 0 to 5 ℃, gradually adding 2-amino-6-nitrobenzothiazole, stirring for reaction for 2 to 4 hours, and after the reaction is finished, adding a small amount of sulfamic acid to remove excessive nitrous acid to obtain 2-amino-6-nitrobenzothiazole diazonium salt;

preferably, the molar ratio of the sodium nitrite to the 2-amino-6-nitrobenzothiazole is 1.05: 1.

10. The method for preparing the benzothiazole heterocyclic azo type water-soluble dye according to claim 3, wherein the coupling reaction in the step 3) is specifically: gradually dripping 2-amino-6-nitrobenzothiazole diazonium salt into the condensation product in the step 1), controlling the pH value to be 1-2, reacting at 0-5 ℃, and adding 1% (w/v) 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, 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 benzothiazole heterocyclic azo type water-soluble dye.

Technical Field

The invention relates to the technical field of dyes, in particular to a benzothiazole heterocyclic azo type water-soluble dye and a preparation method thereof.

Background

Azo dyes are a very important class of dyes due to the readily available raw materials, simple synthetic methods, and high absorption coefficients. Because azo bonds are easy to generate tautomerism of an azo-quinone hydrazone structure, a plurality of monoazo water-soluble dyes often show different color differences in different acid-base environments, and the research on the pH color change effect of azo structure dyes also becomes a research hotspot in the dye field. The 2-amino-6-nitrobenzothiazole is often used as a diazo component for synthesizing high-performance azo dyes in water-insoluble dyes such as disperse dyes, direct dyes and the like due to the existence of sulfur or nitrogen atoms with slightly high electronegativity in a heterocyclic structure, better electron transfer capability of a heterocyclic system and nitro electron withdrawing effect, but has fresh application in active and acid dyes with wide application.

Disclosure of Invention

Aiming at the defects in the prior art, the technical problem to be solved by the invention is to provide the benzothiazole heterocyclic azo type water-soluble dye and the preparation method thereof, wherein 2-amino-6-nitrobenzothiazole is used as a diazo component and is introduced into a water-soluble acidic or reactive dye structure to enable the dye to become an acid-base color-changing dye.

The technical scheme adopted by the invention for realizing the purpose is as follows: a water-soluble dye of the benzothiazole heteroazoic type, which has the general formula (i):

wherein the content of the first and second substances,

a is selected from-OCH₃-OPh or formula (II-a);

n is 1 or 2;

in the general formula (II-a),

x is selected from-Cl or-F;

y is selected from-Cl, -F, -NH₂、-NHCH₃、-NHCH₂CH₃、-NHCH₂COOH、-NHCH(CH₃)COOH、-OH、-OCH₃、-OCH₂CH₃Or general formula (II-b);

in the general formula (II-b),

R₁selected from-H, carboxyl, sulfonic group, methyl, methoxy, nitro, nitrile group, amino, -Cl or-Br;

R₂selected 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-OSO₃R₃，R₃Is selected from-H, -Na or-K.

Further, in the formula (I), the amino naphthol sulfonic acid residue or the amino naphthol disulfonic acid residue attached to 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 benzothiazole heterocyclic azo type water-soluble dye,

1) condensation reaction

Cyanuric chloride, cyanuric fluoride, acetic anhydride or benzoyl chloride and amino naphthol sulfonic acid are subjected to condensation reaction to obtain a condensation product;

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 2-amino-6-nitrobenzothiazole, stirring for reaction, and after the reaction is finished, adding a small amount of sulfamic acid to remove excessive nitrous acid to obtain 2-amino-6-nitrobenzothiazole diazonium;

3) coupling reaction

Gradually dripping the 2-amino-6-nitrobenzothiazole diazonium salt obtained in the step 2) into the condensation product obtained in the step 1), controlling the pH value and carrying out reaction, adding a pH buffering agent after the reaction is finished, then adding potassium acetate or sodium acetate solid in several times, stirring, standing, carrying out suction filtration, drying a filter cake to obtain a crude product, regulating the pH value after the crude product is redissolved, and carrying out salting out again to obtain the benzothiazole heterocyclic azo type water-soluble dye.

Further, in the step 1), the condensation reaction of cyanuric chloride or cyanuric fluoride and amino naphthol sulfonic acid is a primary condensation reaction or a secondary condensation reaction;

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

Further, the primary condensation reaction is as follows: adding 10% of aminonaphthol sulfonic acid solution into cyanuric chloride or cyanuric fluoride solution, reacting under stirring at 0-5 ℃, controlling the pH value of the solution to be 4-5 in the reaction process, and detecting a first condensation reaction end point by using an Ehrlich reagent to obtain a first condensation product;

the secondary condensation reaction comprises the following steps: adding unsubstituted or substituted aminobenzene or aliphatic amine into the first condensation product, raising the temperature to 15-30 ℃, controlling the pH value to be 5-6, reacting, and detecting the end point of the second condensation reaction by thin-layer chromatography to obtain the second 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, in the step 1), the condensation reaction of acetic anhydride or benzoyl chloride and amino naphthol sulfonic acid is as follows: dropwise adding acetic anhydride or benzoyl chloride into an aqueous solution of aminonaphthol sulfonic acid, heating to 60-80 ℃, stirring for reaction, and detecting by using an Ehrlich reagent to determine a reaction end point to obtain a condensation product of the acetic anhydride or benzoyl chloride and the aminonaphthol sulfonic acid.

Further, the molar ratio of the acetic anhydride or the benzoyl chloride to the amino naphthol sulfonic acid is 2-3: 1;

the molar ratio of the acetic anhydride or the benzoyl chloride to the amino naphthol sulfonic acid is 2.5: 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 the temperature of 0 to 5 ℃, gradually adding 2-amino-6-nitrobenzothiazole, stirring for reaction for 2 to 4 hours, and after the reaction is finished, adding a small amount of sulfamic acid to remove excessive nitrous acid to obtain 2-amino-6-nitrobenzothiazole diazonium salt;

the molar ratio of the sodium nitrite to the 2-amino-6-nitrobenzothiazole is 1.05: 1.

Further, the coupling reaction in the step 3) is specifically: gradually dripping 2-amino-6-nitrobenzothiazole diazonium salt into the condensation product in the step 1), controlling the pH value to be 1-2, reacting at 0-5 ℃, and adding 1% (w/v) Na after the reaction is finished₂HPO₄-NaH₂PO₄Then adding potassium acetate or sodium acetate solid in portions, and percolatingAnd detecting the salting-out condition of the dye, stirring, standing, performing suction filtration, drying the filter cake to obtain a crude product, re-dissolving the crude product, adjusting the pH value of the crude product to 6.8-7.0, and re-salting out to obtain the benzothiazole heterocyclic azo type water-soluble dye.

The benzothiazole heterocyclic azo type water-soluble dye and the preparation method thereof have the beneficial effects that: the benzothiazole heterocyclic azo type water-soluble dye provided by the invention has excellent acid-base color changing performance, is simple in synthesis process, can be used for rapidly detecting the pH value of a solution by direct visual observation without any optical device, has the advantages of high sensitivity, good selectivity, quickness, reversibility, visibility by naked eyes and the like, and has wide application prospect.

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 benzothiazole heterocyclic azo type water-soluble dye has the following specific structure:

a method for preparing the benzothiazole heterocyclic azo type water-soluble dye comprises the following steps:

diazotization reaction: placing 11.0g of concentrated sulfuric acid with the mass fraction of 98% in an ice bath at 0-5 ℃ for cooling, gradually adding 0.73g of sodium nitrite solid, stirring, heating until the concentrated sulfuric acid is completely dissolved, stopping heating and cooling, gradually adding 1.99g of 2-amino-6-nitrobenzothiazole (0.01mol and 98%), stirring, continuing to react at 0-5 ℃, detecting the reaction end point 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-6-nitrobenzothiazole 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 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.

Example 2

A benzothiazole heterocyclic azo type water-soluble dye has the following specific structure:

a method for preparing the benzothiazole heterocyclic azo type water-soluble 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 blue solid is obtained by salting out.

Example 3

A benzothiazole heterocyclic azo type water-soluble dye has the following specific structure:

a method for preparing the benzothiazole heterocyclic azo type water-soluble 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 blue solid is obtained by salting out.

Example 4

A benzothiazole heterocyclic azo type water-soluble dye has the following specific structure:

a method for preparing the benzothiazole heterocyclic azo type water-soluble 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 blue solid is obtained by salting out.

Example 5

A benzothiazole heterocyclic azo type water-soluble dye has the following specific structure:

a method for preparing the benzothiazole heterocyclic azo type water-soluble 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 blue solid is obtained by salting out.

Example 6

A benzothiazole heterocyclic azo type water-soluble dye has the following specific structure:

a method for preparing the benzothiazole heterocyclic azo type water-soluble 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 blue solid is obtained by salting out.

Example 7

A benzothiazole heterocyclic azo type water-soluble dye has the following specific structure:

a method for preparing the benzothiazole heterocyclic azo type water-soluble 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 blue solid is obtained by salting out.

Example 8

A benzothiazole heterocyclic azo type water-soluble dye has the following specific structure:

a method for preparing the benzothiazole heterocyclic azo type water-soluble 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 blue solid is obtained by salting out.

Example 9

A benzothiazole heterocyclic azo type water-soluble dye has the following specific structure:

a method for preparing the benzothiazole heterocyclic azo type water-soluble 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 blue solid is obtained by salting out.

Example 10

A benzothiazole heterocyclic azo type water-soluble dye has the following specific structure:

a method for preparing the benzothiazole heterocyclic azo type water-soluble 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 blue solid is obtained by salting out.

Example 11

A benzothiazole heterocyclic azo type water-soluble dye has the following specific structure:

a method for preparing the benzothiazole heterocyclic azo type water-soluble 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 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 the reaction end point by TLC;

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 blue solid is obtained by salting out.

Example 12

A benzothiazole heterocyclic azo type water-soluble dye has the following specific structure:

a method for preparing the benzothiazole heterocyclic azo type water-soluble 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 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 the reaction end point by TLC;

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 blue solid is obtained by salting out.

Example 13

A benzothiazole heterocyclic azo type water-soluble dye has the following specific structure:

a method for preparing the benzothiazole heterocyclic azo type water-soluble 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, 1.77g 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 the reaction end point by TLC;

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 blue solid is obtained by salting out.

Example 14

A benzothiazole heterocyclic azo type water-soluble dye has the following specific structure:

a method for preparing the benzothiazole heterocyclic azo type water-soluble 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-aminobenzenesulfonic 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 between 5 and 6,after reacting for 3-4 h, detecting the reaction end point by TLC;

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 blue solid is obtained by salting out.

Example 15

A benzothiazole heterocyclic azo type water-soluble dye has the following specific structure:

a method for preparing the benzothiazole heterocyclic azo type water-soluble 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 10% of Na is used₂CO₃Controlling the pH value of the solution to be 5-6, reacting for 3-4 h, and detecting the reaction end point by TLC;

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 blue solid is obtained by salting out.

Example 16

A benzothiazole heterocyclic azo type water-soluble dye has the following specific structure:

a method for preparing the benzothiazole heterocyclic azo type water-soluble 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 the reaction end point by TLC;

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 blue solid is obtained by salting out.

Example 17

A benzothiazole heterocyclic azo type water-soluble dye has the following specific structure:

a method for preparing the benzothiazole heterocyclic azo type water-soluble 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 the reaction is carried out by using 10%Na of (2)₂CO₃Controlling the pH value of the solution to be 5-6, reacting for 3-4 h, and detecting the reaction end point by TLC;

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 blue solid is obtained by salting out.

Example 18

A benzothiazole heterocyclic azo type water-soluble dye has the following specific structure:

a method for preparing the benzothiazole heterocyclic azo type water-soluble 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 the reaction end point by TLC;

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 blue solid is obtained by salting out.

Example 19

A benzothiazole heterocyclic azo type water-soluble dye has the following specific structure:

a method for preparing the benzothiazole heterocyclic azo type water-soluble 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, 0.64g 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 the reaction end point by TLC;

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 blue solid is obtained by salting out.

Example 20

A benzothiazole heterocyclic azo type water-soluble dye has the following specific structure:

a method for preparing the benzothiazole heterocyclic azo type water-soluble 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, and the temperature is raised to 15-20%10% Na at DEG C₂CO₃Controlling the pH value of the solution to be 5-6, reacting for 3-4 h, and detecting the reaction end point by TLC;

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 blue solid is obtained by salting out.

Examples 21 to 30

The specific structure of the benzothiazole heterocyclic azo type water-soluble dye is shown in a table 1:

TABLE 1 Structure of benzothiazolylazolylazo type water-soluble dye synthesized in examples 21 to 30

A method for preparing the benzothiazole heterocyclic azo type water-soluble 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 second condensate was prepared in the same manner as in examples 1 to 10;

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 blue solid is obtained by salting out.

Examples 31 to 40

The specific structure of the benzothiazole heterocyclic azo type water-soluble dye is shown in a table 2:

TABLE 2 Structure of benzothiazolylazolylazo type water-soluble dye synthesized in examples 31 to 40

A method for preparing the benzothiazole heterocyclic azo type water-soluble 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 11, and the second condensate was prepared in the same manner as in examples 11 to 20;

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 blue solid is obtained by salting out.

Examples 41 to 50

The specific structure of the benzothiazole heterocyclic azo type water-soluble dye is shown in a table 3:

TABLE 3 Structure of benzothiazolylazolylazo type water-soluble dye synthesized in examples 41 to 50

A method for preparing the benzothiazole heterocyclic azo type water-soluble 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 preparation of the first condensate, the other reactants and reaction conditions were the same as in example 1, and the second condensate was prepared in the same manner as in examples 1 to 10;

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 blue solid is obtained by salting out.

Examples 51 to 60

The specific structure of the benzothiazole heterocyclic azo type water-soluble dye is shown in a table 4:

TABLE 4 Structure of benzothiazolylazolylazo type water-soluble dye synthesized in examples 51 to 60

A method for preparing the benzothiazole heterocyclic azo type water-soluble 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 preparation of the first condensate, the other reactants and reaction conditions were the same as in example 11, and the second condensate was prepared in the same manner as in examples 11 to 20;

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 blue solid is obtained by salting out.

Examples 61 to 70

The specific structure of the benzothiazole heterocyclic azo type water-soluble dye is shown in a table 5:

TABLE 5 Structure of benzothiazolylazolylazo type water-soluble dye synthesized in examples 61 to 70

A method for preparing the benzothiazole heterocyclic azo type water-soluble 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 preparation of the first condensate, the other reactants and reaction conditions were the same as in example 1, and the second condensate was prepared in the same manner as in examples 1 to 10;

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 blue solid is obtained by salting out.

Examples 71 to 80

The specific structure of the benzothiazole heterocyclic azo type water-soluble dye is shown in a table 6:

TABLE 6 Structure of benzothiazolylazolylazo type water-soluble dye synthesized in examples 71 to 80

A method for preparing the benzothiazole heterocyclic azo type water-soluble dye comprises the following steps:

diazotization reaction: same preparation as in example 1;

condensation reaction of the cyanuric fluoride: 4.0g K acid (0.01mol, 85%) 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 11, and the second condensate was prepared in the same manner as in examples 11 to 20;

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 blue solid is obtained by salting out.

Examples 81 to 90

The specific structure of the benzothiazole heterocyclic azo type water-soluble dye is shown in a table 7:

TABLE 7 Structure of benzothiazolylazolylazo type water-soluble dye synthesized in examples 81 to 90

A method for preparing the benzothiazole heterocyclic azo type water-soluble 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 preparation of the first condensate, the other reactants and reaction conditions were the same as in example 1, and the second condensate was prepared in the same manner as in examples 1 to 10;

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 blue solid is obtained by salting out.

Examples 91 to 100

The specific structure of the benzothiazole heterocyclic azo type water-soluble dye is shown in a table 8:

TABLE 8 Structure of benzothiazolylazolylazazo type water-soluble dye synthesized in examples 91 to 100

A method for preparing the benzothiazole heterocyclic azo type water-soluble 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 preparation of the first condensate, the other reactants and reaction conditions were the same as in example 11, and the second condensate was prepared in the same manner as in examples 11 to 20;

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 blue solid is obtained by salting out.

Example 101

A benzothiazole heterocyclic azo type water-soluble dye, the specific structure is shown in a table 9,

a method for preparing the benzothiazole heterocyclic azo type water-soluble 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 cubes, 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 to obtain a condensate of the cyanuric chloride and the H acid;

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 blue solid is obtained by salting out.

Examples 102 to 105

A benzothiazole heterocyclic azo type water-soluble dye, the specific structure is shown in a table 9,

a method for preparing the benzothiazole heterocyclic azo type water-soluble dye comprises the following steps:

diazotization reaction: same preparation as in example 1;

condensation reaction of cyanuric chloride: in examples 102 to 105, J acid, γ acid, K acid and chicago acid were used instead of H acid in the preparation of the condensate, and other reactants and reaction conditions were the same as those in example 101;

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 blue solid is obtained by salting out.

Example 106

A benzothiazole heterocyclic azo type water-soluble dye, the specific structure is shown in a table 9,

a method for preparing the benzothiazole heterocyclic azo type water-soluble dye comprises the following steps:

diazotization reaction: same preparation as in example 1;

condensation reaction of the cyanuric fluoride: adding a certain mass of H-acid monosodium salt into a beakerCooling the aqueous solution to-5-0 ℃, gradually adding 1.39g (0.0103mol) of cyanuric fluoride under mechanical stirring, continuously adding crushed ice in the reaction process, strictly controlling the temperature below 0 ℃, and using 10% by mass of Na 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 to obtain a condensate of the cyanuric fluoride and the H acid;

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 blue solid is obtained by salting out.

Examples 107 to 110

A benzothiazole heterocyclic azo type water-soluble dye, the specific structure is shown in a table 9,

TABLE 9 Structure of benzothiazolylazolylazo type water-soluble dye synthesized in examples 101 to 110

A method for preparing the benzothiazole heterocyclic azo type water-soluble dye comprises the following steps:

diazotization reaction: same preparation as in example 1;

condensation reaction: examples 106 to 110 were prepared by using J acid, gamma acid, K acid and Chicago acid, respectively, in place of H acid, and the other reactants and reaction conditions were the same as those in example 106;

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 blue solid is obtained by salting out.

Example 111

A benzothiazole heterocyclic azo type water-soluble dye, the specific structure is shown in a table 10,

a method for preparing the benzothiazole heterocyclic azo type water-soluble dye comprises the following steps:

diazotization reaction: same preparation as in example 1;

condensation reaction: taking an aqueous solution containing 4.0g (0.01mol, 85.6%) of H acid monosodium salt, gradually adding 0.25mol of acetic anhydride according to the molar ratio of the acetic anhydride to the H acid of 2.5:1, heating to 60-80 ℃, stirring for reaction, and detecting by using an Ehrlich reagent to determine a reaction end point to obtain a condensation product of the acetic anhydride and the amino naphthol sulfonic acid;

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 blue solid is obtained by salting out.

Examples 112 to 115

A benzothiazole heterocyclic azo type water-soluble dye, the specific structure is shown in a table 10,

a method for preparing the benzothiazole heterocyclic azo type water-soluble dye comprises the following steps:

diazotization reaction: same preparation as in example 1;

condensation reaction: examples 112 to 115 were prepared by using J acid, γ acid, K acid and Chicago acid, respectively, in place of H acid, and the other reactants and reaction conditions were the same as those in example 111;

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 blue solid is obtained by salting out.

Example 116

A benzothiazole heterocyclic azo type water-soluble dye, the specific structure is shown in a table 10,

a method for preparing the benzothiazole heterocyclic azo type water-soluble dye comprises the following steps:

diazotization reaction: same preparation as in example 1;

condensation reaction: taking an aqueous solution containing 4.0g (0.01mol, 85.6%) of H acid monosodium salt, gradually adding 0.25mol of benzoyl chloride according to the molar ratio of the benzoyl chloride to the H acid of 2.5:1, heating to 60-80 ℃, stirring for reaction, and detecting by using an Ehrlich reagent to determine a reaction end point to obtain a condensation product of the benzoyl chloride and the amino naphthol sulfonic acid;

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 blue solid is obtained by salting out.

Examples 117 to 120

A benzothiazole heterocyclic azo type water-soluble dye, the specific structure is shown in a table 10,

a method for preparing the benzothiazole heterocyclic azo type water-soluble dye comprises the following steps:

diazotization reaction: same preparation as in example 1;

condensation reaction: examples 117 to 120 were carried out to prepare condensates, in which J acid, γ acid, K acid and Chicago acid were used in place of H acid, and other reactants and reaction conditions were the same as those in example 116;

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 blue solid is obtained by salting out.

TABLE 10 Structure of benzothiazolylazolylazo type water-soluble dye synthesized in examples 111 to 120

Example 121:

a water-soluble dye of the benzothiazole heteroazoic type, which has the general formula (i):

wherein the content of the first and second substances,

a is selected from-OCH₃-OPh or formula (II-a);

n is 1 or 2;

in the general formula (II-a),

x is selected from-Cl or-F;

y is selected from-Cl, -F, -NH₂、-NHCH₃、-NHCH₂CH₃、-NHCH₂COOH、-NHCH(CH₃)COOH、-OH、-OCH₃、-OCH₂CH₃Or general formula (II-b);

in the general formula (II-b),

R₁selected from-H, carboxyl, sulfonic group, methyl, methoxy, nitro, nitrile group, amino, -Cl or-Br;

R₂selected 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-OSO₃R₃，R₃Is selected from-H, -Na or-K.

In the formula (I), the amino naphthol sulfonic acid residue or the amino naphthol disulfonic acid residue linked to 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 benzothiazole heterocyclic azo type water-soluble dye,

1) condensation reaction

Cyanuric chloride, cyanuric fluoride, acetic anhydride or benzoyl chloride and amino naphthol sulfonic acid are subjected to condensation reaction to obtain a condensation product;

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 2-amino-6-nitrobenzothiazole, stirring for reaction, and after the reaction is finished, adding a small amount of sulfamic acid to remove excessive nitrous acid to obtain 2-amino-6-nitrobenzothiazole diazonium;

3) coupling reaction

Gradually dripping the 2-amino-6-nitrobenzothiazole diazonium salt obtained in the step 2) into the condensation product obtained in the step 1), controlling the pH value and carrying out reaction, adding a pH buffering agent after the reaction is finished, then adding potassium acetate or sodium acetate solid in several times, stirring, standing, carrying out suction filtration, drying a filter cake to obtain a crude product, regulating the pH value after the crude product is redissolved, and carrying out salting out again to obtain the benzothiazole heterocyclic azo type water-soluble dye.

In the step 1), the condensation reaction of cyanuric chloride or cyanuric fluoride and amino naphthol sulfonic acid is a primary condensation reaction or a secondary condensation reaction;

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

The primary condensation reaction comprises the following steps: adding 10% of aminonaphthol sulfonic acid solution into cyanuric chloride or cyanuric fluoride solution, reacting under stirring at 0-5 ℃, controlling the pH value of the solution to be 4-5 in the reaction process, and detecting a first condensation reaction end point by using an Ehrlich reagent to obtain a first condensation product;

the secondary condensation reaction comprises the following steps: adding unsubstituted or substituted aminobenzene or aliphatic amine into the first condensation product, raising the temperature to 15-30 ℃, controlling the pH value to be 5-6, reacting, and detecting the end point of the second condensation reaction by thin-layer chromatography to obtain the second 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.

In the step 1), the condensation reaction of acetic anhydride or benzoyl chloride and amino naphthol sulfonic acid is as follows: dropwise adding acetic anhydride or benzoyl chloride into an aqueous solution of aminonaphthol sulfonic acid, heating to 60-80 ℃, stirring for reaction, and detecting by using an Ehrlich reagent to determine a reaction end point to obtain a condensation product of the acetic anhydride or benzoyl chloride and the aminonaphthol sulfonic acid.

The molar ratio of the acetic anhydride or the benzoyl chloride to the amino naphthol sulfonic acid is 2.5: 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 the temperature of 0 to 5 ℃, gradually adding 2-amino-6-nitrobenzothiazole, stirring for reaction for 2 to 4 hours, and after the reaction is finished, adding a small amount of sulfamic acid to remove excessive nitrous acid to obtain 2-amino-6-nitrobenzothiazole diazonium salt;

the molar ratio of the sodium nitrite to the 2-amino-6-nitrobenzothiazole is 1.05: 1.

The coupling reaction in the step 3) is specifically as follows: gradually dripping 2-amino-6-nitrobenzothiazole diazonium salt into the condensation product in the step 1), controlling the pH value to be 1-2, reacting at 0-5 ℃, and adding 1% (w/v) 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, 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 benzothiazole heterocyclic azo type water-soluble dye.

The acid-base color-changing dye is prepared by introducing the 2-amino-6-nitrobenzothiazole into a water-soluble dye parent structure by utilizing the characteristics of good dark color effect, high absorptivity and the like of the 2-amino-6-nitrobenzothiazole structure.

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.