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Method for preparing alpha,beta-unsaturated carboxylic ester by using phosphonium salt and alcohol

An unsaturated, carboxylate technology, which is applied in the preparation of carboxylate, chemical instruments and methods, and the preparation of organic compounds, can solve the problems of high price, difficult preparation and acquisition, reduced practicability and promotion potential, etc. Low price, good research and industrial application prospects, and the effect of reducing synthesis costs

Inactive Publication Date: 2014-05-21
WENZHOU UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, these transition metal catalysts are expensive and difficult to prepare and obtain, which greatly reduces the practicability and promotion potential of the reaction.

Method used

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  • Method for preparing alpha,beta-unsaturated carboxylic ester by using phosphonium salt and alcohol
  • Method for preparing alpha,beta-unsaturated carboxylic ester by using phosphonium salt and alcohol
  • Method for preparing alpha,beta-unsaturated carboxylic ester by using phosphonium salt and alcohol

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0026] Ethoxycarbonyl methylene triphenylphosphine chloride reacts with benzyl alcohol to prepare ethyl cinnamate, and the general reaction formula is as follows:

[0027]

[0028] Benzyl alcohol (0.1031 mL, 1 mmol), ethoxycarbonylmethylene triphenylphosphine chloride (0.5754 g, 1.5 mmol), CuI (0.01 g, 5 mol%), Bipy (0.008 g, 5 mol %), TEMPO ( 0.011g, 5mol%), KOH (0.1120g, 2mmol), and tetrahydropyrrole (0.0016mL, 5mol%) were sequentially added to a 100mL reaction tube, and 1mL of acetonitrile and 1mL of formamide were added as solvents. Reaction 24h. The product was separated and purified by column chromatography, and the separation yield was 96%. 1HNMR (500MHz, CDCl3): δ7.68(d, J=16.0Hz, 1H), 7.50-7.48(m, 2H), 7.35-7.34(m, 3H), 6.43(d, J=16.0Hz, 1H) ,4.25(q,J=7.5Hz,2H),1.31(t,J=7.5Hz,3H).13CNMR(125.4MHz,CDCl3):δ166.6,144.2,134.2,129.9,128.6,127.8,118.0,60.1,14.0 .MS(EI):m / z(%)176(32),148(16),147(14),132(11),131(100),104(13),103(44),102(10 ), 77(23), 51(9).

Embodiment 2

[0030] Ethoxycarbonyl methylene triphenylphosphine chloride reacts with p-methyl benzyl alcohol to prepare ethyl p-methyl cinnamate, and the general reaction formula is as follows:

[0031]

[0032] P-methylbenzyl alcohol (0.1220g, 1mmol), ethoxycarbonylmethylenetriphenylphosphine chloride (0.5754g, 1.5mmol), CuI (0.01g, 5mol%), Bipy (0.008g, 5mol%) , TEMPO (0.011g, 5mol%), KOH (0.1120g, 2mmol), and tetrahydropyrrole (0.0016mL, 5mol%) were sequentially added to a 100mL reaction tube, and 1mL of acetonitrile and 1mL of formamide were added as solvents. Under the condition of ℃, react for 24h. The product was separated and purified by column chromatography, and the separation yield was 93%. 1HNMR(500MHz, CDCl3): δ7.65(d, J=16.0Hz, 1H), 7.39(d, J=8.0Hz, 2H), 7.16(d, J=8.0Hz, 2H), 6.38(d, J =16.0Hz,1H),4.24(q,J=7.0Hz,2H),2.34(s,3H),1.32(t,J=7.0Hz,3H).13CNMR(125.4MHz,CDCl3):δ167.0,144.4, 140.4, 131.6, 129.4, 127.9, 117.0, 60.2, 21.2, 14.2. MS (EI): m / z (%) 190 (46), 162 (15),...

Embodiment 3

[0034] Ethoxycarbonyl methylene triphenylphosphine chloride reacts with p-nitrobenzyl alcohol to prepare ethyl p-nitrocinnamate, and the general reaction formula is as follows:

[0035]

[0036] P-nitrobenzyl alcohol (0.1540g, 1mmol), ethoxycarbonylmethylenetriphenylphosphine chloride (0.5754g, 1.5mmol), CuI (0.01g, 5mol%), Bipy (0.008g, 5mol%) , TEMPO (0.011g, 5mol%), KOH (0.1120g, 2mmol) tetrahydropyrrole (0.0016mL, 5mol%) were sequentially added to a 100mL reaction tube, 1mL acetonitrile and 1mL formamide were added as solvents, and the Under the condition of reaction 24h. The product was separated and purified by column chromatography, and the separation yield was 84%. 1HNMR (300MHz, CDCl3): δ8.25(d, J=8.7Hz, 2H), 7.74-7.66(m, 3H), 6.56(d, J=16.2Hz, 1H), 4.30(q, J=7.2Hz ,2H),1.36(t,J=7.2Hz,3H).13CNMR(125.4MHz,CDCl3):δ166.0,148.5,141.6,140.6,128.6,124.1,122.6,61.0,14.2.MS(EI):m / z (%)221(23),204(12),193(51),177(13),176(100),146(19),130(50),118(13),102(31),91( 12), 85(11...

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Abstract

The invention discloses a method for preparing an alpha,beta-unsaturated carboxylic ester by using a phosphonium salt and an alcohol. The method comprises the following steps: by taking copper salt-TEMPO (Tetramethyl-Piperidin-1-Oxyl) as a catalysis system, carrying out oxidization, proton removal and a Wittig reaction on the alcohol and the phosphonium salt under the condition of no need of nitrogen protection. A reaction formula is shown as the specification, the reaction temperature is 25-100 DEG C and the reaction time is 10-96 hours; the use amount of a Bipy ligand, namely dipyridyl, is recommended to be 1-20mol%; the use amount of copper salt is 1-20mol%; the use amount of TEMPO is 1-20mol%; and the mol ratio of the alcohol to a Wittig reaction reagent ranges from (3:1) to (1:3). According to the method for preparing the alpha,beta-unsaturated carboxylic ester by using the phosphonium salt and the alcohol, the price of a used non-transition metal element catalyst is low, the reaction condition is moderate and the operation is easy to carry out; a product is simple and easy to separate and purify and the recovery rate is high; and the synthesizing cost is greatly reduced and the requirements on reaction conditions are low.

Description

technical field [0001] The invention relates to a preparation method of α, β-unsaturated carboxylic acid ester, in particular to a method for preparing α, β-unsaturated carboxylic acid ester by using phosphonium salt and alcohol. Background technique [0002] As early as 1894, Michaelis and Gimborn produced the first Yelide Ph 3 P=CH-CO 2 C 2 h 5 , but it was not until 1953 that Wittig and Geissler used Ph 3 P=CH 2 The fact that it reacts with benzophenone to form 1,1-stilbene marks the birth of the Wittig reaction. So far, ylide chemistry has been deeply studied and widely used in mechano-synthesis. The Wittig reaction is currently one of the most effective methods for constructing carbon-carbon double bonds. This type of method has been widely used in the synthesis of some natural products, such as unsaturated fatty acids, prostaglandins, vitamins, and insect pheromones. The method of synthesizing vitamin A by Wittig reaction has been used in industrial production. ...

Claims

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Application Information

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IPC IPC(8): C07B37/04C07C69/618C07C69/65C07C69/734C07C67/343C07C205/56C07C201/12C07D213/55C07D333/24
Inventor 余小春胡鹃丁伟杰施震宇刘志青
Owner WENZHOU UNIVERSITY