skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: 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

Abstract

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.

Authors:
; ; ;
Publication Date:
Research Org.:
Lomonosov Moscow State Univ., Moscow (Russian Federation)
OSTI Identifier:
6191989
Resource Type:
Journal Article
Journal Name:
J. Org. Chem. USSR (Engl. Transl.); (United States)
Additional Journal Information:
Journal Volume: 22:5; Other Information: Translated from Zh. Org. Khim.; 22: No.5, 898-908(May 1986)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 74 ATOMIC AND MOLECULAR PHYSICS; ALKENES; ISOMERIZATION; NMR SPECTRA; SULFOCHLORINATION; SULFONATES; ACTIVATION ENERGY; ALKYLATION; BORON FLUORIDES; CARBON 13; CHEMICAL BONDS; CHEMICAL REACTION KINETICS; CHEMICAL SHIFT; CHLORINATED ALIPHATIC HYDROCARBONS; CHLORINE 35; COUPLING CONSTANTS; DEUTERIUM COMPOUNDS; HYPERFINE STRUCTURE; IODINATED ALIPHATIC HYDROCARBONS; IODINATION; J-J COUPLING; METHYLENE CHLORIDE; MULTIPLETS; ORGANIC SOLVENTS; REAGENTS; SOLVENT PROPERTIES; STEREOCHEMISTRY; SULFUR TRIOXIDE; BORON COMPOUNDS; CARBON ISOTOPES; CHALCOGENIDES; CHEMICAL REACTIONS; CHLORINATION; CHLORINE ISOTOPES; COUPLING; ENERGY; EVEN-ODD NUCLEI; FLUORIDES; FLUORINE COMPOUNDS; HALIDES; HALOGEN COMPOUNDS; HALOGENATED ALIPHATIC HYDROCARBONS; HALOGENATION; HYDROCARBONS; HYDROGEN COMPOUNDS; INTERMEDIATE COUPLING; ISOTOPES; KINETICS; LIGHT NUCLEI; NUCLEI; ODD-EVEN NUCLEI; ORGANIC CHLORINE COMPOUNDS; ORGANIC COMPOUNDS; ORGANIC HALOGEN COMPOUNDS; ORGANIC IODINE COMPOUNDS; ORGANIC SULFUR COMPOUNDS; OXIDES; OXYGEN COMPOUNDS; REACTION KINETICS; SOLVENTS; SPECTRA; STABLE ISOTOPES; SULFONATION; SULFUR COMPOUNDS; SULFUR OXIDES; 400201* - Chemical & Physicochemical Properties; 640302 - Atomic, Molecular & Chemical Physics- Atomic & Molecular Properties & Theory

Citation Formats

Zefirov, N S, Koz'min, A S, Sorokin, V D, and Zhdankin, V V. 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. United States: N. p., 1986. Web.
Zefirov, N S, Koz'min, A S, Sorokin, V D, & Zhdankin, V V. 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. United States.
Zefirov, N S, Koz'min, A S, Sorokin, V D, and Zhdankin, V V. 1986. "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". United States.
@article{osti_6191989,
title = {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},
author = {Zefirov, N S and Koz'min, A S and Sorokin, V D and Zhdankin, V V},
abstractNote = {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.},
doi = {},
url = {https://www.osti.gov/biblio/6191989}, journal = {J. Org. Chem. USSR (Engl. Transl.); (United States)},
number = ,
volume = 22:5,
place = {United States},
year = {Fri Oct 10 00:00:00 EDT 1986},
month = {Fri Oct 10 00:00:00 EDT 1986}
}