393. Sulphur chloride pentafluoride: reaction with unsaturated hydrocarbons

Abstract

Sulphur chloride pentafluoride adds to certain olefins and chloro-olefins to give 2-chloroalkylsulphur pentafluorides ; acetylene and propyne give 2-chlorovinyl-and 2-chloropropenyl-sulphur pentafluoride, respectively. These products eliminate hydrogen chloride on treatment with potassium hydroxide, to give pentafluorosulphur-substituted olefins and acetylenes. SULPHUR CHLORIDE PENTAFLUORIDE does not react with paraffin hydrocarbons, but when heated under moderate pressures with certain olefins and chloro-olefins it adds to the double bond, giving 2-chloroalkylsulphur pentafluorides :This reaction has been carried out with ethylene, propene, cyclohexene, butadiene, and vinyl chloride; it failed with isobutene and styrene because these olefins polymerised very rapidly in the presence of sulphur chloride pentafluoride. Ethylene and vinyl chloride also showed a tendency to polymerise, for the simple addition compounds were accompanied by smaller amounts of higher-boiling fractions from which compounds were isolated which were evidently telomers containing two molecules of the olefin. The 2-chloroalkylsulphur pentafluorides eliminated hydrogen chloride on treatment with potassium hydroxide, to give the corresponding unsaturated pentafluorosulphur compounds; however, it was not possible to remove more than one molecule of hydrogen chloride from 2,2-dichloroethylsulphur pentafluoride, and attempts to prepare the substituted acetylene from this compound only resulted in complete decomposition.Addition of sulphur chloride pentafluoride to propene gave a high yield of 2-chloropropylsulphur pentafluoride, the structure of which was established by showing that two isomeric pentafluorosulphur-substituted propenes were formed by elimination of hydrogen chloride whereas 2-chloro-l-methylethylsulphur pentafluoride could only give one compound :

New acrylate systems: derivatives of β-SF5-acrylic acid

“…It has been shown that SF 5 X (X ¼ Cl, Br) will add to alkynes; SF 5 Cl was added to acetylene and propyne [5] and to RCBCOR 0 (R¼CH 3 , H; R 0 ¼CH 3 , CH 3 CH 2 ) [6,7] while in separate reports, SF 5 Br was added to YCBCH (Y ¼ SF 5 , CF 3 ) and to CF 3 CBCH or CH 3 CBCH [8,9]. In all cases, the SF 5 group was attached to the olefinic carbon with the most hydrogen.…”

“…While a significant number of fluorinated acrylates are known only a limited number containing the SF 5 -group have been reported. In all but one of the cases, the SF 5 -group is located in the alcohol portion of the acrylate ester.…”

Sulfur: Inorganic Chemistry

“…With organic alkenes, SF 5 Cl reacts both photochemically and thermally. 112 It is a common feature of the chemistry of SF 5 X to proceed via SF 5 • radicals and a …”

Development of the New Approaches in Designing of Fluoroorganic Derivatives Sulfur (Unsaturated, Heterocyclic, Aromatic Molecular Systems and Polyfunctional Organic Compounds)

“…6 To the start of this work, syntheses of some compounds with pentafluorosulfanyl group have been reported. 7 At the same time, the preparation of F 5 S-substituted dienes with terminal CH 2 -group, to the best of our knowledge, has not been described hitherto.…”