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Phosphanalkylene, 55 Reaktionen von Alkylidentriphenylphosphoranen mit nitrierenden Reagentien
Author(s) -
Bestmann Hans Jürgen,
Kamberger Werner,
Röder Thomas,
Zimmermann Reiner
Publication year - 1996
Publication title -
liebigs annalen
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 0947-3440
DOI - 10.1002/jlac.199619960532
Subject(s) - ylide , chemistry , nitration , phosphonium , nitro , reagent , medicinal chemistry , organic chemistry , alkyl
Phosphane Alkylenes, 55.— Reactions of Alkylidenetriphenylphosphoranes with Nitrating Reagents The reaction of phosphonium ylides 1 with N 2 O 4 ( 2 ) is strongly influenced by the natur of the substituents of the starting ylide. Formation of α‐nitro‐α‐nitrosoalkanoates 8 , nitrolic acid 11 , and nitriles 13 was realized. Nitration at the phenyl group of benzylidenephosphoranes 24 or at the γ‐position of allylidenephosphoranes 30 accompanied by transylidation and oxidation processes leads to the formation of nitro‐substituted ylides 26 and 32 , respectively. Strongly basic ylides and ethyl nitrate ( 34 ) undergo complex reactions as is shown in the formation of the aziridinyl‐substituted ylide 40 from ethylidenetriphenylphosphorane ( 9 ) and 34 . Allylidenetriphenylphosphoranes 41 are nitrated by ethyl nitrate ( 34 ) at the γ‐position affording (γ‐nitroallylidene)triphenylphosphoranes 43 , from which nitro dienes 45 are available. In the reaction of 1‐(dimethylamino)‐2‐nitroethylene ( 46 ) with phosphonium ylides nitro‐vinylation of the starting ylide takes place.