The Fluoroformate Process

It is noteworthy that the heretofore not accessible at acceptable cost diethyleneglycol bis-vinyl carbonate called CVD [see scheme 100] is made in 80% yield using the fluoroformate process as depicted in table 3-15. 

In our continuing trials to extent the scope of the vinylic carbonates synthesis through the fluoroformate process, vinyl menthyl carbonate was obtained in excellent yield (80%) from menthyl fluoroformate. The polymer of vinyl menthyl carbonate was also proposed as menthol-release agent. It is noteworthy that this polymer can be easily prepared by reaction of menthyl fluoroformate with poly(vinyl alcohol) in DM50. 

An alternative means of technical-scale access to fluoroarenes is the fluoroformate method. Starting from the corresponding phenol a fluoroformate is generated by reaction with carbonyl chloride fluoride and subsequently catalytically decarboxy-lated to the aryl fluoride, in the gas phase, by contact with hot platinum [80] (Scheme 2.30). A newer, greener variant of the fluoroformate process has recently been introduced by Rhodia. In this the fluoroformate is formed by the (catalyzed) reaction of the phenol with COj in HF, and the expensive platinum catalyst is replaced by an aluminum-based material. 

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