公开(公告)号：WO1997022590A1

公开(公告)日：1997-06-26

申请号：PCT/GB1996003020

申请日：1996-12-09

Applicant: THE SECRETARY OF STATE FOR DEFENCE ,  MILLAR, Ross, Wood ,  CLARIDGE, Robert, Peter ,  SANDALL, John, Paul, Benet ,  THOMPSON, Claire

Inventor： THE SECRETARY OF STATE FOR DEFENCE

IPC: C07D213/76

CPC classification number: C07D213/76 ,  C07C201/10 ,  C07C201/16 ,  C07C381/10 ,  C07D213/61 ,  C07D239/42 ,  C07D241/16 ,  C07D241/20 ,  C07D251/44 ,  C07D251/46 ,  C07C205/12 ,  C07C205/06

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.

Abstract translation: 硝化电子缺乏的碳环或杂环芳族化合物如吡啶，二嗪和三嗪的方法和具有吸电子取代基的苯系芳族化合物包括首先使芳族物质与亚硫酰胺物质或其相应的N-碱金属盐反应，生成 N-（杂）芳基-S，S-二烷基，二芳基或烷基芳基亚磺酰亚胺衍生物。 然后可以使用过氧羧酸如间氯过苯甲酸，过乙酸或过氧三氟乙酸在相对温和的条件下容易地氧化该中间体。 获得了硝化产物的良好产率，包括一些以前没有准备的产品。 通过使碱金属氢化物，碱金属氢碱或烷基锂与相应的硫化亚胺反应制备新型N-碱（烷基芳基）亚硫酰胺试剂。 优选的盐是N-亚硫基类型，优选的亚硫酰亚胺是二苯基亚硫酰亚胺。 在使用盐的情况下，反应应在非质子溶剂中，但如果亚硫酰胺本身是试剂，则使用极性溶剂。