title: Product studies and laser flash photolysis on alkyl radicals containing two different beta-leaving groups are consonant with the formation of an olefin cation radical.
abstract: 1-Bromo-2-methoxy-1-phenylpropan-2-yl (3) and 2-methoxy-1-phenyl-1-diphenylphosphatopropan-2-yl (4) were generated under continual photolysis from the respective PTOC precursors in a mixture of acetonitrile and methanol. The radicals undergo heterolytic fragmentation of the substituent in the beta-position to generate the olefin cation radical (5). Z-2-Methoxy-1-phenylpropene (15) is the major product formed in the presence of 1,4-cyclohexadiene, and is believed to result from hydrogen atom transfer to the oxygen of the olefin cation radical, followed by deprotonation. Laser flash photolysis experiments indicate that reaction between 5 and 1,4-cyclohexadiene occurs with a rate constant of approximately 6 x 10(5) M(-1) s(-1). 2,2-Dimethoxy-1-phenylpropane (18) is observed as a minor product. Laser flash photolysis experiments place an upper limit on methanol trapping of 5 at k <1 x 10(3) M(-1) s(-1) and do not provide any evidence for the formation of reactive intermediates other than 5. The use of two PTOC precursors containing different leaving groups to generate a common olefin cation radical enables one to utilize product analysis to probe for the intermediacy of other reactive intermediates. The ratio of 15:18 is dependent upon hydrogen atom donor concentration, but is independent of the PTOC precursor. These observations are consistent with the proposal that both products result from trapping of 5 that is formed via heterolysis of 3 and 4.
authors.affiliation: Department of Chemistry, Colorado State University, Fort Collins, Colorado 80523, USA.
authors.forename: B C
authors.initials: BC
authors.lastname: Bales
authors.forename: J H
authors.initials: JH
authors.lastname: Horner
authors.forename: X
authors.initials: X
authors.lastname: Huang
authors.forename: M
authors.initials: M
authors.lastname: Newcomb
authors.forename: D
authors.initials: D
authors.lastname: Crich
authors.forename: M M
authors.initials: MM
authors.lastname: Greenberg
mesh_terms: D000475:Alkenes / Q000138:chemical synthesis*; D002412:Cations; D005609:Free Radicals / Q000737:chemistry*; D007834:Lasers; D008956:Models, Chemical; D010782:Photolysis
chemical_list: D000475:Alkenes; D002412:Cations; D005609:Free Radicals