Methyl fluoroformate, reaction

The same product is obtained from heptafluoropropyl methyl ketone [61]. The reaction resembles the fluoroform reaction of fluorinated alcohols [62] and ketones [63]. 

Goswami and Sarkar3 claimed to have prepared methyl and ethyl fluoroformates by the action of thallium fluoride on the corresponding chloroformates. These fluoroformates were described as powerful lacrimators. We found that no appreciable reaction took place between potassium fluoride and ethyl chloroformate in boiling carbon tetrachloride or nitrobenzene. Ethyl fluoroformate could, however, be readily produced by the action of potassium fluoride on ethyl chloroformate by using the autoclave technique. It was found not to have the lacrimatory properties claimed for it, and was non-toxic in comparison with M.F.A. This non-toxicity was to be expected, as the fluoroformate contains the COF and not the CH2F- group. 

The last point which can be evoked here is conceptually linked to the hot-spot theory. If the limit liquid layers around a bubble are in direct contact with the heated and pressurized bubble content, far above the critical point of the liquid, these layers should be in a supercritical state. 23 This attractive hypothesis (see p. 61) was used by Hoffmann et al to rationalize the sonolysis of nitrophenyl derivatives. Supercritical fluids are characterized by a very high flexibility of important parameters (density, dielectric constant, solubilizing power) as a function of pressure. Experts in the field distinguish gas-like and liquid-like media, in which the kinetics of a reaction can vary over a broad range. For instance, the conjugate addition of piperidine to methyl propiolate was studied in supercritical ethane or fluoroform (Fig. 5). ... 

Photodimerization reactions in supercritical fluid solutions have been used to probe the effects of possible solute-solute clustering. BCimura et al. investigated the dimerization of 2-methyl-2-nitrosopropane in CO2, chlorotrifluoromethane, fluoroform, argon, and xenon (173-176). Their results show that the density dependence of the dimerization equilibrium constant is rather complex, probably due to the existence of various dimerization mechanisms in different density regions. 

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