79597-66-3Relevant academic research and scientific papers
Synthesis of monofluorinated C4-building blocks based on methallyl chloride
Haufe, Guenter,Wessel, Ulrich,Schulze, Klaus,Alvernhe, Gerard
, p. 283 - 292 (2007/10/03)
Halofluorination of methallyl chloride using N-halosuccinimides in combination with triethylamine trishydrofluoride (Et3N*3HF) gave in each case more than 98percent of the Markovnikov products and 2percent of the regioisomers in good yield.The formal addition of methanesulfenyl fluoride with the combination of dimethyl(methylthio)sulfonium fluoroborate (DMTSF) and Et3N*3HF gave a 94:6 mixture of both regioisomers.Only small phenylsulfenyl fluorination of methallyl chloride has been observed when treated with N-phenylthiophthalimide (NPTP) and Olah's reagent.With benzenesulfenyl chloride, 1,3-dichloro-2-methyl-2-(phenylthio)propane is formed which on treatment with Olah's reagent at 0 deg C or with Et3N*3HF at 60 deg C rearranges to 1,2-dichloro-2-methyl-3-(phenylthio)propane.Treatment of 1,3-dichloro-2-methyl-2-(phenylthio)propane with silver fluoride in methylene chloride at -30 deg C gave 1-chloro-2-fluoro-2-methyl-3-(phenylthio)propane which was also obtained by reaction of 1-bromo-3-chloro-2-fluoro-2-methylpropane with thiophenolate.Chlorofluorination of methallylphenylthio ether using NCS/Et3N*3HF failed, while corresponding reactions with NBS or NIS and Et3N*3HF gave mainly the bromo- or iodo-fluorides with Markovnikov orientation in 61percent or 35percent yields.Related halofluorinations of methallylphenyl ether gave the halofluorides in good yield.All attempts to obtain chromanes or thiochromanes bearing a 3-fluorine substituent by cyclization of these halofluorinated ethers or thio ethers failed using different Lewis acids.However, the benzyl protected o-allylphenol which was bromofluorinated with NBS/Et3N*3HF in good yield gave on catalytic hydrogenation over Pd/C the 3-fluoro-2H-chromane in nearly quantitative yield. - Keywords: Electrophilic addition; Halofluorination; Sulfenylfluorination; N-Halosuccinimides; Dimethyl(methylthio)sulfonium tetrafluoroborate; Triethylamine trishydrofluoride
Synthesis of Allyl Thioethers
Giese, Bernd,Mazumdar, Pronab
, p. 2859 - 2865 (2007/10/02)
Addition of C6H5SCl to alkenes 8, 10, and 14 yields allyl thioethers 9, 11, and 15 + 16 after thermolysis at 120 - 200 deg C.Vinyl thioethers are not observed.The influence of substituents R1 and R2 on the regioselectivity (Table 1) and the rate of the elimination (Table 2) is examined.
