Neue Spiroverbindungen aus Cyclophosphazenen und Cyclodi[phosphadiazan]en

New Spiro Compounds from Cyclophosphazenes and Cyclodi[phosphadiazanes] Chlorocyclophosphazenes (Cl₂P = N)₃ and (Cl₂p = N)₄ react with dihydrazidophosphoric acid derivatives in THF in the presence of triethylamine to give the spirocyclic compounds Cl₄N₃P₃(NHN(CH₃))₂P(S)OC₆H₅, Cl₆N₄P₄(NHNH)₂P(S)OC₆H₅. Constitutions have been confirmed by MS, NMR, IR and elemental analysis.     

Arenesulfonylimines of methyl trifluoropyruvate in the cyclocondensation reactions with 1,3-C,N-and-N,N-binucleophiles

Reaction of arenesulfonylimines of methyl trifluoropyruvate with 1,3-C,N-and-N,N-binucleophiles led to a variety of N-sulfonylated fluorine-containing heterocycles, including the fused ones. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2171–2175, November, 2007.     

Mechanism of the reaction of neutral and anionic N-nucleophiles with α-halocarbonyl compounds

N-Acylalkylation of neutral and anionic N-nucleophiles with α-halocarbonyl compounds was investigated by quantum chemical methods in terms of the density functional theory and by experimental methods for 2,3-dihydroimidazo[2,1-b]quinazolin-1(10)H-5-one, its N-anion, and simpler model structures. High reactivity of these reagents is determined primarily by stabilization of transition states (TS) by bridge bonds involving halogen or nitrogen atoms rather than by conjugation, as has been commonly accepted. Bridged TS are formed by both the substitution mechanism S _N 2 and the addition-elimination mechanism. α-Haloalkyl-substituted zwitterions, which are potential intermediates of stepwise N-acylalkylation of neutral N-nucleophiles, do not exist in the isolated state, but they are rather efficiently stabilized upon solvation. These zwitterions, as well as analogous O-anions generated from anionic N-nucleophiles, can serve as intermediates of N-acylalkylation, as was demonstrated by localization of the corresponding TS. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1150–1164, June, 2007.     

Asymmetric intramolecular Diels-Alder reaction of a sulphoximine-substituted triene

The synthesis and thermally-induced intramolecular Diels-Alder (IMDA) reaction of (S)_s-(+)-S-[(1E,7E)-1,7,9-decatrienyl]-S-phenyl-N-(p-tolylsulphonyl)sulphoximine 4 is described. A model is proposed for the cis-selectivity of the cycloaddition based on previous results from the reactions of sulphonyl-substituted trienes. The stereochemistry of the major cis-fused cycloadduct is determined by single-crystal X-ray analysis of that obtained from reaction of racemic 4.     

Synthesis of functional polymers—Vinylidene fluoride based fluorinated copolymers and terpolymers bearing bromoaromatic side‐group

The radical co‐ and terpolymerization of 4‐[(α,β,β‐trifluorovinyl)oxy]bromo benzene (TFVOBB) with 1,1‐difluoroethylene (or vinylidene fluoride, VDF, or VF₂), hexafluoropropene (HFP), perfluoromethyl vinyl ether (PMVE), and chlorotrifluroroethylene (CTFE) is presented. Although TFVOBB could be thermocyclodimerized, it could not homopolymerize under radical initiation. TFVOBB could be copolymerized in solution under a radical initiator with VDF or CTFE comonomers, while its copolymerization with HFP or PMVE were unsuccessful. The terpolymerization of TFVOBB with VDF and HFP, or VDF and PMVE, or VDF and CTFE also led to original fluorinated terpolymers bearing bromoaromatic side‐groups. The conditions of co‐ and terpolymerization were optimized in terms of the nature of the radical initiators, and of the nature of solvents (fluorinated or nonhalogenated). Various monomer concentrations in the co‐ and terpolymers were assessed by ¹⁹F and ¹H‐NMR spectroscopy. The thermal and physico chemical properties were also studied. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5077–5097, 2004     

Spectroscopic studies of new model compounds for poly[N,N′-bis(phenoxyphenyl)pyromellitimide]

New model compounds for poly[N,N′-bis(phenoxyphenyl)pyromellitimide] have been synthesized in order to investigate the formation of imine bonds which are proposed to form during the curing process and lead to crosslinking in the bulk polymer. Raman studies show that terminal amines can react with imide carbonyls during curing to form C?N bonds. The Raman band due to C?N appears at 1656 cm^?1 and the band due to C?O closest to the imine bond is observed at 1742 cm^?1. These results are in agreement with previously published results on vapor deposited polyimide films.     

Spectroscopic study on the complex formation of chromogenic bridged calixarenes with aliphatic amines

The complex formation between chromogenic capped calix 4 arene derivatives comprising indophenol indicator group(s), and aliphatic amines has been studied by UV/Vis spectroscopy. The equilibrium constants have been determined in ethanol, and—for one ligand—also in dimethylsulfoxide. The results have been interpreted in terms of various types of host–guest interactions and of steric effects.     

Diethoxyphosphorylimine of methyl trifluoropyruvate in cyclocondensation with 1,3-C,N-and-N,N-binucleophiles

Reaction of diethoxyphosphorylimine of methyl trifluoropyruvate with 1,3-C,N-and-N,N-binucleophiles led to a variety of N-phosphorylated fluorine-containing heterocycles, including the fused ones. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2176–2178, November, 2007.     

An efficient phosphine-free palladium coupling for the synthesis of new 2-arylbenzo[b]thiophenes

Straightforward and rapid access to 2-arylbenzo[b]thiophenes has been developed. It involved a catalytic coupling of 3-activated benzo[b]thiophenes with several aryl halides in the presence of a phosphine-free palladium system. In case of fragile functional groups such as aldehydes, a quaternary ammonium was used as an additive as with the other substrates, the coupling performed better and faster in the presence of a crown ether, the best one being DCH-18-C-6, with good yields and low reaction times. This method would provide a direct access to novel structures of biological interest.     

Synthesis and properties of tricyclo[6.4.1.0]trideca-1,3(6),7,9,11-pentaene

A new cyclobutene-fused 1,6-methano[10]annulene was synthesized by pyrolysis of the sulfone and sulfinate adducts of 3,4-bis(methylene)-1,6-methano[10]annulene and its physical and chemical properties were disclosed.