Looking for breakthrough ideas for innovation challenges? Try Patsnap Eureka!

A kind of synthetic method of pirimicarb intermediate 2-methyl acetoacetate methyl ester

A technology of methyl acetoacetate and a synthesis method, which is applied in the synthesis field of pirimicarb intermediate 2-methyl acetoacetate, can solve the problems of low yield, side reactions and the like, and achieves high product yield , the effect of high purity

Active Publication Date: 2022-03-29
TAIZHOU BAILLY CHEM CO LTD
View PDF0 Cites 0 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0015] Although the above route avoids the generation of by-product 2,2-dimethylacetoacetate methyl ester, it also brings other side reactions. The more obvious side reactions are shown in Scheme 5, and the by-product 9 can reach up to 10% or so, resulting in a low yield, only about 70%

Method used

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
View more

Image

Smart Image Click on the blue labels to locate them in the text.
Viewing Examples
Smart Image
  • A kind of synthetic method of pirimicarb intermediate 2-methyl acetoacetate methyl ester
  • A kind of synthetic method of pirimicarb intermediate 2-methyl acetoacetate methyl ester
  • A kind of synthetic method of pirimicarb intermediate 2-methyl acetoacetate methyl ester

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0041] (1) Synthesis of methyl 2-acetyl acrylate:

[0042] Under nitrogen protection, add 10.0g methyl acrylate (98%, 114mmol), 10.0g acetyl chloride (98%, 125mmol), 40ml ether and 0.05g 4-methoxyl-phenol in a three-necked flask, add dropwise 12.92g under a water bath Triethylamine (98%, 125mmol), keep the reaction temperature at 20-25°C, keep it warm for 4 hours after the dropwise addition, add 40ml of water solution, wash the organic phase with 30ml of water three times, dry over anhydrous magnesium sulfate, and concentrate under vacuum to obtain 16.5g pale yellow liquid.

[0043] GC-MS(EI): 128.1, 1 H NMR: (400MHz, CDCl 3 ):ppmδH 5.80(s,1H), 5.77(s,1H), 3.75(s,3H) 2.30(s,3H).

[0044] (2) Synthesis of 2-methyl acetoacetate:

[0045] Dissolve 16.5g of the above product in 60ml of ethanol in a hydrogenation kettle, add 1.0g of 5% palladium-carbon catalyst (5g of metal palladium loaded on 95g of activated carbon), replace the air and feed hydrogen to 0.05MPa, and react at ...

Embodiment 2

[0048] (1) Synthesis of methyl 2-acetyl acrylate:

[0049] Under nitrogen protection, add 10.0g methyl acrylate (98%, 114mmol), 10.0g acetyl chloride (98%, 125mmol), 40ml methyl tert-butyl ether and 0.05g 2-tert-butyl-4-methane Base phenol, add 16.5g DIPEA (98%, 125mmol) dropwise in a water bath, keep the reaction temperature at 20-25°C, keep warm for 4 hours after the dropwise addition, add 40ml of water, wash the organic phase three times with 30ml of water, and dry over anhydrous magnesium sulfate , concentrated under reduced pressure in vacuo to obtain 16.8 g of light yellow liquid.

[0050] (2) Synthesis of 2-methyl acetoacetate:

[0051] Dissolve 16.8g of the above product in 60ml of ethanol in a hydrogenation kettle, add 1.0g of 5% palladium-carbon catalyst (5g of metal palladium supported on 95g of activated carbon), replace the air and feed hydrogen to 0.05MPa, and react at room temperature for 5 Hours, after the reaction was completed, the catalyst was removed by fil...

Embodiment 3

[0053] (1) Synthesis of methyl 2-acetyl acrylate:

[0054] Under nitrogen protection, add 10.0g methyl acrylate (98%, 114mmol), 10.0g acetyl chloride (98%, 125mmol), 30ml 2-methyltetrahydrofuran and 0.05g 2,6-di-tert-butyl-4 -Methyl phenol, add DABCO's 2-methyltetrahydrofuran solution (14.3g DABCO (98%, 125mmol), 20ml 2-methyltetrahydrofuran) dropwise under a water bath, keep the reaction temperature at 20-25°C, and keep the temperature for 4 40ml water solution was added, the organic phase was washed three times with 30ml water, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure in vacuo to obtain 16.7g light yellow liquid.

[0055] (2) Synthesis of 2-methyl acetoacetate:

[0056] Dissolve 16.7g of the above product in 60ml of ethanol in a hydrogenation kettle, add 1.0g of 5% palladium-carbon catalyst (5g of metal palladium supported on 95g of gac), replace the air and feed hydrogen to 0.05MPa, and react at room temperature for 5 Hours, after th...

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

PUM

No PUM Login to View More

Abstract

The invention relates to a synthesis method of pirimicarb intermediate 2-methyl acetoacetate, in which raw material methyl acrylate and acetyl chloride undergo addition reaction to obtain 2-acetyl-acrylic acid in the presence of a tertiary amine and a polymerization inhibitor Methyl ester, then hydrogenation reduction obtains product 2 methyl acetoacetate methyl ester. The synthesis method of the pirimicarb intermediate 2-methyl acetoacetate of the present invention has the advantages of high yield, high purity and few by-products.

Description

technical field [0001] The invention belongs to the technical field of synthesis of pesticides and insecticides, and in particular relates to a synthesis method of pirimicarb intermediate 2-methyl acetoacetate. Background technique [0002] Pirimicarb is a highly selective aphidicide, which can effectively control all aphids except cotton aphids, and is also effective for aphids resistant to organophosphate insecticides. It kills insects quickly, is safe to crops, and does not harm crops. Natural enemies are ideal agents for comprehensive control. [0003] The traditional synthetic method of pirimicarb is shown in Scheme 1: methyl acetoacetate (compound 1) and dimethyl sulfate undergo an alkylation reaction in the presence of a base to obtain the intermediate 2-methyl acetoacetate (compound 2), and then N,N-dimethylguanidine ring closure to obtain 2-N,N-dimethyl-4 hydroxyl-5,6-dimethylpyrimidine (compound 3), and finally N,N-di Condensation of methyl formyl chloride gives ...

Claims

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

Application Information

Patent Timeline
no application Login to View More
Patent Type & Authority Patents(China)
IPC IPC(8): C07C69/716C07C67/303
CPCC07C67/303C07C67/343C07C69/716C07C69/738
Inventor 汪静莉李新良朱信辉李大娟王大文焦德荣
Owner TAIZHOU BAILLY CHEM CO LTD
Who we serve
  • R&D Engineer
  • R&D Manager
  • IP Professional
Why Patsnap Eureka
  • Industry Leading Data Capabilities
  • Powerful AI technology
  • Patent DNA Extraction
Social media
Patsnap Eureka Blog
Learn More
PatSnap group products

Browse by: Latest US Patents, China's latest patents, Technical Efficacy Thesaurus, Application Domain, Technology Topic, Popular Technical Reports.

© 2024 PatSnap. All rights reserved.Legal|Privacy policy|Modern Slavery Act Transparency Statement|Sitemap|About US| Contact US: help@patsnap.com