Propellanes. 17. Bridgehead olefins via solvolysis of 10, 10-dibromo (4. 3. 1) propellanes

Journal Article · Wed Jul 20 04:00:00 EDT 1977 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00457a034· OSTI ID:7087569

Warner, P M; Lu, S L; Myers, E; DeHaven, P W; Jacobson, R A

This paper reports the results of the hydrolysis and acetolysis of 10,10-dibromo(4.3.1)propellane (1) and 10,10-dibromo(4.3.1)propell-3-ene (4). Hydrolytically (Ag/sup +/ assisted, aqueous acetone), the former gave five products, while the latter gave rise to only two. The hydroazulenic products were shown to arise via rearrangement of a bicyclo(4.3.1)decane nucleus; one product rearranged to a hydroazulene under prolonged reaction conditions. The stereochemistry of two others was demonstrated via x-ray crystallographic studies of the derived 2,4-DNP; they were both found to undergo transannular cyclizations to bicyclo(4.3.1)decane ring systems. Acetolysis of 1 afforded two products one of which a bridgehead olefin rearranged to cyclopropyl acetates. Cyclopropyl acetates arose primarily from a bridgehead olefin. Acetolysis of tertiary mesylate gave bridgehead olefin, which was shown not to rearrange to a second bridgehead olefin. Mechanistic explanations for the formation of these products are given.

• Research Organization: Ames Lab., IA
• OSTI ID: 7087569
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 99:15; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
ACETOLYSIS
BROMINATED ALICYCLIC HYDROCARBONS
CHEMICAL REACTION KINETICS
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
DECOMPOSITION
HALOGENATED ALICYCLIC HYDROCARBONS
HYDROLYSIS
KINETICS
LYSIS
ORGANIC BROMINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
REACTION KINETICS
SOLVOLYSIS
YIELDS