- Generation of radical species in surface reactions of chlorohydrocarbons and chlorocarbons with fluorinated gallium(III) oxide or indium(III) oxide
-
The reactions of C1 and C2 chlorohydrocarbons and chlorocarbons have been studied with the Lewis acid catalysts fluorinated gallium(III) oxide and fluorinated indium(III) oxide, respectively. Product analysis shows chlorine-for-fluorine exchange reactions together with the formation of 2-methylpropane and its chlorinated analogues 2-chloromethyl-1,3-dichloropropane and 2-chloromethyl-1,2,3-trichloropropane. Reactivities of the chlorohydrocarbon probe molecules show fluorinated gallium(III) oxide to be a stronger Lewis acid than fluorinated indium(III) oxide. The formation of the symmetrical butyl compounds is consistent with the generation of surface radical species and is also consistent with a 1,2-migration mechanism operating within radical moieties at the Lewis acid surface.
- Thomson
-
p. 1881 - 1885
(2007/10/03)
-
- Synthesis and properties of poly
-
The synthesis of poly has been performed in four steps.Chlorination of pentaerythritol produced a mixture of halogenated alcohols, which, in an alkaline medium, led to a mixture of hydroxylated and chlorinated oxetanes.Of these, the bis(3-chloromethyl) oxetane (BCMO) was etherified with C6F13C2H4OH via phase-transfer catalysis to yield the mono- and di-substituted fluorinated oxetanes.In a last step, the mono-substituted oxetane was cationically polymerized using BF3*OEt2 as the catalyst, and was characterized by 1H and 13C NMR spectroscopy.Finally, several physical properties have been determined such as the viscosity, glass transition and decomposition temperatures, and surface properties.
- Ameduri, Bruno,Boutevin, Bernard,Karam, Lina
-
-
- KINETICS OF THE TRANSFORMATION OF 5-R-5-CHLOROMETHYL-2-THIA-2-OXO-1,3-DIOXANES TO 1,3-DICHLORO-2-R-2-CHLOROMETHYLPROPANES
-
Investigation of the kinetics of the formation of 1,3-dichloro-2-R-2-chloromethylpropanes from 5-R-5-chloromethyl-2-thia-2-oxo-1,3-dioxane by the action of an equimolecular mixture of thionyl chloride and dimethylformamide (the Vilsmeier-Haack reagent) led to the conclusion that the low activation energies and the large negative entropy values indicate the participation of a stable intermediate in the investigated complex many-stage reaction.
- Bolotov, A. S.,V'yunov, K. A.
-
p. 187 - 191
(2007/10/02)
-
- PRODUCTION OF CYCLIC SULFITES AND THEIR TRANSFORMATION INTO SUBSTITUTED TRI(CHLOROMETHYL)METHANES
-
The production of cyclic sulfites from trihydric alcohols and their conversion into chlorides by the action of DMFA-SOCl2 complex are described.By PMR and IR spectroscopy it was shown that cyclic sulfites exist preferentially in the chair conformation with the axial orientation of the S=O bond.It was established that the chlorides are formed in two parallel paths, i.e. directly from trihydric alcohols and their cyclic sulfites.
- Bolotov, A. A.,Rodin, A. A.,V'yunov, K. A.,Ginak, A. I.,Sarkisov, Yu. S.
-
p. 1812 - 1819
(2007/10/02)
-
- The Spiropentyl Radical and Some Homolytic Reactions of Spiropentane
-
Spiropentyl radical was generated by Hydrogen abstraction from spiropentane by t-butoxyl radical and its e.s.r. spectrum obtained.The experimental e.s.r. parameters were compared with computational results obtained using semi-empirical SCF MO methods.The spiropentyl radicals do not undergo β-scission in the observable temperature range (T H2 attack by the halogen atom to give 1-(halogenomethyl)cyclopropylmethyl radicals.The β-scission of these latter radicals has been inves tigated by e.s.r. spectroscopy and by the reduction of 1,1-bisbromomethylcyclopropane with tri-n-butyltin hydride.
- Kennedy, Alan J.,Walton, John C.,Ingold, Keith U.
-
p. 751 - 757
(2007/10/02)
-
