CN103833674B - A kind of method of synthesizing 4-methyl-2-hydrazinobenzothiazole - Google Patents

A kind of method of synthesizing 4-methyl-2-hydrazinobenzothiazole Download PDF

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CN103833674B
CN103833674B CN201410092647.1A CN201410092647A CN103833674B CN 103833674 B CN103833674 B CN 103833674B CN 201410092647 A CN201410092647 A CN 201410092647A CN 103833674 B CN103833674 B CN 103833674B
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methyl
hydrazine hydrate
hydrochloric acid
hydrazinobenzothiazole
reaction
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CN103833674A (en
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徐伟明
常雨薇
何红强
章鹏飞
吴南阳
汤淼荣
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Shanxi Rui SECCO Environmental Protection Technology Co., Ltd.
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Hangzhou Normal University
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D277/00Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/60Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
    • C07D277/62Benzothiazoles
    • C07D277/68Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
    • C07D277/82Nitrogen atoms

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Abstract

The present invention discloses a kind of method of synthesizing 4-methyl-2-hydrazinobenzothiazole.The method be with 4-methyl-2-amino benzothiazole for raw material, hydrazine hydrate is joined in the pressurized vessel of aqueous hydrochloric acid, have or emulsifier-free exist under, obtain final product 4-methyl-2-hydrazinobenzothiazole after reacting by heating.Hydrazine water reaction system of the present invention can be applied mechanically, and can effectively reduce the consume of raw material and the energy; The consumption of hydrazine greatly reduces, and meets Green Chemistry concept, is applicable to the advantages such as suitability for industrialized production; Technological operation is easy, and aftertreatment is simple, has good Social benefit and economic benefit, and suitability for industrialized is promoted.

Description

A kind of method of synthesizing 4-methyl-2-hydrazinobenzothiazole
Technical field
The present invention relates to technical field of pesticide, be specifically related to a kind of method of synthesizing 4-methyl-2-hydrazinobenzothiazole.
Background technology
4-methyl-2-hydrazinobenzothiazole is the industrial main intermediate being used for synthesizing fungicide tricyclazole at present.Tricyclazole is a kind of efficient systemic fungicide, and biological activity is high, and the mechanism of action is unique, is the most favourable agents preventing rice blast.As the important pesticide intermediate of a kind of whole world widespread use, to its synthesis, the concern of the research of structure and pharmacologically active extremely vast scientific researcher always.Conventional synthetic method is for raw material with 4-methyl-2-amino benzothiazole (AMBT) and hydrazine hydrate, pyroreaction obtained (US Patent No. 3937714 and Chinese patent CN86104926 Lilly Co., Eli. (EliLillyandCompany) in solvent ethylene glycol, Zhejiang Polytechnical University's journal, 2nd phase in 2010,4-methyl-2-hydrazinobenzothiazole synthesising process research).This class methods organic solvent ethylene glycol usage quantity is larger, the mol ratio of 4-methyl-2-amino benzothiazole and hydrazine hydrate is that 1:3 ~ 9(wherein uses the mol ratio of 4-methyl-2-amino benzothiazole hydrobromate and hydrazine hydrate to be 1:3 simultaneously, the mol ratio using 4-methyl-2-amino benzothiazole hydrochloride and hydrazine hydrate is more than 1:6), therefore when organic solvent and excess hydrazine hydrate are reclaimed in aftertreatment, formality is loaded down with trivial details, thus bring the loss of material and the high consumption of energy, cause the increase of the three wastes, cause the high of cost.Although also useful 1,6-hexylene glycol, phenylcarbinol etc. are as the report (Japanese Patent JP59007179) of solvent, and the advantages such as cost free.Nearest poplar builds (the Sichuan chemical industry such as the fine jade, 11st volume the 1st phase in 2008,4 monomethyl-2-hydrazinobenzothiazole synthesising process research) with 4-methyl-2-amino benzothiazole and hydrazine hydrate for raw material, replace ethylene glycol as reaction medium using water, to add suitable proportion inorganic salt to improve temperature of reaction, but the mole dosage of hydrazine hydrate is also more than 6 times.This method also can cause the loss of raw material hydrazine hydrate comparatively large in aftertreatment, and three industrial wastes increase.
Summary of the invention
The object of the invention is for the deficiencies in the prior art, a kind of method of synthesizing 4-methyl-2-hydrazinobenzothiazole is provided.
The inventive method is:
With 4-methyl-2-amino benzothiazole for raw material, hydrazine hydrate is joined in the pressurized vessel of aqueous hydrochloric acid, have or emulsifier-free exist under, obtain final product 4-methyl-2-hydrazinobenzothiazole after reacting by heating, reaction equation is as follows:
Concrete grammar of the present invention comprises the following steps:
4-methyl-2-amino benzothiazole (AMBT), hydrazine hydrate, deionized water, hydrochloric acid are joined in high-pressure reaction vessel, temperature of reaction be 130 ~ 170 DEG C, reaction pressure be the condition of 2 ~ 10 kilograms under reacting by heating 4 ~ 35h, normal temperature is cooled to after reaction terminates, filter, crude product vacuum-drying obtains product; Wherein the mol ratio of 4-methyl-2-amino benzothiazole and hydrazine hydrate is 1:1.1 ~ 2; The mol ratio of 4-methyl-2-amino benzothiazole and hydrochloric acid is 1:1.0 ~ 1.3;
The present invention is to the add-on no requirement (NR) of deionized water.
Product obtained above can without the synthesis material of purifying as tricyclazole;
The filtrate reusable edible that above-mentioned filtration obtains; Before filtrate carries out recycle, need the amount of substance measuring hydrazine hydrate and hydrochloric acid, then add hydrazine hydrate, hydrochloric acid, make the mol ratio of 4-methyl-2-amino benzothiazole and hydrazine hydrate in reaction system maintain 1:1.1 ~ 2; The mol ratio of 4-methyl-2-amino benzothiazole and hydrochloric acid maintains 1:1.0 ~ 1.3;
Can also add emulsifying agent in reaction system of the present invention, the consumption of emulsifying agent is 1 ~ 5 ﹪ of 4-methyl-2-amino benzothiazole quality.
Described emulsifying agent be nonionic emulsifier, anionic emulsifier one or both; If emulsifying agent is the one of nonionic emulsifier, anionic emulsifier, wherein nonionic emulsifier be alkylphenol polyoxyethylene, fatty alcohol-polyoxyethylene ether, polyoxyethylene glycol one or more, anionic emulsifier be polyoxyethylenated alcohol sodium sulfate, sodium alkyl benzene sulfonate one or both; If emulsifying agent be nonionic emulsifier, two kinds of anionic emulsifier time, wherein nonionic emulsifier is the one of alkylphenol polyoxyethylene, fatty alcohol-polyoxyethylene ether, polyoxyethylene glycol, and anionic emulsifier is the one of polyoxyethylenated alcohol sodium sulfate, sodium alkyl benzene sulfonate.
The beneficial effect that the present invention has is:
1. present method is with water as solvent, and aftertreatment is simple, and pollute few, cost is low.
2. the hydrazine water reaction system that the present invention is used can be applied mechanically, and can effectively reduce the consume of raw material and the energy.
3. compared to technique in the past, the consumption of hydrazine greatly reduces, and meets Green Chemistry concept, is applicable to the advantages such as suitability for industrialized production.
4. this technological operation is easy, and aftertreatment is simple, has good Social benefit and economic benefit, and suitability for industrialized is promoted.
Embodiment
Below in conjunction with specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in this:
Embodiment 1.
In the high-pressure reaction vessel of 250ml, add AMBT16.4 gram (0.1mol), hydrazine hydrate solution 8.83 grams (hydrazine hydrate 0.15mol), water 120ml, concentrated hydrochloric acid 10ml(hydrochloric acid 0.12mol that mass content is 85 ﹪), add polyoxyethylene nonylphenol ether 0.3 gram again, oil bath is heated to 130 DEG C, reaction 6h, is cooled to 20 DEG C, filters, crude product vacuum-drying obtains product 17 grams, purity 97 more than ﹪.Filtrate is applied mechanically for lower batch.
In the high-pressure reaction vessel of 250ml, add batch filtrate, be heated to 90 DEG C and stir 2h, ammonia is allowed to run out of, add the hydrazine hydrate solution 6.2 grams (making the mol ratio of AMBT and hydrazine hydrate in reaction system maintain 1:1.5) that mass content is 85 ﹪, AMBT16.4 gram (0.1mol), concentrated hydrochloric acid 1ml (making the mol ratio of AMBT and hydrochloric acid in reaction system maintain 1:1.2), polyoxyethylene nonylphenol ether 0.1 gram (making the consumption of polyoxyethylene nonylphenol ether in reaction system maintain 1.8 ﹪ of AMBT quality), oil bath is heated to 130 DEG C, reaction 6h, be cooled to 20 DEG C, filter, crude product vacuum-drying obtains product 17 grams, purity 97 more than ﹪.Filtrate is applied mechanically for lower batch.
Embodiment 2.
In the high-pressure reaction vessel of 250ml, add AMBT16.4 gram (0.1mol), hydrazine hydrate solution 8.83 grams (hydrazine hydrate 0.15mol), water 120ml, concentrated hydrochloric acid 10ml(hydrochloric acid 0.12mol that mass content is 85 ﹪), add alkylpolyoxyethylene 0.4 gram again, oil bath is heated to 130 DEG C, reaction 8h, is cooled to 20 DEG C, filters, crude product vacuum-drying obtains product 17 grams, purity 97 more than ﹪.Filtrate is applied mechanically for lower batch.
In the high-pressure reaction vessel of 250ml, add batch filtrate, be heated to 90 DEG C and stir 2h, ammonia is allowed to run out of, add the hydrazine hydrate solution 6.2 grams (making the mol ratio of AMBT and hydrazine hydrate in reaction system maintain 1:1.5) that mass content is 85 ﹪, AMBT16.4 gram (0.1mol), concentrated hydrochloric acid 1ml (making the mol ratio of AMBT and hydrochloric acid in reaction system maintain 1:1.2), alkylpolyoxyethylene 0.1 gram (making the consumption of alkylpolyoxyethylene in reaction system maintain 2.4 ﹪ of AMBT quality), oil bath is heated to 130 DEG C, reaction 8h, be cooled to 20 DEG C, filter, crude product vacuum-drying obtains product 17 grams, purity 97 more than ﹪.Filtrate is applied mechanically for lower batch.
Embodiment 3.
In the high-pressure reaction vessel of 250ml, add AMBT16.4 gram (0.1mol), hydrazine hydrate solution 8.83 grams (hydrazine hydrate 0.15mol), water 120ml, concentrated hydrochloric acid 10ml(hydrochloric acid 0.12mol that mass content is 85 ﹪), add polyoxyethylene glycol 0.3 gram again, oil bath is heated to 140 DEG C, reaction 4h, is cooled to 20 DEG C, filters, crude product vacuum-drying obtains product 17 grams, purity 97 more than ﹪.Filtrate is applied mechanically for lower batch.
In the high-pressure reaction vessel of 250ml, add batch filtrate, be heated to 90 DEG C and stir 2h, ammonia is allowed to run out of, add the hydrazine hydrate solution 6.2 grams (making the mol ratio of AMBT and hydrazine hydrate in reaction system maintain 1:1.5) that mass content is 85 ﹪, AMBT16.4 gram (0.1mol), concentrated hydrochloric acid 1ml (making the mol ratio of AMBT and hydrochloric acid in reaction system maintain 1:1.2), polyoxyethylene glycol 0.1 gram (making the consumption of polyoxyethylene glycol in reaction system maintain 1.8 ﹪ of AMBT quality), oil bath is heated to 140 DEG C, reaction 4h, be cooled to 20 DEG C, filter, crude product vacuum-drying obtains product 17 grams, purity 97 more than ﹪.Filtrate is applied mechanically for lower batch.
Embodiment 4.
In the high-pressure reaction vessel of 250ml, add AMBT16.4 gram (0.1mol), hydrazine hydrate solution 8.83 grams (hydrazine hydrate 0.15mol), water 120ml, concentrated hydrochloric acid 10ml(hydrochloric acid 0.12mol that mass content is 85 ﹪), oil bath is slowly heated to 140 DEG C, reaction 30h, be cooled to 20 DEG C, filter, crude product vacuum-drying obtains product 16.5 grams, purity 97 more than ﹪.Filtrate is applied mechanically for lower batch.
In the high-pressure reaction vessel of 250ml, add batch filtrate, be heated to 90 DEG C and stir 2h, ammonia is allowed to run out of, add hydrazine hydrate solution 6.2 grams (making the mol ratio of AMBT and hydrazine hydrate in reaction system maintain 1:1.5) that mass content is 85 ﹪, AMBT16.4 gram (0.1mol), concentrated hydrochloric acid 1ml (making the mol ratio of AMBT and hydrochloric acid in reaction system maintain 1:1.2), oil bath is heated to 140 DEG C, reaction 30h, be cooled to 20 DEG C, filter, crude product vacuum-drying obtains product 16.5 grams, purity 97 more than ﹪.Filtrate is applied mechanically for lower batch.
Embodiment 5.
In the high-pressure reaction vessel of 250ml, add AMBT16.4 gram (0.1mol), hydrazine hydrate solution 6.48 grams (hydrazine hydrate 0.11mol), water 120ml, concentrated hydrochloric acid 8.33ml(hydrochloric acid 0.1mol that mass content is 85 ﹪), oil bath is slowly heated to 150 DEG C, reaction 20h, be cooled to normal temperature, filter, crude product vacuum-drying obtains product 16.7 grams, purity 97 more than ﹪.Filtrate is applied mechanically for lower batch.
In the high-pressure reaction vessel of 250ml, add batch filtrate, be heated to 90 DEG C and stir 2h, ammonia is allowed to run out of, add hydrazine hydrate solution 6.2 grams (making the mol ratio of AMBT and hydrazine hydrate in reaction system maintain 1:1.1) that mass content is 85 ﹪, AMBT16.4 gram (0.1mol), concentrated hydrochloric acid 1ml (making the mol ratio of AMBT and hydrochloric acid in reaction system maintain 1:1), oil bath is heated to 150 DEG C, reaction 20h, be cooled to normal temperature, filter, crude product vacuum-drying obtains product 16.7 grams, purity 97 more than ﹪.Filtrate is applied mechanically for lower batch.
Embodiment 6.
In the high-pressure reaction vessel of 250ml, add AMBT16.4 gram (0.1mol), hydrazine hydrate solution 10 grams (hydrazine hydrate 0.2mol), water 120ml, concentrated hydrochloric acid 10.83ml(hydrochloric acid 0.13mol that mass content is 85 ﹪), oil bath is slowly heated to 170 DEG C, reaction 15h, be cooled to normal temperature, filter, crude product vacuum-drying obtains product 16.3 grams, purity 97 more than ﹪.Filtrate is applied mechanically for lower batch.
In the high-pressure reaction vessel of 250ml, add batch filtrate, be heated to 90 DEG C and stir 2h, ammonia is allowed to run out of, add hydrazine hydrate solution 6.4 grams (making the mol ratio of AMBT and hydrazine hydrate in reaction system maintain 1:2) that mass content is 85 ﹪, AMBT16.4 gram (0.1mol), concentrated hydrochloric acid 1ml (making the mol ratio of AMBT and hydrochloric acid in reaction system maintain 1:1.3), oil bath is heated to 170 DEG C, reaction 15h, be cooled to normal temperature, filter, crude product vacuum-drying obtains product 16.3 grams, purity 97 more than ﹪.Filtrate is applied mechanically for lower batch.
Embodiment 7.
In the high-pressure reaction vessel of 250ml, add AMBT16.4 gram (0.1mol), hydrazine hydrate solution 8.83 grams (hydrazine hydrate 0.15mol), water 120ml, concentrated hydrochloric acid 9.17ml(hydrochloric acid 0.11mol that mass content is 85 ﹪), oil bath is slowly heated to 130 DEG C, reaction 35h, be cooled to normal temperature, filter, crude product vacuum-drying obtains product 16.6 grams, purity 97 more than ﹪.Filtrate is applied mechanically for lower batch.
In the high-pressure reaction vessel of 250ml, add batch filtrate, be heated to 90 DEG C and stir 2h, ammonia is allowed to run out of, add hydrazine hydrate solution 6.3 grams (making the mol ratio of AMBT and hydrazine hydrate in reaction system maintain 1:1.5) that mass content is 85 ﹪, AMBT16.4 gram (0.1mol), concentrated hydrochloric acid 1ml (making the mol ratio of AMBT and hydrochloric acid in reaction system maintain 1:1.1), oil bath is heated to 130 DEG C, reaction 35h, be cooled to normal temperature, filter, crude product vacuum-drying obtains product 16.6 grams, purity 97 more than ﹪.Filtrate is applied mechanically for lower batch.
Embodiment 8.
In the high-pressure reaction vessel of 250ml, add AMBT16.4 gram (0.1mol), hydrazine hydrate solution 8.83 grams (hydrazine hydrate 0.15mol), water 120ml, concentrated hydrochloric acid 9.17ml(hydrochloric acid 0.11mol that mass content is 85 ﹪), add 0.28 gram, Brij 35 sodium sulfate again, oil bath is slowly heated to 130 DEG C, reaction 6h, is cooled to normal temperature, filters, crude product vacuum-drying obtains product 16.7 grams, purity 97 more than ﹪.Filtrate is applied mechanically for lower batch.
In the high-pressure reaction vessel of 250ml, add batch filtrate, be heated to 90 DEG C and stir 2h, ammonia is allowed to run out of, add the hydrazine hydrate solution 6.3 grams (making the mol ratio of AMBT and hydrazine hydrate in reaction system maintain 1:1.5) that mass content is 85 ﹪, AMBT16.4 gram (0.1mol), concentrated hydrochloric acid 1ml (making the mol ratio of AMBT and hydrochloric acid in reaction system maintain 1:1.1), 0.05 gram, Brij 35 sodium sulfate (making total consumption of Brij 35 sodium sulfate in reaction system maintain 1.7 ﹪ of AMBT quality), oil bath is heated to 130 DEG C, reaction 6h, be cooled to normal temperature, filter, crude product vacuum-drying obtains product 16.7 grams, purity 97 more than ﹪.Filtrate is applied mechanically for lower batch.
Embodiment 9.
In the high-pressure reaction vessel of 250ml, add AMBT16.4 gram (0.1mol), hydrazine hydrate solution 8.83 grams (hydrazine hydrate 0.15mol), water 120ml, concentrated hydrochloric acid 9.17ml(hydrochloric acid 0.11mol that mass content is 85 ﹪), add Sodium dodecylbenzene sulfonate 0.16 gram again, oil bath is slowly heated to 130 DEG C, reaction 6h, is cooled to normal temperature, filters, crude product vacuum-drying obtains product 17 grams, purity 97 more than ﹪.Filtrate is applied mechanically for lower batch.
In the high-pressure reaction vessel of 250ml, add batch filtrate, be heated to 90 DEG C and stir 2h, ammonia is allowed to run out of, add the hydrazine hydrate solution 6.3 grams (making the mol ratio of AMBT and hydrazine hydrate in reaction system maintain 1:1.5) that mass content is 85 ﹪, AMBT16.4 gram (0.1mol), concentrated hydrochloric acid 1ml (making the mol ratio of AMBT and hydrochloric acid in reaction system maintain 1:1.1), Sodium dodecylbenzene sulfonate 0.05 gram (making total consumption of Sodium dodecylbenzene sulfonate in reaction system maintain 1 ﹪ of AMBT quality), oil bath is heated to 130 DEG C, reaction 6h, be cooled to normal temperature, filter, crude product vacuum-drying obtains product 17 grams, purity 97 more than ﹪.Filtrate is applied mechanically for lower batch.
Embodiment 10.
In the high-pressure reaction vessel of 250ml, add AMBT16.4 gram (0.1mol), hydrazine hydrate solution 8.83 grams (hydrazine hydrate 0.15mol), water 120ml, concentrated hydrochloric acid 9.17ml(hydrochloric acid 0.11mol that mass content is 85 ﹪), add polyoxyethylene nonylphenol ether 0.3 gram, Sodium dodecylbenzene sulfonate 0.24 gram again, oil bath is slowly heated to 130 DEG C, reaction 5h, be cooled to normal temperature, filter, crude product vacuum-drying obtains product 16.8 grams, purity 97 more than ﹪.Filtrate is applied mechanically for lower batch.
In the high-pressure reaction vessel of 250ml, add batch filtrate, be heated to 90 DEG C and stir 2h, ammonia is allowed to run out of, add the hydrazine hydrate solution 6.3 grams (making the mol ratio of AMBT and hydrazine hydrate in reaction system maintain 1:1.5) that mass content is 85 ﹪, AMBT16.4 gram (0.1mol), concentrated hydrochloric acid 1ml (making the mol ratio of AMBT and hydrochloric acid in reaction system maintain 1:1.1), polyoxyethylene nonylphenol ether 0.05 gram, Sodium dodecylbenzene sulfonate 0.05 gram 0.05 gram (makes alkylphenol polyoxyethylene in reaction system, total consumption of Sodium dodecylbenzene sulfonate maintains 3.3 ﹪ of AMBT quality), oil bath is heated to 130 DEG C, reaction 5h, be cooled to normal temperature, filter, crude product vacuum-drying obtains product 16.8 grams, purity 97 more than ﹪.Filtrate is applied mechanically for lower batch.
Embodiment 11.
In the high-pressure reaction vessel of 250ml, add AMBT16.4 gram (0.1mol), hydrazine hydrate solution 8.83 grams (hydrazine hydrate 0.15mol), water 120ml, concentrated hydrochloric acid 9.17ml(hydrochloric acid 0.11mol that mass content is 85 ﹪), add alkylpolyoxyethylene 0.4 gram, 0.42 gram, Brij 35 sodium sulfate again, oil bath is slowly heated to 140 DEG C, reaction 5h, be cooled to normal temperature, filter, crude product vacuum-drying obtains product 16.9 grams, purity 97 more than ﹪.Filtrate is applied mechanically for lower batch.
In the high-pressure reaction vessel of 250ml, add batch filtrate, be heated to 90 DEG C and stir 2h, ammonia is allowed to run out of, add the hydrazine hydrate solution 6.3 grams (making the mol ratio of AMBT and hydrazine hydrate in reaction system maintain 1:1.5) that mass content is 85 ﹪, AMBT16.4 gram (0.1mol), concentrated hydrochloric acid 1ml (making the mol ratio of AMBT and hydrochloric acid in reaction system maintain 1:1.1), alkylpolyoxyethylene 0.1 gram, 0.05 gram, Brij 35 sodium sulfate (makes alkylpolyoxyethylene in reaction system, total consumption of Brij 35 sodium sulfate maintains 5 ﹪ of AMBT quality), oil bath is heated to 130 DEG C, reaction 5h, be cooled to normal temperature, filter, crude product vacuum-drying obtains product 16.9 grams, purity 97 more than ﹪.Filtrate is applied mechanically for lower batch.
The reaction of above-described embodiment is all carried out under the pressure of 2 ~ 10 kilograms.
Above-described embodiment is not that the present invention is not limited only to above-described embodiment for restriction of the present invention, as long as meet application claims, all belongs to protection scope of the present invention.

Claims (4)

1. one kind is synthesized the method for 4-methyl-2-hydrazinobenzothiazole, it is characterized in that the method is for raw material with 4-methyl-2-amino benzothiazole, hydrazine hydrate is joined in the pressurized vessel of aqueous hydrochloric acid, obtain final product 4-methyl-2-hydrazinobenzothiazole after reacting by heating, reaction equation is as follows:
Wherein the mol ratio of 4-methyl-2-amino benzothiazole and hydrazine hydrate is 1:1.1 ~ 2; The mol ratio of 4-methyl-2-amino benzothiazole and hydrochloric acid is 1:1.0 ~ 1.3.
2. a kind of method of synthesizing 4-methyl-2-hydrazinobenzothiazole as claimed in claim 1, is characterized in that the method is specifically:
Join in high-pressure reaction vessel by 4-methyl-2-amino benzothiazole, hydrazine hydrate, deionized water, hydrochloric acid, reacting by heating 4 ~ 35h at temperature of reaction is 130 ~ 170 DEG C, be cooled to normal temperature after reaction terminates, filter, crude product vacuum-drying obtains product; Wherein the mol ratio of 4-methyl-2-amino benzothiazole and hydrazine hydrate is 1:1.1 ~ 2; The mol ratio of 4-methyl-2-amino benzothiazole and hydrochloric acid is 1:1.0 ~ 1.3.
3. a kind of method of synthesizing 4-methyl-2-hydrazinobenzothiazole as claimed in claim 1 or 2, is characterized in that can also adding emulsifying agent in reaction system, and the consumption of emulsifying agent is 1 ~ 5 ﹪ of 4-methyl-2-amino benzothiazole quality.
4. a kind of method of synthesizing 4-methyl-2-hydrazinobenzothiazole as claimed in claim 3, it is characterized in that emulsifying agent be nonionic emulsifier, anionic emulsifier one or both; If emulsifying agent is the one of nonionic emulsifier, anionic emulsifier, wherein nonionic emulsifier be alkylphenol polyoxyethylene, fatty alcohol-polyoxyethylene ether, polyoxyethylene glycol one or more, anionic emulsifier be polyoxyethylenated alcohol sodium sulfate, sodium alkyl benzene sulfonate one or both; If emulsifying agent be nonionic emulsifier, two kinds of anionic emulsifier time, wherein nonionic emulsifier is the one of alkylphenol polyoxyethylene, fatty alcohol-polyoxyethylene ether, polyoxyethylene glycol, and anionic emulsifier is the one of polyoxyethylenated alcohol sodium sulfate, sodium alkyl benzene sulfonate.
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