Carbon-sulfur chains

Upon solidification of molten sulfur, Stt rapidly changes into S]l, which is converted into SL, although at a much slower rate. The molecular stmcture of Stt is that of an octatomic sulfur chain (1,2). The symbol S]1 designates long, polymerized chains of elemental sulfur. SX is perhaps the most characteristic molecular form of sulfur, namely, that of a crown-shaped, octatomic sulfur ring designated in more recent Hterature as (3). The allotropes have different solubiUty in carbon disulfide. Stt and SX are soluble in carbon disulfide, whereas S]1 does not dissolve in this solvent. 

The reaction of crotonaldehyde and methyl vinyl ketone with thiophenol in the presence of anhydrous hydrogen chloride effects conjugate addition of thiophenol as well as acetal formation. The resulting j3-phenylthio thioacetals are converted to 1-phenylthio-and 2-phenylthio-1,3-butadiene, respectively, upon reaction with 2 equivalents of copper(I) trifluoromethanesulfonate (Table I). The copper(I)-induced heterolysis of carbon-sulfur bonds has also been used to effect pinacol-type rearrangements of bis(phenyl-thio)methyl carbinols. Thus the addition of bis(phenyl-thio)methyllithium to ketones and aldehydes followed by copper(I)-induced rearrangement results in a one-carbon ring expansion or chain-insertion transformation which gives a-phenylthio ketones. Monothioketals of 1,4-diketones are cyclized to 2,5-disubstituted furans by the action of copper(I) trifluoromethanesulfonate. ... 

The presence of high-molecular weight p-sulfur with chain structure seemed improbable since the sulfur was not extractable with boiling toluene. The p-sulfur is known to convert to the soluble ring structure (Sg) rather rapidly at 115°. Wibaut (119) thought the formation of a carbon-sulfur complex similar to the surface oxide formed with oxygen very likely. He was not able, however, to analyze definite surface groups. Hofmann and Nobbe (123) established that the sulfur content was dependent on the specific surface area. Enoksson and Wetterholm (124) confirmed by X-ray diffraction that no crystalline sulfur was present in exhaustively extracted charcoal with 13% sulfur content. 

PBS (Figure 30) is an alternating copolymer of sulfur dioxide and 1-butene. It undergoes efficient main chain scission upon exposure to electron beam radiation to produce, as major scission products, sulfur dioxide and the olefin monomer. Exposure results first in scission of the main chain carbon-sulfur bond, followed by depolymerization of the radical (and cationic) fragments to an extent that is temperature dependent and results in evolution of the volatile monomers species. The mechanism of the radiochemical degradation of polyolefin sulfones has been the subject of detailed studies by O Donnell et. al. (.41). 

Our early work examined the reaction of PCTFE with sulfur, selenium and phosphorous nucleophiles 9 to achieve high levels of functionalization through a well-precedented (in the case of perfluoroalkyl iodides)20"24 one electron transfer, radical anion chain process. While such a reaction demonstrated the feasibility of using one-electron processes for the functionalization of PCTFE, the carbon-sulfur linkage remained susceptable to oxidation. 

Introduction of a Carbon-Sulfur Unit to a Three-carbon Chain to Form a Thiophene Ring 893... 

Many of the polymers formed from conjugated dienes are elastic and are used to manufacture synthetic rubbers. The raw polymers usually are tacky and of little direct use, except as adhesives and cements. They are transformed into materials with greater elasticity and strength by vulcanization, in which the polymer is heated with sulfur and various other substances called accelerators, with the result that the polymer chains become cross-linked to one another by carbon-sulfur and carbon-carbon bonds. Some of the cross-linking appears to occur by addition to the double bonds, but the amount of sulfur added generally is insufficient to saturate the polymer. With large proportions of sulfur, hard rubberis formed such as is used in storage-battery cases. 

Under the usual commercial hydrodesulfurization conditions (elevated temperatures and pressures, high hydrogen-to-feedstock ratios, and the presence of a catalyst), the various reactions that result in the removal of sulfur from the organic feedstock (Table 4-3) occur. Thus, thiols as well as open chain and cyclic sulfides are converted to saturated and/or aromatic compounds depending, of course, on the nature of the particular sulfur compound involved. Benzothio-phenes are converted to alkyl aromatics, while dibenzothiophenes are usually converted to biphenyl derivatives. In fact, the major reactions that occur as part of the hydrodesulfurization process involve carbon-sulfur bond rupture and saturation of the reactive fragments (as well as saturation of olefins). 

All of the isolated pterin derivatives have a four-carbon side chain attached to the C(6) position of the pterin with unsaturation at the Y and 2 carbons of the side chain (consider the enol forms of the MPT precursor and Form Z). The sulfur atoms at the V and 2 positions of urothione and camMPT are derived from the 1,2-enedithiolate sulfur atoms of the cofactor. All of the dinucleotide MPT derivatives have been isolated and characterized as their carboxymethylam-ide (cam) derivatives camMPTpA, camMPTpC, camMPTpG, and camMPTpH, respectively [45,61],... 

The templates can be simply coordinated rather than attached. For example, complex 100 directed the radical relay chlorination to C-9, although the process was not as clean as with the attached templates [173]. We also used template-directed chlorina-tions to determine the conformations of flexible chains, just as we had previously with the benzophenone probes [174]. Also, by use of a set of tandem free radical chain reactions we could direct the formation of carbon-bromine and carbon-sulfur bonds, again with geometric control by the attached template [175]. 

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