REARRANGEMENT STUDIES WITH CARBON-14 .33. DEAMINATION AND DEOXIDATION STUDIES ON 1-14C-1-PROPYL SYSTEM

The deamination of 1-14C-1-propylamine gave 1-propanol with 2% rearrangement of the label from C-1 to each of the C-2 and C-3 positions, in complete agreement with an earlier finding. The 2-propanol obtained showed no rearrangement of the label to C-2. Degradation of the propene formed in this reaction indicated about 13% rearrangement of the label from C-1 to C-3, no significant amount of activity being found at C-2. The deoxidation of potassium 1-14C-1-propoxide in excess l-14C-1-propanol as solvent gave propene with 10-12% isotope-position rearrangement from C-1 to C-3. When the deoxidation was carried out in an excess of concentrated KOH, the rearrangement from C-1 to C-3 in the propene was only 4-5%. These results indicate that in both deamination and deoxidation reactions, no propene was formed from protonated cyclopropane, and the rearrangement in the propene from C-1 to C-3 can be readily attributed to the elimination of a proton from the 1-14C-2-propyl cation formed from the 1-14C-1-propyl cation. Other mechanistic implications of the results are also discussed. © 1969, American Chemical Society. All rights reserved.