Methanol, reaction with fluorinated dienes

As in the case of the fluorination of alkenes in methanol, reaction with 1,3-dienes depends strongly on the catalyst used, and five products were formed by reaction of 2,3-dimethyl-1,3-butadiene when hydrogen fluoride or boron trifluoride were used as catalysts83 (Scheme 27). 

An oxidizer. The liquid is a sensitive explosive. Explosive reaction with carbon disulfide (when ignited), methanol (when ignited), pentacarbonyl iron (at 50°C), phosphine + oxygen, sodium diphenylketyl, dichlorine oxide, fluorine, nitrogen trichloride, ozone, perchloryl fluoride (at 100-300°C), vinyl chloride. Reacts to form explosive products with dienes (e.g., 1,3-butadiene, cyclopentadiene, propadiene). 

Ionic Reactions.—Reactions of either trans- or m-l-p-methoxyphenylpentafluoro-propene with antimony pentafluoride in sulphur dioxide yields the long-lived allyl cation (27), which yields ester (28) when quenched by methanol. No similar cation was observed with hexafluoropropene instead dimer (29) was isolated. Stable arenonium ions (see p. 377) are readily formed from fluorinated cyclohexa-1,4-dienes and -2,5-dienones. ... 

The olefinic fluorines in octafluorobicyclo [2,2,0 ]hex-2-ene (20 X = F) may be displaced by methyl-lithium, sodium borohydride in (MeO CHj-CH2>20, or sodium methoxide in methanol, to give (20), where X — Me, H, or OMe. The last reaction also yields a methanol adduct, which gives the methoxyheptafluorobexene (21) when treated with KOH at 170 °C. All the bicyclohexenes yield the corresponding c clohexa-l,3>dienes (22) when heated. 

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