The pAa's of eight 3-substituted bicyclo [1.1.1] pentanecarboxylic acids have been measured and found to correlate well with constants. The value of (2.23 ± 0.12) is large but not large enough to propose any special perturbation of normal field-inductive effects by the close proximity (about 1.88 Á) of the bridgehead carbons. Also determined were the products and rates of solvolyses of the p-nitrobenzoates of three 3-substituted l-(2-hydroxy-2propyl)bicyclo [1.1.1] pentanes. The products were primarily unrearranged, and the rates again showed no surprising substituent effects. A practical synthesis of 1,3-disubstituted bicy clo [ 1.1.1 ]pentanes has been developed and is described.Bicyclo [1.1.1] pentane (1) has the very special property 0

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A series of aliphatic and bridgehead aldehydes were decarbonylated in carbon tetrachloride, which served as an inefficient trap for the intermediate acyl radicals.The products were determined quantitatively, and the trapping efficiencies deduced from the product ratios were found to correlate with the stabilities of the alkyl radicals generated from the aliphatic aldehydes. The assumption that the same correlation applies to the bridgehead aldehydes led to the conclusions that the 1-adamantyl and l-bicyclo[2.2.2]octyl radicals are more stable than t-butyl, while l-bicyclo[2.2.1]heptyl is less stable than n-propyl. 182 (1961).