Grignard Reagents and Unsaturated Ethers. VII. The Synthesis

[CONTRIBUTION FROM

THE

DEPARTMEUT O F CHEMISTRY, T E N S E S S E E 1,A Y D I. ST.4TE

ITUIVERSITY]

Grignard Reagents and Unsaturated Ethers. VII. The Synthesis, Properties and Reaction of 6-Substituted Vinyl Ethers with Aliphatic and Aromatic Grignard Reagents BITCARLla,HILL, RUDOLPH ~J~OODBERRY, DORISE. SIMMOXS,hI.4RY E. HILLAND LONNIEHAYNES RECEIVED MARCH28, 1958 Several new 6-substituted vinyl ethers of the type RCH=CHOR’, where R is CHI, CzHsand n-CjHl1, and R ’ is n-CJ-Ig, n-CaH7and n-CiH16, have been synthesized and their physical constants determined. The infrared spectra of the unsaturated ethers have been studied. Reaction of the vinrl ethers with aliphatic arid aromatic Grignard reagents yielded primary alcohols, and internal and terminal olefins.

Experiments in an earlier paper’ of this series demonstrated that aliphatic Grignard reagents react with a-alkyl substituted vinyl ethers to yield ketones. I n the present paper an investigation has been undertaken t o observe the course of the vinyl ether-Grignard reaction when P-alkyl substituted vinyl ethers are allowed to react with aliphatic and aromatic Grignard reagents. It was suspected that the absence of a substituent in the a-position of the vinyl ether molecule might affect its mode of reaction with Grignard reagents. Products obtained from the reaction of four /I-alkyl substituted vinyl ethers with both aliphatic and aromatic Grignard reagents were primary alcohols and internal and terminal olefins. The difference in the nature of the products formed in these two investigations suggests that the course of the vinyl ether-Grignard reaction is influenced by the position of the alkyl group in the vinyl system. For example, when n-hexylmagnesium bromide reacted with n-butyl ethylvinyl ether. 1-butanol (46%) and 3-decene (667,) were isolated.

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