A study of the chemistry of diisopropyl-, cyclopropylisopropyl-, and dicyclopropylcarbene Public Deposited

http://ir.library.oregonstate.edu/concern/graduate_thesis_or_dissertations/r207ts16n

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  • The effect of the conjugation with cyclopropyl rings on the activation parameters for the formation of carbenes from the corresponding diazo compounds was investigated using diisopropylcarbene (46), cyclopropyl-isopropylcarbene (47), and dicyclopropylcarbene (48). Each of these three carbenes was generated by the thermolysis of the parent benzenesulfonylhydrazone potassium salts using DMSO as the solvent. Each of the three carbenes underwent an intramolecular rearrangement or rearrangements to form alkene(s) as well as undergoing a reaction with the DMSO solvent to form the corresponding ketone. Diisopropylcarbene (46) yielded two reaction products: 2,4-dimethyl-2-pentene (62) and diisopropyl ketone (54). 62 was formed by a 1,2-hydride shift and 54 was formed by a reaction between the carbene and DMSO. Cyclopropylisopropylcarbene (47) yielded three reaction products: l-cyclopropyl-2-methyl-l-propene (63), 1-isopropylcyclobutene (64), and cyclopropyl isopropyyl ketone (55). 63 was formed by a 1,2-hydride shift, 64 was formed by ring expansion, and 55 was formed by a reaction between the carbene and DMSO. Dicyclopropyl-carbene (48) yielded two reaction products: 1-cyclopropylcyclobutene (65) and dicyclopropyl ketone (56). 65 was formed by ring expansion and 56 was formed by a reaction between the carbene and DMSO. A kinetic study was performed for each of the three carbenes. The rates for carbene formation were found to decrease in the order 48 > 47 > 46. The values for the activation energies and enthalpies of activation followed the same order. The enhanced rate of formation for the carbenes which possess cyclopropyl groups was determined to be due to their greater entropies of activation. The differences found in the entropies of activation for the formation of the three carbenes were explained by interactions of ground and transition states with the solvent (DMSO). The values for the free energies of activation for the formation of each of the three carbenes were found to be nearly the same.
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