REACTION OF α-CHLOROTOLUENE WITH ELEMENTAL SULFUR IN LIQUID AMMONIA

Abstract

α-Chlorotoluene (1) reacts with elemental sulfur in liquid ammonia affording dibenzyl disulfide (2), dibenzyl trisulfide (3), dibenzyl tetrasulfide (4), dibenzyl pentasulfide (5) and benzylidene benzylimide (6) at a low temperature such as 20°C. This reaction is presumed to be initiated by the nucleophilic attack of ammonium thioaminohydroxylate, “H₂NS^-NH₄ ⁺,” or dithioaminohydroxylate, “H₂NSS^-NH₄,” formed upon treating elemental sulfur in liquid ammonia, on α-chlorotoluene (1). Benzylidene benzylimide (6) is presumed to be formed from benzylamine, which can be formed by treatment of α-chlorotoluene (1) with ammonia.     

Preparation,Properties and Complexation Behaviour of P,P-Di-tert. Butylphosphinothioic Amides

Abstract

Starting from tBu₂PCl, the title compounds tBu₂P(S)NHR′ (R′= Me Et, iPr, tBu) may be easily prepared according to With R′=tBu the amine has to be substituted by its Li-salt [tBuNH]^?Li^+.     

The Structure of o-Hydroxyaryloxy-bis-(o-arylenedioxy)-phosphoranes and their Acid-Base Properties

Abstract

The crystalline phosphoranes have been obtained. IR-, UV- and NMR spectra of phosphoranes (Ia,b) and their interaction products with nitrogen bases have been investigated. It was determined that phosphoranes have structure (I) with pentacoordinate phosphorus and phenolic hydroxy group, while their products of interactions with nitrogen bases have the ionic structure (II) with hexacoordinate phosphorus (II). The X-ray difraction approves the structure (I) for phosphorane Ib.     

Reactions of Unsaturated Phosphonic Acids with 2-Aminopyridine

Abstract

Different unsaturated phosphonic acids of the general formula (R=C1, OCH₃, OH, NMe₂, C₆H₅; R′=C1, OCH₃, H, NMe₂) have been prepared starting from propargyl alcohol. Reaction of chlorophosphonic acids with 2-amino-pyridine yields phosphoramidates, which in the next step undergo a base-catalyzed cyclization by addition of the ring nitrogen across the unsaturated bond, leading to the unstable derivative 1. In the case of the allenic phosphonic acid in which R=R′=NMe₂, the NH₂ group of 2-aminopyridine adds first to the allenic system yielding an enamine, which on heating cyclizes to give a new phosphorus-nitrogen heterocyclic system 2.