Organosulfur compounds chemistry

The chemistry of organic sulfur compounds is very rich and organosulfur compounds are incorporated into many molecules. Thiols, or mercaptans as they were originally called, are essential as feedstocks in the manufacture of many types of mbber (qv) and plastics (qv). They are utilized as intermediates in agricultural chemicals, pharmaceuticals (qv), ia flavors and fragrances, and as animal feed supplements. Many reviews have been undertaken on the chemistry of the thiols, regarding both their preparation and their reactions (1 7). 

Although desulfurization is a process, which has been in use in the oil industry for many years, renewed research has recently been started, aimed at improving the efficiency of the process. Envii onmental pressure and legislation to further reduce Sulfur levels in the various fuels has forced process development to place an increased emphasis on hydrodesulfurization (HDS). For a clear comprehension of the process kinetics involved in HDS, a detailed analyses of all the organosulfur compounds clarifying the desulfurization chemistry is a prerequisite. The reactivities of the Sulfur-containing structures present in middle distillates decrease sharply in the sequence thiols sulfides thiophenes benzothiophenes dibenzothio-phenes (32). However, in addition, within the various families the reactivities of the Substituted species are different. 

E. Block, Reactions of organosulfur compounds, Vol 37 in Organic Chemistry, A.T. Blomquist and H.H. Wasserman (eds), Academic Press, New York, 1978. 

Organosulfur chemistry is presently a particularly dynamic subject area. The stereochemical aspects of this field are surveyed by M. Mikojajczyk and J. Drabowicz. in the fifth chapter, entitled Qural Organosulfur Compounds. The synthesis, resolution, and application of a wide range of chiral sulfur compounds are described as are the determination of absolute configuration and of enantiomeric purity of these substances. A discussion of the dynamic stereochemistry of chiral sulfur compounds including racemization processes follows. Finally, nucleophilic substitution on and reaction of such compounds with electrophiles, their use in asymmetric synthesis, and asymmetric induction in the transfer of chirality from sulfur to other centers is discussed in a chapter that should be of interest to chemists in several disciplines, in particular synthetic and natural product chemistry. 

MI1 S. Oae, Chemistry of Organosulfur Compounds (Yuki lo-Kagobutsu... 

With each of the C, P and S centers, compounds with several oxidation states are possible, thus multiplying the types of nucleophilic reactions extant. Importantly, the types of compounds cover a variety of classes each with its characteristic behaviors and reactivities, each defining a specific area in chemistry. Since the C, P and S reactive centers are incorporated in the majority of molecules in living systems it follows that the chemistry to be considered in this chapter is closely tied with the chemistry of life, i.e. bioorganic reaction mechanisms. It is known in fact that many organophosphorus and organosulfur compounds are toxic toward mammalian organisms which renders their destruction under mild conditions of critical importance. 

For a monograph on sulfur ylides. see Trost Melvin Sulfur Ylides Academic Press New York. 1975. For reviews, sec Fava in Bcrnardi Csizmadia Mangini Organic Sulfur Chemistry Elsevier New York. 1985, pp. 299-354 Belkin Polczhaeva Russ. Chem. Rev. 1981, 50, 481-497 Block, in Stirling The Chemistry of the Sulphonium Group, part 2. Wiley New York. 1981. pp. 680-702 Block Reactions of Organosulfur Compounds Academic Press New York. 1978. pp. 91-127. 

For reviews, see Belen kii. in Belcn kii Chemistry of Organosulfur Compounds Ellis Horwood Chichester. 1990, pp. 193-228 Pettit van Tamelen Org. React. 1962,12. 356-529 Hauptmann Waller Chem. Rev. 1962,62. 347-404. 

Different macerals have different distributions and types of organosulfur compounds. The sulfur chemistry varies not only between macerals from the same coal, but between similar macerals from different coals. 

Chemistry of Organosulfur Compounds at the Gold Interface and Characterization 115... 

CHEMISTRY OF ORGANOSULFUR COMPOUNDS AT THE GOLD INTERFACE AND CHARACTERIZATION OF SAMs... 

Volume 2 begins with a thorough survey of sulfur radical cations, covering their synthesis, structure, stability, and reactivity, by Prof. Richard Glass. Prof. Naomichi Furukawa and Prof. Soichi Sato describe recent developments in the area of hypervalent organosulfur compounds, and the volume is completed by a discussion of the chemistry of thiophene 1,1 -dioxides by Prof. Juzo Nakayama and Prof. Yoshiaki Sugihara. 

In general, the sulfanes have a less well-developed chemistry, partly because of the difficulty in isolating them pure, although they have been used for the synthesis of some organosulfur compounds see Sulfur Organic Polysulfanes). 

Although binary carbon sulfides appear to be something of a curiosity at the moment, given their stability (especially compared to binary S-N compounds) and their usefulness in the synthesis of new organosulfur compounds and ligands that may be redox active, it is to be expected that their chemistry will develop rapidly over the next few years. 

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