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Chloridization method for nitrogen heterocyclic butanone isobutene derivatives

A technology of azetidinone isobutene and azetidinone isobutene, which is applied in the field of chlorination of azetidinone isobutene derivatives, can solve environmental protection requirements and reduce cost disadvantages, poor selectivity and yield, and olefinic bis Bond displacement and other issues, to achieve the effects of environmental protection restrictions and high recovery rate, fast response, mild process conditions

Inactive Publication Date: 2009-05-27
北京金源化学集团有限公司 +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The problem that this kind of molecular chlorination exists is that except the allyl position methyl group on the isobutenyl group, there are many chlorinated sites, such as just having many easy chlorinated sites in the side chain, each substituted group (such as There are also many sites for chlorination reactions on ester groups, amido groups and mercapto protecting groups, etc., and the double bond of isobutenyl group can undergo addition reaction, and at the same time, the terminal double bond can be displaced
However, the solvent used is carbon tetrachloride, which is banned in the world. At the same time, the amount of solvent is large, and the amount of waste acid is also large, which is very unfavorable for environmental protection requirements and cost reduction.
(4) Chlorine (Cl 2 ), the chlorination reagent is cheap and easy to get, and is easy to mass-produce, but its selectivity and yield are generally poor (see "Tetrahedron Letters" Vol.21, pp351-354, 1980 and EP500081A2)

Method used

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  • Chloridization method for nitrogen heterocyclic butanone isobutene derivatives
  • Chloridization method for nitrogen heterocyclic butanone isobutene derivatives
  • Chloridization method for nitrogen heterocyclic butanone isobutene derivatives

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Experimental program
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Effect test

Embodiment 1

[0021] Take compound 1 (R 1 is phenylacetyl, R 2 p-Methoxybenzyl, R 3 10 millimoles of benzenesulfinic acid group) were dissolved in 100 milliliters of a mixed solution of carbon disulfide, carbon dichloride and propylene oxide (volume ratio 3:2:1), and the temperature was cooled to -5°C with ice brine. In addition, carbon disulfide is used to dissolve chlorine gas, the concentration of the chlorine solution is 1%, and the temperature is controlled at 5° C. with cold water. Under the condition of effective stirring, quickly add the chlorine solution dropwise to the azetidinone isobutene derivative solution to ensure that the reaction temperature is 0°C, the reaction time is 3 minutes, and the molar ratio of the azetidinone isobutene derivative to chlorine gas is 1 :1.3.

[0022] After the dropwise addition, the temperature was kept at 0° C. and stirring was continued for 30 minutes. After the reaction was completed, the solvent was evaporated under reduced pressure in vacu...

Embodiment 2

[0027] Take compound 3 (R 2 p-Methoxybenzyl, R 5 is formyl, R6 Benzyl) 10 millimoles were dissolved in 100 milliliters of dioxane, a mixed solution of ethyl acetate and ethylene oxide (volume ratio 3:2:1), and cooled to 10° C. with cold water. In addition, dilute the chlorine gas with helium gas, the concentration of the chlorine gas is 1%, and the temperature of the serpentine coil cooled by cold water is 10°C. Slowly add dilute chlorine gas to the azetidinone isobutene derivative solution under effective stirring, the reaction time is 3 hours, the reaction temperature is guaranteed to be 10°C, and the mol ratio of the azetidinone isobutene derivative to chlorine is 1:1.5.

[0028] After aeration, the temperature was kept at 10° C., and the reaction was continued for 2 hours. After the reaction was completed, the solvent was evaporated under reduced pressure in vacuo to obtain a yellow viscous body, which was the chloride allylic monochloride 6. Place in a refrigerator at...

Embodiment 3

[0033] Take compound 1 (R 1 is phenoxyacetyl, R 2 Methyl, R 3 10 mmoles of 2-mercaptobenzothiazolyl) were dissolved in 100 ml of a mixed solution of carbon dichloride and ethylene oxide (volume ratio 4:1), and cooled to -5°C with ice-cold brine. In addition, carbon dichloride was used to dissolve chlorine gas, the concentration of the chlorine solution was 5%, and the temperature was controlled at -5°C with ice-salt water. Slowly add chlorine solution dropwise to the azetidinone isobutene derivative solution under effective stirring to ensure that the reaction temperature is -5°C, and the molar ratio of the azetidinone isobutene derivative to chlorine gas is 1:1.1.

[0034] After the dropwise addition, the temperature was kept at 0° C., and the reaction was continued for 2 hours. After the reaction was completed, the solvent was distilled off under reduced pressure in vacuo to obtain a yellow viscous body, which was allyl monochloride 4. Place in a refrigerator at 5°C to ...

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PUM

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Abstract

The invention relates to a method for chloridizing a nitrogen heterocyclic cyclobutanone isobutene derivant. The method has mild process condition, stable reaction, available materials; dilute chlorine is adopted for chlorination and has high chlorination selectivity and high yield; the reaction solvent is a non-phenoxin solvent, has no limitation of environmental protection, high reclaiming rate, little environmental pollution and rapid reaction and can improve production efficiency; the raw materials are common industrial products and are cheap and available; and the method is in particular suitable for production in chemical industry and medical industry and is suitable for middle- and small-scale production.

Description

technical field [0001] The present invention relates to a chlorination process of azetidinone isobutene derivatives. Background technique [0002] Azetidinone isobutenyl monochlorinated derivatives are important intermediates for the preparation of various antibiotics (see "Encyclopedia of Chemical Engineering", Volume Nine, pp691-743, 1995), the three types of azetidinones shown in the figure below Cyclobutanone isobutenyl monochlorinated derivatives 4, 5 and 6, after ring closure reaction, can obtain various important cephalosporin derivatives, such as 7-ACA (7-amino-3-cephalosporanic acid), GCLE (7-amino-3 chloromethyl cephalosporanic acid p-methoxybenzyl ester), etc. These cephalosporin derivatives are necessary intermediates for the preparation of cephalosporin antibiotics. [0003] The preparation of the azetidinone isobutenyl monochlorinated derivative is obtained by monochlorinating the allyl methyl group of the corresponding azetidinone isobutenyl derivative. The...

Claims

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Application Information

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IPC IPC(8): C07D205/095C07D417/04
CPCY02P20/55
Inventor 邱明建陈朝晖姚加郭秀彬杨中民张雅丽张炜张春山张云堂
Owner 北京金源化学集团有限公司
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