CN111333593B - Method for synthesizing 4-methyl-2 hydrazinobenzothiazole - Google Patents
- ️Fri Apr 29 2022
CN111333593B - Method for synthesizing 4-methyl-2 hydrazinobenzothiazole - Google Patents
Method for synthesizing 4-methyl-2 hydrazinobenzothiazole Download PDFInfo
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- CN111333593B CN111333593B CN202010319863.0A CN202010319863A CN111333593B CN 111333593 B CN111333593 B CN 111333593B CN 202010319863 A CN202010319863 A CN 202010319863A CN 111333593 B CN111333593 B CN 111333593B Authority
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- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/62—Benzothiazoles
- C07D277/68—Benzothiazoles 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
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Abstract
The invention discloses a method for synthesizing 4-methyl-2 hydrazinobenzothiazole, which comprises the following steps: carrying out synthetic reaction on o-toluidine and thiocyanate in acid to obtain o-toluylthiourea; carrying out synthetic reaction on the o-methyl phenylthiosemicarbazide and a catalyst in water to obtain 4-methyl-2-aminobenzothiazole; and (2) carrying out synthetic reaction on the 4-methyl-2-aminobenzothiazole in hydrazine hydrate to obtain 4-methyl-2-hydrazinobenzothiazole. The method for synthesizing 4-methyl-2 hydrazinobenzothiazole provided by the invention is simple to operate, has less three wastes, can repeatedly apply waste water, has high product content and good quality, and can be suitable for industrial mass production.
Description
Technical Field
The invention relates to the technical field of medicines, in particular to a method for synthesizing 4-methyl-2 hydrazinobenzothiazole.
Background
The 4-methyl-2 hydrazinobenzothiazole is an important intermediate of pesticide tricyclazole, and the tricyclazole is one of the main pesticides for preventing and treating rice blast at present, and is a pesticide which has high efficiency, low toxicity, low residue and is harmonious with the environment and ecological and reasonable. 4-methyl-2-hydrazinobenzothiazole is used as an important pesticide intermediate which is widely applied all over the world, and the research on the synthetic structure and the pharmacological activity of the intermediate is concerned all the time. The existing synthesis methods of 4-methyl-2 hydrazino benzothiazole mainly comprise the following two methods: 1. substituted acyl aniline is used as an initial raw material, and is subjected to substitution reaction with phosphorus pentasulfide to generate N-o-methyl phenylthiourea, then cyclization reaction is carried out under the condition of chlorine introduction, and then the N-o-methyl phenylthiourea is reacted with hydrazine hydrate to obtain a target product; 2. o-toluidine is taken as an initial raw material, firstly, the o-toluidine and ammonium thiocyanate are subjected to addition reaction to generate N-o-methylphenyl thiourea, then, cyclization reaction is carried out under the catalysis of chlorine, and finally, nucleophilic substitution is carried out on the o-toluidine and hydrazine hydrate to generate the 4-methyl-2-hydrazino benzothiazole. The existing 4-methyl-2 hydrazinobenzothiazole synthesis technology has the problems of low reaction efficiency and low product purity.
Disclosure of Invention
The invention mainly aims to provide a method for synthesizing 4-methyl-2 hydrazinobenzothiazole, aiming at improving the product purity, reducing the generation of three wastes and being suitable for industrial mass production.
In order to achieve the above object, the present invention provides a method for synthesizing 4-methyl-2 hydrazinobenzothiazole, comprising the following steps:
carrying out synthetic reaction on o-toluidine and thiocyanate in acid to obtain o-toluylthiourea;
carrying out synthetic reaction on the o-methyl phenylthiosemicarbazide and a catalyst in water to obtain 4-methyl-2-aminobenzothiazole;
and (2) carrying out synthetic reaction on the 4-methyl-2-aminobenzothiazole in hydrazine hydrate to obtain 4-methyl-2-hydrazinobenzothiazole.
Optionally, the step of performing a synthesis reaction of o-toluidine and thiocyanate in acid to obtain o-methylthiophenyl thiourea comprises:
putting o-toluidine into a reaction kettle, adding acid, adding thiocyanate while stirring, and heating the reaction kettle to perform a reflux reaction to obtain a reaction solution, wherein the reaction temperature is 90-105 ℃;
cooling the reaction liquid, discharging and centrifuging to obtain a filter cake;
and washing the filter cake to be neutral by using water, and drying to obtain the o-methylthiophenylthiourea.
Optionally, the acid is sulfuric acid, hydrochloric acid, acetic acid, propionic acid, or formic acid; and/or the thiocyanate is ammonium thiocyanate, sodium thiocyanate, potassium thiocyanate, calcium thiocyanate or magnesium thiocyanate.
Optionally, the molar ratio of the o-toluidine to the thiocyanate is from 1:0.9 to 1: 2; and/or the presence of a gas in the gas,
the molar ratio of the o-toluidine to the acid is 1:0.5 to 1: 0.7.
Optionally, the step of performing a synthesis reaction on the o-methylthiophenyl thiourea and a catalyst in water to obtain the 4-methyl-2-aminobenzothiazole comprises:
adding water into a reaction kettle, adding the o-methylthiophenylthiourea into the reaction kettle, and adding a catalyst for a synthesis reaction to obtain a reaction solution, wherein the reaction temperature is 20-60 ℃;
cooling the reaction liquid, discharging and centrifuging to obtain a filter cake;
and drying the filter cake to obtain the 4-methyl-2-aminobenzothiazole.
Optionally, the catalyst is sodium bromide, potassium bromide, lithium bromide, calcium bromide, sodium chloride, potassium chloride, or calcium chloride.
Optionally, the molar ratio of the catalyst to the o-tolylthiourea is 0.01 to 0.05.
Optionally, the step of subjecting the 4-methyl-2-aminobenzothiazole to a synthesis reaction in hydrazine hydrate to obtain 4-methyl-2-hydrazinobenzothiazole comprises:
hydrazine hydrate is added into a reaction kettle, the 4-methyl-2-aminobenzothiazole is put into the reaction kettle, the reaction kettle is heated under stirring to carry out reflux reaction, so as to obtain a reaction solution, wherein the reaction temperature is 105-130 ℃;
cooling the reaction liquid, discharging and centrifuging to obtain a filter cake;
and washing the filter cake with water and drying to obtain the 4-methyl-2-hydrazinobenzothiazole.
Optionally, the hydrazine hydrate content is 40% to 80%.
Optionally, the molar ratio of the hydrazine hydrate to the 4-methyl-2-aminobenzothiazole is 1.3 to 6.
In the technical scheme provided by the invention, water is used as a solvent in the whole process, the post-treatment is simple, the pollution is less, and the cost is low; the hydrazine hydrate in the synthesis method is low in consumption and accords with the green chemical principle; the synthesis method has simple process operation, good social benefit and economic benefit, and is suitable for industrial production; the wastewater in the synthesis method can be used indiscriminately; the synthesis method has the advantages of high product content and good quality.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other related drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic flow diagram of one embodiment of a method for synthesizing 4-methyl-2 hydrazinobenzothiazole provided by the invention.
The implementation, functional features and advantages of the objects of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The 4-methyl-2 hydrazinobenzothiazole is an important intermediate of pesticide tricyclazole, and the tricyclazole is one of the main pesticides for preventing and treating rice blast at present, and is a pesticide which has high efficiency, low toxicity, low residue and is harmonious with the environment and ecological and reasonable. 4-methyl-2-hydrazinobenzothiazole is used as an important pesticide intermediate which is widely applied all over the world, and the research on the synthetic structure and the pharmacological activity of the intermediate is concerned all the time. The existing synthesis methods of 4-methyl-2 hydrazino benzothiazole mainly comprise the following two methods: 1. substituted acyl aniline is used as an initial raw material, and is subjected to substitution reaction with phosphorus pentasulfide to generate N-o-methyl phenylthiourea, then cyclization reaction is carried out under the condition of chlorine introduction, and then the N-o-methyl phenylthiourea is reacted with hydrazine hydrate to obtain a target product; 2. o-toluidine is taken as an initial raw material, firstly, the o-toluidine and ammonium thiocyanate are subjected to addition reaction to generate N-o-methylphenyl thiourea, then, cyclization reaction is carried out under the catalysis of chlorine, and finally, nucleophilic substitution is carried out on the o-toluidine and hydrazine hydrate to generate the 4-methyl-2-hydrazino benzothiazole. The existing 4-methyl-2 hydrazinobenzothiazole synthesis technology has the problems of low reaction efficiency and low product purity.
In view of this, the invention provides a method for synthesizing 4-methyl-2 hydrazinobenzothiazole, which aims to improve the product purity, reduce the generation of three wastes and be suitable for industrial mass production. FIG. 1 shows an embodiment of the method for synthesizing 4-methyl-2 hydrazinobenzothiazole provided by the invention.
Referring to FIG. 1, in this example, the method for synthesizing 4-methyl-2 hydrazinobenzothiazole includes the following steps:
step S110: and (3) carrying out synthetic reaction on o-toluidine and thiocyanate in acid to obtain o-methylthiophenylthiourea.
Specifically, putting o-toluidine into a reaction kettle, adding acid, adding thiocyanate while stirring, and heating the reaction kettle to perform a reflux reaction to obtain a reaction solution; cooling the reaction liquid, discharging and centrifuging to obtain a filter cake; and washing the filter cake to be neutral by using water, and drying to obtain the o-methylthiophenylthiourea. Wherein the reaction temperature is 90-105 ℃.
In this embodiment, the thiocyanate may be ammonium thiocyanate, sodium thiocyanate, potassium thiocyanate, calcium thiocyanate, or magnesium thiocyanate, etc.
In this embodiment, the acid may be sulfuric acid, hydrochloric acid, acetic acid, propionic acid, formic acid, or the like.
In the present embodiment, the molar ratio of the o-toluidine to the thiocyanate salt is 1:0.9 to 1: 2.
In this embodiment, the molar ratio of the o-toluidine to the acid is 1:0.5 to 1:0.7
In this example, the reaction equation for the synthesis of o-methylthiophenylthiourea is as follows:
step S120: and (3) carrying out synthetic reaction on the o-methyl phenylthiourea and a catalyst in water to obtain the 4-methyl-2-aminobenzothiazole.
Specifically, adding water into a reaction kettle, putting the o-methylthiophenylthiourea into the reaction kettle, and adding a catalyst to perform a synthesis reaction to obtain a reaction solution; cooling the reaction liquid, discharging and centrifuging to obtain a filter cake; and drying the filter cake to obtain the 4-methyl-2-aminobenzothiazole. Wherein the reaction temperature is 20-60 ℃.
In this embodiment, the catalyst may be a metal chloride or a metal bromide, for example, the catalyst may be sodium bromide, potassium bromide, lithium bromide, calcium bromide, sodium chloride, potassium chloride, calcium chloride, or the like.
In the embodiment, the molar ratio of the catalyst to the o-tolylthiourea is 0.01-0.05.
In this example, the synthesis reaction equation of 4-methyl-2-aminobenzothiazole is as follows:
step S130: and (2) carrying out synthetic reaction on the 4-methyl-2-aminobenzothiazole in hydrazine hydrate to obtain 4-methyl-2-hydrazinobenzothiazole.
Specifically, hydrazine hydrate is added into a reaction kettle, the 4-methyl-2-aminobenzothiazole is put into the reaction kettle, and the reaction kettle is heated under stirring to carry out reflux reaction, so as to obtain a reaction solution; cooling the reaction liquid, discharging and centrifuging to obtain a filter cake; and washing the filter cake with water and drying to obtain the 4-methyl-2-hydrazinobenzothiazole. Wherein the reaction temperature is 105-130 ℃.
In this embodiment, the hydrazine hydrate content is 40% to 80%.
In the embodiment, the molar ratio of the hydrazine hydrate to the 4-methyl-2-aminobenzothiazole is 1.3-6.
In this example, the reaction equation for the synthesis of 4-methyl-2-hydrazinobenzothiazole is as follows:
in the technical scheme provided by the invention, water is used as a solvent in the whole process, the post-treatment is simple, the pollution is less, and the cost is low; the hydrazine hydrate in the synthesis method is low in consumption and accords with the green chemical principle; the synthesis method has simple process operation, good social benefit and economic benefit, and is suitable for industrial production; the wastewater in the synthesis method can be used indiscriminately; the synthesis method has the advantages of high product content and good quality.
The technical solutions of the present invention are further described in detail below with reference to specific examples and drawings, it should be understood that the following examples are merely illustrative of the present invention and are not intended to limit the present invention.
Example 1
1. Synthesis of o-methyl phenylthiourea: 1477Kg of o-toluidine is put into a 5000L reaction kettle, 1830Kg of prepared 42% sulfuric acid is added, 1336Kg of sodium thiocyanate is added under stirring, steam is started to heat, reflux reaction is carried out for 4 hours, cooling is carried out, discharging and centrifugation are carried out, a filter cake is washed to be neutral by water, and the filter cake is dried, thus obtaining 1410Kg of o-toluylthiourea.
2. Synthesis of 4-methyl-2-aminobenzothiazole: adding 600Kg of water into a 3000L reaction kettle, then adding the o-methylbenzylthiourea obtained in the previous step into the reaction kettle, adding 28Kg of sodium bromide serving as a catalyst, controlling the temperature to be 25-30 ℃, reacting for 6 hours, cooling, discharging, centrifuging, and drying a filter cake to obtain 1280Kg of 4-methyl-2-aminobenzothiazole.
3. Synthesis of 4-methyl-2-hydrazinobenzothiazole: adding 1076Kg of 40% hydrazine hydrate into a 3000L reaction kettle, adding the 4-methyl-2-aminobenzothiazole obtained in the previous step into the reaction kettle, stirring, starting heating and heating to reflux, reacting for 12 hours, cooling after the reaction is finished, discharging and centrifuging, washing a filter cake with water, and drying to obtain 1305Kg of the target product, namely 4-methyl-2-hydrazinobenzothiazole, with the product content of 99.1%.
Example 2
1. Synthesis of o-methyl phenylthiourea: 1477Kg of o-toluidine is added in 5000L of reaction, 2560Kg of prepared 30% sulfuric acid is added, 1470Kg of sodium thiocyanate is added under stirring, steam is started to heat, reflux reaction is carried out for 4 hours, cooling, discharging and centrifuging are carried out, a filter cake is washed to be neutral by water, and the filter cake is dried to obtain 1420Kg of o-toluylthiourea.
2. Synthesis of 4-methyl-2-aminobenzothiazole: adding 800Kg of water into a 3000L reaction kettle, then adding the o-methylbenzylthiourea obtained in the previous step into the reaction kettle, adding 29Kg of calcium bromide serving as a catalyst, controlling the temperature to be 20-30 ℃, reacting for 6 hours, cooling, discharging, centrifuging, and drying a filter cake to obtain 1210Kg of 4-methyl-2-aminobenzothiazole.
3. Synthesis of 4-methyl-2-hydrazinobenzothiazole: adding 1050Kg of 80% hydrazine hydrate into a 3000L reaction kettle, putting the 4-methyl-2-aminobenzothiazole obtained in the previous step into the reaction kettle, stirring, starting heating and heating to reflux, reacting for 12 hours, cooling after the reaction is finished, discharging and centrifuging, washing a filter cake with water, and drying to obtain 1225Kg of a target product, namely 4-methyl-2-hydrazinobenzothiazole, wherein the content of the product is 98.7%.
Example 3
1. Synthesis of o-methyl phenylthiourea: 1605Kg of o-toluidine is added in 5000L reaction, 2500Kg of prepared 30% sulfuric acid is added, 1337Kg of sodium thiocyanate is added under stirring, steam heating is started, reflux reaction is carried out for 6 hours, cooling, discharging and centrifuging are carried out, a filter cake is washed to be neutral by water, and the filter cake is dried, thus 2270Kg of o-toluylthiourea is obtained.
2. Synthesis of 4-methyl-2-aminobenzothiazole: adding 1200Kg of water into a 5000L reaction kettle, then adding 50Kg of sodium bromide serving as a catalyst into the reaction kettle, controlling the temperature to be 40-50 ℃, reacting for 6 hours, cooling, discharging, centrifuging, and drying a filter cake to obtain 2050Kg of 4-methyl-2-aminobenzothiazole.
3. Synthesis of 4-methyl-2-hydrazinobenzothiazole: adding 1570Kg of 80% hydrazine hydrate into a 5000L reaction kettle, putting the 4-methyl-2-aminobenzothiazole obtained in the previous step into the reaction kettle, stirring, starting heating and heating to reflux, reacting for 12 hours, cooling after the reaction is finished, discharging and centrifuging, washing a filter cake with water, and drying to obtain 1850Kg of the target product 4-methyl-2-hydrazinobenzothiazole, wherein the content of the product is 99.3%.
Example 4
1. Synthesis of o-methyl phenylthiourea: 1477Kg of o-toluidine is added in 5000L of reaction, 1560Kg of prepared 50% sulfuric acid is added, 1600Kg of sodium thiocyanate is added under stirring, steam is started for heating, reflux reaction is carried out for 4 hours, cooling, discharging and centrifuging are carried out, a filter cake is washed to be neutral by water, and 1430Kg of o-toluylthiourea is obtained after the filter cake is dried.
2. Synthesis of 4-methyl-2-aminobenzothiazole: adding 800Kg of water into a 3000L reaction kettle, then adding the o-methylbenzylthiourea obtained in the previous step into the reaction kettle, adding 29Kg of potassium bromide as a catalyst, controlling the temperature to be 50-60 ℃, reacting for 6 hours, cooling, discharging, centrifuging, and drying a filter cake to obtain 1250Kg of 4-methyl-2-aminobenzothiazole.
3. Synthesis of 4-methyl-2-hydrazinobenzothiazole: adding 1070Kg of 60 percent hydrazine hydrate into a 3000L reaction kettle, putting the 4-methyl-2-aminobenzothiazole obtained in the previous step into the reaction kettle, stirring, starting heating and heating to reflux, reacting for 12 hours, cooling after the reaction is finished, discharging and centrifuging, washing a filter cake with water, and drying to obtain 1240Kg of the target product 4-methyl-2-hydrazinobenzothiazole, wherein the content of the product is 98.9 percent.
The above is only a preferred embodiment of the present invention, and it is not intended to limit the scope of the invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall be included in the scope of the present invention.
Claims (9)
1. A method for synthesizing 4-methyl-2 hydrazinobenzothiazole is characterized by comprising the following steps:
carrying out synthetic reaction on o-toluidine and thiocyanate in acid to obtain o-toluylthiourea;
carrying out synthetic reaction on the o-methyl phenylthiosemicarbazide and a catalyst in water to obtain 4-methyl-2-aminobenzothiazole, wherein the catalyst is sodium bromide, potassium bromide, lithium bromide, calcium bromide, sodium chloride, potassium chloride or calcium chloride;
and (2) carrying out synthetic reaction on the 4-methyl-2-aminobenzothiazole in hydrazine hydrate to obtain 4-methyl-2-hydrazinobenzothiazole.
2. The method of synthesizing 4-methyl-2 hydrazinobenzothiazole of claim 1, wherein the step of reacting o-toluidine and thiocyanate in acid to obtain o-toluylthiourea comprises:
putting o-toluidine into a reaction kettle, adding acid, adding thiocyanate while stirring, and heating the reaction kettle to perform a reflux reaction to obtain a reaction solution, wherein the reaction temperature is 90-105 ℃;
cooling the reaction liquid, discharging and centrifuging to obtain a filter cake;
and washing the filter cake to be neutral by using water, and drying to obtain the o-methylthiophenylthiourea.
3. The method of synthesizing 4-methyl-2 hydrazinobenzothiazole of claim 1,
the acid is sulfuric acid, hydrochloric acid, acetic acid, propionic acid or formic acid; and/or the presence of a gas in the gas,
the thiocyanate is ammonium thiocyanate, sodium thiocyanate, potassium thiocyanate, calcium thiocyanate or magnesium thiocyanate.
4. The method of synthesizing 4-methyl-2 hydrazinobenzothiazole of claim 1,
the molar ratio of the o-toluidine to the thiocyanate is 1: 0.9-1: 2; and/or the presence of a gas in the gas,
the molar ratio of the o-toluidine to the acid is 1:0.5 to 1: 0.7.
5. The method of synthesizing 4-methyl-2-hydrazinobenzothiazole of claim 1, wherein the step of reacting the o-methylbenzylthiourea with a catalyst in water to obtain 4-methyl-2-aminobenzothiazole comprises:
adding water into a reaction kettle, adding the o-methylthiophenylthiourea into the reaction kettle, and adding a catalyst for a synthesis reaction to obtain a reaction solution, wherein the reaction temperature is 20-60 ℃;
cooling the reaction liquid, discharging and centrifuging to obtain a filter cake;
and drying the filter cake to obtain the 4-methyl-2-aminobenzothiazole.
6. The method of synthesizing 4-methyl-2 hydrazinobenzothiazole of claim 1, wherein the molar ratio of the catalyst to the o-tolylthiourea is 0.01 to 0.05.
7. The method of synthesizing 4-methyl-2-hydrazinobenzothiazole of claim 1, wherein the step of subjecting the 4-methyl-2-aminobenzothiazole to a synthesis reaction in hydrazine hydrate to obtain 4-methyl-2-hydrazinobenzothiazole comprises:
hydrazine hydrate is added into a reaction kettle, the 4-methyl-2-aminobenzothiazole is put into the reaction kettle, the reaction kettle is heated under stirring to carry out reflux reaction, so as to obtain a reaction solution, wherein the reaction temperature is 105-130 ℃;
cooling the reaction liquid, discharging and centrifuging to obtain a filter cake;
and washing the filter cake with water and drying to obtain the 4-methyl-2-hydrazinobenzothiazole.
8. The method of synthesizing 4-methyl-2 hydrazinobenzothiazole of claim 1, wherein the hydrazine hydrate content is 40% to 80%.
9. The method of synthesizing 4-methyl-2-hydrazinobenzothiazole of claim 1, wherein the molar ratio of hydrazine hydrate to the 4-methyl-2-aminobenzothiazole is 1.3 to 6.
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