Premium
First Stable O ‐Amidinylhydroxylamines and Their Transformations into Sulfenamides by Intramolecular 1,5‐O→S Amine Migration
Author(s) -
Sączewski Franciszek,
Kornicka Anita,
Gdaniec Maria,
Hałasa Rafal,
Werel Władyslaw
Publication year - 2004
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.200400229
Subject(s) - chemistry , intramolecular force , amine gas treating , amination , carbon disulfide , nucleophile , intermolecular force , medicinal chemistry , electrophile , disulfide bond , polymer chemistry , organic chemistry , molecule , catalysis , biochemistry
The reaction of 2‐chloro‐4,5‐dihydroimidazole ( 1 ) with aliphatic hydroxylamines 2 − 4 gives O ‐amidinylhydroxylamines 5 − 7 in contrast to the analogous reaction of 1 with N ‐arylhydroxylamines in which N ‐substitution occurs. A number of thiocarbamoylsulfenamides 8 − 10 have been prepared by the reaction of 5 − 7 with carbon disulfide under basic and mild conditions. The key step in the 1,5‐O→S amine migration involves the tandem nucleophilic addition‐electrophilic amination reaction. The intermolecular version of this process using preformed triethylammonium dithiocarbamates gives the corresponding sulfenamides 14 − 16 . Functionalized ethylenediamines 17 − 19 are obtained by treatment of 8 and 9 with amines. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)