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.     

Bistrifluoromethylcyclopropenes

Hexafluorobut-2-yne reacts with dichlorocarbene [generated by thermal decomposition of the silane CC1₃SiF₃] to give 3,3-dichlorobistrifluoromethyl- (I) and 1,3-dichlorobistrifluoromethyl-cyclopropene (II).

The 3,3-dichloro-compound (I) is isomerised to (II) by heat, light, or chemical catalysis, but high yields of either pure cyclopropene may be obtained by modification of the reaction conditions. The cyclopropenium ion (III) is formed when either (I) or (II) is treated with antimony pentafluoride.Both (I) and (II) undergo free-radical addition of halogens, but the slow reaction of (II) with trifluoromethyl radicals gives a mixture of products. Nucleophilic substitution of chloride ion from both cyclopropenes occurs very readily, and with ethoxide ions both mono- and di-ethoxybistrifluoromethylcyclopropenes are obtained. The cyclopropenes also react with fluoride ion, iodide ion, or Grignard compounds.     

Cyclopropane chemistry. Part 5 [1,2]. Hexafluorocyclopropane as a source of difluorocarbene

Thermolysis of hexafluorocyclopropane in the presence of ethylene, propene, vinyl chloride, and vinyl bromide gives good yields of the corresponding 1,1-difluorocyclopropanes, formed by addition of difluorocarbene to the olefin. The tetrafluoroethylene formed dimerises to octafluorocyclobutane, co-dimerises with the olefin, or survives, depending on the reaction conditions. With allene, hexafluorocyclopropane gives 1-(difluoromethylene)cyclopropane, 2,2,3,3-tetrafluorospiropentane, and products derived from tetrafluoroethylene and allene.     

Perfluoroalkyl derivatives of nitrogen. Part LI [1]. Reaction of the N-halogenobistrifluoromethylamines (CF3)2NX (X=Cl,Br) with norbornadiene

Reaction of the amines (CF₃)₂NX (X=Cl,Br) with norbornadiene either in solvent (CH₂Cl₂) at ?78 °C in the dark or in the vapour phase at 20 °C in daylight gives a mixture of 3-halogeno-5-($\text{NN}$-bistrifluoromethylamino)nortricyclene ($\text{exo}$, $\text{endo}$-and $\text{exo}$, $\text{exo}$-isomers) and $\text{exo}$-5-($\text{NN}$-bistrifluoromethylamino)- $\text{anti}$-7-halogenonorbornene in quantitative yield formed $\text{via}$ halonium ion addition to the diene. The reaction of the amine (CF₃)₂NBr in solvent Me₂O or Et₂O at ?78 °C in the dark gives the same products in low yield, together with 3-bromo-5-alkoxynortricyclene ($\text{exo}$, $\text{endo}$- and $\text{exo}$, $\text{exo}$-isomers) and the amine (CF₃)₂NR (R=Me, Et) in high yield.     

Some Isoperimetric Inequalities in Electrochemistry and Hele Shaw Flows

Isoperimetric inequalities are applied to a moving-boundaryproblem for doubly-connected domains. This problem occurs forexample in electrochemistry, in which case the domains in questionare the electrolyte of an electrolytic cell. The two electrodessurrounding the electrolyte are assumed to grow or dissolve,at different rates in general, by electrochemical reaction.We obtain optimal estimates showing, for example, that the leastchange in volume of each electrode always occurs in sphericalsymmetry.     

Reaction of hexafluoropropene with halogenoalkanes

Insertion of hexafluoropropene under thermal and/ or photochemical conditions occurs into C-H bonds of the halogenomethanes MeCl, CH₂Cl₂, CHCl₃, MeF, CH₂F₂ and CHF₂Cl and the fluoroethanes EtF, MeCHF₂ and MeCF₃, into CH and CCl bonds of the monochloroalkanes EtCl, MeCHFCl, prⁿCl, prⁱCl, Bu^tCl and BuⁱCl and into CCl bonds of allyl chloride and the chloroalkanes CH₂ClCH₂Cl, MeCHCl₂, CH₂ClCHCl₂ and MeCCl₃.     

Organosilicon chemistry : XXX. Homogeneous catalysis by iridium(I) complexes of the reaction between silanes and alcohols or dideuterium

The complexes IrX(CO)L₂, IrCl(N₂)(PPh₃)₂, [IrCl(C₈H₁₄)₂]₂, and IrClL₂ (X = halide, L = tertiary phosphine or arsine) are excellent catalysts for the reactions of HSiR₃ (R = Ph, Et, OEt) with R′OH (R′ = Et, Me). With IrX(CO)L₂ the reactionis inhibited by an excess of HSiR₃ and by the product, H₂. The proposed mechanism involves intermediate formation of ClSiR₃ by elimination from the silyl complex IrHX(SiR₃)(CO)L₂. The iridium(I) complex IrH(CO)L₂, also formed in this step, reacts with HCl in the catalytic cycle or with H₂ or HSiR₃ in the inhibition reactions. The exchange reaction of HSiR₃ (R = OEt, Et) with D₂ is catalysed by IrCl(CO)(PPh₃)₂ or IrH₃(CO)(PPh₃)₂, and probably has a similar mechanism. Catalysis of the HSiR₃-R′OH reaction by the other iridium(I) complexes probably involves direct attack by the alcohol on the coordinated silyl group of the intermediate IrHCl(SiR₃)L₂.     

Organophosphorus chemistry. Part 21 [1]. Insertion of olefins into P  CF3 bonds

Tris(trifluoromethyl)phosphine and ethylene reacted efficiently under u.v. irradiation to give 3,3,3-trifluoropropylbis(trifuomothyl) phosphine in good yield. With vinyl fluoride, vinylidene fluoride, and propene the reaction was regioselective rather than regiospecific, and the yield of 1:1 adduct was low. In these reactions, and in those with vinyl chloride, but-1-ene, and hexafluoropropene, in which only traces of 1:1-adduct could be detected, the bulk of the olefin and of the phosphine was recovered, and numerous by-products consistent with radical intermediates were identified. With propyne, 1,1,1-trifluoro-3-bis(trifluoromethyl)phosphino-cis-but-2-ene was obtained in moderate yield, but no reaction occurred between the phosphine and either but-2-yne or hexafluorcbut-2-yne. Tris(trifluoromethyl)phosphine oxide did not form an adduct with ethylene, tetrafluoroethylene, or propyne.Bis(trifluoromethyl)phosphine and dimethylphosphine both reacted readily under u.v. irradiation with 3,3,3-trifluoropropene, the phosphinyl radical attacking the terminal carbon in each case.     

Application of mass spectrometry to the study of fluoropolymers. II. The copolymer from trifluoronitrosomethane (CF3NO) and tetrafluoroethylene (C2F4)

The techniques of mass spectrometry have been applied to the copolymer from tri-fluoronitrosomethane (CF₃NO) and tetrafluoroethylene (C₂F₄). The copolymer yields spectra of a repetitive nature, typical of the repeating units in the polymer chain. Molecules with masses up to m/e 6400 can be distilled from the unfractionated polymer which is stable up to 220°C. Interpretation of the mass spectrum suggests a linear structure for the regular polymer.