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Preparation for alpha, beta-di-hydroxyl carboxylic ether compound

A bishydroxycarboxylate and compound technology, applied in the field of organic synthesis, can solve problems such as heavy metal rhodium cannot be recycled, environmental pollution, etc., and achieve the effects of broad prospects for industrial production, short process routes, and mild reaction conditions

Inactive Publication Date: 2008-10-01
EAST CHINA NORMAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, this method also has disadvantages
First of all, the three-component product constructed by this reaction needs to undergo Pd / C hydrogenation reaction to catalyze the hydrogenolysis of benzyl or alkyl, and then obtain α, β-dihydroxycarboxylate compounds; secondly, heavy metal rhodium cannot be recovered, and The use of volatile dichloromethane as a reaction solvent has caused pollution to the environment

Method used

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  • Preparation for alpha, beta-di-hydroxyl carboxylic ether compound
  • Preparation for alpha, beta-di-hydroxyl carboxylic ether compound
  • Preparation for alpha, beta-di-hydroxyl carboxylic ether compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025] Take a 25mL two-necked bottle, add p-nitrobenzaldehyde 0.1511g (1mmol) and 0.01mmol of Rh 2 (OAc) 4 . Subsequently, 5 mL of the above-prepared ionic liquid [bmim]PF was added 6 , stir well, and after the substrate is completely dissolved, add 3 mL of water. Continue to stir and heat to 60°C. Dissolve 0.352 g (2 mmol) of methyl diazophenylacetate in 3 mL of the above-mentioned ionic liquid, and add it dropwise to the system through a sample injector, and the sample injection is completed in 3 hours. Continue to react for 3h, stop the reaction. Separate the aqueous phase, extract the ionic liquid five times with 50 mL of ether, concentrate the extraction solution, and use ethyl acetate / petroleum ether=1 / 5 as the developing agent to separate the product through a column to obtain the product 2,3-dihydroxy-3-(4 -Nitrophenyl)-2-phenylpropionic acid methyl ester, 0.2379 g of α, β-dihydroxycarboxylate compound, yield 75%.

Embodiment 2

[0027] Take a 25mL two-necked bottle, add m-nitrobenzaldehyde 0.1512g (1mmol) and 0.02mmol of Rh 2 (OAc) 4 . Subsequently, 10 mL of the above-prepared ionic liquid [bmim]PF was added 6 , stir well, and after the substrate is completely dissolved, add 1 mL of water. Continue to stir and react at room temperature at 25°C. Dissolve 0.264 g (1.5 mmol) of methyl diazophenylacetate in 4 mL of the above-mentioned ionic liquid, and add it dropwise to the system through a sample injector, and the sample injection is completed in 3 hours. Continue to react for 2h, stop the reaction. Separate the aqueous phase, extract the ionic liquid five times with 50 mL of ether, concentrate the extraction solution, and use ethyl acetate / petroleum ether=1 / 5 as the developing agent to separate the product through a column to obtain the product 2,3-dihydroxy-3-(3 -Nitrophenyl)-2-phenylpropionic acid methyl ester, 0.2220 g of α, β-dihydroxycarboxylate compound, yield 70%.

Embodiment 3

[0029] Take a 25mL two-necked bottle, add o-nitrobenzaldehyde 0.1512g (1mmol) and 0.05mmol of Rh 2 (OAc) 4 . Subsequently, 5 mL of the above-prepared ionic liquid [bmim]PF was added 6, stir well, and after the substrate is completely dissolved, add 2 mL of water. Continue to stir and heat to 60°C. Dissolve 0.317 g (1.8 mmol) of methyl diazophenylacetate in 3 mL of the above-mentioned ionic liquid, and add it dropwise to the system through a sample injector, and the sample injection is completed in 3 hours. Continue to react for 5h, stop the reaction. Separate the aqueous phase, extract the ionic liquid five times with 50 mL of ether, concentrate the extraction solution, and use ethyl acetate / petroleum ether=1 / 5 as the developing agent to separate the product through a column to obtain the product 2,3-dihydroxy-3-(2 -Nitrophenyl)-2-phenylpropionic acid methyl ester, 0.1681 g of α, β-dihydroxycarboxylate compound, yield 53%.

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Abstract

The invention relates to a method for preparing the compound of Alpha, Beta-di-hydroxyl carboxylic ester. Ionic liquid [bmim] PF6 and water are used to form two phase reaction media; phenyl diazotate or EDA reacts with water to form hydroxyl oxy ylide under the catalysis of a catalyst rhodium acetate and then aldehyde which withdraws electrons is applied to catching the active intermediate, thereby constructing the compounds of the target product of formula (I) and (II), namely, the compound of the Alpha, Beta-di-hydroxyl carboxylic ester. The method of the invention adopts raw materials which are cheap and easy to get and a 'one-pot' method to construct two chiral carbons at the same time, has short preparation line, simple operation, mild reaction conditions, a catalyst which can be recycled and reused for a plurality of times, low synthesis cost, no pollution to environment and comparatively good economic and social benefits and is conducive to industrial production. Ar1 in the formula is phenyl or phenyl with a substituent group and Ar2 is substituted phenyl with an electron withdrawing group.

Description

technical field [0001] The invention relates to a synthesis method for preparing α, β-dihydroxycarboxylate compound. The compound prepared by the method is green, environment-friendly and pollution-free, and has high yield, belonging to the technical field of organic synthesis. Background technique [0002] α, β-dihydroxy compounds, such as cyclic peptide compound TMC-95 series, widely exist in many natural products, it is an inhibitor of proteolytic enzymes, and it is a potential drug molecule. Therefore, how to construct α, β-dihydroxycarboxylate compounds is also one of the important research topics in organic synthesis methodology. The traditional method of constructing α, β-dihydroxycarboxylate compounds is to start from a substrate with a double bond, react with neutral or alkaline potassium permanganate, and generate it after hydrolysis. In this route, due to the strong oxidation of potassium permanganate, the reaction after generating α, β-dihydroxycarboxylate compo...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C205/56C07C201/12
CPCY02P20/584
Inventor 石洵予胡文浩杨琍苹邱林
Owner EAST CHINA NORMAL UNIV