公开(公告)号：GB2322857A

公开(公告)日：1998-09-09

申请号：GB9811567

申请日：1996-12-09

Applicant: SECR DEFENCE

Inventor： MILLAR ROSS WOOD ,  CLARIDGE ROBERT PETER ,  SANDALL JOHN PAUL BENET ,  THOMPSON CLAIRE

IPC: C07C201/10 ,  C07C205/12 ,  C07C381/10 ,  C07D213/61 ,  C07D213/76 ,  C07D239/42 ,  C07D241/16 ,  C07D241/20 ,  C07D251/44 ,  C07D251/46 ,  C07B43/02 ,  C07D239/30 ,  C07D251/26 ,  C07D251/42 ,  C07D251/52

Abstract: A method of nitrating electron-deficient carbocyclic or heterocyclic aromatic compounds such as pyridines, diazines and triazines and benzenoid aromatics having electron-withdrawing substituents involves first reacting the aromatic species with a sulphilimine species or with the corresponding N-alkali metal salt thereof to generate an N-(hetero)aryl-S,S-dialkyl, diaryl or alkylarysulphilimine derivative. This intermediate may then be readily oxidised under relatively mild conditions using a peroxycarboxylic acid such as m-chloroperbenzoic acid, peracetic or peroxytrifluoroacetic acid. Good yields of nitrated products are obtained including some previously unprepared. The novel N-alkali(alkylaryl)sulphilimine reagents are prepared by reacting an alkali metal hydride, an alkali metal hydrogenous base or an alkyl lithium with the corresponding sulphilimine. Preferred salts are the N-lithio types and the preferred sulphilimine is diphenylsulphilimine. Where the salt is used reaction should be in an aprotic solvent but if the sulphilimine per se is the reagent a polar solvent is used.

公开(公告)号：CA2240644A1

公开(公告)日：1997-06-26

申请号：CA2240644

申请日：1996-12-09

Applicant: SECR DEFENCE BRIT

Inventor： SANDALL JOHN PAUL BENET ,  MILLAR ROSS WOOD ,  THOMPSON CLAIRE ,  CLARIDGE ROBERT PETER

IPC: C07C201/10 ,  C07C205/12 ,  C07C381/10 ,  C07D213/61 ,  C07D213/76 ,  C07D239/42 ,  C07D241/16 ,  C07D241/20 ,  C07D251/44 ,  C07D251/46 ,  C07D251/52 ,  C07D237/12 ,  C07D239/30 ,  C07D251/42

Abstract: A method of nitrating electron-deficient carbocyclic or heterocyclic aromatic compounds such as pyridines, diazines and triazines and benzenoid aromatics having electron-withdrawing substituents involves first reacting the aromatic species with a sulphilimine species or with the corresponding N-alkali metal salt thereof to generate an N-(hetero)aryl-S,S-dialkyl, diaryl or alkylarylsulphilimine derivative. This intermediate may then be readily oxidised under relatively mild conditions using a peroxycarboxylic acid such as m-chloroperbenzoic acid, peracetic or peroxytrifluoroacetic acid. Good yields of nitrated products are obtained including some previously unprepared. The novel N-alkali(alkylaryl)sulphilimine reagents are prepared by reacting an alkali metal hydride, an alkali metal hydrogenous base or an alkyl lithium with the corresponding sulphilimine. Preferred salts are the N-lithio types and the preferred sulphilimine is diphenylsulphilimine. Where the salt is used reaction should be in an aprotic solvent but if the sulphilimine per se is the reagent a polar solvent is used.