Bactericidal agent intermediate (E)-2-(2'-bromomethyl)phenyl-3-methoxylacrylate preparation method

A technology of methyl methoxyacrylate and o-methylphenylacetic acid, which is applied in the field of preparation of formula intermediates, can solve the problems of low reaction yield, difficult market source of isochromanone, and high price

Inactive Publication Date: 2009-03-11
JIANGSU GENGYUN CHEM CO LTD
View PDF12 Cites 15 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Patent WO95 / 25729 teaches a method for the preparation of compound (E)-2-(2'-chloromethyl)phenyl-3-methoxymethyl acrylate of a formula (I) intermediate, which method uses isobenzene Dihydropyrone is the starting raw material, and the market source of isochromanone is difficult, the price is expensive, and the reaction yield of each step described is relatively low

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
  • Bactericidal agent intermediate (E)-2-(2'-bromomethyl)phenyl-3-methoxylacrylate preparation method
  • Bactericidal agent intermediate (E)-2-(2'-bromomethyl)phenyl-3-methoxylacrylate preparation method
  • Bactericidal agent intermediate (E)-2-(2'-bromomethyl)phenyl-3-methoxylacrylate preparation method

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0027] Embodiment 1, the preparation method of agricultural fungicide chemical intermediate (E)-2-(2'-bromomethyl)phenyl-3-methoxymethyl acrylate, with reference to Fig. 1:

[0028] step 1)

[0029] Preparation of methyl o-tolyl acetate

[0030] Add 151.7g (1.0mol, 99%) o-methylphenylacetic acid into a 1000ml reaction bottle, add 500ml methanol to dissolve under stirring, add 25ml concentrated sulfuric acid, heat and reflux for 6-12 hours, evaporate the solvent under reduced pressure after cooling, and distill The product was extracted with toluene, washed with water three times, dried with anhydrous magnesium sulfate, the solvent was evaporated under reduced pressure, and the product was evaporated under reduced pressure to obtain 162.1g, a colorless liquid with a content of 99.3% and a yield of 98%.

[0031] 1 H-NMR (CDCl 3 , TMS) δ: 7.21-7.01 (m, 4H), 3.61 (s, 3H), 3.60 (s, 2H), 2.35 (s, 3H); MS (m / e): 164 (M + , 42), 133(100), 31(82).

[0032] Step 2)

[0033] Prepar...

Embodiment 2

[0050] Embodiment 2 is basically the same as Embodiment 1, but step 4 wherein is changed to:

[0051] Preparation of (E)-2-(2'-chloromethyl)phenyl-3-methoxymethyl acrylate

[0052] 21g (0.1mol, 98%) 2-(2'-methyl) phenyl-3-methoxymethyl acrylate, 0.42g (2.5mmol, 99%) AIBN and 60ml benzene drop into 100ml reaction bottle, heat up 80 ℃, slowly feed chlorine gas, and follow up analysis by gas chromatography. After 2 hours, the chlorine feed is completed. The solvent is distilled off on a rotary evaporator, purified by a chromatographic column, and eluted with n-hexane / ethyl acetate = 4 / 1 to obtain 18.25 g(E)-2-(2'-chloromethyl)phenyl-3-methoxymethyl acrylate, a light yellow colloid.

[0053] 1 H-NMR (CDCl 3 , TMS) δ: 7.61 (s, 1H), 7.5-7.0 (m, 4H), 4.49 (s, 2H), 3.80 (s, 3H), 3.69 (s, 3H);

[0054] MS(m / e): 240(M + , 10), 210(12), 196(21), 149(38), 129(100).

Embodiment 3

[0055] Embodiment 3 is basically the same as Embodiment 1, but has the following changes:

[0056] The catalyst of step 1) is changed into: p-toluenesulfonic acid;

[0057] Add 151.7g (1.0mol, 99%) of o-toluene acetic acid to a 1000ml reaction flask, add 500ml of methanol to dissolve under stirring, add 26.4g (0.15mol, 98%) of p-toluenesulfonic acid, heat and reflux for 6-12 hours, After cooling, the solvent was evaporated under reduced pressure, the residue was extracted with toluene, washed with water three times, dried with anhydrous magnesium sulfate, the solvent was evaporated under reduced pressure, and the product was evaporated under reduced pressure to obtain 159.9 g, the content was 99.6%, and the yield was 97%. %, colorless liquid,

[0058] The alkali of step 2) is changed into sodium methylate; Alkyl formate is changed into: ethyl formate;

[0059] 600ml of toluene, 216g (2.0mol, 50%) sodium methoxide, 82.7g (0.5mol, 99.3%) of methyl o-toluene acetate were put in...

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

PropertyMeasurementUnit
melting pointaaaaaaaaaa
Login to view more

Abstract

The invention provides a method for preparing intermediate compound (E)-2-(2'-bromomethyl) phenyl-3-methoxy methyl acrylate of bactericide. The method comprises the following steps: 1) in the presence of a catalyst, o-tolyl-acetic acid reacts with methanol, and the catalyst is selected from sulfuric acid or paratoluenesulfonic acid; 2) in the presence of alkali, the product of step 1) reacts with alkyl formate; 3) in the presence of alkali, the product of step 2) reacts with methylating reagent; 4) in the presence of catalyst, the product of step 3) reacts with halogen, wherein the dosage of the halogen is between 1.0 and 1.5 mol against that of the product of step 3), and the obtained product is recrystallized in solvent methanol to obtain a pure compound, the catalyst is selected from azodiisobutyronitrile or dibenzoyl peroxide, and the solvent is selected from benzene, carbon tetrachloride or cyclohexane. The method avoids using expensive solvent, or methyl chloride gas which has higher toxicity and influences the atmospheric ozone layer as the methylating reagent, thereby meeting the requirement of environmental protection.

Description

technical field [0001] The present invention relates to a kind of preparation method of formula (I) intermediate, be specifically related to a kind of compound (E)-2-(2'- The preparation method of methyl bromomethyl) phenyl-3-methoxyacrylate. Background technique [0002] Methoxyacrylates are widely used agricultural fungicides, such as patents CN1030749, CN1201657, CN1646472, WO90 / 07493, WO92 / 18494, EP-178826, EP-370629, EP-414153, EP-460575 or WO94 / 08968 known compounds. (E)-2-(2'-chloromethyl)phenyl-3-methoxymethyl acrylate is generally used as an intermediate in the production of this agent. Patent WO95 / 25729 teaches a method for the preparation of compound (E)-2-(2'-chloromethyl)phenyl-3-methoxymethyl acrylate of a formula (I) intermediate, which method uses isobenzene Dihydropyrone is the starting raw material, and the market source of isochromanone is difficult, the price is expensive, and the reaction yield of each step is relatively low. [0003] The method rep...

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 Applications(China)
IPC IPC(8): C07C69/734C07C67/08C07C67/343
Inventor 于康平李泽方赵金鹏罗志会
Owner JIANGSU GENGYUN CHEM CO LTD
Who we serve
  • R&D Engineer
  • R&D Manager
  • IP Professional
Why Eureka
  • Industry Leading Data Capabilities
  • Powerful AI technology
  • Patent DNA Extraction
Social media
Try Eureka
PatSnap group products

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

© 2024 PatSnap. All rights reserved.Legal|Privacy policy|Modern Slavery Act Transparency Statement|Sitemap