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In each case electron supply assists the reaction. The slow rate for 1 -chloroethanesulf onyl chloride cannot be attributed to a steric effect, because in the carbonyl chloride series the following Sn2 solvolytic rate sequence is observed18: Cl2CHCOCl > C1CH2-COC1 > CH3COCI.As noted above, the reactions of methanesul-II Acknowledgments.-We are indebted to Dr. Paul W. Morgan for inspiration and encouragement and to Mr. Donald G. Preis for invaluable technical assistance.

SOLVOLYSIS OF ~-KETOCYCI,ODECYL p-TOLUENESULFONATE 5371 mole) of sulfur trioxide in 175 ml. of ethylene chloride. Aliquots withdrawn at various intervals were hydrolyzed, and the aqueous layer and washings from the ethylene chloride layer were digested with excess barium carbonate. After removal of the barium sulfate and barium carbonate, the filtrate was analyzed for barium ion as barium sulfate.After 0.5, 1.5 and 19.5 hours the percentages of sulfur trioxide reactingThe solution was kept a t 0' for 19.5 hours.to form soluble barium salts were 9.3, 9.5 and 12.7, respectively. The solution was then allowed to warm to 25'. After a total of 25.5 hr. the percentage of sulfur trioxideforming soluble barium salts was still 12.7; after a total of 116.5 hr. the amount had risen to 13.8%. Chloride ion from ethylene chloride reaction amounted to less than 2% of the soluble barium salts produced. EVANSTON, ILLINOIS [CONTRIBUTION FROM THE DEPARTMENT O F CHEMISTRY, THE UNIVERSITY O F WISCONSIN]The solvolysis of 6-ketocyclodecyl p-toluenesulfonate (Ia) in ethanol results in the formation of a mixture of cis-and trans-The composition of this mixture (SO-SO% trans isomer) is indistinguishable from that re-Ethanolysis of Ia is autocatalytic-the solvolysis is acid cata-The dependence of the rate on various concentrations indicates that solvolysis involves an acid-catalyzed (second-The enol I11 is solvolyzed much faster The high reactivity of the enol and its conversion to the bicyclic ketone I1 are evi-[5.3.0] bicyclodecan-2-one (11). sulting from treatment of the p-toluenesulfonate with base. lyzed. order) reversible enolization followed by conversion of the enol I11 to product 11. than cyclodecyl p-toluenesulfonate. dently manifestations of a transannular interaction between the carbon-carbon double bond and CI.