Kinetics and products of the reaction of diazo compounds with SO2

Data were obtained on the composition of products and kinetics of the reaction of SO₂ with Ph(R)CN₂ (R=Ph, Me) in solutions of isooctane, 1,4-di-oxane, and ethanol at 295 K. A mechanism was proposed for the process in accordance with which the sulfene being formed participates in concurrent reactions with the starting reagents. The relative rate constants for the process stages were determined.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2496–2500, November, 1990.     

Accessibility of hydroxy groups of pectin substances for deuteration

An apparatus for the deuteration of solid samples and for recording their IR spectra in a current of D₂O vapor, and an IR-spectroscopic method of determining the degree of deuteration (q) of the hydroxy groups of pectin substances (PSs) are described. It has been established that there are no zones of structurally different nature in films of derivatives of PSs at the carboxy group. The rate of deuterium-exchange of the water of hydration of PSs is higher than for the hydroxy groups of the pyranose rings. The rate of deuterium exchange depends on the density of packing of the polymer chains of the pectin derivatives.Center for the Automation of Scientific Investigations and Metrology, Academy of Sciences of the Moldavian SSR, Kishinev. Translated from Khimiya Priorodnykh Soedinenii, No. 3, pp. 343–348, May–June, 1987.     

Über P–P-haltige cyclische Verbindungen. II

On P? P Containing Cyclic Compounds. II. Reaction of N,N'-dimethylthiourea with phenyl dichlorophosphane yields 1.4-dimethyl-2. 3-diphenyl-1.4.2.3-diazadiphospholidine-5-thione-2-sulfide ( II ). The compound is characterized by its nmr, vibration and mass spectra as well as the results of an X-ray structural analysis. Byproduct of the reaction is N-(N,N'-dimethylcarbamimidoyl)-N,N'-dimethyl thiourea hydrochloride ( III ), which crystallizes with pyridinium chloride. Molecular and crystal structure are reported. With methyl dichlorophosphane N,N'-dimethylthiourea forms 1.2.3.4-tetramethyl-1.4.2.3-diazadiphospholidine-5-thione-2-sulfide ( IV ), which is characterized by its nmr and vibration spectra.     

Polymerisation en phase homogene du methyl-2 thiiranne amorcee par les thiolates de cadmium et de zinc. Influence des interactions monomere-metal sur la stereoregularite des polymeres

The stereoregularity of polymethylthiiranes initiated by zinc and cadmium thiolates depends upon the nature of the metal, temperature, solvent and the monomer/initiator concentrations ratio. Complexation of the metal with monomer has been studied by (¹³C) and (¹H) NMR on a model molecule, dimethylcadmium. Cryoscopic measurements made on a soluble cadmium thiolate have shown the presence of aggregates. The relationship between these observations and polymer stereoregularity is discussed.