heptafluorobutyranilide was obtained in 21% yield as colorless needles, m.p. 97°. The product was identical with the amide prepared directly from p-anisidine.Products from N-Phenylmalonamic Acid.-Treatment of this amic acid with trifluoroacetic or heptafluorobutyric anhydrides gave a colorless powder in yields of 60-80% (calculated as dehydration product). The melting point varied with different preparations (210°, 186-190°dec.) and appeared to depend on the rate of heating. The infrared spectrum contained bands at 3.08 and 5.95 µ.
We have previously reported convenient methods for the syntheses of 1-chloro-, 1-bromo-, and 1-iodobicyclo[2. It has been theorized that the reaction of ethers with acyl halides proceeds via acyl oxonium ions.1) The synthetic utility of acyl oxonium ions as a carbonium ion generator has been confirmed. Diazonium ions,4) isocarboxonium ions,5) and carboxylium ions6) have been established as carbonium ion sources.The treatment of 1-methoxybicyclo[2.2.2]octane (1) with an excess of acetyl fluoride in the presence of a catalytic amount of anhydrous stannic chloride gave a mixture (ca. 1:1) of 1-fluoroand 1-chlorobicyclo[2.2.2]octane in about an 80% yield. When the boron trifluoride-phosphoric acid complex was used as a catalyst, the reaction between 1 and acetyl fluoride afforded 1-fluorobicyclowithout melting) in a 70% yield. Among the other catalysts examined were boron trifluoride etherate and zinc fluoride, in which cases 3 was also obtained.An analogous treatment of 1-methoxy-4-methylbicyclo[2.2.2] octane (2) with acetyl fluoride in the presence of the boron trifluoride-phosphoric acid complex gave 1-fluoro-4-methylbicyclo[2.2.2]octane reaction of methoxycyclohexane (5) with acetyl fluoride in the presence of the boron trifluoridephosphoric acid complex furnished a mixture of fluorocyclohexane (6) (25%), cyclohexene (7) (6%), and acetoxycyclohexane (8) (18%).The formation of 1-acetoxybicyclo[2.2.2]octanes could not be detected when either 1 or 2 was reacted with acetyl fluoride in the presence of an acid catalyst. The formation of acetoxycyclohexane (8) in the case of 5 suggests that a 1-bicyclo[2.2.2]-octyl cation is more stable than a cyclohexyl cation. The mass spectra imply that a methyl carbonium ion is less stable than an ethyl carbonium ion7)
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