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Preparation method of (Z)-sulfonyl olefine acid ester

A technology of sulfonyl enoate and alkynoate, which is applied in the field of preparation of sulfonyl enoate, can solve the problems of low selectivity, low atom economy, narrow substrate range, etc., and achieve simplified process steps, Wide application value, high selectivity effect

Inactive Publication Date: 2016-08-24
HUNAN UNIV OF SCI & ENG
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0005] However, there are many defects in these two methods. For example, it takes two-step reactions to obtain the target product from the raw material to the product, and various additives, metal catalysts, etc. need to be added. In addition, there is a relatively narrow range of substrates, atomic Disadvantages such as low economy and low selectivity

Method used

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  • Preparation method of (Z)-sulfonyl olefine acid ester
  • Preparation method of (Z)-sulfonyl olefine acid ester
  • Preparation method of (Z)-sulfonyl olefine acid ester

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0033] At room temperature, benzenesulfonylhydrazide (43mg, 0.25mmol), ethyl propiolate (74mg, 0.75mmol) and water (2mL) were successively added into a 10mL round bottom flask. Then, the reaction mixture was stirred at 70° C. for 50 minutes (reaction checked by TLC). Then, stop the reaction, add 10 mL of water, extract with dichloromethane (3*10 mL), combine the organic phases, dry over magnesium sulfate, and filter with suction. Finally wash with the mixed eluent of petroleum ether and ethyl acetate (petroleum ether and ethyl acetate volume ratio 5:1), flash column chromatography (silica gel column) obtains corresponding product (Z)-sulfonylenoate compound (Colorless liquid 52.8mg, yield 88%).

[0034] The reaction formula of this embodiment is:

[0035]

[0036] 1 H NMR (400MHz, CDCl 3 )δ7.91(d, J=8.2Hz, 2H), 7.56(s, 1H), 7.50(t, J=7.6Hz, 4H), 6.45(d, J=2.1Hz, 2H), 4.29(q, J=7.1Hz, 3H), 1.36–1.27(m, 5H); 13 C NMR (100MHz, CDCl 3 )δ163.99,139.43,135.16,134.05,131.95,1...

Embodiment 2

[0038] At room temperature, p-fluorobenzenesulfonyl hydrazide (48mg, 0.25mmol), ethyl propiolate (74mg, 0.75mmol) and water (2mL) were successively added into a 10mL round bottom flask. Then, the reaction mixture was stirred at 80° C. for 80 minutes (reaction checked by TLC). Then, stop the reaction, add 10 mL of water, extract with dichloromethane (3*10 mL), combine the organic phases, dry over magnesium sulfate, and filter with suction. Finally wash with the mixed eluent of petroleum ether and ethyl acetate (petroleum ether and ethyl acetate volume ratio 5:1), flash column chromatography (silica gel column) obtains corresponding product (Z)-sulfonylenoate compound (yellow solid 58.1 mg, yield 90%).

[0039] The reaction formula of this embodiment is:

[0040]

[0041] 1 H NMR (400MHz, CDCl 3 )δ8.06(dd, J=8.8,5.1Hz,2H),7.22(d,J=8.1Hz,2H),6.56(s,2H),4.40(q,J=7.1Hz,2H),1.42( t,J=7.1Hz,3H); 13 C NMR (100MHz, CDCl 3 )δ167.35, 164.79, 163.89, 135.53, 135.18, 132.19, 131....

Embodiment 3

[0043] At room temperature, p-chlorobenzenesulfonyl hydrazide (52mg, 0.25mmol), ethyl propiolate (74mg, 0.75mmol) and water (2mL) were successively added into a 10mL round bottom flask. The reaction mixture was then stirred at 55°C for 80 minutes (reaction checked by TLC). Then, stop the reaction, add 10 mL of water, extract with dichloromethane (3*10 mL), combine the organic phases, dry over magnesium sulfate, and filter with suction. Finally wash with the mixed eluent of petroleum ether and ethyl acetate (petroleum ether and ethyl acetate volume ratio 5:1), flash column chromatography (silica gel column) obtains corresponding product (Z)-sulfonylenoate compound (White solid 62.6 mg, yield 91%).

[0044] The reaction formula of this embodiment is:

[0045]

[0046] 1 H NMR (400MHz, CDCl 3 )δ7.94(d, J=8.6Hz, 2H), 7.56(d,, J=8.5Hz, 2H), 6.53(s, 2H), 4.36(q, J=7.3Hz, 1H), 1.36(t ,J=7.2Hz,2H); 13 C NMR (100MHz, CDCl 3 )δ163.81, 140.91, 137.96, 135.04, 132.51, 129.79, 12...

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Abstract

The invention discloses a preparation method of (Z)-sulfonyl olefine acid ester. The method includes: allowing a sulfohydrazide compound and an acetylenic acid ester compound to have an addition-elimination reaction through a one-pot method so as to obtain the sulfonyl olefine acid ester. The method has the advantages that the (Z)-sulfonyl olefine acid ester compound is synthesized in a high-yield and high-selectivity manner under mild conditions through the one-pot reaction, and the method is simple to operate, environmentally friendly and beneficial to industrial production and does not need catalysts.

Description

technical field [0001] The invention relates to a preparation method of (Z)-sulfonylenoate, which belongs to the field of organic synthesis. Background technique [0002] The carbon-carbon double bond is one of the most variable functional groups in the field of organic chemistry. Many reactions can synthesize carbon-carbon double bonds (Chem.Commun.2006,3646–3647; Synlett 2006,11,1783–1785). Among these reactions, The formation of monosubstituted coupled alkenes is an important reaction because these alkenes are very important intermediates and building blocks in natural products and optical materials (Adv. Mater. 2003, 15, 1176–1180; Polym. Chem. 2003 , 41, 674–683). In the past few decades, due to the special influence of sulfonyl functional groups on molecular structure stability, molecular activity and biological activity, organic chemists have tried to introduce them into organic molecules (Sulfones in Organic Synthesis; Pergamon Press: Oxford ,1993; Bioorg.Med.Chem....

Claims

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Application Information

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IPC IPC(8): C07C317/44C07C315/00
CPCC07C315/00C07C317/44
Inventor 何卫民李文艺刘芳李治章王星星肖艳
Owner HUNAN UNIV OF SCI & ENG
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