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Process for chloridizing dithio-aza cyclo-butanone derivatives

A technology of dithioazetidinone and derivatives is applied in the field of chlorination of dithioazetidinone derivatives, and can solve the problems of many chlorinable sites, poor selectivity and yield, etc. problems, to achieve mild process conditions, less environmental pollution, and good chlorination selectivity.

Inactive Publication Date: 2002-03-13
TSINGHUA UNIV +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The problem with the chlorination of this type of molecule is that there are many sites that can be chlorinated except for the allyl position.
(2) Chlorine (Cl 2 ), but its selectivity and yield are generally poor (see "Tetrahedron Letters" Vol.21, pp351-354, 1980, and European Patent 0500081 A2 1992)

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0018] (1) take compound 1 (make wherein R 2 =-CH 2 Ph-Ome-P) 6.0g (10mmol) was dissolved in a mixed solvent of 300ml carbon tetrachloride and 30ml acetic acid to form a yellow clear solution, cooled to 5°C in icy brine, slowly added dropwise 25ml sodium hypochlorite solution (active chlorine) under effective stirring 2.0%), dripped in about 1 hour.

[0019] (2) The reaction was stirred for 2 hours, and the reaction temperature was controlled at 2°C.

[0020] (3) After the reaction is completed, the reaction solution is separated, and the water layer is separated. The organic layer was washed 3 times with saturated brine (about 3×100 ml). The organic phase was dried over anhydrous sodium sulfate. Sodium sulfate was removed by filtration. The solvent was evaporated in vacuo to obtain 6.2 g of a yellow viscous liquid, which would gradually solidify in the air or refrigerated at 5°C. Purified by column chromatography (silica gel 40 μm, eluent using benzene:ethyl acetate equ...

Embodiment 2

[0022] (1) take compound 1 (make wherein R 2 =-CHPh 2 ) 6.4g (10mmol) was dissolved in the mixed solvent of 300ml carbon tetrachloride and 30ml acetic acid to form a yellow clear solution, and the ice salt solution was cooled to 0°C, and 25ml sodium hypochlorite solution (active chlorine 2.0%) was slowly added dropwise under effective stirring, about 1 hour to drip.

[0023] (2) The reaction was stirred for 2 hours, and the reaction temperature was controlled at 0°C.

[0024] (3) After the reaction is completed, the reaction solution is separated, and the water layer is separated. The organic layer was washed 3 times with saturated brine (about 300 ml). The organic phase was dried over anhydrous sodium sulfate. Sodium sulfate was removed by filtration. The solvent was evaporated in vacuo to obtain 6.7 g of a yellow viscous liquid, which would gradually solidify in the air or refrigerated at 5°C. Purified by column chromatography (silica gel 40 μm, eluent using benzene:et...

Embodiment 3

[0026] (1) take compound 1 (make wherein R 2 =-CH 2 Ph-OMe-P) 6.0g (10mmol) was dissolved in the mixed solvent of 300ml carbon tetrachloride and 30ml acetic acid to form a yellow clear solution, and the iced brine was cooled to 3°C, and 16ml of potassium hypochlorite solution was slowly added dropwise under effective stirring (active Chlorine 3.0%), dripped in about 1 hour.

[0027] (2) The reaction was stirred for 2 hours, and the reaction temperature was controlled at 1°C.

[0028] (3) After the reaction is completed, the reaction solution is separated, and the water layer is separated. The organic layer was washed 3 times with saturated brine (about 3×100 ml). The organic phase was dried over anhydrous sodium sulfate. Sodium sulfate was removed by filtration. The solvent was evaporated in vacuo to obtain 6.2 g of a yellow viscous liquid, which would gradually solidify in the air or refrigerated at 5°C. Purified by column chromatography (silica gel 40 μm, eluent using ...

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PUM

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Abstract

During the chlorination of dithioaza cyclobutanone derivative, dithioaza cyclobutanone derivative is first dissolved in some solvent and glacial acetic acid is added to the solution through stirring,and sodium hypochlorite or potassium hypochlorite is then added into the solution to react at 0 deg.c for 2 hr. After finishing reaction, water layer is separated from the reacted liquid, the organicmatter layer is washed with table salt solution, dried with anhydrous sodium sulfate, filtered to obtain filtrate, and the filtrate is vacuum evaporated to eliminate solvent and to obtain yellow ropyliquid of the required chloride. The method of the present invention has mild technological conditions and less environmental pollution and is suitable for industrial production.

Description

Technical field: [0001] The invention relates to a chlorination method of dithioazetidinone derivatives, belonging to the technical field of polymer materials. Background technique: [0002] Chlorination of dithioazetidinone derivatives is allylic chlorination. The problem with the chlorination of this type of molecule is that there are many sites that can be chlorinated except for the allyl position. For example, there are many sites that are easy to be chlorinated in the side chain. Therefore this reaction is difficult to carry out directionally, and side reaction is many. The key to chlorination is to find selective chlorination reagents and other reagents and process conditions. [0003] There are currently two main methods for the chlorination of dithioazetidinone derivatives: electrolytic chlorination and chemical reagent chlorination. [0004] Electrolytic chlorination is considered to be the most successful chlorination method. It has high selectivity and the yie...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D205/08
Inventor 石鸿昌金家辉尹芊范学政张凤森陈邦和
Owner TSINGHUA UNIV
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