Fluorination and chlorination of nitroalkyl groups

被引：22

作者：

Butler, Philip ^{[1
]}

Golding, Bernard T. ^{[1
]}

Laval, Gilles ^{[1
]}

Loghmani-Khouzani, Hossein ^{[2
]}

Ranjbar-Karimi, Reza ^{[2
]}

Sadeghi, Majid M. ^{[2
]}

机构：

[1] Univ Newcastle Upon Tyne, Sch Nat Sci Chem, Newcastle Upon Tyne NE1 7RU, Tyne & Wear, England

[2] Isfahan Univ, Dept Chem, Esfahan 8174673441, Iran

来源：

TETRAHEDRON | 2007年 / 63卷 / 45期

基金：

英国工程与自然科学研究理事会;

关键词：

heterocycle; nitration; chlorination; fluorination; Selectfluor (TM); N-fluorobenzenesulfonimide; triphenyltin hydride;

D O I：

10.1016/j.tet.2007.08.020

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Heterocycles substituted with a nitromethyl (CH2NO2) or phenyl-nitromethyl (CHPhNO2) group were prepared by reaction of a methyl- or phenylmethyl-substituted heterocycle, respectively, with lithium di-isopropylamide followed by quenching the intermediate carbanion with methyl nitrate. Conversion of CH2NO2 attached to an alkyl or aryl moiety into a dichloronitromethyl (CCl2NO2) group was achieved using N-chlorosuccinimide and 1,8-diazabicyclo[5.4.0] undec-7-ene (DBU) in dichloromethane. Similarly, CH2NO2 attached to an alkyl or aryl group was converted into difluoronitromethyl (CF2NO2) using either 1-chloromethyl-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane bis( tetrafluoroborate) (Selectfluor (TM)) or N-fluorobenzenesulfonimide with DBU as base and dichloromethane as solvent. Reaction of omega-nitroacetophenone with Selectfluor/DBU in dimethylformamide followed by acidification and distillation gave the parent difluoronitromethane in a useful 'one-pot' procedure. (c) 2007 Elsevier Ltd. All rights reserved.

引用

页码：11160 / 11166

页数：7

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