CN106631941A - Preparation method of 2-methyl-3-chlorophenylmethyl sulfide - Google Patents
Preparation method of 2-methyl-3-chlorophenylmethyl sulfide Download PDFInfo
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- CN106631941A CN106631941A CN201611250819.9A CN201611250819A CN106631941A CN 106631941 A CN106631941 A CN 106631941A CN 201611250819 A CN201611250819 A CN 201611250819A CN 106631941 A CN106631941 A CN 106631941A
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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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Abstract
The present invention relates to the technical field of fluorine-containing tri-ketone pesticides and more particularly relates to a preparation method of 2-methyl-3-chlorophenylmethyl sulfide. The method comprises the following steps: 1) methyl sulfidation: 2-methyl-3-chloroaniline and methanthiol metal salts are refluxed in a solvent to synthesize 2-methyl-3-methylthio benzenamine; and 2) diazotization and chlorination: the 2-methyl-3-methylthio benzenamine is subjected to the diazotization and chlorination to synthesize the 2-methyl-3-chlorophenylmethyl sulfide. In each step of the chemical reactions, only one group of the used raw materials can conduct the reaction, so that the preparation method fundamentally avoids formation of impurities and thus improves the yield and purity of the products. The content of the prepared intermediate 2-methyl-3-chlorophenylmethyl sulfide of tembotrione is larger than or equal to 95%, the yield accounted as 2-methyl-3-methylthio benzenamine is larger than or equal to 90%, the raw materials are easy to obtain and the preparation method is easy to achieve in the industry.
Description
Technical field
The invention belongs to fluorine-containing three ketones technical field of pesticide, and in particular to a kind of system of the chlorphenyl methyl sulfide of 2- methyl -3
Preparation Method.
Background technology
Ring sulphur ketone is the three ketones corn field herbicide developed for 2007 by Beyer Co., Ltd, and its activity is higher than nitre sulphur ketone (nitre
Sulphur oxadiazon, mesotrione), to crop safety.The chlorphenyl methyl sulfide of 2- methyl -3 is the key intermediate for synthesizing ring sulphur ketone, existing
Method is more with 2, and 6 dichlorotoleune and sodium methyl mercaptide react, it is impossible to avoid double first sulfuration problems, the two property from being close to, it is difficult to utilize
Commonsense method is separated, and using the inventive method the problem is successfully avoided.
The content of the invention
It is an object of the invention to provide a kind of ring sulphur ketone active compound intermediate --- the system of the chlorphenyl methyl sulfide of 2- methyl -3
Preparation Method, it is to avoid the problem of double first sulfurations is produced when preparing as raw material with 2,6-DCT, and is improve in building-up process
Target product yield and purity.
The concrete technical scheme that adopts of the present invention for：
A kind of preparation method of the chlorphenyl methyl sulfide of 2- methyl -3, comprises the following steps：
1) first sulfuration：The chloroaniline of 2- methyl -3 flows back in a solvent with methanthiol slaine, the methyl mercapto of synthesis 2- methyl -3
Aniline；
2) diazotising, chlorination：The methyl mercapto aniline Jing diazotising of 2- methyl -3, chlorination synthesis 2- methyl -3- chlorobenzene methyl sulfides.
The step 1) in solvent be HMPA.
The step 1) in methanthiol slaine be sodium methyl mercaptide or methanthiol potassium.
The step 1) in the chloroaniline of reaction mass 2- methyl -3：Methanthiol slaine：HMPA mole
Than for 1.0:1.0-1.8:2-5.
The step 1) specifically include：The chloroaniline of 2- methyl -3 is heated to backflow, slow drop in HMPA
Plus the aqueous solution of methanthiol slaine, maintain the reflux for reacting 3-4 hours after being added dropwise to complete, room temperature is cooled to, iodomethane is added, plus
Water dilutes, ethyl acetate extraction, washes, is dried, is spin-dried for obtaining the methyl mercapto aniline of 2- methyl -3.
The step 2) carry out in the presence of nitrite, hydrochloric acid, catalyst and a small amount of cosolvent.
The step 2) in the methyl mercapto aniline of reaction mass 2- methyl -3：Nitrite：The mol ratio of hydrochloric acid is 1.0:
1.0-1.8:2-5。
The step 2) specifically include：The methyl mercapto aniline of 2- methyl -3 and hydrochloric acid and catalyst, the stirring of a small amount of cosolvent
Lower cooling, maintains less than 0 DEG C Deca nitrite solution, drips rear insulation reaction 0-4 hour, then is slowly warmed up to 80-85
DEG C, insulation reaction 0-5 hour, then neutralization is to faintly acid, ethyl acetate extraction, washing, be dried, be spin-dried for after product 2- first
The chlorphenyl methyl sulfide of base -3.
The catalyst is Cu-series catalyst, and its addition is 2 ‰～the 5 ‰ of the methyl mercapto aniline weight of 2- methyl -3.
The Cu-series catalyst is selected from copper powder, copper oxide, Red copper oxide, copper chloride, Cu-lyt. and copper sulfate
Kind.
The nitrite is sodium nitrite or potassium nitrite, and the cosolvent is in the alcohols material such as methanol or ethanol
One or more combination.
All raw materials that the present invention is adopted all are commercially available industrial products.
It is an advantage of the current invention that：
(1) content >=95% of the chlorphenyl methyl sulfide of ring sulphur ketone active compound intermediate 2- methyl -3 prepared by the present invention, yield
In terms of the chloroaniline of 2- methyl -3 >=90%.
(2) raw material only has a unique group to be reacted in each step chemical reaction, fundamentally avoids
The generation of impurity, so as to improve the yield and purity of product, and raw material is cheap and easy to get, industrial easily to realize.
Specific embodiment
The present invention is further explained with reference to embodiments：
Embodiment 1
(1) the chloroaniline 14.2g (0.1mol) of 2- methyl -3 is heated to backflow, slow drop in 40ml HMPA
Plus 20% sodium methyl mercaptide aqueous solution 42g (0.12mol), maintain the reflux for after being added dropwise to complete react 3-4 hour, be cooled to room
Temperature, adds iodomethane 1.4g (0.01mol), dilute, ethyl acetate extraction to wash, be dried, be spin-dried for obtaining the chlorobenzene of 2- methyl -3
Amine.
Its reaction equation is：
(2) (1) is obtained methyl mercapto aniline 15.3g (0.951mol) of 2- methyl -3 and 36.5% dense salt of content 95.1%
The copper sulfate of sour 40g and catalytic amount, under the stirring of 20ml cosolvents methanol -5 DEG C are cooled to, and maintain the Asia of less than 0 DEG C Deca 35%
Sodium nitrate solution 20.7g (0.102mol), drips rear insulation reaction 1 hour, is slowly warmed up to 80-85 DEG C, and insulation reaction 2 is little
When, neutralization to faintly acid, ethyl acetate extraction, washing, be dried, be spin-dried for after the chlorphenyl methyl sulfide of product 2- methyl -3, obtain
16.3g, content 95.1%, yield is calculated as 90% with the chloroaniline of 2- methyl -3.
Its reaction equation is：
Embodiment 2
(1) the chloroaniline 14.2g (0.1mol) of 2- methyl -3 is heated to backflow, slow drop in 40ml HMPA
Plus 20% sodium methyl mercaptide aqueous solution 42g (0.12mol), maintain the reflux for after being added dropwise to complete react 3-4 hour, be cooled to room
Temperature, adds iodomethane 1.4g (0.01mol), dilute, ethyl acetate extraction to wash, be dried, be spin-dried for obtaining the chlorobenzene of 2- methyl -3
Amine.
(2) (1) is obtained methyl mercapto aniline 15.3g (0.951mol) of 2- methyl -3 and 36.5% dense salt of content 95.1%
The copper sulfate of sour 40g and catalytic amount, under the stirring of 20ml cosolvents methanol 5 DEG C are cooled to, and maintain the nitrous of the temperature Deca 35%
Acid sodium solution 20.7g (0.102mol), drips rear insulation reaction 1 hour, is slowly warmed up to 80-85 DEG C, and insulation reaction 2 is little
When, neutralization to faintly acid, ethyl acetate extraction, washing, be dried, be spin-dried for after the chlorphenyl methyl sulfide of product 2- methyl -3, obtain
15.8g, content 94.8%, yield is calculated as 86% with the chloroaniline of 2- methyl -3.
Claims (10)
1. the preparation method of the chlorphenyl methyl sulfide of a kind of 2- methyl -3, it is characterised in that comprise the following steps：
1) first sulfuration：The chloroaniline of 2- methyl -3 flows back in a solvent with methanthiol slaine, the methyl mercapto aniline of synthesis 2- methyl -3；
2) diazotising, chlorination：The methyl mercapto aniline Jing diazotising of 2- methyl -3, chlorination synthesis 2- methyl -3- chlorobenzene methyl sulfides.
2. the preparation method of the chlorphenyl methyl sulfide of 2- methyl according to claim 1-3, it is characterised in that the step 1)
Middle solvent is HMPA, and methanthiol slaine is sodium methyl mercaptide or methanthiol potassium.
3. the preparation method of the chlorphenyl methyl sulfide of 2- methyl according to claim 2-3, it is characterised in that the step 1)
The middle chloroaniline of reaction mass 2- methyl -3：Methanthiol slaine：The mol ratio of HMPA is 1.0:1.0-1.8:2-
5。
4. the preparation method of the chlorphenyl methyl sulfide of 2- methyl -3 according to Claims 2 or 3, it is characterised in that the step
It is rapid 1) to specifically include：The chloroaniline of 2- methyl -3 is heated to backflow in HMPA, is slowly added dropwise methanthiol slaine
Aqueous solution, maintain the reflux for reacting 3-4 hours after being added dropwise to complete, be cooled to room temperature, add iodomethane, dilute, acetic acid second
Ester is extracted, and is washed, is dried, is spin-dried for obtaining the methyl mercapto aniline of 2- methyl -3.
5. the preparation method of the chlorphenyl methyl sulfide of 2- methyl according to claim 1-3, it is characterised in that the step 2)
Carry out in the presence of nitrite, hydrochloric acid, catalyst and a small amount of cosolvent.
6. the preparation method of the chlorphenyl methyl sulfide of 2- methyl according to claim 5-3, it is characterised in that the step 2)
The middle methyl mercapto aniline of reaction mass 2- methyl -3：Nitrite：The mol ratio of hydrochloric acid is 1.0:1.0-1.8:2-5.
7. the preparation method of the chlorphenyl methyl sulfide of 2- methyl -3 according to claim 5 or 6, it is characterised in that the step
It is rapid 2) to specifically include：The methyl mercapto aniline of 2- methyl -3 and hydrochloric acid and catalyst, the lower cooling of a small amount of cosolvent stirring, 0 DEG C is maintained
Following Deca nitrite solution, drips rear insulation reaction 0-4 hour, then is slowly warmed up to 80-85 DEG C, insulation reaction 0-5
Hour, then neutralization is to faintly acid, ethyl acetate extraction, washing, be dried, be spin-dried for after the chlorphenyl first sulfur of product 2- methyl -3
Ether.
8. the preparation method of the chlorphenyl methyl sulfide of 2- methyl according to claim 5-3, it is characterised in that the catalyst
For Cu-series catalyst, its addition is 2 ‰～the 5 ‰ of the methyl mercapto aniline weight of 2- methyl -3.
9. the preparation method of the chlorphenyl methyl sulfide of 2- methyl according to claim 8-3, it is characterised in that the copper system is urged
The one kind of agent in copper powder, copper oxide, Red copper oxide, copper chloride, Cu-lyt. and copper sulfate.
10. the preparation method of the chlorphenyl methyl sulfide of 2- methyl according to claim 5-3, it is characterised in that the nitrous
Hydrochlorate is sodium nitrite or potassium nitrite, and the cosolvent is methanol, ethanol or its mixture.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108947878A (en) * | 2018-07-24 | 2018-12-07 | 浙江中山化工集团股份有限公司 | A kind of preparation method of the chloro- 6- (methylthiomethyl) of 2- |
| WO2020029720A1 (en) * | 2018-08-10 | 2020-02-13 | 安徽久易农业股份有限公司 | Method for preparing 2-chloro-6-methylthiotoluene |
| 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 |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4942246A (en) * | 1988-06-03 | 1990-07-17 | Nissan Chemical Industries Ltd. | Process for producing 4-benzoyl-5-hydroxypyrazoles |
| US5804532A (en) * | 1991-01-25 | 1998-09-08 | Rhone-Poulenc Agriculture Limited | Herbicidal 2-cyano-1,3-diones |
| CN1269800A (en) * | 1997-09-08 | 2000-10-11 | 詹森药业有限公司 | Tetrahydro Gamma-carbolines |
| CN1364160A (en) * | 1999-07-27 | 2002-08-14 | 阿温提斯作物科学有限公司 | Isoxazolyl-and isoxazolinyl-substituted benzoylcyclohexanediones, production method and use thereof as herbicides and plant growth regulators |
| US6472349B1 (en) * | 1999-03-31 | 2002-10-29 | Basf Aktiengesellschaft | Pyridine-2,3-dicarboxylic acid diamides |
| CN1793118A (en) * | 2005-09-29 | 2006-06-28 | 上海康鹏化学有限公司 | Process for preparing 3-chloro-2-methyl thiobenzoxide |
| CN102159718A (en) * | 2008-09-15 | 2011-08-17 | 辛根塔有限公司 | Herbicide tolerant plants |
| CN106008295A (en) * | 2016-06-03 | 2016-10-12 | 北京颖泰嘉和生物科技股份有限公司 | Preparation method of 2-halogen-6-alkylthio toluene |
-
2016
- 2016-12-30 CN CN201611250819.9A patent/CN106631941B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4942246A (en) * | 1988-06-03 | 1990-07-17 | Nissan Chemical Industries Ltd. | Process for producing 4-benzoyl-5-hydroxypyrazoles |
| US5804532A (en) * | 1991-01-25 | 1998-09-08 | Rhone-Poulenc Agriculture Limited | Herbicidal 2-cyano-1,3-diones |
| CN1269800A (en) * | 1997-09-08 | 2000-10-11 | 詹森药业有限公司 | Tetrahydro Gamma-carbolines |
| US6472349B1 (en) * | 1999-03-31 | 2002-10-29 | Basf Aktiengesellschaft | Pyridine-2,3-dicarboxylic acid diamides |
| CN1364160A (en) * | 1999-07-27 | 2002-08-14 | 阿温提斯作物科学有限公司 | Isoxazolyl-and isoxazolinyl-substituted benzoylcyclohexanediones, production method and use thereof as herbicides and plant growth regulators |
| CN1793118A (en) * | 2005-09-29 | 2006-06-28 | 上海康鹏化学有限公司 | Process for preparing 3-chloro-2-methyl thiobenzoxide |
| CN102159718A (en) * | 2008-09-15 | 2011-08-17 | 辛根塔有限公司 | Herbicide tolerant plants |
| CN106008295A (en) * | 2016-06-03 | 2016-10-12 | 北京颖泰嘉和生物科技股份有限公司 | Preparation method of 2-halogen-6-alkylthio toluene |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108947878A (en) * | 2018-07-24 | 2018-12-07 | 浙江中山化工集团股份有限公司 | A kind of preparation method of the chloro- 6- (methylthiomethyl) of 2- |
| 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 |
| WO2020029720A1 (en) * | 2018-08-10 | 2020-02-13 | 安徽久易农业股份有限公司 | Method for preparing 2-chloro-6-methylthiotoluene |
| 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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