A. F. Kolomiets

Reaction of α,α,ω-trihydroperfluoroalkyl esters of phosphorous acid with polyfluorocarbonyl compounds

Conclusions1.The α,α,ω-trihydroperfluoroalkyl esters of phosphorous acid react with polyfluorocarbonyl compounds the same as unfluorinated phosphites, but exhibit a lower reactivity.2.The reaction of tris (1,1,3-trihydroperfluoropropyl) phosphite with the hydrates of hexafluoroacetone and trifluoroacetaldehyde respectively givesα-monohydroperfluoroisopropyl bis (1,1,3-trihydroperfluoropropyl) phosphate and 2,2,2-trifluoroethyl bis (1,1,3-trihydroperfluoropropyl) phosphate.

Certain reactions of tris(α,α,ω-trihydroperfluoroalkyl) phosphites

ConclusionsCertain properties of tris(1,1,3-trihydroperfluoropropyl), tris(1,1,5-trihydroperfluoropentyl), and tris(1,1,7-trihydroperfluoroheptyl) phosphites were studied, and it was shown that the presence of theα,α,ω-trihydroperfluoroalkoxyl groups determines their behavior as the result of an increase in the v-acceptor and decrease in the n-donor ability of the phosphorus atom.

Solvent effect on the reaction of alkenes with phosphorus pentachloride

Conclusions1.The solvent effect on the conditions and course of reactions of PCl5 with alkenes was studied. The temperature at the onset of these reactions decreased with increasing polarity of the medium and donor properties of the solvents.2.The reaction pathways for PCl5 with alkenes are determined not only by the alkene structure, as had been assumed previously, but also by the temperature conditions for the condensation and decomposition of the adducts and also by the solvent properties. Depending on these factors, the final reaction products may be chloroalkenes, dichloroalkanes, phosphorylated alkenes, or 2-chloroalkanes.3.Proposals were offered for the nature of the transition states in the reactions of PCl5 with alkenes.

Structure and properties of haloacyl isothiocyanates

The stable form of the haloacyl isothiocyanates ia the isothiocyanate form, independent of the nature of the acyl moiety. In reactions with nucleophilic reagents these compounds exhibit a dual reactivity, which is caused by the enhanced electrophilic properties of the carbonyl carbon.

Mercury salt of difluoronitroacetic acid

1. n nWe obtained and characterized the stable mercury salt of difluoronitroacetic acid, which exists as the intramolecular donor-acceptor complex. n n n n n2. n nThe alkylation of the mercury salt of difluoronitroacetic acid with alkylhalides in ether and acetonitrile was studied.

Mechanism of reaction of organylisothiocyanatosilanes with ethylene oxide

1. n nThe reaction of trimethylisothiocyanatosilane with ethylene oxide is catalyzed by hydroxyl-containing compounds. n n n n n2. n nA mechanism was proposed for the reaction of organylisothiocyanatosilanes with ethylene oxide, which includes the formation of thiocyanic acid, condensation of the latter with ethylene oxide, and exchange reaction of the organylisothiocyanatosilane with the formed 2-thiocyanatoethanol.

Synthesis of haloacyl isothiocyanates

The acid chlorides and acid fluorides of halocarboxylic acids under mild conditions enter into exchange reactions with trimethylthiocyanosilane and tetrathiocyanotin to give the isothiocyanates of halocarboxylic acids.

Reactions of acid chlorides of halocarboxylic acids and tetracoordinated phosphorus acids with 2-thiocyanatoethoxytrimethylsilane

1. n nThe reactions of 2-thiocyanatoethoxytrimethylsilane with the acid chlorides of halocarboxylic acids and tetracoordinated phosphorus acids proceed according to equilibrium reactions, with the formation of the 2-thiocyanato esters of the corresponding acids. n n n n n2. n nThe equilibrium of the reaction is shifted to the right more strongly the more polar and polarizable the bond between the chlorine atom and the carbonyl carbon in the case of the halocarboxylic acids, and the greater the ability of the phosphorus atoms to form an additional bond via the d-orbitals.