Methyl hypofluorite

Isopropyl hypochlorite, 1247 Methyl hypochlorite, 0434 Methyl hypofluorite, 0433 Nitryl hypochlorite, 4026 Pentafluoroselenium hypofluorite, 4368 Pentafluorosulfur hypofluorite, 4367... 

When fluorine is passed through a mixture of methanol in acetonitrile at -45 °C or propionitrile at -75 °C a solution of methyl hypofluorite, stabilised by the solvent, is produced [200]. While methyl hypofluorite can be isolated, its chemistry has been investigated by treating various substrates with freshly prepared solutions rather than with isolated material. Unlike the hypofluorites which have been discussed so far, methyl hypofluorite behaves as a synthon for the rare methoxylium species, MeO+ , and adds to various alkenes electrophilically in accordance with Markovnikov s Rule [201]. In the reaction between methyl hypofluorite and indene, almost exclusive trans addition occurred. 

Reactions with Methyl Hypofluorite and ferf-Butyi Hypofluorite... 

Methyl hypofluorite (McOF) and tert-butyl hypofluorite (f-BuOF) have been prepared by the reaction of elemental fluorine with methanol and tert-butyl alcohol, respectively, in acetonitrile or propionitrile at — 78 °C. Methyl hypofluorite can be removed from the reaction mixture in a stream of nitrogen and purified by fractional distillation the liquid compound has a freezing point of — 142 C, is moderately long-lived, but explodes upon rapid warming.is tert-Butyl hypofluorite melts around — 94 °C and has an extrapolated boiling point of about 40 C the neat reagent must be regarded as a substance the hazards of which have not been fully defined.16... 

Reaction of aromatic molecules with methyl hypofluorite results in the formation of the methoxy products, e. g. 1,2,4,5-tetramethylbenzene (durene) gives methoxydurene in 90 % yield, and hexamethylbenzene provides the mono- (23) and dibenzylic (24) products. 9... 

Fluoro-1,2,4-trioxolane, see Fluoroethylene ozonide, 0749 Fluoroxymethane, see Methyl hypofluorite, 0441 f Formaldehyde, 0415... 

Fluorine perchlorate, 3970 Heptafluoroisopropyl hypofluorite, 1031 Heptafluoropropyl hypofluorite, 1057 Hypochlorous acid, 3989 Isopropyl hypochlorite, 1243 Methyl hypochlorite, 0433 Methyl hypofluorite, 0441 Nitryl hypochlorite, 4020 Pentafluoroselenium hypofluorite, 4362 Pentafluorosulfur hypofluorite, 4361... 

Calculations have shown that the rotational barrier of the C-O bond in methanol (1.1 kcal/mol) is significantly lower than the corresponding rotational barrier of methyl hypofluorite (MeOF, 3.7 kcal/mol) or methyl hypochlorite (MeOCl, 3.5 kcal/mol), in which a strong [Pg.19]

The hypofluorite process, known since the 1970s, has been developed only recently for commercial application. The starting material is carbonyl fluoride, which is fluorinated in the presence of a catalyst to produce methyl hypofluorite ... 

Subsequent addition of methyl hypofluorite to 1,2-dichlorofluoroethylene followed by dehalogenation yields methylvinyl ether (MVE), another fluoroalkoxy monomer38 ... 

The simultaneous addition of fluorine and an alkoxy group to give 1 can be carried out by the use of methyl hypofluorite or by fluorination in alkanols with cesium fluoroxysul-fate," " perchloryl fluoride, xenon difluoride,fluorine, 1-fluoro-... 

Addition of Methyl Hypofluorite to Alkenes General Procedure ... 

The retardation of the reaction with chlorine (which reacts with CF3 to form CF3CI) makes it possible to study step (1). Stewart and Cady found that for this step, A = 1.33 X 10 exp (—25,000/ 7 ) l.mole sec . Porter and Cady (refs. - ) estimated a energy of 47 kcal.mole for the O-F bond in trifluoro-methyl hypofluorite, from equilibrium studies at 367-467 °C in the system... 

Nonfluorinated alkyl hypofluorites (ROF) are mostly unstable and decompose through HF elimination with formation of the corresponding carbonyl compounds. However, tert-butyl [24] and methyl hypofluorites (RO+ F ) [25] can be generated and employed in situ for alkoxy-fluorination of alkenes. The relatively higher stability of both hypofluorites comes from the nonavailability of a-hydrogens which are reactive to the radical hydrogen abstraction [26]. Both of the hypofluorites add to carbon-carbon double bonds regio- and stereoselectively as shown in Scheme 2.48. The anti-addition mode (37-39) is in sharp contrast to the syn-addition mode of electrophilic fluoroalkoxy and acetoxy reactions of fluorinated alkyl and acetyl hypofluorites (RfO F+, 40-41) [27]. 

Acetyl hypofluorite (AcOF) and methyl hypofluorite (MeOF) as fluorinating agents of olefins and aromatics3 HOF-MeCN an oxygen transfer agent in epoxidation of electron poor olefins, in Baeyer-Villiger reaction, in oxidation of a-amino acids to a-nitro acids. 

The cationic intermediate in this reaction appears to have some bridged ion character. Addition of (CH3)3COF to acenaphthylene (23) gave threo-1-fluoro-2-f-butoxyacenaphthene (27) as the only adduct (equation 9.21). Similarly, methyl hypofluorite (H3COF, prepared in situ from the reaction of F2 with methanol) also adds to alkenes, as in ttie conversion of indene (28) into ( )-fra s-l-fluoro-2-methoxyindane (29, equation 9.22). ... 

Xenon(II) Fluoride and methanol react to form Methyl Hypofluorite, which reacts as a positive oxygen electrophile in the presence of BF3 (etherate or methanol complex) to yield anti-Markovnikov fluoromethoxy products from alkenes." " ... 

Deamination of 9a-amino-ll-keto steroids (e.g., 337) (400) is an alternate means to accomplish the Cio- Cg methyl rearrangement (400, 432). In the fluorination of a steroid with methyl hypofluorite,... 

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