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Alpha, beta-unsaturated carboxylic ester compound and preparation method thereof

An ester compound, unsaturated technology, applied in the field of unsaturated carboxylic acid ester compounds, can solve the problems of reduced practicality and promotion potential, difficult preparation of oxidants, high toxicity of oxidation systems, etc., and achieves good research and industrial application prospects , Reduce synthesis cost, easy product separation and purification

Inactive Publication Date: 2014-03-26
WENZHOU UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In the past ten years, chemists have successively reported the oxidation-Wittig series reaction of some alcohols and Wittig reagents to prepare alkenes. These methods have many disadvantages: 1. Some oxidants are themselves explosive, such as Dess-Martin high iodine oxidant; 2. .Oxidants are difficult to prepare, such as iodobenzene diacetate; 3. There are highly toxic, unstable, and difficult-to-handle reagents in the oxidation system, such as oxalyl chloride (COCl)2, 4. Or the by-products of the oxidation system have an odor, such as Sven Dimethyl sulfide, one of the by-products of oxidation reactions, has a well-known foul smell in organic chemistry
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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  • Alpha, beta-unsaturated carboxylic ester compound and preparation method thereof
  • Alpha, beta-unsaturated carboxylic ester compound and preparation method thereof
  • Alpha, beta-unsaturated carboxylic ester compound and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0026] Utilize ethyl (triphenylphosphine) acetate to react with benzyl alcohol to prepare ethyl cinnamate,

[0027]

[0028] 0.1031mL, 1mmol of benzyl alcohol, 0.5225g, 1.5mmol of ethyl (triphenylphosphine) acetate, 0.01g, 5mol% of CuI, 0.008g, 5mol% of Bipy, 0.011g, 5mol% of TEMPO , 0.0016mL, 5mol% tetrahydropyrrole were sequentially added to a 100mL reaction tube, 2mL of acetonitrile was added as a solvent, an air balloon was added to the reaction tube, and the reaction was carried out at 65°C for 24h. The product was separated and purified by column chromatography, and the separation yield was 98%. 1HNMR (300MHz, CDCl3): δ7.68(d, J=16.2Hz, 1H), 7.52-7.49(m, 2H), 7.37-7.35(m, 3H), 6.43(d, J=15.9Hz, 1H) ,4.26(q,J=7.2Hz,2H),1.33(t,J=7.2Hz,3H).13CNMR(125.4MHz,CDCl3):δ166.7,144.4,134.4,130.0,128.7,127.9,118.2,60.3,14.2 .MS(EI):m / z(%)176(20),148(19),147(17),132(10),131(100),104(19),103(64),102(15 ), 77(44), 51(20).

Embodiment 2

[0030] Ethyl (triphenylphosphine) acetate reacts with p-methylbenzyl alcohol to prepare ethyl p-methyl cinnamate:

[0031]

[0032] 0.1220g, 1mmol of p-methyl benzyl alcohol, 0.5225g, 1.5mmol of ethyl (triphenylphosphine) acetate, 0.01g, 5mol% of CuI, 0.008g, 5mol% of Bipy, 0.011g, Add 5mol% TEMPO, 0.0016mL, and 5mol% tetrahydropyrrole to a 100mL reaction tube in turn, add 2mL acetonitrile as a solvent, add an air balloon to the reaction tube, and react at 65°C for 24h. The product was separated and purified by column chromatography, and the separation yield was 66%. 1HNMR (500MHz, CDCl3): δ7.66(d, J=16.0Hz, 1H), 7.40(d, J=8.0Hz, 2H), 7.16(d, J=8.0Hz, 2H), 6.38(d, J =16.0Hz,1H),4.25(q,J=7.0Hz,2H),2.35(s,3H),1.32(t,J=7.0Hz,3H).13CNMR(125.4MHz,CDCl3):δ167.0,144.4, 140.4, 131.7, 129.5, 127.9, 117.1, 60.2, 21.3, 14.2. MS (EI): m / z (%) 190 (41), 162 (16), 146 (11), 145 (100), 118 (26 ), 117(41), 116(14), 115(43), 91(20).

Embodiment 3

[0034] Preparation of ethyl o-methoxycinnamate by reaction of ethyl (triphenylphosphine) acetate with o-methoxybenzyl alcohol

[0035]

[0036]With 0.1328mL, 1mmol o-methoxybenzyl alcohol, 0.5225g, 1.5mmol ethyl (triphenylphosphine) acetate, 0.01g, 5mol% CuI, 0.008g, 5mol% Bipy, 0.011g, Add 5mol% TEMPO, 0.0016mL, and 5mol% tetrahydropyrrole into a 100mL reaction tube in turn, add 2mL acetonitrile as a solvent, add an air balloon to the reaction tube, and react at 65°C for 24h. The product was separated and purified by column chromatography, and the separation yield was 98%. 1HNMR (500MHz, CDCl3): δ7.99(d, J=16.5Hz, 1H), 7.51-7.49(m, 1H), 7.35-7.32(m, 1H), 6.96-6.89(m, 2H), 6.52( d,J=16.0Hz,1H),4.26(q,J=7.0Hz,2H),3.87(s,3H)1.33(t,J=7.0Hz,3H).13CNMR(125.4MHz,CDCl3):δ167. 4,158.3,139.9,131.3,128.8,120.6,118.8,111.1,60.2,55.4,14.3.MS(EI):m / z(%)206(41),176(11),175(92),162(11) ,161(100),147(88),146(18),132(15),131(26),119(24),118(37),105(39),103(23),91(28) ,90(16),89(22),79(1...

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Abstract

The invention discloses an alpha, beta-unsaturated carboxylic ester compound and a preparation method thereof. According to the invention, reaction is performed in air by using transition metal Cu as a catalyst. The adopted transition metal Cu as the catalyst is cheap, so that the production cost is lowered, the reaction condition is mild due to the catalyst system, and the product treatment, separation and purification are simple. As alcohols which are cheap, and easy to obtain are used as the raw material, the synthesis cost is greatly lowered, meanwhile, the requirements for reaction conditions are very low, and the compound and preparation method have excellent study and industrial application prospects.

Description

technical field [0001] The invention relates to the technical field of unsaturated carboxylic acid ester compounds, in particular to an α,β-unsaturated carboxylic acid ester compound and a preparation method thereof. Background technique [0002] The reaction of Wittig reagents with aldehydes is one of the most effective methods for constructing carbon-carbon double bonds. This method has been widely used in the synthesis of some natural products, such as unsaturated fatty acids, prostaglandins, vitamins, and insect pheromones. Among them, the method of synthesizing vitamin A by Wittig reaction has been used in industrial production. [0003] The research on applying the alcohol oxidation reaction to the Wittig reaction was the earliest in 1985. Ireland and Norbeck applied the Swern oxidation reaction to the Wittig reaction, and first realized the one-pot method of alcohol oxidation and Wittig reaction to prepare alkenes. In the past ten years, chemists have successively re...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C69/618C07C67/343C07C69/734C07C69/65C07C205/56C07C201/12C07D213/55C07D333/24B01J31/30
CPCC07C69/618B01J31/1815B01J31/182B01J31/2208B01J2531/16C07C67/343C07C69/65C07C69/734C07C201/12C07C205/56C07D213/55C07D333/24
Inventor 余小春刘志青施震宇张二磊胡娟丁伟杰
Owner WENZHOU UNIVERSITY
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