CN109704960A - A kind of synthetic method of m-trifluoromethylbenzoic acid methyl esters - Google Patents
A kind of synthetic method of m-trifluoromethylbenzoic acid methyl esters Download PDFInfo
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- CN109704960A CN109704960A CN201811627568.0A CN201811627568A CN109704960A CN 109704960 A CN109704960 A CN 109704960A CN 201811627568 A CN201811627568 A CN 201811627568A CN 109704960 A CN109704960 A CN 109704960A
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- methyl esters
- trifluoromethylbenzoic acid
- acid methyl
- synthetic method
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention belongs to the synthesis technical field of pesticide intermediate, specially a kind of synthetic method of m-trifluoromethylbenzoic acid methyl esters, which is a kind of important intermediate of synthetic pesticide metaflumizone.It is reacted using m-trifluoromethylbenzoic acid with methanol esterification, prepare m-trifluoromethylbenzoic acid methyl esters, use new catalyst-cation acidic resins that the concentrated sulfuric acid is replaced to carry out esterification for catalyst, on the one hand the cationic acidic resins that reaction is completed to filter out directly can continuously apply 20 batches, 20 batch rear catalysts can continue to use after being regenerated, and substantially reduce cost；On the other hand it after replacing the concentrated sulfuric acid with cationic acidic resins, avoids and generates a large amount of acid waste water, there is important environmental benefit.
Description
Technical field
The invention belongs to chemosynthesis technical fields, are related to a kind of synthetic technology of pesticide intermediate, specially an inter-species
The synthetic method of trifluoromethyl benzoic acid methyl ester, the compound are a kind of important intermediates of synthetic pesticide metaflumizone.
Background technique
Metaflumizone is a kind of efficient, less toxic, low-residual insecticide, and m-trifluoromethylbenzoic acid methyl esters is synthesis cyanogen
The process route of the important intermediate of fluorine worm hydrazone, nearly all synthesis metaflumizone requires m-trifluoromethylbenzoic acid first first
Ketone compounds are made in ester, then by obtaining metaflumizone at hydrazone reaction.Trifluoromethyl benzoic acid methyl ester sterling is colourless
Prescribed liquid.
By m-trifluoromethylbenzoic acid Lipase absobed m-trifluoromethylbenzoic acid methyl esters, in previous synthesis technology, often
Catalyst is made using the concentrated sulfuric acid, reaction is general relatively acutely, risk with higher, and can generate a large amount of spent acidic in reaction
Water pollutes environment.If being used for industrialized production, there is very strong corrosivity to equipment.
Summary of the invention:
In view of the above problems, the present invention provides a green, environmental protection, the conjunctions of efficient m-trifluoromethylbenzoic acid methyl esters
At route, use cationic acidic resins that the concentrated sulfuric acid is replaced to carry out esterification for catalyst in process, reaction condition is mild,
The three wastes are few, and catalyst can continuous recycled 20 batches, save the cost.Furthermore use with the immiscible organic solvent of water into
Row reaction realizes that side border ring takes the water that reaction generates out of, improves reaction conversion ratio and yield, has significant economy and ring
Protect benefit.
To achieve the above object, technical scheme is as follows:
A kind of synthetic method of m-trifluoromethylbenzoic acid methyl esters, using m-trifluoromethylbenzoic acid and methanol as raw material, with
Cationic acidic resins are catalyst, and esterification obtains m-trifluoromethylbenzoic acid methyl esters, and specific reaction route is as follows:
The structural formula of the cation acidic resins is as follows:
Specific synthetic method are as follows: m-trifluoromethylbenzoic acid is added into reactor, after being dissolved with organic solvent, was added
The methanol of amount is added catalyst stirring, is warming up to back flow reaction, and in time takes the water that system generates out of, drops after the reaction was completed
Temperature filters out catalyst, and reaction material liquid negative pressure steams organic solvent, after solvent steams only, continues negative pressure and steams product m-trifluoromethyl
Methyl benzoate, 99% or more content, 95% or more yield.
Preferably, organic solvent used is one of 1,2- dichloroethanes, hexamethylene, hexane.Present invention use with
The immiscible organic solvent of water such as 1,2- dichloroethanes, hexamethylene, hexane etc. make reaction dissolvent, realize and incite somebody to action in back flow reaction
The water that reaction generates is taken out of, carries out so that reacting to forward direction, the conversion ratio of reaction is improved, to improve yield.
Preferably, reaction temperature is 50-90 DEG C.
Preferably, the mass ratio of the m-trifluoromethylbenzoic acid and organic solvent is 1:3-1:8.
Preferably, the molar ratio of the m-trifluoromethylbenzoic acid and methanol is 1:1-1:3.
Preferably, the mass ratio of the m-trifluoromethylbenzoic acid and catalyst is 1:5%-1:10%.
Beneficial effect
In synthetic method of the present invention, new catalyst-cation acidic resins is used to replace the concentrated sulfuric acid for catalysis
Agent carries out esterification, and on the one hand the cationic acidic resins that filter out are completed in reaction directly can continuously apply 20 batches, and 20
Batch rear catalyst can continue to use after being regenerated, and substantially reduce cost；On the other hand it is replaced with cationic acidic resins
It after the concentrated sulfuric acid, avoids and generates a large amount of acid waste water, there is important environmental benefit.
Synthetic method of the present invention, using with the immiscible organic solvent of water such as 1,2- dichloroethanes, hexamethylene, oneself
Alkane etc. makees reaction dissolvent, realizes and takes the water that reaction generates out of in back flow reaction, promotes reaction and carries out to forward direction, significantly
The conversion ratio of reaction is improved, to improve yield, is a green, environmental protection, efficient technology path, there is application well
Prospect.
Specific embodiment
Embodiment 1
A kind of synthetic method of m-trifluoromethylbenzoic acid methyl esters, specific reaction route are as follows:
The structural formula of the cation acidic resins is as follows:
Specific synthetic method are as follows: m-trifluoromethylbenzoic acid 38.8g (0.2mol) is added into reactor, with 155g 1,
After the dissolution of 2- dichloroethanes, 13g methanol is added, the stirring of 2g cation acid resin catalyst is added, is warming up to back flow reaction, and
The water that system generates is taken out of in time.Cooling filters out catalyst after the reaction was completed, and reaction material liquid negative pressure steams organic solvent, molten
After agent is steamed only, continues negative pressure and steam colorless and transparent product m-trifluoromethylbenzoic acid methyl esters, content 99%, yield 95.5%.
Embodiment 2
A kind of synthetic method of m-trifluoromethylbenzoic acid methyl esters, specific reaction route are as follows:
The structural formula of the cation acidic resins is as follows:
Specific synthetic method are as follows: m-trifluoromethylbenzoic acid 38.8g (0.2mol) is added into reactor, with 170g hexamethylene
After alkane dissolution, 15g methanol is added, the stirring of 4g cation acid resin catalyst is added, is warming up to back flow reaction, and in time by body
The water that system generates is taken out of.Cooling filters out catalyst after the reaction was completed, and reaction material liquid negative pressure steams organic solvent, and solvent steams net
Afterwards, continue negative pressure and steam colorless and transparent product m-trifluoromethylbenzoic acid methyl esters, content 99.6%, yield 95.8%.
Embodiment 3
A kind of synthetic method of m-trifluoromethylbenzoic acid methyl esters, specific synthetic method are as follows: three between being added into reactor
18g methanol is added after the dissolution of 210g hexane in methyl fluoride benzoic acid 38.8g (0.2mol), and 3g cation acidic resins are added and urge
Agent stirring, is warming up to back flow reaction, and in time takes the water that system generates out of.Cooling filters out catalyst after the reaction was completed,
Reaction material liquid negative pressure steams organic solvent, after solvent steams only, continues negative pressure and steams colorless and transparent product m-trifluoromethylbenzoic acid
Methyl esters, content 99.2%, yield 95.2%.
The structural formula of the cation acidic resins is as follows:
Claims (8)
1. a kind of synthetic method of m-trifluoromethylbenzoic acid methyl esters, which is characterized in that with m-trifluoromethylbenzoic acid and methanol
For raw material, using cationic acidic resins as catalyst, esterification obtains m-trifluoromethylbenzoic acid methyl esters, specific reaction route
It is as follows:
The structural formula of the cation acidic resins is as follows:
2. the synthetic method of m-trifluoromethylbenzoic acid methyl esters as described in claim 1, which is characterized in that specific synthetic method
Are as follows: m-trifluoromethylbenzoic acid is added into reactor, after being dissolved with organic solvent, excessive methanol is added, catalyst is added
Stirring, is warming up to back flow reaction, and cooling filters out catalyst after the reaction was completed, and reaction material liquid negative pressure steams organic solvent, solvent
After steaming only, continues negative pressure and steam product m-trifluoromethylbenzoic acid methyl esters.
3. the synthetic method of m-trifluoromethylbenzoic acid methyl esters as claimed in claim 2, which is characterized in that organic solvent used is
One of 1,2- dichloroethanes, hexamethylene, hexane.
4. the synthetic method of m-trifluoromethylbenzoic acid methyl esters as claimed in claim 2, which is characterized in that reaction temperature 50-
90℃。
5. the synthetic method of m-trifluoromethylbenzoic acid methyl esters as claimed in claim 2, which is characterized in that the m-trifluoromethyl
The mass ratio of benzoic acid and organic solvent is 1:3-1:8.
6. the synthetic method of m-trifluoromethylbenzoic acid methyl esters as claimed in claim 2, which is characterized in that the m-trifluoromethyl
The molar ratio of benzoic acid and methanol is 1:1-1:3.
7. the synthetic method of m-trifluoromethylbenzoic acid methyl esters as claimed in claim 2, which is characterized in that the m-trifluoromethyl
The mass ratio of benzoic acid and catalyst is 1:5%-1:10%.
8. the synthetic method of m-trifluoromethylbenzoic acid methyl esters as claimed in claim 2, which is characterized in that trifluoro between the product
99% or more the content of methyl toluate, 95% or more yield.
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| CN201811627568.0A CN109704960A (en) | 2018-12-28 | 2018-12-28 | A kind of synthetic method of m-trifluoromethylbenzoic acid methyl esters |
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| US6017768A (en) * | 1994-05-06 | 2000-01-25 | Pharmacopeia, Inc. | Combinatorial dihydrobenzopyran library |
| CN102351704A (en) * | 2011-08-25 | 2012-02-15 | 浙江巍华化工有限公司 | Method for synthesizing methyl 3-(trifluoromethyl)benzoate |
| CN103265538A (en) * | 2013-02-19 | 2013-08-28 | 中国人民解放军南京军区南京总医院 | Azole antifungal compound and preparation method and application thereof |
| CN103739604A (en) * | 2012-11-12 | 2014-04-23 | 国药一心制药有限公司 | Preparation method of Pralatrexate suitable for industrial large scale production |
| CN106957242A (en) * | 2017-04-24 | 2017-07-18 | 四川省人民医院 | A kind of schiff base compounds and preparation method thereof and pharmaceutical applications |
| CN107311868A (en) * | 2017-06-23 | 2017-11-03 | 北京理工大学 | A kind of method for preparing p-tert-butyl benzoic acid methyl esters |
-
2018
- 2018-12-28 CN CN201811627568.0A patent/CN109704960A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6017768A (en) * | 1994-05-06 | 2000-01-25 | Pharmacopeia, Inc. | Combinatorial dihydrobenzopyran library |
| CN102351704A (en) * | 2011-08-25 | 2012-02-15 | 浙江巍华化工有限公司 | Method for synthesizing methyl 3-(trifluoromethyl)benzoate |
| CN103739604A (en) * | 2012-11-12 | 2014-04-23 | 国药一心制药有限公司 | Preparation method of Pralatrexate suitable for industrial large scale production |
| CN103265538A (en) * | 2013-02-19 | 2013-08-28 | 中国人民解放军南京军区南京总医院 | Azole antifungal compound and preparation method and application thereof |
| CN106957242A (en) * | 2017-04-24 | 2017-07-18 | 四川省人民医院 | A kind of schiff base compounds and preparation method thereof and pharmaceutical applications |
| CN107311868A (en) * | 2017-06-23 | 2017-11-03 | 北京理工大学 | A kind of method for preparing p-tert-butyl benzoic acid methyl esters |
Non-Patent Citations (4)
| Title |
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| 上海市棉纺公司供销科主编: "《芳纺织实用物质手册》", 31 December 1984 * |
| 文瑞明等: "强酸性阳离子交换树脂催化合成乳酸异戊酯", 《湖南化工》 * |
| 胡济宁主编: "《合成C5-9混合脂肪酸制塑料增塑剂》", 31 December 1981, 轻工业出版社 * |
| 赵丹主编: "《钢铁表面化学镀镍技术》", 31 July 2017, 冶金工业出版社 * |
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Application publication date: 20190503 |