Reaction of acetyloxiranes with acetonitrile

2-Acetyloxiranes react with acetonitrile in the presence of equimolar amounts of Lewis acids. It was established that the use of boron trifluoride etherate or sulfuric acid as the catalyst leads to 2,7- and 3,6-diepoxy-1,5-dioxocanes, the use of aluminum trichloride, as well as stannic chloride, leads to the corresponding chlorohydrins, while the use of gaseous boron trifluoride leads to 2-oxazolines in satisfactory yields. It is shown that the reaction is regio- and stereospecific and that the resulting substituted 2-methyl-5-acetyl-2-oxazolines have a cis configuration.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No, 8, pp. 1022–1024, August, 1982.     

Stereoelective polymerization of tert-butyl thiirane

The polymerization in bulk of racemic tert-butyl thiirane with a chiral initiator resulting from the reaction between diethylzinc and (? )3,3-dimethyl-1,2-butanediol produces an optically active polymer by preferential consumption of R enantiomer. The unreacted monomer is enriched in S enantiomer. The relative rate r of consumption of R enantiomer versus S enantiomer is as high as 2.8. Obtained polymer could be separated into two crystalline fractions: an optically active fraction, formed from regular sequences of R type enantiomeric units, and an optically inactive fraction which corresponds to a racemate. Experimental results are consistent with a stereospecific mechanism of addition, the two enantiomers being chosen by two different type of sites. The stereoelective process is due to an unequal number of these two types of sites.     

Isomerization of the thiirane ring to the thietane ring

Conclusions Compounds having the 3-thietanyl radical and not the thioglycidyl radical are obtained during the reaction of thioepichlorohydrin with potassium carbonate, potassium acetate, and the acid chlorides of acrylic acids.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2318–2321, October, 1968.     

Mechanism of sulfur extrusion from thiirane

The thermal decomposition of thiirane $\text{1}$ to olefin $\text{2}$ is not a first order reaction, and is therefore not a simple chelotropic process.     

Properties of adhesive compositions based on thiirane

Comparative investigations of adhesive composite materials based on thiirane and its oxirane analog are carried out. It is shown that compositions based on thiirane provide for a high rate of adhesion and cohesion strength gain. It is established that the maximal values of the adhesion strength for thiirane are reached at essentially lower concentrations of a curing agent than in the case of oxirane derivatives.     

Reaction for nucleophilic opening of thiirane ring by thiols

Conclusions The nucleophilic opening of the thiirane ring by thiols proceeds with greater difficulty than that of the oxirane ring. Aliphatic and aromatic thiols in nonpolar solvents, using homogeneous catalysis by bases, can be unambiguously mercaptoethylated by selecting the necessary ratios of thiol compound and ethylene sulfide.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 660–662, March, 1975.     

Properties of adhesive compositions based on thiirane and oxirane mixtures

Deformation, strength, dynamic-mechanical, and adhesive properties of polymers based on thiirane and oxirane mixtures were studied. The character of changes in indicators of properties on the ratio of the components in a mixture, as well as the duration and temperature of curing, was found to be quite complicated.     

Alkylation of N-arylcyanamides and electron-deficient phenols with (chloromethyl)thiirane

Alkylation of N-arylcyanamides with (chloromethyl)thiirane in aqueous alkaline solution provides an easy synthetic approach to N-aryl-N-(thietan-3-yl)cyanamides. Yields vary from 34 to 76% and are lower in the case of electron-deficient aryl substituents. The reaction with phenols containing electron-withdrawing groups results in formation of 3-(aryloxy)thietanes in 19–45% yields.     

Modification of epoxy polymers with epoxy thiirane derivative of benzimidazolone-2

An epoxy thiirane derivative of benzimidazolone-2 was synthesized. An addition of epoxy thiirane derivative of denzimidazolone-2 to epoxy rubber and epoxy composites was shown to increase their thermal stability, elasticity modulus, and cohesion and adhesion strengths, especially at higher test temperatures. The effect depends on the concentration of additive, hardening temperature, type of rubber, and other factors.     

Stereochemistry of the lithium aluminum deuteride reduction of the thiirane ring

Inversion of configuration has been demonstrated for the opening of the thiirane ring using lithium aluminum deuteride. This is based on a comparison of the optical activity of butane-2- obtained from 2,3-dimethylthiirane with that from reductive displacement of other functional groups.     

Reaction of singlet oxygen with thiirane: Implication for a spirodioxathiirane intermediate

Photosensitized oxygenation of biadamantylidene thiirane afforded, in addition to the corresponding thiirane oxide, the desulfurization products i.e., biadamantylidene and its oxidized products, dioxetane and oxirane, via a spirodioxathiirane intermediate.     

Oxiranyl-Β-aminovinylketones. 1. Preparation of oxiranyl-Β-dialkylaminovinylketones from acetyloxiranes and acetals of amides

Condensation of acetyloxiranes with dimethylacetals of N,N-dimethylformamide, N,N-diethylformamide, and N,N-dimethylacetamide gives the corresponding oxiranyl--dialkylaminovinylketones in good yield.For a preliminary communication, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1028–1031, August, 1987.