Photochemical generation and intramolecular chemistry of 2-hydroxy-2-methylpropylidene

Author (Your Name)

Robin Farlow, Colby College

Date of Award

2001

Document Type

Honors Thesis (Open Access)

Department

Colby College. Chemistry Dept.

Advisor(s)

Dasan M. Thamattoor

Second Advisor

Mundy, Bradford P.

Abstract

2-(1a,9b-Dihydro-lH-cyclopropa[l]phenanthren-1-yl)-propan-2-ol was synthesized by two different but related synthetic routes and characterized by melting point, IR GC/MS, CHN, and NMR spectroscopy. Photolysis of the alcohol in benzene d-6 led to the formation of 2-butanone, 1-methylcyclopropanol, and 2,2-dimethyloxirane in a 26:10:1 ratio via 2-hydroxy-2methylpropylidene, a novel ?-hydroxycarbene. These products are a consequence of intramolecular insertions of the carbene into C-C, C-H, and O-H bonds. Molecular orbital calculations performed at the Becke-3LYP/6-31G(d) level indicate that the singlet form of this carbene is more thermodynamically stable than the triplet. Furthermore, the transition states to the three products from the singlet species were modeled at the same level of theory. Results from these computational studies are consistent with experimental observations.

Keywords

Carbenes (Methylene compounds), Photochemistry, Organic compounds -- Synthesis, 2-hydroxy-2-methylpropylidene

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