Reaction of. cap alpha. -bromocyclopropyl phenyl ketones with lithium thiophenolate by a mechanism or latent nucleophilic substitution at the halogen atom

Journal Article · Sat Oct 10 04:00:00 EDT 1987 · J. Org. Chem. USSR (Engl. Transl.); (United States)

OSTI ID:6974813

Kulinkovich, O G; Tishchenko, I G; Sviridov, S V; Divak, V A

The reaction of E-1-benzoyl-1-bromo-2-phenylcyclopropane with lithium thiophenolate in THF leads to the formation of E-1-benzoyl-2-phenyl-1-phenylthiocyclopropane. Phenyl ..cap alpha..-phenylthiocyclopropyl ketones are also produced with good yields by the action of sodium thiophenolate on 7-endo-benzoyl-7-exo-bromobicyclo(4.1.0)-heptane, E-1-benzoyl-1-bromo-2-butylcyclopropane, and 1-benzoyl-1-bromocyclopropane, whereas Z-1-benzoyl-1-bromo-2-phenylcyclopropane undergoes reductive dehalogenation under analogous conditions. The stereochemical data and also the data on the composition of the products from the reaction in the presence of methanol indicate that the phenyl ..cap alpha..-phenylthiocyclopropyl ketones are formed by a mechanism of latent nucleophilic substitution at the halogen atom in the initial ..cap alpha..-bromocyclopropyl phenyl ketones. The PMR spectra of solutions of the substances in carbon tetrachloride or benzene were obtained on a Tesla BS-467A spectrometer at 60 MHz with HMDS as internal standard. The IR spectra of solutions of the substances in carbon tetrachloride were recorded on a Specord IR-75 spectrometer. The reactions were carried out in an atmosphere of dry argon.

• Research Organization: V. I. Lenin Belorussian State Univ., Minsk (USSR)
• OSTI ID: 6974813
• Journal Information: J. Org. Chem. USSR (Engl. Transl.); (United States), Journal Name: J. Org. Chem. USSR (Engl. Transl.); (United States) Vol. 23:5; ISSN JOCYA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
640302 -- Atomic
Molecular & Chemical Physics-- Atomic & Molecular Properties & Theory
74 ATOMIC AND MOLECULAR PHYSICS
ALKANES
BROMINATED ALIPHATIC HYDROCARBONS
BROMINATION
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHEMICAL SHIFT
COMPLEXES
COUPLING
COUPLING CONSTANTS
CYCLOALKANES
HALOGENATED ALIPHATIC HYDROCARBONS
HALOGENATION
HYDROCARBONS
INFRARED SPECTRA
INTERMEDIATE COUPLING
ISOMERIZATION
J-J COUPLING
KETONES
KINETICS
LITHIUM COMPLEXES
NMR SPECTRA
ORGANIC BROMINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
ORGANIC SULFUR COMPOUNDS
PHENOLATES
REACTION KINETICS
SPECTRA
STEREOCHEMISTRY
THIOPHENOLS