CN104926702A - Preparation method for 2-methylmercapto-4-thrifluoromethyl benzoate - Google Patents
Preparation method for 2-methylmercapto-4-thrifluoromethyl benzoate Download PDFInfo
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- CN104926702A CN104926702A CN201510218657.XA CN201510218657A CN104926702A CN 104926702 A CN104926702 A CN 104926702A CN 201510218657 A CN201510218657 A CN 201510218657A CN 104926702 A CN104926702 A CN 104926702A
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Abstract
The invention discloses a preparation method for 2-methylmercapto-4-thrifluoromethyl benzoate. The method comprises the following steps: using 2-methylmercapto-4-trifluoromethylbenzonitrile as a raw material; then under atmospheric pressure, carrying out hydrolysis and esterification reactions with methanol as the raw material and a solvent under acid condition provided by a H2SO4 aqueous solution; and using a one-pot method so as to prepare 2-methylmercapto-4-thrifluoromethyl benzoate, wherein the 2-methylmercapto-4-thrifluoromethyl benzoate has a mass content of 96.8% to 99.2% and a yield of 92.9% to 98.5%, and has a reaction formula as shown in the specification. The preparation method provided by the invention improves and innovates synthetic raw materials and reaction conditions; and 2-methylmercapto-4-thrifluoromethyl benzoate is prepared by directly subjecting 2-methylmercapto-4-trifluoromethylbenzonitrile to hydrolysis and esterification reactions under the acid condition; thus, three-wastes treatment and three-wastes discharge are reduced; process operation flow is simplified; reaction steps are shortened; and reaction conversion rate and selectivity can reach more than 90%.
Description
Technical field
The present invention relates to the preparation method of 2-methylthio group-4-trifluoromethyl benzoic acid methyl ester.
Background technology
2-methylthio group-4-trifluoromethyl benzoic acid methyl ester is the intermediate of weedicide isoxazole humulone, and its molecular structural formula is:
Isoxazole humulone belongs to p-hydroxybenzene pyruvate dual oxide enzyme inhibitors (HPPD inhibitor).Do soil treatment for the Dry crop such as corn, sugarcane field, be a kind of organic heterocyclic class selectivity internal-suction type herbicide before seedling stage, mainly work via weeds young root Assimilation and conductivity.After susceptible weeds absorbs, by suppressing ethyl-para-hydroxyphenyl ketone dioxygenase to destroy chlorophyllous formation, thus causing injurious weed chlorosis to be withered, finally reaching the object of selective herbicidal.
The preparation method of the 2-methylthio group-4-trifluoromethyl benzoic acid methyl ester of report is had to mainly contain following several at present:
Prepared by 2-methylthio group-4-trifluoromethylbenzene cyanogen, Niu Jifeng reports a kind of synthetic method being prepared 2-methylthio group-4-trifluoromethyl benzoic acid methyl ester by 2-methylthio group-4-trifluoromethylbenzene cyanogen " agricultural chemicals " 2013 06 is interim, the method uses glycerine and water to make solvent, under the alkaline condition that KOH provides, then hydrolysis obtains 2-methylthio group-4-trifluoromethylbenzoic acid, and resterification obtains 2-methylthio group-4-trifluoromethyl benzoic acid methyl ester.But the method reactions steps has two steps, follow-up three-protection design comparatively bothers, as glycerine reclaims and treatment of Organic Wastewater problem.
CN1262673 discloses a kind of method being raw material and anhydrous Sodium thiomethoxide synthesis 2-methylthio group-4-trifluoromethyl benzoic acid methyl ester with 2-chloro-4-trifluoromethyl benzoic acid methyl ester, the method can be carried out at normal temperatures and pressures, but the chloro-4-trifluoromethyl benzoic acid methyl ester of the raw material 2-needed for this reaction is difficult to obtain, reaction conditions is harsher, require anhydrous response environment, and solvent is not easy to recovery of applied.
EP0780371 and US5744021 discloses a kind of with 3,4-bis-chlorobenzotrifluoride is the ester derivative that after raw material electrochemical reaction, resterification obtains phenylfluoroform, replace with alkyl sulfur compounds again and obtain 2-methylthio group-4-trifluoromethyl benzoic acid methyl ester, raw material 3 needed for the method, 4-bis-chlorobenzotrifluoride is easy to get, but electrolytic solution aftertreatment bothers, and product yield is not high.
EP524018 and CN91105623.8 disclose a kind of with 3-amino-4-5 bromine benzotrifluoride for raw material be substituted after obtain 3-methylthio group-4-5 bromine benzotrifluoride, 2-methylthio group-4-trifluoromethylbenzoic acid is obtained again after carboxylation, last resterification obtains 2-methylthio group-4-trifluoromethyl benzoic acid methyl ester, raw material 3-amino-4-5 bromine benzotrifluoride needed for the method is difficult to obtain, the use of BuLi makes reaction conditions harsher, and reactions steps is tediously long.
In sum, change the raw materials cost that conventional synthesis route exists high, to environment the factor such as unfriendly or severe reaction conditions, it is necessary to invent a kind of synthesis 2-methylthio group-4-trifluoromethyl benzoic acid methyl ester method newly.
Summary of the invention
The object of the invention is to provide a kind of preparation method of 2-methylthio group-4-trifluoromethyl benzoic acid methyl ester, to it is characterized in that with 2-methylthio group-4-4-trifluoromethylbenzonitrile, for raw material, at ambient pressure, making raw material and solvent, at H with methyl alcohol
2sO
4be hydrolyzed and esterification under the acidic conditions that the aqueous solution provides, one kettle way prepares 2-methylthio group-4-trifluoromethyl benzoic acid methyl ester reaction solution, reaction solution, through distillation precipitation, washing, filtration, drying, namely obtains solid 2-methylthio group-4-trifluoromethyl benzoic acid methyl ester product.The mass percentage of gained 2-methylthio group-4-trifluoromethyl benzoic acid methyl ester is 96.8% ~ 99.2% (liquid chromatography, external standard), and yield is 92.9% ~ 98.5% (in 2-methylthio group-4-trifluoromethylbenzene cyanogen).
Reaction formula is:
Described methanol usage is 1 ~ 10 times of 2-methylthio group-4-4-trifluoromethylbenzonitrile quality.
Described H
2sO
4concentration of aqueous solution is 30% ~ 90%, H
2sO
4the consumption of the aqueous solution is 1 ~ 5 times of 2-methylthio group-4-4-trifluoromethylbenzonitrile quality.Temperature of reaction 60 DEG C ~ 110 DEG C, reaction times 3h ~ l2h.
Concrete operation step of the present invention is:
First in reactor, add methyl alcohol, add 2-methylthio group-4-4-trifluoromethylbenzonitrile again, then aqueous sulfuric acid is added, control temperature of reaction, reaction times, react complete and reaction solution is carried out distillation precipitation, concentrated solution washes rear filtration with water, drying obtains 2-methylthio group-4-trifluoromethyl benzoic acid methyl ester.
One kettle way provided by the invention prepares the method for 2-methylthio group-4-trifluoromethyl benzoic acid methyl ester, synthesis material and reaction conditions have carried out improvement and bring new ideas, make 2-methylthio group-4-trifluoromethylbenzene cyanogen direct hydrolysis and esterification in acid condition, prepare 2-methylthio group-4-trifluoromethyl benzoic acid methyl ester, decrease three-protection design and three waste discharge, simplify technical operation flow, shorten reactions steps, make the transformation efficiency of reaction and selectivity all reach more than 90%.
Embodiment
Embodiment 1
100ml methyl alcohol is added in reaction flask, add 21.7g (0.1mol) 2-methylthio group-4-4-trifluoromethylbenzonitrile again, then the aqueous sulfuric acid of 22.6g90% is added, 80 DEG C of heated mixt 10 hours, then reaction solution is carried out distillation desolvation methyl alcohol, concentrated solution washes rear filtration, dry 24.8g (0.0983mol) 2-methylthio group-4-trifluoromethyl benzoic acid methyl ester with water, content 99.1%, yield 98.3% (in 2-methylthio group-4-trifluoromethylbenzene cyanogen).
Embodiment 2
100ml methyl alcohol is added in reaction flask, add 21.7g (0.1mol) 2-methylthio group-4-4-trifluoromethylbenzonitrile again, then the aqueous sulfuric acid of 22.6g60% is added, at 80 DEG C of heated mixt after 10 hours, reaction solution is evaporated methyl alcohol, concentrated solution washes rear filtration, dry 24.7g (0.0967mol) 2-methylthio group-4-trifluoromethyl benzoic acid methyl ester with water, content 97.9%, yield 96.7% (in 2-methylthio group-4-trifluoromethylbenzene cyanogen).
Embodiment 3
100ml methyl alcohol is added in reaction flask, add 21.7g (0.1mol) 2-methylthio group-4-4-trifluoromethylbenzonitrile again, then the aqueous sulfuric acid of 22.6g 30% is added, at 80 DEG C of heated mixt after 10 hours, reaction solution is evaporated methyl alcohol, concentrated solution washes rear filtration, dry 24.0g (0.0933mol) 2-methylthio group-4-trifluoromethyl benzoic acid methyl ester with water, content 97.2%, yield 93.3% (in 2-methylthio group-4-trifluoromethylbenzene cyanogen).
Embodiment 4
100ml methyl alcohol is added in reaction flask, add 21.7g (0.1mol) 2-methylthio group-4-4-trifluoromethylbenzonitrile again, then the aqueous sulfuric acid of 22.6g80% is added, at 110 DEG C of heated mixt after 12 hours, reaction solution is evaporated methyl alcohol, concentrated solution washes rear filtration, dry 24.8g (0.0984mol) 2-methylthio group-4-trifluoromethyl benzoic acid methyl ester with water, content 99.2%, yield 98.4% (in 2-methylthio group-4-trifluoromethylbenzene cyanogen).
Embodiment 5
100ml methyl alcohol is added in reaction flask, add 21.7g (0.1mol) 2-methylthio group-4-4-trifluoromethylbenzonitrile again, then the aqueous sulfuric acid of 22.6g80% is added, at 60 DEG C of heated mixt after 12 hours, reaction solution is evaporated methyl alcohol, concentrated solution washes rear filtration, dry 24.0g (0.0929mol) 2-methylthio group-4-trifluoromethyl benzoic acid methyl ester with water, content 96.8%, yield 92.9% (in 2-methylthio group-4-trifluoromethylbenzene cyanogen).
Embodiment 6
100ml methyl alcohol is added in reaction flask, add 21.7g (0.1mol) 2-methylthio group-4-4-trifluoromethylbenzonitrile again, then the aqueous sulfuric acid of 22.6g80% is added, at 80 DEG C of heated mixt after 12 hours, reaction solution is evaporated methyl alcohol, concentrated solution washes rear filtration, dry 24.8g (0.0982mol) 2-methylthio group-4-trifluoromethyl benzoic acid methyl ester with water, content 99.0%, yield 98.2% (in 2-methylthio group-4-trifluoromethylbenzene cyanogen).
Embodiment 7
100ml methyl alcohol is added in reaction flask, add 21.7g (0.1mol) 2-methylthio group-4-4-trifluoromethylbenzonitrile again, then the aqueous sulfuric acid of 22.6g80% is added, at 80 DEG C of heated mixt after 3 hours, reaction solution is evaporated methyl alcohol, concentrated solution washes rear filtration, dry 24.3g (0.0942mol) 2-methylthio group-4-trifluoromethyl benzoic acid methyl ester with water, content 96.9%, yield 94.2% (in 2-methylthio group-4-trifluoromethylbenzene cyanogen).
Embodiment 8
100ml methyl alcohol is added in reaction flask, add 21.7g (0.1mol) 2-methylthio group-4-4-trifluoromethylbenzonitrile again, then the aqueous sulfuric acid of 22.6g80% is added, at 80 DEG C of heated mixt after 10 hours, reaction solution is evaporated methyl alcohol, concentrated solution washes rear filtration, dry 24.6g (0.0959mol) 2-methylthio group-4-trifluoromethyl benzoic acid methyl ester with water, content 97.5%, yield 95.9% (in 2-methylthio group-4-trifluoromethylbenzene cyanogen).
Embodiment 9
27.4ml methyl alcohol is added in reaction flask, add 21.7g (0.1mol) 2-methylthio group-4-4-trifluoromethylbenzonitrile again, then the aqueous sulfuric acid of 22.6g80% is added, at 80 DEG C of heated mixt after 10 hours, reaction solution is evaporated methyl alcohol, concentrated solution washes rear filtration, dry 24.0g (0.0932mol) 2-methylthio group-4-trifluoromethyl benzoic acid methyl ester with water, content 97.1%, yield 93.2% (in 2-methylthio group-4-trifluoromethylbenzene cyanogen).
Embodiment 10
274ml methyl alcohol is added in reaction flask, add 21.7g (0.1mol) 2-methylthio group-4-4-trifluoromethylbenzonitrile again, then the aqueous sulfuric acid of 22.6g80% is added, at 80 DEG C of heated mixt after 10 hours, reaction solution is evaporated methyl alcohol, concentrated solution washes rear filtration, dry 24.0g (0.0931mol) 2-methylthio group-4-trifluoromethyl benzoic acid methyl ester with water, content 97.0%, yield 93.1% (in 2-methylthio group-4-trifluoromethylbenzene cyanogen).
Embodiment 11
100ml methyl alcohol is added in reaction flask, add 21.7g (0.1mol) 2-methylthio group-4-4-trifluoromethylbenzonitrile again, then the aqueous sulfuric acid of 21.7g80% is added, at 80 DEG C of heated mixt after 10 hours, reaction solution is evaporated methyl alcohol, concentrated solution washes rear filtration, dry 24.7g (0.0961mol) 2-methylthio group-4-trifluoromethyl benzoic acid methyl ester with water, content 97.3%, yield 96.1% (in 2-methylthio group-4-trifluoromethylbenzene cyanogen).
Embodiment 12
100ml methyl alcohol is added in reaction flask, add 21.7g (0.1mol) 2-methylthio group-4-4-trifluoromethylbenzonitrile again, then the aqueous sulfuric acid of 108.5g80% is added, at 80 DEG C of heated mixt after 10 hours, reaction solution is evaporated methyl alcohol, concentrated solution washes rear filtration, dry 23.8g (0.0933mol) 2-methylthio group-4-trifluoromethyl benzoic acid methyl ester with water, content 98.0%, yield 93.3% (in 2-methylthio group-4-trifluoromethylbenzene cyanogen).
Embodiment 13
100ml methyl alcohol is added in reaction flask, add 21.7g (0.1mol) 2-methylthio group-4-4-trifluoromethylbenzonitrile again, then the aqueous sulfuric acid of 43.4g80% is added, at 80 DEG C of heated mixt after 10 hours, reaction solution is evaporated methyl alcohol, concentrated solution washes rear filtration, dry 24.7g (0.0969mol) 2-methylthio group-4-trifluoromethyl benzoic acid methyl ester with water, content 98.1%, yield 96.9% (in 2-methylthio group-4-trifluoromethylbenzene cyanogen).
Claims (2)
- The preparation method of 1.2-methylthio group-4-trifluoromethyl benzoic acid methyl ester, to is characterized in that with 2-methylthio group-4-4-trifluoromethylbenzonitrile, for raw material, at ambient pressure, making raw material and solvent, at H with methyl alcohol 2sO 4be hydrolyzed and esterification under the acidic conditions that the aqueous solution provides, one kettle way prepares 2-methylthio group-4-trifluoromethyl benzoic acid methyl ester reaction solution, reaction solution, through distillation precipitation, washing, filtration, drying, namely obtains solid 2-methylthio group-4-trifluoromethyl benzoic acid methyl ester productReaction formula is:
- 2. the preparation method of 2-methylthio group-4-trifluoromethyl benzoic acid methyl ester according to claim 1, is characterized in that methanol usage is 1 ~ 10 times of 2-methylthio group-4-4-trifluoromethylbenzonitrile quality, H 2sO 4concentration of aqueous solution is 30% ~ 90%, H 2sO 4the consumption of the aqueous solution is 1 ~ 5 times of 2-methylthio group-4-4-trifluoromethylbenzonitrile quality, temperature of reaction 60 DEG C ~ 110 DEG C, reaction times 3h ~ l2h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107417587A (en) * | 2017-03-22 | 2017-12-01 | 京博农化科技股份有限公司 | A kind of 1 cyclopropyl 3（The trifluoromethyl of 2 methyl mercapto 4）The synthetic method of the third 1,3 diketone |
| CN107540583A (en) * | 2017-08-23 | 2018-01-05 | 连云港世杰农化有限公司 | A kind of method for synthesizing the trifluoromethylbenzoic acid ethyl ester of 2 methyl mercapto 4 |
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| US5744021A (en) * | 1995-12-22 | 1998-04-28 | Hoechst Ag | 2-alkylmercapto-4-(trifluoromethyl)benzoic esters and a process for their preparation |
| CN101863782A (en) * | 2010-06-25 | 2010-10-20 | 北京英力精化技术发展有限公司 | Method for synthesizing ultraviolet photoinitiator of p-dimethylamin benzoic ether compounds |
| CN103145638A (en) * | 2013-03-18 | 2013-06-12 | 上海添蓝生物科技有限公司 | New preparation method of 2-butyl-1,2-benzoisothiazolin-3-ketone (BBIT) |
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2015
- 2015-04-30 CN CN201510218657.XA patent/CN104926702A/en active Pending
Patent Citations (3)
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| US5744021A (en) * | 1995-12-22 | 1998-04-28 | Hoechst Ag | 2-alkylmercapto-4-(trifluoromethyl)benzoic esters and a process for their preparation |
| CN101863782A (en) * | 2010-06-25 | 2010-10-20 | 北京英力精化技术发展有限公司 | Method for synthesizing ultraviolet photoinitiator of p-dimethylamin benzoic ether compounds |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107417587A (en) * | 2017-03-22 | 2017-12-01 | 京博农化科技股份有限公司 | A kind of 1 cyclopropyl 3（The trifluoromethyl of 2 methyl mercapto 4）The synthetic method of the third 1,3 diketone |
| CN107540583A (en) * | 2017-08-23 | 2018-01-05 | 连云港世杰农化有限公司 | A kind of method for synthesizing the trifluoromethylbenzoic acid ethyl ester of 2 methyl mercapto 4 |
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