CN106631941B - A kind of preparation method of -3 chlorphenyl methyl sulfide of 2- methyl - Google Patents
A kind of preparation method of -3 chlorphenyl methyl sulfide of 2- methyl Download PDFInfo
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- CN106631941B CN106631941B CN201611250819.9A CN201611250819A CN106631941B CN 106631941 B CN106631941 B CN 106631941B CN 201611250819 A CN201611250819 A CN 201611250819A CN 106631941 B CN106631941 B CN 106631941B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to fluorine-containing three ketones technical field of pesticide, and in particular to a kind of preparation method of 2 methyl, 3 chlorphenyl methyl sulfide.It includes the following steps：1) first vulcanizes：2 methyl, 3 chloroaniline flows back in a solvent with methyl mercaptan metal salt, synthesizes 2 methyl, 3 methyl mercapto aniline；2) diazotising, chlorination：2 methyl, 3 methyl mercapto aniline synthesizes 2 methyl, 3 chlorobenzene methyl sulfide through diazotising, chlorination.The raw materials used in the present invention only unique group in the chemical reaction of each step can be reacted, fundamentally avoid the generation of impurity, to improve the yield and purity of product, content >=95% of 2 methyl of tembotrions active compound intermediate, the 3 chlorphenyl methyl sulfide of preparation, yield in terms of 2 methyl, 3 chloroaniline >=90%, and raw material is cheap and easy to get, it is industrial easy to implement.
Description
Technical field
The invention belongs to fluorine-containing three ketones technical field of pesticide, and in particular to a kind of system of -3 chlorphenyl methyl sulfide of 2- methyl
Preparation Method.
Background technology
Tembotrions are by Beyer Co., Ltd's three ketones corn field herbicide developed in 2007, and activity is higher than nitre sulphur ketone (nitre
Sulphur humulone, mesotrione), to crop safety.- 3 chlorphenyl methyl sulfide of 2- methyl is the key intermediate for synthesizing tembotrions, existing
Method is mostly reacted with 2,6 dichlorotoleune and sodium methyl mercaptide, double first vulcanization problems, the two property can not be avoided close, it is difficult to from utilizing
Commonsense method detaches, and the problem is successfully avoided using the method for the present invention.
Invention content
The purpose of the present invention is to provide a kind of tembotrions active compound intermediates --- the system of -3 chlorphenyl methyl sulfide of 2- methyl
Preparation Method is generated double first vulcanizations, and improved in the synthesis process when avoiding the problem that being prepared as raw material using 2,6-DCT
Target product yield and purity.
The specific technical solution that the present invention uses for：
A kind of preparation method of -3 chlorphenyl methyl sulfide of 2- methyl, includes the following steps：
1) first vulcanizes：- 3 chloroaniline of 2- methyl flows back in a solvent with methyl mercaptan metal salt, -3 methyl mercapto of synthesis 2- methyl
Aniline；
2) diazotising, chlorination：- 3 methyl mercapto aniline of 2- methyl synthesizes 2- methyl -3- chlorobenzene methyl sulfides through diazotising, chlorination.
Solvent is hexamethylphosphoramide in the step 1).
Methyl mercaptan metal salt is sodium methyl mercaptide or methyl mercaptan potassium in the step 1).
- 3 chloroaniline of reaction mass 2- methyl in the step 1)：Methyl mercaptan metal salt：Mole of hexamethylphosphoramide
Than being 1.0:1.0-1.8:2-5.
The step 1) specifically includes：- 3 chloroaniline of 2- methyl is heated to flow back in hexamethylphosphoramide, slowly drips
The aqueous solution for adding methyl mercaptan metal salt maintains the reflux for reaction 3-4 hours after being added dropwise to complete, be cooled to room temperature, and iodomethane is added, adds
Water dilutes, and ethyl acetate extraction, washing, is spin-dried for obtaining -3 methyl mercapto aniline of 2- methyl at drying.
The step 2) carries out in the presence of nitrite, hydrochloric acid, catalyst and a small amount of cosolvent.
- 3 methyl mercapto aniline of reaction mass 2- methyl in the step 2)：Nitrite：The molar ratio of hydrochloric acid is 1.0:
1.0-1.8:2-5。
The step 2) specifically includes：- 3 methyl mercapto aniline of 2- methyl and hydrochloric acid and catalyst, the stirring of a small amount of cosolvent
Lower cooling maintains 0 DEG C or less nitrite solution is added dropwise, drips latter insulation reaction 0-4 hours, then be slowly warming up to 80-85
DEG C, faintly acid, ethyl acetate extraction are arrived in insulation reaction 0-5 hours, then neutralization, and washing, drying obtain product 2- first after being spin-dried for
- 3 chlorphenyl methyl sulfide of base.
The catalyst is Cu-series catalyst, and addition is 2 ‰~the 5 ‰ of -3 methyl mercapto aniline weight of 2- methyl.
The Cu-series catalyst in copper powder, copper oxide, cuprous oxide, copper chloride, stannous chloride and copper sulphate one
Kind.
The nitrite is sodium nitrite or potassium nitrite, and the cosolvent is in the alcohols materials such as methanol or ethyl alcohol
One or more combinations.
All raw materials that the present invention uses all are commercially available industrial products.
The advantage of the invention is that：
(1) content >=95% of -3 chlorphenyl methyl sulfide of tembotrions active compound intermediate 2- methyl prepared by the present invention, yield
In terms of -3 chloroaniline of 2- methyl >=90%.
(2) raw material only unique group in the chemical reaction of each step can be reacted, and fundamentally be avoided
The generation of impurity, to improve the yield and purity of product, and raw material is cheap and easy to get, industrial easy to implement.
Specific implementation mode
The present invention is further explained with reference to embodiments：
Embodiment 1
(1) -3 chloroaniline 14.2g (0.1mol) of 2- methyl is heated to flow back in 40ml hexamethylphosphoramide, slowly drips
The aqueous solution 42g (0.12mol) for adding 20% sodium methyl mercaptide maintains the reflux for 3-4 hour of reaction, is cooled to room after being added dropwise to complete
Temperature is added iodomethane 1.4g (0.01mol), is diluted with water, and ethyl acetate extraction, washing, is spin-dried for obtaining -3 chlorobenzene of 2- methyl at drying
Amine.
Its reaction equation is：
(2) (1) is obtained -3 methyl mercapto aniline 15.3g (0.951mol) of 2- methyl and 36.5% dense salt of content 95.1%
The copper sulphate of sour 40g and catalytic amount cool to -5 DEG C under the stirring of 20ml cosolvent methanol, maintain 0 DEG C or less the Asia for being added dropwise 35%
Sodium nitrate solution 20.7g (0.102mol), drips rear insulation reaction 1 hour, is slowly warming up to 80-85 DEG C, insulation reaction 2 is small
When, neutralize and arrive faintly acid, ethyl acetate extraction, washing, it is dry, be spin-dried for after -3 chlorphenyl methyl sulfide of product 2- methyl, obtain
16.3g, content 95.1%, yield are calculated as 90% with -3 chloroaniline of 2- methyl.
Its reaction equation is：
Embodiment 2
(1) -3 chloroaniline 14.2g (0.1mol) of 2- methyl is heated to flow back in 40ml hexamethylphosphoramide, slowly drips
The aqueous solution 42g (0.12mol) for adding 20% sodium methyl mercaptide maintains the reflux for 3-4 hour of reaction, is cooled to room after being added dropwise to complete
Temperature is added iodomethane 1.4g (0.01mol), is diluted with water, and ethyl acetate extraction, washing, is spin-dried for obtaining -3 chlorobenzene of 2- methyl at drying
Amine.
(2) (1) is obtained -3 methyl mercapto aniline 15.3g (0.951mol) of 2- methyl and 36.5% dense salt of content 95.1%
The copper sulphate of sour 40g and catalytic amount cool to 5 DEG C under the stirring of 20ml cosolvent methanol, maintain the temperature that 35% nitrous is added dropwise
Acid sodium solution 20.7g (0.102mol), drips rear insulation reaction 1 hour, is slowly warming up to 80-85 DEG C, insulation reaction 2 is small
When, neutralize and arrive faintly acid, ethyl acetate extraction, washing, it is dry, be spin-dried for after -3 chlorphenyl methyl sulfide of product 2- methyl, obtain
15.8g, content 94.8%, yield are calculated as 86% with -3 chloroaniline of 2- methyl.
Claims (10)
1. a kind of preparation method of -3 chlorphenyl methyl sulfide of 2- methyl, which is characterized in that include the following steps：
1) first vulcanizes：- 3 chloroaniline of 2- methyl flows back with methyl mercaptan metal salt in hexamethylphosphoramide, synthesis 2- methyl -3
Methyl mercapto aniline；
2) diazotising, chlorination：- 3 methyl mercapto aniline of 2- methyl synthesizes 2- methyl -3- chlorobenzene methyl sulfides through diazotising, chlorination.
2. the preparation method of -3 chlorphenyl methyl sulfide of 2- methyl according to claim 1, which is characterized in that the step 1)
In methyl mercaptan metal salt be sodium methyl mercaptide or methyl mercaptan potassium.
3. the preparation method of -3 chlorphenyl methyl sulfide of 2- methyl according to claim 2, which is characterized in that the step 1)
Middle -3 chloroaniline of reaction mass 2- methyl：Methyl mercaptan metal salt：The molar ratio of hexamethylphosphoramide is 1.0:1.0-1.8:2-
5。
4. the preparation method of -3 chlorphenyl methyl sulfide of 2- methyl according to claim 2 or 3, which is characterized in that the step
It is rapid 1) to specifically include：- 3 chloroaniline of 2- methyl is heated to flow back in hexamethylphosphoramide, and methyl mercaptan metal salt is slowly added dropwise
Aqueous solution, reaction 3-4 hour are maintained the reflux for after being added dropwise to complete, are cooled to room temperature, addition iodomethane is diluted with water, acetic acid second
Ester extracts, and washing, is spin-dried for obtaining -3 methyl mercapto aniline of 2- methyl at drying.
5. the preparation method of -3 chlorphenyl methyl sulfide of 2- methyl according to claim 1, which is characterized in that the step 2)
It is carried out in the presence of nitrite, hydrochloric acid, catalyst and a small amount of cosolvent.
6. the preparation method of -3 chlorphenyl methyl sulfide of 2- methyl according to claim 5, which is characterized in that the step 2)
Middle -3 methyl mercapto aniline of reaction mass 2- methyl：Nitrite：The molar ratio of hydrochloric acid is 1.0:1.0-1.8:2-5.
7. the preparation method of -3 chlorphenyl methyl sulfide of 2- methyl according to claim 5 or 6, which is characterized in that the step
It is rapid 2) to specifically include：- 3 methyl mercapto aniline of 2- methyl and hydrochloric acid and catalyst, the lower cooling of a small amount of cosolvent stirring, 0 DEG C is maintained
Nitrite solution is added dropwise below, drips latter insulation reaction 0-4 hours, then be slowly warming up to 80-85 DEG C, insulation reaction 0-5
Faintly acid, ethyl acetate extraction are arrived in hour, then neutralization, and washing, drying obtain -3 chlorphenyl first sulphur of product 2- methyl after being spin-dried for
Ether.
8. the preparation method of -3 chlorphenyl methyl sulfide of 2- methyl according to claim 5, which is characterized in that the catalyst
For Cu-series catalyst, addition is 2 ‰~the 5 ‰ of -3 methyl mercapto aniline weight of 2- methyl.
9. the preparation method of -3 chlorphenyl methyl sulfide of 2- methyl according to claim 8, which is characterized in that the copper system is urged
The one kind of agent in copper powder, copper oxide, cuprous oxide, copper chloride, stannous chloride and copper sulphate.
10. the preparation method of -3 chlorphenyl methyl sulfide of 2- methyl according to claim 5, which is characterized in that the nitrous
Hydrochlorate is sodium nitrite or potassium nitrite, and the cosolvent is or mixtures thereof methanol, ethyl alcohol.
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| CN108947878B (en) * | 2018-07-24 | 2020-07-03 | 浙江中山化工集团股份有限公司 | Preparation method of 2-chloro-6-methylthiotoluene |
| CN109053511A (en) * | 2018-08-10 | 2018-12-21 | 安徽久易农业股份有限公司 | A kind of preparation method of the chloro- 6- (methylthiomethyl) of 2- |
| CN115806515A (en) * | 2022-12-16 | 2023-03-17 | 启农生物科技(北京)有限公司 | Synthesis process of intermediate 2-methyl-3-methylthio-chlorobenzene |
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| JP2699549B2 (en) * | 1988-06-03 | 1998-01-19 | 日産化学工業株式会社 | Method for producing 4-benzoyl-5-hydroxypyrazoles |
| US5804532A (en) * | 1991-01-25 | 1998-09-08 | Rhone-Poulenc Agriculture Limited | Herbicidal 2-cyano-1,3-diones |
| EP0905136A1 (en) * | 1997-09-08 | 1999-03-31 | Janssen Pharmaceutica N.V. | Tetrahydro gamma-carbolines |
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