CN1305843C - Process for preparing 3-chloro-2-methyl thiobenzoxide - Google Patents
Process for preparing 3-chloro-2-methyl thiobenzoxide Download PDFInfo
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- CN1305843C CN1305843C CNB2005100301635A CN200510030163A CN1305843C CN 1305843 C CN1305843 C CN 1305843C CN B2005100301635 A CNB2005100301635 A CN B2005100301635A CN 200510030163 A CN200510030163 A CN 200510030163A CN 1305843 C CN1305843 C CN 1305843C
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Abstract
The present invention belongs to the technical field of a preparation method of 3-chlorine-2-methyl thiobenzoxide. In the preparation method of the 3-chlorine-2-methyl thiobenzoxide, 3-chlorine-2-methylaniline is used as a raw material; a diazotization reagent is added into an acidic solution to carry out diazoreaction and prepare a diazonium salt I, wherein X <-> is an acid ion; the diazonium salt I reacts with a water solution of an amethanethiol metal salt to obtain a product II; the product II is treated to obtain the 3-chlorine-2-methyl thiobenzoxide. The raw materials of the 3-chlorine-2-methylaniline and a water solution of sodium methyl mercaptide used by the present invention are both commercialized in large scale at home and abroad, and the price is low; any organic solvent does not need in a reaction process, so a post-treatment process can be reduced. The present invention has the advantages of simple preparation process, cheap raw material, easy raw material acquirement and high yield; the yield can reach more than 80%; the preparation method is used for large-scale commercial production.
Description
Technical field
The invention belongs to preparation method's technical field of 3-chloro-2-methyl thiobenzoxide.
Background technology
3-chloro-2-methyl thiobenzoxide is agricultural chemicals and medical useful as intermediates, its production method such as document (Synthesis 1982 such as Chianelli, 6,475) in, with 2, the 6-toluene dichloride is that the preparation method of raw material is as follows substantially: by 2,6-toluene dichloride and exsiccant sodium methyl mercaptide solid are in the solvent HMPA, reacting by heating under the anhydrous condition, yield is about 86%.But when using this method and preparing, wherein raw material 2, and the 6-toluene dichloride is on the high side: another kind of raw material, and the exsiccant sodium methyl mercaptide solid commercial prod utmost point is difficult to obtain, and at present domestic still do not have commodity; The solvent HMPA price of reacting used is also very expensive, and reclaims difficult.According to aforesaid method, raw material is difficult for obtaining with production cost too high, so the utmost point is not suitable for large-scale industrial production.
Summary of the invention
The purpose of this invention is to provide a kind of easy, economical and be suitable for the method for preparing 3-chloro-2-methyl thiobenzoxide of large-scale commercial production.
The preparation method of 3-chloro-2-methyl thiobenzoxide of the present invention, its reaction formula is as follows:
Concrete steps are:
(1), with 3-chloro-2-aminotoluene as raw material, in acidic solution, add diazo reagent, carry out diazotization reaction and prepare diazonium salt I, wherein X
-Be acid ion;
(2), the above-mentioned diazonium salt I that will make and the reaction of thiomethyl alcohol aqueous metal salt obtain product II, aftertreatment gets final product.
The preparation method of 3-chloro-2-methyl thiobenzoxide of the present invention, wherein the used acid of step (1) can be sulfuric acid, hydrochloric acid or acetic acid etc., and wherein hydrochloric acid is more suitable.The consumption of acid is generally excessive slightly than the molar weight of 3-chloro-2-aminotoluene, and yield is reduced, and can be 1.5～10 times of 3-chloro-2-aminotoluene molar weight, is the best with 2～2.5 wherein; Its mass percent concentration can be 10～50%, is the best with 20～30% acidic solutions.
The preparation method of 3-chloro-2-methyl thiobenzoxide of the present invention, wherein the used diazo reagent of step (1) can be nitrite or nitrous acid ester, as Sodium Nitrite, potassium nitrite, ethyl nitrite, nitrous acid isopropyl ester etc., is preferably Sodium Nitrite; The concentration of sodium nitrite solution is 5～50%, considers the economy of production and the generation of waste water, and wherein 40% sodium nitrite solution is best; The mol ratio of 3-chloro-2-aminotoluene and diazo reagent is 1: (0.8～1.5) is preferably (1～1.1).
The preparation method of 3-chloro-2-methyl thiobenzoxide of the present invention, wherein step (1) can be carried out at-20～20 ℃, and is more suitable-5～5 ℃ of reactions.
The preparation method of 3-chloro-2-methyl thiobenzoxide of the present invention, wherein the used thiomethyl alcohol metal-salt of step (2) alkaline aqueous solution as sodium methyl mercaptide alkaline aqueous solution, the thiomethyl alcohol potash aqueous solution etc., is preferably the sodium methyl mercaptide alkaline aqueous solution.
The preparation method of 3-chloro-2-methyl thiobenzoxide of the present invention, wherein the mass percent concentration of the used thiomethyl alcohol saline alkali of step (2) aqueous solution is 15～25%, is preferably 20～25%.
The preparation method of 3-chloro-2-methyl thiobenzoxide of the present invention, wherein the temperature of reaction of step (2) is-20～40 ℃, the temperature of reaction of optimization is 0～10 ℃; If reaction after diazonium salt adds, removes cryostat at low temperatures, make it nature and be warming up to room temperature, generally at 15～50 ℃, be controlled at 25～30 ℃ preferably, continuation reaction for some time makes and reacts completely.At last with the product that obtains through extraction, phase-splitting, precipitation, the rectifying aftertreatment obtains content＞99.5% of 3-chloro-2-methyl thiobenzoxide.
Beneficial effect of the present invention: the raw material 3-chloro-2-aminotoluene that the present invention is used and the sodium methyl mercaptide aqueous solution reach in the world all large-scale commercial and cheap at home, without any need for organic solvent, can reduce last handling process in the reaction process.The inventive method preparation process is simple, raw material is cheap and easy to get, productive rate is high, can reach more than 80%, and the utmost point is suitable for large-scale commercial production.
Embodiment
Embodiment 1
(1) preparation 3-chloro-2-aminotoluene diazonium salt
In the 10L four-hole bottle of thermometer, prolong is housed, drop into the hydrochloric acid of 4198g (23mol) 20%, be cooled to T
InAbout=10 ℃, stir fast down, be added dropwise to 1415g (10mol) 3-chloro-2-aminotoluene, after dropwising, stirred 0.5 hour.Reaction system is cooled to T
In=0～5 ℃, to wherein dripping 1815g 40% sodium nitrite solution, keep temperature of reaction at 0～5 ℃, dropwised in 2.5 hours, make clarifying diazonium liquid, standby in-5～5 ℃ of preservations.
(2) preparation 3-chloro-2-methyl thiobenzoxide
Have in the 20L four-hole bottle of prolong that thermometer, constant pressure funnel, top be connected with bubbler in another and to add 5000g 20% sodium methyl mercaptide alkaline aqueous solution, be cooled to T
In=5～10 ℃, in bottle, drip above-mentioned diazonium liquid, exothermic heat of reaction is kept reaction T
In=5～10 ℃, N
2Constantly emit, dropwised in 2 hours, whole system is always strong basicity.After dripping diazonium liquid, continue to keep low temperature to stir 0.5 hour, remove cryostat, be warming up to room temperature naturally, stirring reaction 2.5 hours does not have bubble substantially and emits, and reaction terminating leaves standstill, and reaction solution is divided into two-layer, lower floor's yellow oil.Add 2L toluene, stirred 2 hours, leave standstill phase-splitting, water again with the extraction of 2L toluene once, combining extraction liquid adds anhydrous magnesium sulfate drying, filters, after filtrate decompression is sloughed about 2/3rds toluene, rectifying obtains product 1466g, productive rate 85%, its b.p.117/10mmHg.
Embodiment 2
(1) preparation 3-chloro-2-aminotoluene diazonium salt
Drop into 5635g (23mol) 20% sulfuric acid at the 10L four-hole bottle that thermometer, prolong are being housed, other operational conditions all with
Embodiment 1 step (1) is identical.
(2) preparation 3-chloro-2-methyl thiobenzoxide
Operational condition is all identical with embodiment 1 step (2), obtains product 1380g, productive rate 80%.
Embodiment 3
(1) preparation 3-chloro-2-aminotoluene diazonium salt
Drop into 2738g (15mol) 20% hydrochloric acid, other operational conditions are all identical with embodiment 1 step (1).
(2) preparation 3-chloro-2-methyl thiobenzoxide
Operational condition is all identical with embodiment 1 step (2), obtains product 724.5g, productive rate 42%.
Embodiment 4
(1) preparation 3-chloro-2-aminotoluene diazonium salt
Drop into 18250g (100mol) 20% hydrochloric acid, other operational conditions are all identical with embodiment 1 step (1).
(2) preparation 3-chloro-2-methyl thiobenzoxide
Operational condition is all identical with embodiment 1 step (2), obtains product 1052g, productive rate 30%.
Embodiment 5
(1) preparation 3-chloro-2-aminotoluene diazonium salt
Drop into 2798g (23mol) 30% hydrochloric acid, other operational conditions are all identical with embodiment 1 step (1).
(2) preparation 3-chloro-2-methyl thiobenzoxide
Operational condition is all identical with embodiment 1 step (2), obtains product 1052g, productive rate 54%.
Embodiment 6
(1) preparation 3-chloro-2-aminotoluene diazonium salt
Operational condition is all identical with embodiment 1 step (1).
(2) preparation 3-chloro-2-methyl thiobenzoxide
Adding temperature except that the diazonium drop is that 35～40 ℃ of operational conditions are all identical with embodiment 1 step (2), obtains product 1069g, productive rate 62%.
Embodiment 7
(1) preparation 3-chloro-2-aminotoluene diazonium salt
Operational condition is all identical with embodiment 1 step (1).
(2) preparation 3-chloro-2-methyl thiobenzoxide
Adding temperature except that the diazonium drop is that-20～-10 ℃ of operational conditions are all identical with embodiment 1 step (2), obtains product 1362g, productive rate 79%.
Embodiment 8
(1) preparation 3-chloro-2-aminotoluene diazonium salt
Drop into 2136g (24mol) nitrous acid isopropyl ester, other operational conditions are all identical with embodiment 1 step (1).
(2) preparation 3-chloro-2-methyl thiobenzoxide
Operational condition is all identical with embodiment 1 step (2), obtains product 1397g, productive rate 81%.
Embodiment 9
(1) preparation 3-chloro-2-aminotoluene diazonium salt
Removing temperature of reaction is that-20 ℃ of other operational conditions are all identical with embodiment 1 step (1).
(2) preparation 3-chloro-2-methyl thiobenzoxide
Operational condition is all identical with embodiment 1 step (2), obtains product 1293g, productive rate 75%.
Embodiment 10
(1) preparation 3-chloro-2-aminotoluene diazonium salt
Removing temperature of reaction is that 20 ℃ of other operational conditions are all identical with embodiment 1 step (1).
(2) preparation 3-chloro-2-methyl thiobenzoxide
Operational condition is all identical with embodiment 1 step (2), obtains product 966g, productive rate 56%.
Claims (12)
1, the preparation method of 3-chloro-2-methyl thiobenzoxide, its reaction formula is as follows:
Concrete steps are:
(1), with 3-chloro-2-aminotoluene as raw material, in acidic solution, add diazo reagent, carry out diazotization reaction and prepare diazonium salt I, wherein X-is an acid ion;
(2), the above-mentioned diazonium salt I that will make and the reaction of thiomethyl alcohol aqueous metal salt obtain product II, aftertreatment gets final product.
2, the preparation method of 3-chloro-2-methyl thiobenzoxide as claimed in claim 1 is characterized in that, the said acidic solution of step (1) is meant hydrochloric acid, sulfuric acid or acetic acid.
3, the preparation method of 3-chloro-2-methyl thiobenzoxide as claimed in claim 2 is characterized in that, the consumption of acid is 1.5～10 times of 3-chloro-2-aminotoluene molar weight.
4, the preparation method of 3-chloro-2-methyl thiobenzoxide as claimed in claim 3 is characterized in that, the consumption of acid is 2～2.5 times of 3-chloro-2-aminotoluene molar weight.
5, the preparation method of 3-chloro-2-methyl thiobenzoxide as claimed in claim 2 is characterized in that, the mass percent concentration of acidic solution is 10～50%.
6, the preparation method of 3-chloro-2-methyl thiobenzoxide as claimed in claim 1 is characterized in that, the used diazo reagent of step (1) is following nitrite or nitrous acid ester: Sodium Nitrite, potassium nitrite, ethyl nitrite, nitrous acid isopropyl ester.
7, the preparation method of 3-chloro-2-methyl thiobenzoxide as claimed in claim 1 is characterized in that, the mol ratio of 3-chloro-2-aminotoluene and diazo reagent is 1 in the step (1): (0.8～1.5).
8, the preparation method of 3-chloro-2-methyl thiobenzoxide as claimed in claim 1 is characterized in that, the temperature of reaction of step (1) is-20～20 ℃.
9, the preparation method of 3-chloro-2-methyl thiobenzoxide as claimed in claim 1 is characterized in that, the used thiomethyl alcohol metal-salt of step (2) alkaline aqueous solution is the sodium methyl mercaptide alkaline aqueous solution or the thiomethyl alcohol potash aqueous solution.
10, the preparation method of 3-chloro-2-methyl thiobenzoxide as claimed in claim 9 is characterized in that, the mass percent concentration of the thiomethyl alcohol saline alkali aqueous solution is 15～25%.
11, the preparation method of 3-chloro-2-methyl thiobenzoxide as claimed in claim 1 is characterized in that, the temperature of reaction of step (2) is-20～40 ℃.
12, the preparation method of 3-chloro-2-methyl thiobenzoxide as claimed in claim 11 is characterized in that, the temperature of reaction of step (2) is 0～10 ℃.
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| CNB2005100301635A CN1305843C (en) | 2005-09-29 | 2005-09-29 | Process for preparing 3-chloro-2-methyl thiobenzoxide |
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| CNB2005100301635A CN1305843C (en) | 2005-09-29 | 2005-09-29 | Process for preparing 3-chloro-2-methyl thiobenzoxide |
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| CN1305843C true CN1305843C (en) | 2007-03-21 |
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| CN106008295B (en) * | 2016-06-03 | 2017-12-08 | 北京颖泰嘉和生物科技股份有限公司 | A kind of preparation method of the alkylthio group toluene of 2 halo 6 |
| CN106496086B (en) * | 2016-10-10 | 2018-11-06 | 沈阳药科大学 | The synthetic method of 4- methylsulfonyl butyl isothiocyanates |
| CN106631941B (en) * | 2016-12-30 | 2018-09-28 | 青岛瀚生生物科技股份有限公司 | A kind of preparation method of -3 chlorphenyl methyl sulfide of 2- methyl |
| CN107162944B (en) * | 2017-04-27 | 2019-02-26 | 湖南化工研究院有限公司 | The preparation method of 2,3- dimethyl benzene methyl sulfide |
| CN110526844B (en) * | 2018-05-25 | 2021-11-12 | 江苏中旗科技股份有限公司 | Synthetic method of topramezone intermediate 2, 3-dimethyl benzylthio-ether |
| 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- |
| CN112694427B (en) * | 2019-10-23 | 2022-11-18 | 江西天宇化工有限公司 | Method for preparing 2, 3-dimethyl sulfide |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1146548C (en) * | 1999-07-27 | 2004-04-21 | 阿温提斯作物科学有限公司 | Isoxazolyl-and isoxazolinyl-substituted benzoylcyclohexanediones, method for the production thereof and use thereof as herbicides and plant growth regulators |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1146548C (en) * | 1999-07-27 | 2004-04-21 | 阿温提斯作物科学有限公司 | Isoxazolyl-and isoxazolinyl-substituted benzoylcyclohexanediones, method for the production thereof and use thereof as herbicides and plant growth regulators |
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Assignee: Jiangsu Weier Chemical Co., Ltd. Assignor: Shanghai Kangpeng Chemical Co., Ltd. Contract fulfillment period: 2007.12.1 to 2018.11.30 contract change Contract record no.: 2009990000590 Denomination of invention: Process for preparing 3-chloro-2-methyl thiobenzoxide Granted publication date: 20070321 License type: Exclusive license Record date: 2009.6.1 |
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Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2007.12.1 TO 2018.11.30; CHANGE OF CONTRACT Name of requester: JIANGSU WEIER CHEMICAL CO., LTD. Effective date: 20090601 |
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Assignee: Jiangsu Weier Chemical Co., Ltd. Assignor: Shanghai Kangpeng Chemical Co., Ltd. Contract record no.: 2009990000590 Date of cancellation: 20100507 |
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Assignee: Jiangsu Weier Chemical Co., Ltd. Assignor: Shanghai Kangpeng Chemical Co., Ltd. Contract record no.: 2010310000129 Denomination of invention: Process for preparing 3-chloro-2-methyl thiobenzoxide Granted publication date: 20070321 License type: Exclusive License Open date: 20060628 Record date: 20100728 |
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