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Method for removing carbonylazathia acetal protection group

A technology of heteroketal and carbonyl nitrogen, which is applied in the field of deprotection of carbonyl protecting groups, can solve the problems of mercury chloride toxicity, complex reaction behavior, and inability to apply industrial production, and achieve mild reaction conditions, cheap and easy-to-obtain reagents, and reaction solution cleaning effect

Inactive Publication Date: 2008-07-02
FUDAN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, silver nitrate is expensive, mercury chloride is toxic, and cannot be applied to industrial production; the condition of chloramine T is effective for the removal of aldehyde protecting groups, but the removal yield of ketone protecting groups is low; NBS aqueous solution is suitable for more complex The substrate reaction behavior is complex and the reproducibility is poor

Method used

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  • Method for removing carbonylazathia acetal protection group
  • Method for removing carbonylazathia acetal protection group
  • Method for removing carbonylazathia acetal protection group

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 117

[0029] Example 1 17α-Acetoxy-17β-cyano-androst-1,4,9(11)-trien-3-one

[0030] 1.06mmol 3'-methylspiro[androst-1,4,9(11)-triene-3,2'(3'H)benzothiazole]-17β-cyano-17α-acetate, 10mL Dissolve the organic solvent, add 1.06mmol p-toluenesulfonic acid, measure the pH as 1, add 10.6mmol CH 2 =CH-OC 2 h 5 , stirred at room temperature for 15min, stopped the reaction, diluted with ethyl acetate, washed three times with aqueous sodium carbonate solution, back pumped the aqueous layer twice, combined the organic phases, and anhydrous Na 2 SO 4 Drying, filtration, concentration, ethyl acetate gave yellow crystals, yield: 91.07%, mp: 206-208 ° C, identified as 17α-acetoxy-17β-cyano-androst-1,4,9 (11 )-trien-3-one.

[0031] The mixed sample of the mother liquor was applied to a silica gel column, and eluted with petroleum ether: ethyl acetate / 100:1 to obtain 137.9 mg of a colorless oil, which was identified as 2-(1-ethoxy-ethylthio)-N-methyl- aniline.

[0032] The product 2-(1-ethoxyl...

Embodiment 2

[0033] Example 2 17α-Acetoxy-17β-cyano-androst-1,4,9(11)-trien-3-one

[0034] 1.06mmol 3'-methylspiro[androst-1,4,9(11)-triene-3,2'(3'H)benzothiazole]-17β-cyano-17α-acetate, 10mL Dissolve the organic solvent, add 1.06mmol benzenesulfonic acid, measure the pH as 1, add 10.6mmol CH 2 =CH-OC 4 h 9 , stirred at room temperature for 15min, stopped the reaction, diluted with ethyl acetate, washed three times with sodium hydroxide solution, back pumped the water layer twice, combined the organic phases, anhydrous Na 2 SO 4 Drying, filtration, concentration, ethyl acetate gave yellow crystals, yield: 93.66%, mp: 205-207 ° C, identified as 17α-acetoxy-17β-cyano-androst-1,4,9 (11 )-trien-3-one.

[0035] The mixed sample of the mother liquor was applied to a silica gel column, and eluted with petroleum ether: ethyl acetate / 100:1 to obtain 175.7 mg of a colorless oil, which was identified as 2-(1-butoxy-ethylthio)-N-methyl- aniline.

Embodiment 3

[0036] Example 3 17α-Acetoxy-17β-cyano-androst-1,4,9(11)-trien-3-one

[0037] 1.06mmol 3'-methylspiro[androst-1,4,9(11)-triene-3,2'(3'H)benzothiazole]-17β-cyano-17α-acetate, 10mL Dissolve the organic solvent, add 1.06mmol methanesulfonic acid, measure the pH to 1, add 10.6mmol dihydropyran, stir at room temperature for 20min, stop the reaction, dilute with ethyl acetate, wash three times with triethylamine aqueous solution, and back pump the water layer twice, Combined organic phases, anhydrous Na 2 SO 4 Drying, filtration, concentration, ethyl acetate gave yellow crystals, yield: 92.87%, mp: 206-207 ° C, identified as 17α-acetoxy-17β-cyano-androst-1,4,9 (11 )-trien-3-one.

[0038] The mixed sample of the mother liquor was applied to a silica gel column, and eluted with petroleum ether: ethyl acetate / 100:1 to obtain 166.4 mg of a colorless oil, which was identified as 2-(2-tetrahydropyranyl-sulfanyl)-N-methyl -aniline.

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Abstract

The invention relates to a carbonyl protecting group deprotecting method. It adopts olefin ether or agent the could produce carbonium ion to take reaction with acid agent to form carbonium ion intermediate, then combining with nitrogen atoms or sulphur atoms to achieve deprotecting effect of taking further aqueous alkali open loop and hydrolyzing. The invention has mild and easy reacting condition, low cost agent, and has high yield.

Description

technical field [0001] The invention belongs to the field of organic chemistry, and in particular relates to a method for deprotecting a carbonyl protecting group in the synthesis process of organic chemistry. Background technique [0002] The protection of carbonyls into ketals is an important step widely used in organic synthesis, but ketals cannot tolerate acidity, and some less active carbonyls such as α, β-unsaturated carbonyls react poorly or do not react, especially sterols. Body Δ 1，4 The protection of the bad cross-conjugated carbonyl system of -3-ketone is very difficult. It has been reported in the literature that α, β-unsaturated carbonyl can be protected conveniently and highly chemoselectively by using o-methylaminobenzenethiol, and the protected product (benzazepine ketal) can withstand acid and alkali conditions. [0003] Some methods for removing such azathioketal protecting groups have been reported in the literature, such as: silver nitrate / acetonitrile-...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07J3/00C07B41/06
CPCY02P20/55
Inventor 夏鹏张蓓娜陈瑛张倩
Owner FUDAN UNIV
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