Synthesis and structures of 1,1"-dialkyl-3,3"-bidiaziridines

First representatives of 3,3"-bidiaziridines, viz., 1,1"-dialkyl-3,3"-bidiaziridines, were synthesized and isolated as mixtures of two diastereomers. In the case of Alk = Me, the diastereomers were separated. It was demonstrated by nuclear Overhauser effect experiments and X-ray diffraction analysis that the diastereomers are the racemate (rac-1R*,2R*,3S*,1"R*,2"R*,3"S*) and the meso-form (1S*,2S*,3R*,1"R*,2"R*,3"S*).     

Synthesis of thienothiopyranthiones by a new molecular rearrangement

On heating with alkynes, the readily prepared 1,3-dithioles 3 undergo a new cycloaddition reaction and an unprecedented molecular rearrangement with loss of chlorine to give the first 7H-thieno[2,3-c]thiopyran-7-thiones 4 and 4H-thieno[3,2-c]thiopyran-4-thiones 5 whose structures were confirmed by X-ray diffraction. Unexpectedly, the different alkynes used to form 3 and to convert it into 4 and 5 were incorporated regiospecifically into the thiophene and thiopyran rings, respectively. [reaction: see text]     

Structures of cationic metallacarborane complexes [(η-9-Me2S-7,8-C2B9H10)Ni(μ-Cp)Ni(η-9-Me2S-7,8-C2B9H10)]+ and [Cp*Ru(Me2S-C2B9H10)RuCp*]+

The structures of the metallacarborane cations [(-9-Me₂S-7,8-C₂B₉H₁₀)Ni(-Cp)Ni(-9-Me₂S-7,8-C₂B₉H₁₀)]⁺ (2) and [Cp*Ru(Me₂S-C₂B₉H₁₀)RuCp*]⁺ (4b) were established by X-ray diffraction analysis. These results confirmed the triple-decker structure proposed for complex 2 earlier, whereas complex 4b proved to be 13-vertex dimetallacarborane rather than the triple-decker complex, as has been suggested earlier.Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1879–1883, September, 2004.     

Diastereoselective synthesis of substituted 1,3,6-triazabicyclo[3.1.0]hexanes

A general method was developed for the synthesis of substituted 1,3,6-triazabicyclo[3.1.0]hexanes via intramolecular aminomethylation of the NH group of the diaziridine ring by the reactions of 3-aminomethyl-1,3-dimethyldiaziridine with aliphatic, aromatic, and heteroaromatic carbonyl compounds. These reactions with aldehydes proceeded diastereoselectively to form mixtures of two racemates, viz., 1R*,2R*,5R*,6R* and 1R*,2S*,5R*,6R*, in a ratio of (3—20) : 1, the predominant diastereomer being isolated in all cases. The reactions with symmetrical ketones gave rise exclusively to the (1R*,5R*,6R*) racemate. The predominant diastereomer 1R*,2R*,5R*,6R*-2-(2-bromothien-5-yl)-1,3,6-triazabicyclo[3.1.0]hexane crystallized as a conglomerate. The structure of one of its enantiomers was established by X-ray diffraction analysis.     

Mono and bis[N-aryl(benzyl)]amides of phosphorylacetic acids. One-pot synthesis and extraction of actinides from nitric acid solutions

A one-pot synthetic route to phosphorylacetic acid N-aryl(alkylaryl)amides, including those containing two phosphorylmethylcarbamoyl moieties attached to the arene framework, has been developed. The method is based on reactions of amines with the corresponding acid chlorides generated in situ with the use of phosphorus trichloride as a mild chlorinating agent. The compositions and structures of the compounds obtained and their extraction ability toward Am^III were determined. Suggestions were made about the compositions of the extracted complexes with phosphorylacetic acid N-aryl(alkylaryl)amides. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1387–1394, August, 2006.     

New approach to chemical modification of PIM-1 for gas separation membranes

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