1.3- Butadiene-1 -sulfonyl chlorides

Exposure of 3-sulfolenes to BuLi and then A(-chlorosuccinimide accomplishes the synthesis of substituted 1,3-butadiene-1-sulfonyl chlorides. ... 

In order to impose crystallinity on all the intermediates, several sulfonamides, derived in two steps from (+)- or (-)-camphor-lO-sulfonyl chloride, were examined. Their acrylates 17a and 17b are added to cyclopentadiene (19) and to 1,3-butadiene (18) in the presence of dichlorodi-isopropoxytitanium. The resulting cycloadducts can be purified to give a d.r. 99.5 0.5 by simple recrystallization21. Examination of the X-ray crystal structure of 17b22 confirmed the hypothetical conformation of the acrylate, earlier proposed and later calculated23. Analogous sulfones 21a-c are less diastereoselective (d.r. 82 18 - 84.5 15.5)24. 

Scheme 24 Synthesis of 1,3.4-trifluoroisoquinohne via copyrolysis of pyridine-4-sulfonyl chloride with butadiene...

Kolechkina VG, Maksimov AM, Platonov VE, Osina OI (2001) Synthesis of 1,3,4-trifluoroisoquinoline by copyrolysis of 2,3,5,6-tetrafluoropyridine-4-sulfonyl chloride with butadiene. Russ Chem Bull Int Ed 50 322-323... 

Pentachloro-1,3-butadiene 19 by heating with excess chlorosulfonic acid at 100-110 °C gave a mixture of the 3-sulfonyl chloride 20, 30% and hexachlorobutadiene 21, 16% (Equation 1) The products presumably result from chlorosulfonation and chlorination respectively of the reactive 3-alkenic hydrogen atom by the reagent. 

Cycloadditions to a cyano group are comparatively rare. The high-temperature reactions of 1,3-dienes, e.g. butadiene, isoprene and 2-chloro-l,3-butadiene, with dicyanogen, propionitrile or benzonitrile result in formation of pyridines (equation 80)70. Sulfonyl cyanides 147, obtained by the action of cyanogen chloride on sodium salts of sulfinic acids, add to dienes to give dihydropyridines 148, which are transformed into pyridines 149 by oxidation (equation 81)71. 

The tosylation of carbon can be accomplished using electron transfer conditions. Treatment of styrene and analogs with Copper(II) Chloride and tosyl chloride or Benzenesulfonyl Chloride results in a formal replacement of the vinyl proton by the sulfonyl moiety (eq 35). The intermediacy of a trans-(S-chloro sulfone has been demonstrated by H NMR. Treatment with base induced the elimination of HCl. A variety of other sulfonyl transfer reagents can be ertployed in the synthesis of isolated /3-chloro sulfones, with good results (60-97% yield) for a variety of alkenes (ethylene, 1-butene, 2-butene, 1-octene, acrylonitrile, methyl acrylate, and 1,3-butadiene). ... 

Organic polymers Polyethylene maleate Ethyl cellulose, fluoropolyol, phenoxy resin, poly(amidoxime), poly-1-butadiene, poly(epichloro-hydrin), polyethylene, poly-(ethylene m eate), poly(iso-prene), poly(methylmethacrylate), polystyrene, poly(vinyl chloride), poly(vinyl stearate), 1,1,1-tri-fluoroisopropyl methyl siloxane Cyclopentadiene [200 ppm-min] Benzene, 1-butanol, 2-buta-none, 1,2-dichloroethane, dichloropentane, methylacetamide, dimethyl-phosphite, dodecane, methane-sulfonyl fluoride, octane, a-pinene oxide, /-propyl-acetate, toluene, triamylphos-phite, tributylphosphate, water... 

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