Phosphorylated Allylchlorides: A Source of new Structures and Transformations

Abstract

General methods have been elaborated for the synthesis of O (or S)-phosphorylated vinylcholines, including the corresponding betaines of mono-, bis- and polymer structures, 5-membered heterocycles with P, O, S, N atoms in the cycle and exo- CHX= (X=H, C1) bond. The key substances, O-phos- phorylated allylchlorides, were obtained either by the well known Perkov reaction or according to scheme (I), worked out by us. The scheme is based on the reactions of 3- or 4-coordinated phosphorus with substituted ketones in the presence of triethylamine (B:).     

Formation of carbamates by reaction between ester carbanions and isocyanates: General regularities and scope

General regularities and scope of reactions carbanions with the ester group at carbanionic center and arylisocyanates resulting formation of carbamates by C → N migrations of ester groups have been described. The use of tosylisocyanates terminated reactions at the first stage with formation of corresponding tosylacylamides. © 2010 Wiley Periodicals, Inc. Heteroatom Chem 21:119–125, 2010; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20585     

New Aspects of the Staudinger React

Abstract

The unique inductive control of the first step of the Staudinger reaction is used for determination of the inductive characteristics of various radicals. The data are used for elaboration of a new direction in a purposeful synthesis of phosphorus pesticides which are more safe for people and surroundings.     

Synthesis,Properties, and Atropisomerism of Arylcarbamates with a Phosphonium Group

The reactions of the zwitterionic species 1 with ortho -substituted aryl isocyanates proceed in an unusual way, resulting in the formation of the P-containing carbamates 3. In the latter (except for X=F) the CH 2 P protons are anisochronous and give rise to an AB pattern at the corresponding temperatures (1H{31P}). When the temperature is increased, the AB pattern coalesces to a singlet. The j G c # values, together with all pertinent data, are listed.     

Novel Rearrangements and Heterocyclisation of P-Imides

Abstract

The preliminary introduction of electron accepting dichlorophosphine group at nitrogen atom of N-monosub-stituted α-aminoketones or α-aminocarbon acid esters increases the mobility of the α-carbon hydrogen atom so, that the intermolecular O-phosphorylation is enabled.¹     

Variation of the cosmic ray intensity in an 11-yr solar activity cycle: Experiment and theory

To study long-term variations of the cosmic ray intensity in a wide energy range, a basic model of the modulation of cosmic rays in the heliosphere has been developed at the Institute of Cosmophysical Research and Aeronomy, Siberian Branch, Russian Academy of Sciences. The model involves only one free modulation parameter, the ratio of the regular magnetic field to the turbulent field. It can be used to describe variations of the cosmic ray intensity in a wide energy range of 0.1 to 100 GeV. Attempts have been made to most correctly describe the features of the behavior of the cosmic ray intensity in several solar activity cycles.     

Molecular and crystal structure of 2-cyano-(2E)-pentadien-2,4-oic acid and ethyl-2-cyano-(2E)-pentadien-2,4-oate

X-ray study of 2-cyano-(2E)-pentadien-2,4-oic acid (1) and its ethyl ester (2) showed that the molecules of1 and2 in the crystalline phase form stacks by translating along the shortest crystallographic axis. The nature of the intermolecular interactions favoring the formation of such β-structures was analyzed within the framework of the Bader topological theory. Possible routes of topochemical reactions of compounds1 and2 are considered. Dedicated to the memory of Academician M. I. Kabachnik on his 90th birthday. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1991–1995, October, 1998.     

Synthesis of functionally substituted 2-cyanoacrylates

The conditions for the Knoevenagel synthesis of 2-cyanoacrylates containing double and triple bonds in the alkoxycarbonyl group have been studied. It was found that the esters are formed in 10–70 % yields by the condensation of the respective cyanoacetates with formaldehyde in the 11 ratio in the presence of piperidine, followed by the pyrolysis of the oligomers formedin vacuo at 170–200 °C in the presence ofpara-toluenesulfonic acid. The compounds synthesized readily undergo polymerization at room temperature and can be used as the basis for thermostable rapidly polymerizing adhesives.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 646–649, April, 1994.