Organic ions in the gas phase—XXI: Synthesis and mass spectra of deuteriothiophenes

Mass-spectral and n.m.r. analysis of thiophenes labeled by exchange with deuteriosulfuric acid establishes that exchange at the 2 and 5 positions is essentially complete before any deuterium is incorporated at positions 3 and 4. Thus, such exchange is a satisfactory procedure for position-specific labeling. Mass spectra of the labeled thiophenes show that about 60% of the [CHS]⁺ ion yield is derived from molecular ions that have not undergone prior rearrangement. The remaining 40% arises by a path or paths in which the four hydrogen atoms lose position identity. Other decomposition paths contributing to the mass spectrum are characterized by more nearly complete scrambling of hydrogens.     

Fluorine-containing nitrogen compounds—VI Sulfur tetrafluoride fluorination of aliphatic nitro acids

Sulfur tetrafluoride converts aliphatic nitro acids to the corresponding trifluoromethyl compounds. The yield is poor with primary nitro acids; but high yields of fluoronitrocarbons, otherwise difficult to obtain, are produced from certain γ-substituted butyric acids and from substituted acrylic acids. Eleven new fluoronitrocarbons are described.     

Carbene chemistry. Part 13 [1]. Preparation of sole fluoroallenes by a carbene route,and the reaction of allenes with halogenocarbenes

Fluoroallene and 1, 3-difluoroallene are prepared in good overall yield by the addition of dichlorocarbene to vinyl fluoride and 1, 2-difluoroethylene respectively, followed by pyrolysis of the dichlorocyclopropanes and treatment of the resulting dichloropropenes with zinc. Pyrolysis of 1, 1-dichloro-2-fluorocyclopropane over zinc gives fluoroallene directly.The reaction of allene with 2, 2, 3-trifluoro-3-trifluoro- methyloxiran at 180°C as a source of difluorocarbene gives both 1, 1-difluoro-2-methylenecyclopropane and its rearrangement product 1-(difluoromethylene)cyclopropane, the latter reacting more readily with a second difluorocarbene to give 2, 2, 3, 3- tetrafluorospiropentane. In an analogous way, fluoroallene reacts with dichlorocarbene, generated from trifluoro(trichloromethyl) silane at 140°C, to give $\text{E}$- and $\text{Z}$-1, 1-dichloro-2- (fluoromethylene)cyclopropane, 1-(dichloromethylene)-2-fluorocyclopropane, and 2, 2, 3, 3-tetrachloro-4-fluorospiropentane.