CN102219712A - Synthetic method of methyl-4-(trifluoromethoxy) phenyl carbamate - Google Patents
Synthetic method of methyl-4-(trifluoromethoxy) phenyl carbamate Download PDFInfo
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- CN102219712A CN102219712A CN201110109685XA CN201110109685A CN102219712A CN 102219712 A CN102219712 A CN 102219712A CN 201110109685X A CN201110109685X A CN 201110109685XA CN 201110109685 A CN201110109685 A CN 201110109685A CN 102219712 A CN102219712 A CN 102219712A
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- urethylane
- trifluoromethoxyphen
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Abstract
A synthetic method of methyl-4-(trifluoromethoxy) phenyl carbamate. Raw materials of 4-trifluoromethoxy-aniline, methyl chloroformate and alkalis and a mixed solvent of water and organic solvents are mixed and undergo directly a reaction to produce a product of methyl-4-(trifluoromethoxy) phenyl carbamate. The synthetic method comprises the following steps of 1, adding 4-trifluoromethoxy-aniline, sodium hydroxide, tetrahydrofuran and water into a container, mixing well and make the mixture undergo a reaction at a temperature of 0 to 5 DEG C for 2 hours, 2, heating the reaction products to room temperature and stirring for 30 minutes, adding slowly methyl chloroformate into the heated reaction products and stirring at room temperature for 6 to 7 hours, 3, cooling the reaction products obtained from the step 2 to 0 DEG C and stirring for 30 minutes, and 4, carrying out a suction filtration process for the reaction products obtained from the step 3 to collect solids, and washing and drying the solids to obtain desired products. The synthetic method has the advantages that the synthetic method is simple and practical, has a high efficiency and can realize an end product yield more than 95%; reagents adopted in synthesizing processes have the advantages of low toxicity, high economic efficiency, less side effects, less corrosion on equipment and less pollution on environment; and prices of raw materials are cheap thus a production cost is low and the synthetic method has a high economic efficiency and good application prospects.
Description
Technical field
The present invention relates to the preparation of fine chemical product and the field of utilisation technology, particularly a kind of synthetic method of 4-Trifluoromethoxyphen-l-Urethylane.
Background technology
4-Trifluoromethoxyphen-l-Urethylane, English name: methyl-4-(trifluoromethoxy) phenyl carbamate, methyl 4-(trifluoromethoxy) phenyl carbamate are a kind of
Soluble in water, the colourless transparent liquid of organic solvents such as alcohol, ether, density: 1.32g/ml, boiling point: 130-132
℃ (5mmHg), molecular formula: C
9H
8F
3NO
3, molecular weight: 187, it is the intermediate of a lot of important Chemicals, wherein most important applications is exactly relatively more novel at present agricultural chemicals metaflumizone and indenes worm prestige, (metaflumizone is a kind of brand-new compound that BASF Aktiengesellschaft and Japanese agricultural chemicals company develop jointly BAS320I) to metaflumizone, belongs to the semicarbazone insecticides, has the mechanism of action uniqueness, itself has insecticidal activity, does not need bioactivation, does not have the advantage of cross resistance with existing each insecticides.It can prevent and treat the lepidoptera pest of various places and larva, the adult of some Coleoptera effectively, and the insect that chews and sting food is had tangible prevention effect, as common kind have rice indulge the leaf snout moth's larva,
Beet armyworm,
Bollworm,
Pink bollworm, small white, wild cabbage
Noctuid, small cabbage moth, Hellula undalis,
Black cutworm, rice-stem borer etc., right
Leaf rollerThe preventive effect of class is medium, this medicine especially for control ant, termite,
Red fire ant, non-crop pests aspect such as fly and cockroach is very potential.Has very high practical value so the success of 4-Trifluoromethoxyphen-l-Urethylane is synthetic for the promotion efficiency that reduces raw materials cost, this agricultural chemicals of increase.At present the method for synthetic this compound is to be that raw material synthesizes with 4-trifluoro-methoxyaniline and methylcarbonate, but this byproduct of reaction is many and be difficult to remove, and raw material sources are limited, the building-up process complexity, and yield is not high about 48%, and the processing requirement height, the purifying products difficulty.Pertinent literature ZrClO is also arranged
2/ SiO
2As catalyzer (Huaxue Shijie (2009), 50 (4), 244-246,233), still aftertreatment complexity in this kind method has increased the intractability that reacts undoubtedly, and the raw materials cost of product is higher, is not suitable for the scale operation of industry.
Based on above-mentioned a variety of causes, be badly in need of the marketing ability that a kind of synthetic method with economy height, yield is good, side reaction is few and environmental pollution is little 4-Trifluoromethoxyphen-l-Urethylane is strengthened the good agricultural chemicals of this kind at present.This seminar has carried out deep research test on the empirical basis in the past to this test, has finally found to meet the test method and the condition of above-mentioned requirements.The report of contrast pertinent literature and patent, the present invention has following some advantage: 1) adopting 4-trifluoro-methoxyaniline, methyl-chloroformate and salt of wormwood is raw material, directly obtains final product in the aqueous phase reaction, raw material is cheap and easy to get; 2) adopting water and organic solvent is solvent system, does not almost have this kind method in document in the past; 3) water as solvent that adopts cost to be almost equal to zero, organic solvent cheapness and the environmental protection of adopting in the additive method relatively; 4) aftertreatment technology is simple, and refuse is environmentally friendly, makees solvent with water, can reach the productive rate more than 95%, so the present invention has very high superiority in industrial production.
Summary of the invention
The objective of the invention is at above-mentioned existing problems, provide a kind of efficient, economical, green and meet the synthetic method of 4-Trifluoromethoxyphen-l-Urethylane that industrial production requires.
Technical scheme of the present invention:
A kind of synthetic method of 4-Trifluoromethoxyphen-l-Urethylane, it is characterized in that: with 4-trifluoro-methoxyaniline, methyl-chloroformate and alkali is raw material, with water and organic solvent as mixed solvent, directly react after mixing and obtain product, concrete steps are: add 4-trifluoro-methoxyaniline, sodium hydroxide, tetrahydrofuran (THF) and water successively in container, mix the back and react 2h under 0 ℃ of-50 ℃ of temperature condition; Rise to stirring at room then 30 minutes, and slowly added methyl-chloroformate, and stirring reaction 6-7h at room temperature; After finishing, reaction is cooled to 0 ℃, stirring reaction 30 minutes; The suction filtration solid is after washing, drying obtains target product.
The mol ratio of described 4-trifluoro-methoxyaniline and methyl-chloroformate is 1:1-5.
Described alkali is sodium hydroxide, yellow soda ash, salt of wormwood or lime carbonate, and the consumption of alkali is 2-3 a times of 4-trifluoro-methoxyaniline quality.
Described organic solvent is tetrahydrofuran (THF), dioxane, DMF or ketone.
The amount ratio of organic solvent and water is 1:1-10 in the described mixed solvent.
The consumption of described mixed solvent is 10-20 a times of 4-trifluoro-methoxyaniline quality.
The drop rate of described methyl-chloroformate is 10 seconds/.
Synthetic route of the present invention is as follows:
Advantage of the present invention is: the preparation method is simple and practical, the efficient height, and the yield of final product is more than 95%; The reagent toxicity that adopts in the building-up process is low, economy is high and side reaction is few, little to equipment corrosion, environmental pollution is little; Because cost of material is cheap, production cost is reduced, therefore good economy performance has a good application prospect.
Embodiment
Embodiment 1:
To 150 mL four-hole boiling flasks of backflow and gas absorbing device be housed, add 4-trifluoro-methoxyaniline 13.28g (0.075 mo1), sodium hydroxide 6g (0.15 mo1), tetrahydrofuran (THF) 10ml and water 100ml successively, mixing the back is to react 2h under the 15-20 ℃ of condition in temperature; Rose to stirring at room then 30 minutes, and slowly dripped methyl-chloroformate 10ml with the 10 seconds/speed of dripping, and stirring reaction 6h at room temperature; After finishing, reaction is cooled to 0 ℃, stirring reaction 30 minutes; The suction filtration solid is after washing, drying obtains target product 4-Trifluoromethoxyphen-l-Urethylane 16-18g, transformation efficiency: 95%-99%
1HNMR (400MHz, CDCl
3): δ (ppm) 3.67 (s, 3H, CH
3), 8.0 (t, 1H, NH), 6.75 (d, 2H, ArH) .7.53 (d, 2H, ArH).
Embodiment 2:
To 150 mL four-hole boiling flasks of backflow and gas absorbing device be housed, add 4-trifluoro-methoxyaniline 13.28g (0.075 mo1), yellow soda ash 15.9g (0.15 mo1), dioxane 10ml and water 100ml successively, mixing the back is to react 2h under the 10-15 ℃ of condition in temperature; Rose to stirring at room then 30 minutes, and slowly dripped methyl-chloroformate 10ml with the 10 seconds/speed of dripping, and stirring reaction 7h at room temperature; After finishing, reaction is cooled to 0 ℃, stirring reaction 30 minutes; The suction filtration solid obtains product summary product 4-Trifluoromethoxyphen-l-Urethylane 16.5-18g, transformation efficiency: 95%-99% through washing, drying
1HNMR (400 MHz, CDCl
3): δ (ppm) 3.67 (s, 3H, CH
3), 8.0 (t, 1H, NH), 6.75 (d, 2H, ArH). 7.53 (d, 2H, ArH).
Claims (7)
1. the synthetic method of a 4-Trifluoromethoxyphen-l-Urethylane, it is characterized in that: with 4-trifluoro-methoxyaniline, methyl-chloroformate and alkali is raw material, with water and organic solvent as mixed solvent, directly react after mixing and obtain product, concrete steps are: add 4-trifluoro-methoxyaniline, sodium hydroxide, tetrahydrofuran (THF) and water successively in container, mix the back and react 2h under 0 ℃ of-50 ℃ of temperature condition; Rise to stirring at room then 30 minutes, and slowly added methyl-chloroformate, and stirring reaction 6-7h at room temperature; After finishing, reaction is cooled to 0 ℃, stirring reaction 30 minutes; The suction filtration solid is after washing, drying obtains target product.
2. according to the synthetic method of the described 4-Trifluoromethoxyphen-l-Urethylane of claim 1, it is characterized in that: the mol ratio of described 4-trifluoro-methoxyaniline and methyl-chloroformate is 1:1-5.
3. according to the synthetic method of the described 4-Trifluoromethoxyphen-l-Urethylane of claim 1, it is characterized in that: described alkali is sodium hydroxide, yellow soda ash, salt of wormwood or lime carbonate, and the consumption of alkali is 2-3 a times of 4-trifluoro-methoxyaniline quality.
4. according to the synthetic method of the described 4-Trifluoromethoxyphen-l-Urethylane of claim 1, it is characterized in that: described organic solvent is tetrahydrofuran (THF), dioxane, DMF or ketone.
5. according to the synthetic method of the described 4-Trifluoromethoxyphen-l-Urethylane of claim 1, it is characterized in that: the amount ratio of organic solvent and water is 1:1-10 in the described mixed solvent.
6. according to the synthetic method of the described 4-Trifluoromethoxyphen-l-Urethylane of claim 1, it is characterized in that: the consumption of described mixed solvent is 10-20 a times of 4-trifluoro-methoxyaniline quality.
7. according to the synthetic method of the described 4-Trifluoromethoxyphen-l-Urethylane of claim 1, it is characterized in that: the drop rate of described methyl-chloroformate is 10 seconds/.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103073457A (en) * | 2013-02-05 | 2013-05-01 | 上海化工研究院 | Synthetic method for carbaryl-(methyl-D3) |
| CN103910653A (en) * | 2014-04-04 | 2014-07-09 | 京博农化科技股份有限公司 | Preparation method of chlorocarbonyl[4-(trifluoromethoxy)phenyl]methyl carbamate |
| CN103936630A (en) * | 2014-04-04 | 2014-07-23 | 京博农化科技股份有限公司 | Method for preparing chlorocarbonyl[4-(trifluoromethoxy)phenyl] methyl carbamate |
| CN109704994A (en) * | 2018-12-26 | 2019-05-03 | 山东华阳农药化工集团有限公司 | A kind of improved method synthesizing indoxacarb intermediate chloroformyl [4- (trifluoromethoxy) phenyl] methyl carbamate |
| CN112479934A (en) * | 2020-12-09 | 2021-03-12 | 安徽广信农化股份有限公司 | Synthesis method of methyl amino chloroformate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101774951A (en) * | 2010-01-29 | 2010-07-14 | 南开大学 | Metaflumizone synthesis method |
-
2011
- 2011-04-29 CN CN201110109685XA patent/CN102219712A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101774951A (en) * | 2010-01-29 | 2010-07-14 | 南开大学 | Metaflumizone synthesis method |
Non-Patent Citations (1)
| Title |
|---|
| ZHANG, J. F.: "A novel method to prepare methyl (4-trifluoromethoxy)phenylcarbamate and its analogues under mild conditions", 《JOURNAL OF PESTICIDE SCIENCE》, vol. 36, no. 2, 1 April 2011 (2011-04-01), pages 252 - 254 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103073457A (en) * | 2013-02-05 | 2013-05-01 | 上海化工研究院 | Synthetic method for carbaryl-(methyl-D3) |
| CN103910653A (en) * | 2014-04-04 | 2014-07-09 | 京博农化科技股份有限公司 | Preparation method of chlorocarbonyl[4-(trifluoromethoxy)phenyl]methyl carbamate |
| CN103936630A (en) * | 2014-04-04 | 2014-07-23 | 京博农化科技股份有限公司 | Method for preparing chlorocarbonyl[4-(trifluoromethoxy)phenyl] methyl carbamate |
| CN103936630B (en) * | 2014-04-04 | 2015-10-07 | 京博农化科技股份有限公司 | The preparation method of chloroformyl [4-(trifluoromethoxy) phenyl] Urethylane |
| CN103910653B (en) * | 2014-04-04 | 2016-05-25 | 京博农化科技股份有限公司 | The preparation method of chlorocarbonyl [4-(trifluoromethoxy) phenyl] methyl carbamate |
| CN109704994A (en) * | 2018-12-26 | 2019-05-03 | 山东华阳农药化工集团有限公司 | A kind of improved method synthesizing indoxacarb intermediate chloroformyl [4- (trifluoromethoxy) phenyl] methyl carbamate |
| CN112479934A (en) * | 2020-12-09 | 2021-03-12 | 安徽广信农化股份有限公司 | Synthesis method of methyl amino chloroformate |
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Application publication date: 20111019 |