Ueber die Einwirkung von Benzolsulfonsäurechlorid auf Amidoxime

Application of α-chloroaldoxime O-methanesulfonates to one-pot synthesis of N,N′,N″-substituted guanidines via Tiemann rearrangement

“…1). 1,2 The primary product of the reaction is the amidoxime O-benzenesulfonate, which then rearranges to give a carbodiimide (Eq. 2).…”

“…3 Although this rearrangement provides an efficient pathway to carbodiimides, which are versatile synthetic intermediates, 4 only a few synthetic applications of this potentially useful reaction have appeared in the literature. 1,3,5 ð1Þ ð2Þ…”

Photochemistry of Azides: The Azide/Nitrene Interface

“…Scheme 11. 16 Step -wise mechanism of vinyl azide photolysis and thermolysis 101 However, singlet vinylnitrenes have never been observed by time resolved spectroscopy and triplet vinylnitrenes have not been observed by either time resolved or matrix spectroscopy. The formation of an azirine was observed upon photolysis of α -azidostyrene in an argon matrix at cryogenic temperature (8 K), but even under these conditions nitrene species were not detected.…”

“…10 It is commonly believed 1 -3,11 -15 that photolysis and thermolysis of the organic azides leads mainly to the dissociation of N -N bond with formation of molecular nitrogen and nitrenes, as fi rst proposed by Tiemann in 1891. 16 Nitrenes, species containing neutral, monovalent nitrogen atoms, are typically very reactive and short -lived intermediates. Azides form bonds to many elements, 1 -3,11 -15 and, consequently, many types of nitrenes are known or can be imagined.…”

A New Approach to Modification of Rearrangements in Metallorganic Chemistry of Phosphorus, Arsenic, Antimony and Bismuth

“…It is known that the Tiemann Rearrangement amidoximes carboxylic acid derivatives of urea by reaction with benzenesulfonyl chloride (C 6 H 5 SO 2 Cl) and subsequent hydrolysis [79,80]: R'R"N-CR=NOH + C 6 H 5 SO 2 Cl → R'R"N-CR=N-OSO 2 C 6 H 5 → R'R"N-CO-NHR (44) where, R = C 6 H 5 , CH 2 C 6 H 5 .…”