Durch Bromierung ausgelöste Umlagerung tertiärer Allylalkohole: Der Einfluss eines Fluor-Substituenten auf Reaktionsgeschwindigkeit und Reaktionsverlauf

Reaction of Me3CCMe(OH)CR:CH2 (I; R = H) with Br2 or NBS in aq. medium resulted in rearrangement, yielding ketones Me3CCOCHMeCH2Br and MeCOCR(CH2Br)CMe3 (III) and the oxirane II. With I (R = F, Me), bromination gave only ketone III. Competition expts. showed that I (R = F) underwent bromination at a much slower rate than I (R = H or Me). [on SciFinder (R)]

[1]  M. Schlosser,et al.  Die Stereochemie der fragmentierenden Enthalogenierung von 1‐Chlor‐1‐fluor‐2‐(1‐halogenalkyl)cyclopropanen , 1980 .

[2]  M. Schlosser,et al.  "3-Fluorisopren" (2-Fluor-3-methyl-1,3-butadien) und einige heterosubstituierte Abkömmlinge , 1980 .

[3]  M. Schlosser,et al.  Structurally Biased 2-Fluoroallyl Cations as Generated - or not Generated - in Cyclopropane Ring-opening Reactions† , 1977 .

[4]  M. Schlosser,et al.  Darstellung und Abwandlung von Chlorfluorcyclopropanen : Ein gezielter Zugang zu Fluorallylalkoholen , 1975 .

[5]  M. Schlosser,et al.  Bessere CC‐Verknüpfungen durch kontrollierte Kupfer‐Katalyse , 1974 .

[6]  M. Schlosser,et al.  Improved Carbon‐Carbon Linking by Controlled Copper Catalysis , 1974 .

[7]  Carl R. Johnson,et al.  Substituent effects in the ring expansion reactions of isopropenylcycloalkanols by tert-butyl hypochlorite , 1973 .

[8]  M. Saunders,et al.  Evidence for protonated cyclopropane intermediates from studies of stable solutions of carbonium ions , 1973 .

[9]  M. Schlosser,et al.  Fluororganische Synthesen, II. Fluorchlorcyclopropane — ihre Darstellung und Abwandlung , 1971 .

[10]  P. Schleyer.  Conformational Analysis of Carbonium Ions , 1971 .

[11]  J. Crandall,et al.  Base-promoted reactions of epoxides. I. Isomerization of some cyclic and acyclic epoxides by lithium diethylamide , 1967 .

[12]  F. Bordwell,et al.  The Effect of the Carbonyl and Related Groups on the Reactivity of Halides in SN2 Reactions , 1964 .

[13]  Carl R. Johnson,et al.  A Chlorinative Ring Expansion. The Reaction of t-Butyl Hypochlorite and 1-Vinylcycloalkanols1 , 1964 .

[14]  M. Dewar.  Die polare Addition von Halogenwasserstoffen an Olefine [1] , 1964 .

[15]  R. C. Fahey,et al.  Polar Addition of Hydrogen Halides onto Olefins , 1964 .

[16]  P. Skell,et al.  The Mechanism of Aliphatic Bromination by N-Bromosuccinimide , 1963 .

[17]  H. Metz,et al.  Reaktionen an 16‐Methylen‐ und 16‐Hydroxymethylen‐17‐Keto‐steroiden , 1961 .

[18]  H. Rydon,et al.  458. The organic chemistry of phosphorus. Part I. Some new methods for the preparation of alkyl halides , 1953 .