80632-83-3Relevant academic research and scientific papers
REACTIONS OF TETRAFLUOROETHENE OLIGOMERS. PART XII. CYCLOADDITION REACTIONS OF 3,3,4,4,4-PENTAFLUORO-2-PENTAFLUOROETHYL-2-TRIFLUOROMETHYLDIAZOBUTANE. A NOVEL SYNTHESIS OF PYRAZOLES
Coe, Paul L.,Cook, Michael I.
, p. 323 - 330 (2007/10/02)
The title diazoalkane (1) reacts smoothly with a variety of electron deficient alkenes to give, unexpectedly, the corresponding pyrazole derivatives.Thus, reaction with methyl or ethyl propenoate affords the methyl and ethyl esters of pyrazole-3-carboxylic acid (2) and (3).Reaction with diethyl maleate yields 3,4-bis-(ethoxycarbonyl)pyrazole (4), and dimethyl maleate gives the corresponding dimethyl ester (5).Treatment of (1) with propenonitrile afforded 3-cyanopyrazole (6), and with propenoic acid the corresponding pyrazole-3-carboxylic acid (7) was obtained.In all of these reactions two side products were isolated, namely perfluoro-(3-methylpent-2-ene) (8) and 3H-3-trifluoromethyldecafluoropentane (9).A mechanistic rationale for these unusual and potentially useful reactions is given.
REACTIONS OF TETRAFLUOROETHYLENE OLIGOMERS. PART 1. SOME PYROLYTIC REACTIONS OF THE PENTAMER AND HEXAMER AND OF THE FLUORINE ADDUCTS OF THE TETRAMER AND PENTAMER
Coe, Paul L.,Sellers, Simon F.,Tatlow, John Colin
, p. 417 - 440 (2007/10/02)
Pyrolyses of these highly branched fluorocarbons over glass beads caused the preferential thermolyses of C-C bonds where there is maximum carbon substitution.Fluorinations of perfluoro-3,4-dimethylhex-3-ene (tetramer) (I) and perfluoro-4-ethyl-3,4-dimethylhex-2-ene (pentamer) (II) over cobalt (III) fluoride at 230 deg C and 145 deg C respectively afforded the corresponding saturated fluorocarbons (III) and (IV), though II gave principally the saturated tetramer (III) at 250 deg C.Pyrolysis of III alone at 500-520 deg C gave perfluoro-2-methylbutane (V), whilst pyrolysis of III in the presence of bromine or toluene afforded 2-bromononafluoorobutane (VI) and 2H-nonafluorobutane (VII) respectively.Pyrolysis of perfluoro-3-ethyl-3,4-dimethylhexane (IV) alone gave a mixture of perfluoro-2-methylbutane (V), perfluoro-2-methylbut-1-ene (VIII), perfluoro-3-methylpentane (IX), perfluoro-3,3-dimethylpentane (X), and perfluoro-3,4-dimethylhexane (III).Pyrolysis of IV in the presence of bromine gave (VI) and 3-bromo-3-trifluoromethyldecafluoropentane (XI): with toluene, pyrolysis gave VII and 3H-3-trifluoromethyldecafluoropentane (XII).Pyrolysis of II at 500 deg C over glass gave perfluoro-1,2,3-trimethylcyclobutane (XIII) and perfluoro-2,3-dimethylpenta-1,3(E)- and (Z)-diene (XIV) and (XV) respectively.The diene mixture (XIV and XV) was fluorinated with CoF3 to give perfluoro-2,3-dimethylpentane (XVI) and was cyclised thermally to give the cyclobutene (XIII).Pyrolysis of perfluoro-2-(1'-ethyl-1'-methylpropyl)-3-methylpent-1-ene (XVII) (TFE hexamer major isomer) at 500 deg C gave perfluoro-1-methyl-2-(1'-methylpropyl)cyclobut-1-ene (XVIII) and perfluoro-2-methyl-3-(1'-methylpropyl)buta-1,3-diene (XIX).Fluorination of XVIII over CoF3 gave perfluoro -1-methyl-2-(1'-methylpropyl)cyclobutane (XX), which on co-pyrolysis with bromine gave VI.XIX on heating gave XVIII.Reaction of XVIII with ammonia in ether gave a mixture of E and Z 1-trifluoromethyl-2-(1'-trifluoromethylpentafluoropropyliden-1'-yl)tetrafluorocyclobutylamine (XXI) which on diazotisation and hydrolysis afforded 2-(2'trifluoromethyltetrafluorocyclobut-1-en-1'-yl)-octafluorobutan-2-ol (XXII).
