Fluorinated Oxetane Derivatives and Production Process Thereof

Patent Fluorinated Oxetane Derivatives and Production Process Thereof 

Masutani etal, US Patent 6,673,948 (January 6, 2004) Assignee Daikin Industries, Ltd. 

To 3-methyl-oxetane methanol (20.4 g) was added 50% aqueous NaOH (268 g), NBU4CI (2.8 g) and 300 ml hexane at ambient temperature. Thereafter, allyl bromide (19.4 g) was added drop wise and the solution refluxed 2 hours. The solution was cooled, the phases separated, and the aqueous phase extracted with EtOAc and added to the organic phase. The solvent was removed by distillation and the product isolated in 61% yield in 98% purity. H-NMR data supplied. 

The product from Step 1 (7.1 g), nonafluorobutyl iodide (51.9g) and AIBN (0.245 g) were heated to 70 °C 1 hour. Thereafter unreacted nonafluorobutyl iodide was removed by distillation and the product isolated in 85% yield in 94% purity. H- and F-NMR data supplied. 

The product from Step 2 (19.5 g) and 25 ml methyl alcohol containing KOH (4.2 g) were reacted at ambient temperature overnight. Thereafter, the reaction was filtered, washed, dried, and the product isolated in 59% yield as cis/trans isomers, 78 22, respectively, in 93% purity. H- and F-NMR data supplied. 

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