The principle of vinylogy recognizes the possibility that the inductive effect of a functional group is transmitted through a double bond or a conjugated system of double bonds.
VOL. 30 carbonyl peak at approximately 5.7 employing a Perkin-Elmer Model 21 recording infrared spectrophotometer. This method was chosen after repeated attempts to use the iodometric method of Silbert and Swernl* proved unreliable with the later stages of a kinetic run.The perester solutions in carbon tetrachloride were degassed, then sealed in thoroughly cleaned ampoules prepared from 9-mm. Pyrex tubing. The samples were immersed into an electrically heated oil bath controlled to f0.2' by means of a Fisher-Serfass electronic relay. An equilibration time of 2 min. was allowed for the samples to reach bath temperature. At definite time intervals an ampoule was removed and immediately quenched by immersion in ice-water. The ampoules were stored a t -70' until the completion of the kinetic run, then they were broken, and the sample was transferred directly to an infrared cell.The rate constants determined are the average of at least two runs and are summarized in Table I V .The energies of activation were calculated from a plot of the log of the rate constant os. the reciprocal of the absolute temperature employing the method of least squares to determine the slope. The entropies of activation were calculated by the method of Foster, Cope, and Daniels.% (20) E . G. Foster, A.Desulfurization of the two stereoisomeric 4-t-b11tylcyclohexanone ethylene monothioketals (I) with Raney nickel in benzene at room temperature gave 4-t-butylcyclohexanone (53-55%), cis-4-t-butylcyclohexyl ethyl ether (12-14%), 4-t-butylcyclohexanone diethyl ketal (6-11%), 4-t-butylcyclohex-1-enyl ethyl ether (16%), and 4-t-butylcyclohexene (7-12%), in addition to much ethane and a little ethylene. Product composition waa independent of the stereochemistry of the starting material. Similarly, the two 3-cholestanone ethylene monothioketals (11) gave 3-cholestanone (43-4770), 3a-ethoxycholestane (11-127?), 3-ethoxy-2-cholestene (20-21%), 3-cholestanone diethyl ketal (7-8%), and 2-cholestene ( P 5 % ) . The two isomers of 4-t-butylcyclohexanone trimethylene monothioketal (111) gave 4-~-butylcyclohexanone ( 47-48y0), cis-4-t-butylcyclohexyl n-propyl ether (1270), 4-1-butylcyclohex-1-enyl n-propyl ether ( 16y0), 4-t-butylcyclohexanone di-n-propyl ketal (7%), and 4-t-butylcyclohexene (7%). The recovery of the three-carbon fragment as propane (with traces of propylene and cyclopropane) was low in this case.
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