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Synthesis method of 3-methoxy-2-aryl(methyl)acrylate compounds

A technique for the synthesis of aromatic methyl acrylate, which is applied in the preparation of organic compounds, chemical instruments and methods, and preparation of carboxylic acid esters. Amplified, easy-to-control, low-cost effects

Active Publication Date: 2011-07-06
DALIAN JOIN KING FINE CHEM CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Since the formylation reaction reacts under the action of strong alkali sodium hydrogen, there are many by-products and low yield, and the next step of methylation reaction must be carried out after the formylation product is purified, resulting in low overall yield and low cost. increased
On the other hand, due to the characteristics of sodium hydride, which is flammable in the air and sensitive to water vapor, there will be some safety hazards in the scale-up production

Method used

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  • Synthesis method of 3-methoxy-2-aryl(methyl)acrylate compounds

Examples

Experimental program
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Effect test

Embodiment 1

[0031] Preparation of (E)-methyl 3-methoxy-2{2-[6-(trifluoromethyl)-2-pyridyloxymethyl]phenyl}acrylate.

[0032] Under the protection of dry nitrogen, dichloromethane (350ml) and titanium tetrachloride (58.1g, 0.3mol) were successively added to the reaction flask, the temperature was lowered to 10°C, and trimethyl orthoformate (31.9 g, 0.3mol). After stirring at room temperature for 1 h, the reaction solution was cooled to 0° C., and methyl 2-[6-(trifluoromethyl)-2-pyridyloxymethyl]phenylacetate (97.6 g, 0.3 mol) was added dropwise. After stirring at room temperature for 2 h, the reaction solution was cooled to 5° C., and triethylamine (61.9 g, 0.6 mol) was added. After stirring at room temperature for 1 h, the reaction solution was cooled to 10° C., and 10% dilute hydrochloric acid (219.2 g, 0.6 mol) was added dropwise. After 10 min, add 200 mL of water to wash, separate the layers, and take the organic layer as the intermediate.

[0033] At room temperature, benzyltriethy...

Embodiment 2

[0035] Preparation of (E)-methyl 3-methoxy-2{2-[6-(trifluoromethyl)-2-pyridyloxymethyl]phenyl}acrylate.

[0036] Under the protection of dry nitrogen, 1,2-dichloroethane (350ml) and titanium tetrachloride (87.1g, 0.45mol) were successively added to the reaction flask, the temperature was lowered to 10°C, and orthoformic acid was added dropwise under vigorous stirring Trimethyl ester (47.8 g, 0.45 mol). After stirring at room temperature for 1 h, the reaction solution was cooled to 0° C., and methyl 2-[6-(trifluoromethyl)-2-pyridyloxymethyl]phenylacetate (97.6 g, 0.3 mol) was added dropwise. After stirring at room temperature for 2 h, the reaction solution was cooled to 5° C., and triethylamine (74.3 g, 0.72 mol) was added. After stirring at room temperature for 1 h, the reaction solution was cooled to 10° C., and 10% dilute hydrochloric acid (263 g, 0.72 mol) was added dropwise. After 10 min, add 200 mL of water to wash, separate the layers, and take the organic layer as the...

Embodiment 3～10

[0039] Preparation of (E)-methyl 3-methoxy-2{2-[6-(trifluoromethyl)-2-pyridyloxymethyl]phenyl}acrylate under different reaction conditions.

[0040] According to the method of Example 2, prepare (E)-3-methoxy-2{2-[6-(trifluoromethyl)-2-pyridyloxymethyl]phenyl} under the following different reaction reagent conditions Methyl acrylate, the results obtained are listed in Table 1:

[0041] Preparation of (E)-3-methoxy-2{2-[6-(trifluoromethyl)-2-pyridyloxymethyl]phenyl}methyl acrylate under different reaction reagent conditions in Table 1

[0042]

[0043] According to the method of Example 2, (E)-3-methoxy-2{2-[6-(trifluoromethyl)-2-pyridyloxymethyl]phenyl}acrylic acid was prepared at the following different reaction temperatures Methyl ester, the obtained results are listed in Table 2:

[0044] Preparation of (E)-3-methoxy-2{2-[6-(trifluoromethyl)-2-pyridyloxymethyl]phenyl}methyl acrylate at different reaction temperatures in Table 2

[0045]

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Abstract

The invention relates to a synthesis method of 3-methoxy-2-aryl(methyl)acrylate compounds, which comprises the following steps: by using phenylmethyl acetate with or without substituting groups as a raw material, carrying out formylation reaction at -20-100 DEG C for 4-6 hours in a nitrogen atmosphere in the presence of Lewis acid in an aprotic solvent neutralized formylation reagent, dissociating with an organic base, hydrolyzing with hydrochloric acid, and stratifying, wherein the organic layer is an intermediate; carrying out methylation reaction on the intermediate, benzyltriethylammonium chloride, a methylation reagent and an inorganic base at 20-100 DEG C for 1-3 hours; after the reaction finishes, washing with water, desolventizing, and recrystallizing or distilling while depressurizing to obtain the product. The invention has the advantages of fewer processing steps (the methylation reaction can be directly carried out without purifying and separating the intermediate product), favorable selectivity, higher yield and low cost; and the reaction process is easy to control, and is safe and easy to amplify.

Description

technical field [0001] The invention belongs to the technical field of synthesis methods of oxymethyl compounds with acrylate groups, halogen substituents, and aromatic or heterocyclic substituents in aromatic rings, and relates to a method for synthesizing 3-methoxy-2-aryl acrylate Compound preparation methods. Background technique [0002] Methoxyacrylate fungicides are a new type of agricultural fungicides with a unique mechanism of action, great development potential and good market prospects. The active group has (E)-β-methoxyacrylate methyl ester or similar units structure. [0003] The core technology for the synthesis of such products is methoxymethylation technology, that is, how to introduce a methoxymethylenyl (CH 3 OCH=) technology. [0004] The current conventional method (Pest Management Science 58: 649-662 (online: 2002)) is to first introduce a hydroxymethenyl group at the ortho position of the substrate carboxylate through sodium hydride and a formylating...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D213/643C07C69/734C07C67/31C07D241/18
Inventor 王荣良李雨王俊春李永路谭瑞淀
Owner DALIAN JOIN KING FINE CHEM CO LTD
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