Fluoroformic acid esters fluoroformates

Attempts to apply the thermal decarboxylation reaction in the liquid phase to aromatic halofor-mic acid esters have shown that their reaction is different from that ol the aliphatic haloformates. It was found that evolution of carbon dioxide occurs, but only high boiling products could be isolated.136 On heating in the presence of aromatics and Lewis acids, aryl chloroformates do not react to give chlorinated aromatics with concomitant decarboxylation, but undergo a Friedel-Crafts reaction to give phenyl benzoates.137 Under similar conditions phenyl fluoroformate undergoes only polymerization and carbonate formation.137... 

Fluorides from fluoroformic acid esters OGOF F... 

Fluoroformic from chloroformic acid esters ROCOCl -> ROCOF... 

Difluoroborinic acid esters Fluoroformic acid esters... 

Phosgene is reported to combine with a wide range of oxygenated materials, including alcohols, ethers, ketones, carboxylic acids, anhydrides, lactones, esters, carbonic acid derivatives, etc. Only the reactions of COCIF with alcohols, phenols and cyclic ethers have been reported, resulting usually in the generation of fluoroformates. Such materials can often be usefully converted into the corresponding fluoro compound by means of decarboxylation in the presence of BF3, EtjO, pyridine, or other materials. 

Cinnamic acids. A soln. of triethyl phosphate in THF added to an ethereal soln. of ethyllithium in the same solvent at —78° under N2, allowed to warm slowly to 0°, stirred for 30 min, re-cooled to — 78°, LDA in THF added followed after a few min by /er/-butyl fluoroformate in the same solvent, allowed to warm slowly to room temp., heated to 35-40°, an excess of benzaldehyde in THF added with efficient stirring, heated at 40° for 4-5 h, left one night at room temp., the crude /cr/-butyl ester dissolved in trifluoroacetic acid, and the precipitated acid worked up - (E)-a-methyl-cinnamic acid. Y 81%. F.e.s. M.-P. Teuladeet al., Synth. Commun. 19, 71-81 (1989). 

Carbonofluoridic acid methyl ester Fluoroformic acid methyl ester... 

Azirines, Diazirines, and Related Compounds. Tiifluoropyruvic acid, postulated previously " as an intermediate in the basic hydrolysis of perfluoro-(2-methyl-2/f-azirine) (25a) to fluoroform and oxalic acid, has now been isolated as its monohydrate CF3-C(OH)3 COsH, following treatment of the azirine with water at room temperature. Ethanolysis of the azirine at ambient temperature yields the esters CF8-C(0H)2-CO2Et and CFs QOH)-(0Et) C02Et, By contrast, basic hydrolysis of 3-methoxy-2,2-bis(tri-... 

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