Synthesis method of pirimicarb intermediate 2-methyl acetoacetate

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

Active Publication Date: 2020-11-27
TAIZHOU BAILLY CHEM CO LTD
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  • 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

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  • Synthesis method of pirimicarb intermediate 2-methyl acetoacetate
  • Synthesis method of pirimicarb intermediate 2-methyl acetoacetate
  • Synthesis method of pirimicarb intermediate 2-methyl acetoacetate

Examples

Experimental program
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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...

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Abstract

The invention relates to a synthesis method of a pirimicarb intermediate 2-methyl acetoacetate, comprising the following steps of: in the presence of tertiary amine and a polymerization inhibitor, carrying out an addition reaction on raw materials methyl acrylate and acetyl chloride to obtain 2-acetyl-methyl acrylate, and carrying out hydrogenation reduction to obtain the product 2-methyl acetoacetate. The synthetic method of the pirimicarb intermediate 2-methyl acetoacetate has the advantages of high yield, high purity and few byproducts.

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

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C69/716C07C67/303
CPCC07C67/303C07C67/343
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
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