91949-01-8Relevant academic research and scientific papers
Chlorine Chlorosulfate: Synthesis and Addition Reactions with Olefins
Zefirov, Nikolai S.,Koz'min, Anatoly S.,Sorokin, Viktor D.
, p. 4086 - 4087 (1984)
Chlorine and sulfur trioxide combine in methylene chloride at -78 deg C to form chlorine chlorosulfate (1), a highly electrophilic reagent which adds to olefins to form β-chloroalkyl chlorosulfates 2 (both Markovnikov and anti-Markovnikov adducts).
SULFONATE ACTIVATION OF THE ELECTROPHILIC REACTIVITY OF CHLORINE AND ALKYL HYPOCHLORITES BY THE INSERTION OF SULFUR TRIOXIDE AT THE Cl-Cl AND O-Cl BONDS. ADDITION OF CHLORINE CHLORO- AND ETHOXYSULFATE TO OLEFINS
Zefirov, N. S.,Koz'min, A. S.,Sorokin, V. D.,Zhdankin, V. V.
, p. 802 - 811 (2007/10/02)
At low temperatures (-40 to -80 deg 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 β-chloroalkyl chlorosulfates with yields of 24-85percent, and the addition of chlorine ethoxysulfate leads to β-chloroalkyl ethylsulfates with yields of 65-85percent.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.
