Sulfonate activation of the electrophilic reactivity of chlorine and alkyl hypochlorides by the insertion of sulfur trioxide at the C1-C1 and O-C1 bonds. Addition of chlorine chloro- and ethoxysulfate to olefins

Journal Article · Fri Oct 10 04:00:00 EDT 1986 · J. Org. Chem. USSR (Engl. Transl.); (United States)

OSTI ID:6191989

Zefirov, N S; Koz'min, A S; Sorokin, V D; Zhdankin, V V

At low temperatures (-40 to -80/sup 0/C) sulfur trioxide enters the chlorine molecule (with the formation of chlorine chlorosulfate) and the ethyl hypochlorite molecule (giving chlorine ethoxysulfate). Both new compounds are highly reactive electrophilic chlorinating reagents and add to ethylene, activated alkenes (1-hexene and cyclohexene), and deactivated olefins (methyl methacrylate, tri- and tetrachloroethylene) in methylene chloride solution at low temperatures. The addition of chlorine chlorosulfate leads to the formation of ..beta..-chloroalkyl chlorosulfates with yields of 24-85%, and the addition of chlorine ethoxysulfate leads to ..beta..-chloroalkyl ethylsulfates with yields of 65-85%. The reactions with unsymmetrical olefins lead to mixtures of the regioisomers with a preference for the products from addition according to the Markovnikov rule; the addition to cyclohexene is trans-stereospecific. The investigated processes represent a new simple approach to the production of sulfate-activated chlorinating reagents and extend the possibilities for functional substitution of olefins.

• Research Organization: M.V. Lomonosov Moscow State Univ., USSR
• OSTI ID: 6191989
• Journal Information: J. Org. Chem. USSR (Engl. Transl.); (United States), Journal Name: J. Org. Chem. USSR (Engl. Transl.); (United States) Vol. 22:5; 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
ACTIVATION ENERGY
ALKENES
ALKYLATION
BORON COMPOUNDS
BORON FLUORIDES
CARBON 13
CARBON ISOTOPES
CHALCOGENIDES
CHEMICAL BONDS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHEMICAL SHIFT
CHLORINATED ALIPHATIC HYDROCARBONS
CHLORINATION
CHLORINE 35
CHLORINE ISOTOPES
COUPLING
COUPLING CONSTANTS
DEUTERIUM COMPOUNDS
ENERGY
EVEN-ODD NUCLEI
FLUORIDES
FLUORINE COMPOUNDS
HALIDES
HALOGEN COMPOUNDS
HALOGENATED ALIPHATIC HYDROCARBONS
HALOGENATION
HYDROCARBONS
HYDROGEN COMPOUNDS
HYPERFINE STRUCTURE
INTERMEDIATE COUPLING
IODINATED ALIPHATIC HYDROCARBONS
IODINATION
ISOMERIZATION
ISOTOPES
J-J COUPLING
KINETICS
LIGHT NUCLEI
METHYLENE CHLORIDE
MULTIPLETS
NMR SPECTRA
NUCLEI
ODD-EVEN NUCLEI
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
ORGANIC IODINE COMPOUNDS
ORGANIC SOLVENTS
ORGANIC SULFUR COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
REACTION KINETICS
REAGENTS
SOLVENT PROPERTIES
SOLVENTS
SPECTRA
STABLE ISOTOPES
STEREOCHEMISTRY
SULFOCHLORINATION
SULFONATES
SULFONATION
SULFUR COMPOUNDS
SULFUR OXIDES
SULFUR TRIOXIDE