Reaction of Sulfur Compounds

Nearly all the kinetic data available on sulfur compounds is for organic materials. An excellent recent review of these reactions has been written by Gunning and Stausz .  

Only a few attempts have been made to obtain kinetic data on the formation of H2S from and S. Bodenstein has shown that the reaction in a static system at temperatures near 300 °C is mainly surface catalyzed. Norrish and Rideal have also investigated this system finding both a homogeneous and heterogeneous component. All these studies were carried out at temperatures in the range 265-340 °C where molten sulfur is present in the system. For this reason and also because the identification of the species participating in the homogeneous reaction is not known, no rate coefficient data are available. 

The reaction between two HS radicals has been studied by Darwent et Darwent and Roberts , during the course of an investigation of the reactions of H atoms with hydrocarbons, had occasion to consider the fate of HS radicals produced by the photolysis of H2S. They estimated the rate coefficient ratio for 

Wright has followed the decay of S2 species after the flash photolysis of CS2 near room temperature. He finds the decay to be second order in S2 and in view of Callear s work presumably yielding the S4 polymer of sulfur. The rate coefficient cannot be calculated because the extinction coefficient for S2 is not known. 

In a study of the flash photolysis of CS2, Callear has observed vibrationally excited CS radicals which are rapidly relaxed in collisions with sulfur atoms. The 

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Y. Yano and S. Oae, 3d Orbital Resonance in the Bivalent Sulfur Atom, Mechanisms of Reactions of Sulfur Compounds, Vol. 4, Intra-Science, 1969, p. 167. 

S. Braverman and C. Simons, in Mechanisms of Reactions of Sulfur Compounds (Eds. N. Kharasch, B. S. Thyagarajan and A. I. Khodair), Vol. 2, Intra-Science Research Foundation, Santa-Monica, Calif., 1968, p. 102. 

Numerous oxidation reactions of sulfur compounds have been described in which S2O or its precursor SO are formed as intermediates but most of these reactions are not suitable to investigate the properties of S2O because of the low yield or the interference from by-products [1]. A relatively clean process is the reaction of oxygen atoms with COS producing SO and CO. The formation of S2O from gaseous SO is a stepwise process according to the following equations (M is a collision partner) [21] ... 

The use of soft metal ions to direct the course of reactions of sulfur compounds has been utilised in the preparation of nitriles from thioamides. The first step involves the alkylation of the thioamide to give the iminothioester, which is then converted to the nitrile on treatment with mercury(n) salts (Fig. 4-41). 

A specialist review dealing with the reactions of sulfur compounds. 

Journal of Sulfur Chemistry was previously divided into Part A [Int. J. Sulfur Chem., Part A] (1971-1972) (original experimental and theoretical studies) Part B Int. J. Sulfur Chem., Part E (1971-1972), previously Quarterly Reports on Sulfur Chemistry [Q. Rep. Sulfur Chem.] (1966-1970) and Part C [Int. J. Sulfur Chem., Part C] (1971-1972), previously Mechanisms of Reactions of Sulfur Compounds [Mech. React. Sulfur Compd.] (1966-1970). Publisher Taylor Francis. 

The C,C coupling reactions of sulfur compounds are less numerous. One example is mentioned here. When 1,3-dithioles are oxidized in MeCN containing pyridine, tetrathio-fulvalenes are obtained in moderate to fair yields (13 0%) [111]. 

Quarterly Reports on Sulfur Chemistry, and Annual Reports on Mechanism and Reactions of Sulfur Compounds, Intra Science Research Foundation, Santa Monica, Calif. 

Reactions of sulfur compounds. AtAt-Bis(sulfonyl) arylamines lose one of the sulfonyl groups on heating with BU4NF in THF. Cyclic disulfides are obtained from 1, (o-dithiocyanotoalkanes. "... 

Moriconi, E.J., "Mechanisms of Reactions of Sulfur Compounds", Vol.3, Intra - Science Foundation, Santa Monica, Calif, p. 131 (1968). 

The most common oxidation-reduction reaction of sulfur compounds in biological systems is interconversion between a thiol and a disulfide. The functional group of a disulfide is an —S—S— group. 

Most of oxidation reactions of sulfur compounds in the troposphere are initiated by OH radicals, but the reactions with NO, and active halogen species such as BrO and 10 has to be considered in the polluted air and in the marine boundary layer, respectively. As for SO2, other than the gas phase reaction with OH, oxidation reaction in cloud and fog droplet is important which will be described later. 

Smyth, C. V., Some Enzyme Reactions of Sulfur Compounds... V 237... 

Fontana, A., and E. Scoffone Sulfenyl Halides as Reagents in Peptide and Protein Chemistry. Mechanisms of Reactions of Sulfur Compounds (N. Kharasch, Ed.), Intra-Science Res. Foundation, Santa Monica, Calif. 4, 15-24 (1969). 

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