Preparation method of oxalyl sulfonyl hydrazide and application of oxalyl sulfonyl hydrazide in olefin sulfonation reaction

A technology for the reaction of oxalylsulfonyl hydrazide and oxalyl chloride, which is applied to the preparation of sulfonic acid amide, the preparation of organic compounds, chemical instruments and methods, etc., can solve the problems that the preparation of oxalylsulfonyl hydrazide has not been reported, and achieve cheap raw materials , simple process and easy preparation

Active Publication Date: 2019-05-14
SHANGHAI MAIPU NEW MATERIAL TECH CO LTD
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

The preparation and related application of the oxalylsulfonyl...

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  • Preparation method of oxalyl sulfonyl hydrazide and application of oxalyl sulfonyl hydrazide in olefin sulfonation reaction
  • Preparation method of oxalyl sulfonyl hydrazide and application of oxalyl sulfonyl hydrazide in olefin sulfonation reaction
  • Preparation method of oxalyl sulfonyl hydrazide and application of oxalyl sulfonyl hydrazide in olefin sulfonation reaction

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Experimental program
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Embodiment 1

[0021] Embodiment one (preparation of oxalyl p-toluenesulfonyl hydrazide):

[0022]

[0023] In a 100ml reaction flask, add 50ml of solvent methylene chloride and 3.2 grams (25mmol) of oxalyl chloride successively, cool in an ice bath to zero degree, then add 9.3 grams (50mmol) of p-toluenesulfonyl hydrazide and 5 grams (50mmol) of triethylamine successively dropwise. ), each dropping time was 10 minutes. After the dropwise addition, the reaction was continued at zero temperature for 5 hours, extracted three times with water and ethyl acetate. The water layer was removed, and the organic layer was dried with anhydrous sodium sulfate. The solvent was removed with a rotary evaporator, and then it was purified by silica gel chromatography (methanol / dichloromethane=1 / 10) to obtain 8.8 grams of pure oxalyl-p-toluenesulfonyl hydrazide, with a yield of 82%.

Embodiment 2

[0025] Add 2ml of solvent ethanol, 0.26g (0.6mmol) of oxalyl-p-toluenesulfonyl hydrazide, 0.052g (0.5mmol) of styrene, and 1.9mg (0.01mmol) of catalyst cuprous iodide in a 10ml reaction tube, open the Reaction at room temperature. Track the reaction until the complete disappearance of oxalyl-p-toluenesulfonyl hydrazide. After the reaction, it was extracted three times with water and ethyl acetate. The aqueous layer was removed, and the organic layer was dried over anhydrous sodium sulfate. The solvent was removed by a rotary evaporator, and then purified by silica gel chromatography (ethyl acetate / petroleum ether=1 / 10) to obtain 0.114 g of pure 2-p-toluenesulfonylacetophenone with a yield of 84%. 1 H NMR (400MHz, CDCl 3 )δ7.97(d, J=7.7Hz, 2H), 7.78(d, J=8.1Hz, 2H), 7.64(t, J=7.3Hz, 1H), 7.50(t, J=7.6Hz, 2H) ,7.35(d,J=8.0Hz,2H),4.74(s,2H),2.46(s,3H). 13 C NMR (101MHz, CDCl 3 ) δ 188.15, 145.36, 135.82, 134.31, 129.84, 129.34, 128.84, 128.62, 63.61, 21.70.

Embodiment 3

[0027] In Reaction Example 2, except that 0.052 g (0.5 mmol) of styrene was changed to 0.092 g (0.5 mmol) of 1-bromo-4-vinylbenzene, the reaction was carried out in the same manner as in Example 2. 2-p-toluenesulfonyl-4'-bromoacetophenone, yield 85%. 1 HNMR (400MHz, CDCl 3 )δ8.02(t, J=1.8Hz, 1H), 7.91(ddd, J=7.8, 1.6, 1.0Hz, 1H), 7.80–7.71(m, 3H), 7.38(dd, J=15.3, 7.8Hz ,3H),4.70(s,2H),2.47(s,3H). 13 C NMR (101MHz, CDCl 3 ) δ 186.69, 144.92, 137.41, 132.04, 130.34, 128.55, 127.98, 123.18, 63.98.

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Abstract

The invention belongs to the technical field of organic chemical synthesis and particularly relates to a preparation method of oxalyl sulfonyl hydrazide and application of the oxalyl sulfonyl hydrazide in olefin sulfonation reaction. The preparation method allows aryl sulfonyl hydrazide to have reaction with oxalyl chloride in the presence of alkali to prepare the oxalyl sulfonyl hydrazide. The invention further provides a novel method using the oxalyl sulfonyl hydrazide to have reaction with substituted olefin to prepare beta-keto-sulfone or beta-hydroxyl sulfone. The novel method uses the substituted olefin and the oxalyl sulfonyl hydrazide as the raw materials and oxygen in air as the oxidizing agent to perform oxidative addition reaction in the presence of a catalyst to generate the beta-keto-sulfone or beta-hydroxyl sulfone.

Description

technical field [0001] The invention belongs to the technical field of organic chemical synthesis, and in particular relates to a preparation method of oxalylsulfonyl hydrazide, a sulfonylation reagent, and its application in the sulfonylation reaction of olefins. Background technique [0002] Aryl sulfone is an important class of organic functional groups. Related compounds are widely used in the fields of organic chemistry and polymer chemistry, including fine chemicals, pharmaceutical and pesticide raw materials, resin / plastic raw materials, electronic information materials, optical materials, etc. [0003] Common aryl sulfonation reagents include aryl sulfinic acid, aryl sulfonyl chloride, aryl sulfonyl hydrazide, etc. The preparation and related application of the oxalylsulfonyl hydrazide involved in the present invention have not been reported. Contents of the invention [0004] The object of the present invention is to provide a preparation method of oxalylsulfonyl...

Claims

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Application Information

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IPC IPC(8): C07C303/40C07C311/49C07C315/00C07C317/18C07C317/24
Inventor 朱纯银刘运淼胡启明谢子恒
Owner SHANGHAI MAIPU NEW MATERIAL TECH CO LTD
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