On the reaction of diphenylketene with isocyanides

The products obtained from the reaction of diphenylketene with a variety of isocyanides are shown to depend heavily on the concentration of diphenylketene; a high concentration results in the precedented dioxolane derivatives, at much lower concentrations the reactions follow an alternative course and polycyclic beta-lactams are generated by a cascade of formal pericyclic reactions.     

Reaction of hexafluoroacetone with azacyclohexanes

Conclusions Piperidine and its C-methyl derivatives are aromatized by hexafluoroacetone with simultaneous C-alkylation at one or both of the -positions of the ring, and in the case of - and -methylpyridines also at the CH₃ group.For previous communication, see [1].Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1652–1656, July, 1989.     

Reactions of diarylamines with hexafluoroacetone

Diphenylamine reacts with hexafluoroacetone to give a mixture of products, of which 2-(1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl)diphenylamine (II) was isolated. N-Arylanthranilic acids modify the 1,1,1,3,3,3-hexafluoro-2-hydroxy-2-propyl group upon the reaction of its sodium salt with the hydrate of hexafluoroacetone (I) under mild conditions. This method gave 4-(1-hydroxy-1-trifluoromethyl-2,2,3-trifluoroethyl)-N-(2,3-xylyl)anthranilic acid from N-(2,3-xylyl)anthranilic acid in 93% yield.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 952–954, April, 1991.     

Reaction of O-triphenylphosphiminoformylisobutyrohydroximoyl chloride with hexafluoroacetone

O-Triphenylphosphiminoformylisobutyrohydroximoyl chloride reacts with hexafluoroacetone to give the product of a sigmatropic rearrangement, namely,-(O-isopropylchloroformimino) hexafluoroisopropyl isocyanate.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1921–1923, August, 1991.     

Reaction of hexafluoroacetone with acetic anhydride

Conclusions When acetic anhydride reacts with hexafluoroacetone it acts not as an acetylating agent, but as a compound containing an active methylene group.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 1661–1662, September, 1966.     

N-benzoylimine of hexafluoroacetone

Conclusions The N-benzoylimine of hexafluoroacetone is considerably more active than the imine of hexafluoroacetone in reaction with nucleophilic reagents.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2046–2048, November 1965     

Reactions of ytterbium and magnesium gallylene complexes with carbon dioxide and diphenylketene

Reactivity of ytterbium and magnesium complexes of gallylenes against carbon dioxide and diphenylketene has been assessed. Ytterbium complex of redox-active gallylene [{(dpp-bian)Ga}₂Yb(DME)₂] (dpp-bian = 1,2-bis[(2,6-diiso-propylphenyl)imino]acenaphthene) on treatment with CO₂ gives complex [(dpp-bian)Ga(DME)Me], while the treatment of magnesium-stabilized gallylene[{(dpp-bian)Ga}₂Mg(DME)₂] with Ph₂CCO affords cycloadduct [(dpp-bian)(Ph₂CCO)GaMe].     

Reaction of phosphorus-containing cyanoguanidines with hexafluoroacetone imines

Substituted hexafluoroacetone imines react with 1-(2-cyanoguanidino) alkylphosphonates at the CN group at –5-0°C, forming [2+4]-cycloaddition products, which are phosphorus-containing 4,4-bis(trifluoromethyl)1,3,5-oxadiazines. The reaction products are readily alkylated by substituted hexafluoroacetone imines at the nitrogen atom of the guanidine fragment. The two reactions are accompanied by tautomeric transformations of the guanidine fragment of the molecules. An NMR spectral analysis was carried out.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2815–2819, December, 1989.     

Reaction of hexafluoroacetone and pentafluoronitroacetone with methyl propargyl ether

Conclusions The reaction of hexafluoroacetone and pentafluoronitroacetone with metkyl propargyl ether was studied. The intermediate methoxyallenylcarbinols give [2+2]-cycloadducts with the starting fluoroketones and also cyclize to give substituted 2,5-dihydrofurans.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 933–935, April, 1988.     

The addition of methyl radicals to hexafluoroacetone

The reaction of methyl radicals (Me) with hexafluoroacetone (HFA), generated from ditertiary butyl peroxide (dtBP), was studied over the temperature range of 402–433 K and the pressure range of 38–111 torr. The reaction resulted in the following displacement process taking place: where TFA refers to trifluoroacetone. The trifluoromethyl radicals that were generated abstract a hydrogen atom from the peroxide: such that k_6a is given by: where θ = 2.303RT kcal/mol. The interaction of methyl and trifluoromethyl radicals results in the following steps: Product analysis shows that k₁₇/kk = 2.0 ± 0.2 such that k₁₇ = 10^10.4±0.5M^?1 · s^?1. The rate constant k₅ is given by: It is concluded that the preexponential factor for the addition of methyl radicals to ketones is lower than that for the addition of methyl radicals to olefins.     

Reaction of hexafluoroacetone ethoxycarbonylimine with trimethyl phosphite

Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2879–2880. December, 1990.