Simplified Synthesis of Pentafluoro-1-iodoethane and Heptafluoro-2-iodopropane
✍ Scribed by Dr. Hans Millauer
- Publisher
- John Wiley and Sons
- Year
- 1973
- Tongue
- English
- Weight
- 117 KB
- Volume
- 12
- Category
- Article
- ISSN
- 0044-8249
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✦ Synopsis
Catalysts that can be used with triphenylphosphane, in place of palladium acetate, are bis(pentanedionat0)palladium, palladium chloride, bis(benzonitri1e)palladium chloride and tetrakis(tripheny1phosphane)palladium; also a combination of tributylphosphane and palladium acetate. The molar ratio Pd : P should be at least 1 : 4 to prevent separation of palladium. The reaction of ally1 acetate and formic acid occurs differently from the formally similar reduction of, e. g., butyralde-hyder3] and alkenesF4] by formic acid in the presence of transition-metal catalysts. Monodeuteriopropene is obtained on treatment of allyl acetate with DCOOD and CH,COOH (1 :I) but not with HCOOH and CH, C O O D (1 : 1). We also observed a kinetic isotope effect : At 80°C in the second experiment deallylation occurred twice as fast as in the first experiment. Thus fission of the C-H bond of formic acid is slow, as well as in the oxidative degradation of formic acid on a Pd"/Cu" cataly~t'~! On incomplete reaction of allyl acetate with formic acid the solution contained about 2 % of allyl formate which decomposed rapidly into CO, and propene even at 60°C in presence of (tripheny1phosphane)palladium acetate. Cleavage of a substituted allyl formate, 2,7-octadienyl formate, in presence of palladium acetate and dimethylformamide has been described recently'?