Method for preparing α,β-unsaturated butyrolactone from keto acid and alkyne

A technology of unsaturated butyrolactone, which is applied in the direction of organic chemistry, can solve the problems of high requirements for the reaction environment and complicated operation, and achieve the effect of simple operation, low price and improved economic benefits

Active Publication Date: 2017-11-07
SUZHOU UNIV
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  • Application Information

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Problems solved by technology

[0004] The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, to provide a method for preparing α, β-unsaturated butyrolactone from ketoacids and alkynes, and to solve the problem of complex operation of preparing α, β-unsaturated butyrolactone and the difficulty in reacting. High environmental requirements

Method used

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  • Method for preparing α,β-unsaturated butyrolactone from keto acid and alkyne
  • Method for preparing α,β-unsaturated butyrolactone from keto acid and alkyne
  • Method for preparing α,β-unsaturated butyrolactone from keto acid and alkyne

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025] Example 1 A compound was synthesized by using the reaction of benzoylformic acid and phenylacetylene. Its molecular formula is:

[0026]

[0027] Add 0.3mmol benzoylformic acid, 0.9mmol phenylacetylene, 0.6mmol p-toluenesulfonic acid monohydrate, 0.06mmol boron trifluoride ether and 2mL chlorobenzene to a reaction tube at one time, react at 70°C for 6h, and the reaction is completed Afterwards, the solvent was evaporated under reduced pressure, and petroleum ether:ethyl acetate was used for column chromatography. The volume ratio of petroleum ether:ethyl acetate was 10:1, and then the pure product was obtained with a yield of 78% and a purity of 98%.

[0028] After NMR analysis: 1 H NMR (400MHz, CDCl 3 )δ8.35(s,1H),7.92-7.86(m,4H),7.59-7.53(m,3H),7.46-7.30(m,8H),4.13(d,J=16.4Hz,1H),3.70 (d,J=16.4Hz,1H). 13 C NMR (100MHz, CDCl 3 )δ 195.1, 169.8, 149.9, 138.2, 136.0, 133.2, 130.1, 129.0, 128.8, 128.3, 128.2, 128.2, 128.1, 127.8, 126.8, 125.3, 85.7, 48.2.

Embodiment 2

[0029] Example 2 A compound was synthesized by using the reaction of p-methoxybenzoylformic acid and phenylacetylene. Its molecular formula is:

[0030]

[0031] Add 0.3mmol p-methoxybenzoylformic acid, 0.9mmol phenylacetylene, 0.6mmol p-toluenesulfonic acid monohydrate, 0.06mmol boron trifluoride diethyl ether and 2mL chlorobenzene in one reaction tube, and react at 70°C 9h, after the reaction was completed, the solvent was evaporated under reduced pressure, and petroleum ether: ethyl acetate column chromatography was used. The volume ratio of petroleum ether: ethyl acetate was 10:1, and then the pure product was obtained with a yield of 88% and a purity of 98.5 %.

[0032] After NMR analysis: 1 H NMR (400MHz, CDCl 3 )δ8.23(s,1H),7.91-7.82(m,4H),7.58-7.51(m,3H),7.46-7.40(m,2H),7.39-7.34(m,2H),7.33-7.28( m,1H),6.92(d,J=8.8Hz,2H),4.12(d,J=16.4Hz,1H),3.81(s,3H),3.67(d,J=16.4Hz,1H). 13 C NMR (100MHz, CDCl 3 )δ 195.7, 170.6, 160.5, 148.1, 138.9, 136.6, 133.7, 129.9, 128.8...

Embodiment 3

[0033] Example 3 Compounds were synthesized by using the reaction of p-methoxybenzoylformic acid and p-methylphenylacetylene. Its molecular formula is:

[0034]

[0035] Add 0.3mmol p-methoxybenzoylformic acid, 0.9mmol p-toluene acetylene, 0.6mmol p-toluenesulfonic acid monohydrate, 0.06mmol boron trifluoride diethyl ether and 2mL chlorobenzene in one reaction tube, at 70 Reaction at ℃ for 13 hours, after the reaction was completed, the solvent was evaporated under reduced pressure, and petroleum ether: ethyl acetate column chromatography was used. The volume ratio of petroleum ether: ethyl acetate was 10:1, and then the pure product was obtained with a yield of 81%. , 98% purity.

[0036] After NMR analysis: 1 H NMR (400MHz, CDCl 3 )δ8.22(s,1H),7.89-7.83(m,2H),7.79(d,J=8.0Hz,2H),7.42(d,J=8.0Hz,2H),7.23(d,J=8.0 Hz,2H),7.17(d,J=8.0Hz,2H),6.95-6.89(m,2H),4.10(d,J=16.4Hz,1H),3.82(s,3H),3.62(d,J =16.4Hz,1H),2.39(s,3H),2.32(s,3H). 13 C NMR (100MHz, CDCl 3 )δ 194.8, 170.1,...

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Abstract

The present invention discloses a preparation method of alpha, beta-unsaturated butyrolactone from keto acid and alkyne. Keto acid, alkyne, p-toluenesulfonic acid monohydrate and boron trifluoride etherate in a solvent of chlorobenzene to obtain a crude product; then pressure reduction method is employed to remove the solvent under reduced pressure; column chromatography is carried out in an organic solvent to obtain a fine product. A synthesis route is as below, wherein R1 represents aryl group or tert-butyl group, and R2 represents aryl group. All the raw materials used in the reaction process are inexpensive and readily available. The method has the advantages of a wide application scope of substrates, simple operation, yield of about 80% and great reduction of the reaction cost.

Description

technical field [0001] The invention relates to a method for preparing α,β-unsaturated butyrolactone with ketoacid and alkyne. Background technique [0002] α,β-Unsaturated butyrolactone is an important class of organic synthesis intermediates. In recent years, the wide application of α, β-unsaturated butyrolactone in organic synthesis has aroused people's interest and attention, and the synthesis method of α, β-unsaturated butyrolactone has also made great progress. [0003] In 1990, under the catalysis of acid, Bruce B. Jarvis et al. used α-carbonyl acid and alkenes to react to obtain α, β-unsaturated butyrolactone in a good yield. However, there are certain limitations in the selection of raw materials. In 1997, Howard Alper synthesized the product using internal acetylenic alcohols under the catalysis of palladium. However, the use of complex acetylenic alcohols as raw materials limits the range of substrates, and the reaction needs to be carried out under the protect...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D307/58
CPCC07D307/58
Inventor 朱晨茅文彬
Owner SUZHOU UNIV
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