Organosulfurs

2-(4-terJ-Butylphenoxy)Cyclohexyl Prop-2-ynyl Sulfite 

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Organosulfur Halides. When sulfur is directly linked only to an organic radical and to a halogen atom, the radical name is attached to the word sulfur and the name(s) and number of the halide(s) are stated as a separate word. Alternatively, the name can be formed from R—SOH, a sulfenic acid whose radical prefix is sulfenyl-. For example, CH3CH2—S — Br would be named either ethylsulfur monobromide or ethanesulfenyl bromide. When another principal group is present, a composite prefix is formed from the number and substitutive name(s) of the halogen atoms in front of the syllable thio. For example, BrS—COOH is (bromothio)formic acid. 

Acetic anhydride is a useful solvent in certain nitrations, acetylation of amines and organosulfur compounds for mbber processing, and in pesticides. Though acetic acid is unexceptional as a fungicide, small percentages of anhydride in acetic acid, or in cold water solutions are powerful fungicides and bactericides. There are no reports of this appHcation in commerce. It is possible that anhydride may replace formaldehyde for certain mycocidal apphcations. 

Organosulfur Compounds. These compounds, Hsted in Table 8, are used in a variety of appHcations, including cooling water, paint, and metalworking. Methylenebisthiocyanate hydroly2es rapidly at a pH above 8 to cyanate ion which complexes with ferric iron to poison the cytochrome systems (36). 

Cross-country gas pipelines generally must odorize the normally odorless, colorless, and tasteless gas ia urban and suburban areas, as is required of gas distribution companies. Organosulfur compounds, such as mercaptans, are usually used for this purpose, and code requires that the odor must be strong enough for someone with a normal sense of smell to detect a gas leak iato air at one-fifth the lower explosive limit of gas—air mixtures. The latter is about 5%, so the odorant concentration should be about 1%, but most companies odorize more heavily than this as a safety precaution. 

E. Block, Reactions of Organosulfur Compounds, Academic Press, Inc., New York, 1978, p. 278. 

The chemical properties of organosulfur, organoselenium, and organoteUurium compounds are markedly similar. Because bond stabUity with carbon decreases with the increasing atomic number of the element, thermal stabUity decreases, whereas oxidation susceptibUity increases to such an extent that alkyl teUurides are oxidized rapidly by air at room temperature. As a result, less has been written concerning the chemistry of organoteUurium than organoselenium compounds. Nevertheless, a sizable Uterature exists (29,55—59). 

Organosulfur Adsorbates on Metal and Semiconductor Surfaces. Sulfur compounds (qv) and selenium compounds (qv) have a strong affinity for transition metal surfaces (206—211). The number of reported surface-active organosulfur compounds that form monolayers on gold includes di- -alkyl sulfide (212,213), di- -alkyl disulfides (108), thiophenols (214,215), mercaptopyridines (216), mercaptoanilines (217), thiophenes (217), cysteines (218,219), xanthates (220), thiocarbaminates (220), thiocarbamates (221), thioureas (222), mercaptoimidazoles (223—225), and alkaneselenoles (226) (Fig. 11). However, the most studied, and probably most understood, SAM is that of alkanethiolates on Au(lll) surfaces. 

Fig. 11. Surface-active organosulfur compounds that form monolayers on gold (a) alkanethiol (b) dialkyl disulfide (c) dialkyl sulfide (d) alkyl xanthate ...

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). 

The heat capacities and entropies of organic compounds, including many thiols, have been compiled (19,20). The thermochemistry of thiols and other organosulfur compounds has been extensively reviewed (21). 

Over the years, a diverse group of products made use of the rather unique chemistry of organosulfur chemicals. These include the following ... 

Organosulfur chemicals serve a diverse group of industries. In these appHcations ways have been found to control the odor of the thiols, thus utilizing these compounds effectively in a wide range of products. 

J. W. Eitzgerald, "Naturally Occurring Organosulfur Compounds in Soil," inJ. O. Ntiagu, ed.. Sulfur in the Environment, Part II Ecological Impacts, Wiley-lnterscience, New York, 1978, pp. 391—443. 

Synthetic applications of organosulfur reagents are expanding rapidly. Stable sulfuranes are included for the first time in BIS[2,-2,2-TRIPLUORO-l-PHENYL-l-(TRIFLUOROMETHYL)ETHOXY] diphenyl SULFURANE and DIETHYLAMINOSULFUR TRI-FLUORIDE. The latter is used to transform an alcohol to a fluoride in p-NITROBENZYL FLUORIDE. The direct homologation of a ketone to a nitrile by use of p-TOLYLSULFONYLMETHYL ISOCYANIDE is illustrated in 2-ADAMANTANECARBONITRILE. Reagents with... 

Multiple reactors achieve 95-96% conversion and recovery, and stringent air pollution legislation has now pushed this to 99%. A similar sequence of reactions is used for sulfur production from crude oil except that the organosulfur compounds must first be removed from the refinery feed and converted to H2S by a hydrogenation process before the sulfur can be recovered. 

These facts, together with many other examples of the peculiar chemical behavior of organotellurium compounds (95UK527), emphasize their specific reactivity and explain why a number of methods developed for preparation of organosulfur and organoselenium compounds are inapplicable for their tellurium analogues. 

Thiophene, benzo[d]thiophene and dibenzo[d,organosulfur compounds formed at Rh- and Ir-mediated thiophene ring opening 97SL643. 

TransmetalaLion of OrganoLin, Organosulfur, artd OrganoLellurium Reagents... 

Y. Pico, A. J. H. Eouter, J. J. Vreuls and U. A. Th Brinkman, On-line tr-ace-level enrichment gas cliromatography of triazine herbicides, organophosphoms pesticides and organosulfur compounds from drinking and surface waters . Analyst 119 2025-2031 (1994). 

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. 

Sulfur in crude oils is mainly present in the form of organosulfur compounds. Hydrogen sulfide is the only important inorganic sulfur compound found in crude oil. Its presence, however, is harmful because of its corrosive nature. Organosulfur compounds may generally be classified as acidic and non-acidic. Acidic sulfur compounds are the thiols (mercap-tans). Thiophene, sulfides, and disulfides are examples of non-acidic sulfur compounds found in crude fractions. Extensive research has been carried out to identify some sulfur compounds in a narrow light petroleum fraction.Examples of some sulfur compounds from the two types are ... 

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