ChemInform Abstract: PHOTODECARBONYLATION OF PERFLUOROOXAALKYL KETONES

Abstract

Bestrahlt man Perfluorketon (Ia) oder (Ib) bei 20°C mit einer Quarzlampe, so wird CO abgespalten und man erhält quantitativ Perfluorderivate (IIa) bzw. (IIb).

2,3-Epoxyperfluoro-2-methylpentane in reactions with urea and thiourea

“…In the 19 In the 1 H NMR spectrum of compound VI in DMSOd 6 solution the signal of OH proton appears as a doublet with the coupling constant of 2.8 Hz due to its coupling with F A atom of the difl uoromethylene group at C 4 . Note that analogous coupling 4 J HF we observed previously in oxazolines obtained from 2,3-epoxyperfl uoroalkanes of normal structure [10].…”

“…The stabilization of carbanion intermediate A is the most probable to occur along route a in the process of the intramolecular "haloform" cleavage of intermediate ketone B resulting from the intramolecular attack of the amino group at the carbonyl carbon atom leading to the formation of isothiourea derivative II. The tendency of perfl uoroalkyl isopropyl ketones to suffer the haloform cleavage in reactions with amines was demonstrated in [18,19].…”

“…The structure of compound VI was confi rmed by IR, 1 H, 19 F, 13 C NMR spectra, elemental and XRD analysis.…”

“…To obtain more complete information on the structure of isothiourea II in supplement to the data of IR, 1 H, 13 C, 19 F spectroscopy and elemental analysis we carried out XRD study of its single crystal. XRD analysis confi rmed the formation of compound II in the reaction of perfl uorooxirane I with thiourea (Scheme 1, Fig.…”

“…The analysis of 19 F NMR spectra of the reaction mixture obtained in the reaction of oxide I with urea in acetonitrile revealed the presence of perfl uoro-2-methyl-3-pentanone (V) that apparently forms as a result of elimination of urea molecule from intermediate C or by ionic isomerization of epoxide I effected by F -arising in the course of the reaction [12].…”