Sulfides reactions with

The reaction with sodium sulfite or bisulfite (5,11) to yield sodium-P-sulfopropionamide [19298-89-6] (C3H7N04S-Na) is very useful since it can be used as a scavenger for acrylamide monomer. The reaction proceeds very rapidly even at room temperature, and the product has low toxicity. Reactions with phosphines and phosphine oxides have been studied (12), and the products are potentially useful because of thek fire retardant properties. Reactions with sulfide and dithiocarbamates proceed readily but have no appHcations (5). However, the reaction with mercaptide ions has been used for analytical purposes (13)). Water reacts with the amide group (5) to form hydrolysis products, and other hydroxy compounds, such as alcohols and phenols, react readily to form ether compounds. Primary aUphatic alcohols are the most reactive and the reactions are compHcated by partial hydrolysis of the amide groups by any water present. 

Through reaction with sulfide or elemental sulfur at 215°C, lignosulfonates can also be used in the commercial production of dimethyl sulfide and methyl mercaptan (77). Dimethyl sulfide produced in the reaction is further oxidized to dimethyl sulfoxide (DMSO), a useful industrial solvent (see Sulfoxides). 

These three methods are employed commercially. In addition, decomposition of polythionates in alkaline solution or their reaction with sulfide or sulfite gives thiosulfates ... 

Reactions with sulfides, polysulfides, sulfur oxides and the oxoacids of sulfur are complex and the products depend markedly on reaction conditions (see also p. 745 for blue crystals in chamber acid). Some examples are ... 

In the case of ACSO it was found also that N20 addition reduces the yield of S-allyl-L-cysteine (ACS), indicating that this product is formed by eaq - but not by OH radicals. As a result it can be expected that KBr addition will not reduce the ACS yield. It was found that KBr not only does not reduce the yield of ACS, but it rather increases i ts formation. This is explained as due to ACS formation by reaction of eaq" with ACSO, and its disappearance by reaction with OH radicals to give back ACSO as it is known for the reaction with sulfides. The authors suggest the same reactions for PCSO and PCS (propyl-L-cysteine) although the yield of PCS was not determined. 

The reaction with sulfides occurs efficiently only when the resulting carbon-centered radicals are further stabilized by a a-heteroatom. Indeed, (TMSfsSiH can induce the efficient radical chain monoreduction of 1,3-dithiolane, 1,3-dithiane, 1,3-oxathiolane, 1,3-oxathiolanone, and 1,3-thiazolidine derivatives. Three examples are outlined in Reaction (12). The reaction of benzothiazole sulfenamide with (TMS)3SiH, initiated by the decomposition of AIBN at 76 °C, is an efficient chain process producing the corresponding dialkylamine quantitatively. However, the mechanism of this chain reaction is complex as it is also an example of a degenerate-branched chain process. 

Scheme 1.39 Test reaction with sulfide-tertiary amine ligands incorporating 1,2-aminothioethers.

Metal contaminants can in some cases be immobilized in situ by oxidation or reduction, or precipitated by reaction with sulfide. Sulfate reducing bacteria are sometimes stimulated to produce sulfide, or a sulfur-bearing compound such as calcium polysulfide can be injected into the subsurface as a reductant and sulfide source. In certain cases where the contamination poses little immediate threat, it can safely be left to attenuate naturally (e.g., Brady et al., 1998), a procedure known as monitored natural attenuation. 

MoGj] centers, reactions with sulfiding agents, 40 43... 

Metal-catalysed Grignard reaction with sulfides and dithioacetals... 

In addition to a better understanding of the reaction of sulfide with ferric oxides and its role in pyrite formation, a more exact definition of the term reactive iron is critical. Does reactive iron mean a different iron oxide fraction for bacterial dissolution (e.g., weathering products such as goethite or hematite) than for reaction with sulfide (e.g., reoxidized lepidocrocite) In other words, is there a predigestion of ferric oxides by bacteria that allows a subsequent rapid interaction of sulfide with ferric oxides ... 

Adams JQ (1970) Electron paramagnetic resonance of f-butoxy radical reactions with sulfides and disulfides. J Am Chem Soc 92 4535-4537... 

The mesoionic 1,3,2-oxathiazolone (12) behaves in its reaction with sulfide ion (Scheme 17) (76MI43400) more as structure (12b) than the generally accepted azolylium-5-olate form (12d), consistent with X-ray bond parameters (see Section 4.34.2.3.1). 

The dithiophenol derivative 315, prepared from the dinitro 314 via reduction, diazotization, and subsequent reaction with sulfide, under mild oxidative conditions, afforded the cyclic disulfide 310, which was converted into dioxide 316 with hydrogen peroxide or a peracid (Scheme 66) <2004W0099162>. The already known, dithiocin 310, obtained... 

Deactivation of growing carbenium ions by reaction with sulfides is evidently very fast. Sulfonium ion formation is exothermic (AH = -40 kJ/mol) and exoentropic (AS = -74 J/mol-K) [271]. High equilibrium constants (Keq = 104 moI-1L) for sulfonium ion formation were calculated from the apparent rate constants of propagation and the rate constants of carbocationic growth. Dynamic NMR experiments of model systems with tetrahydrothiophene indicate that the bimolecular deactivation rate constant is kdeacl 106 mol-1-Lsec-1 at 0° C (AH = 20 kJ/mol, AS = -37 J-mol-K), and that activation is faster than bimolecular exchange (k act foe) [67]. 

SAFETY PROFILE Confirmed human carcinogen. A powerful oxidizing agent. Flammable by chemical reaction with reducing agents. Moderate explosion hazard when shocked or exposed to heat. Violent or explosive reaction with sulfides (e.g., copper(II) sulfide (explodes) antimony(II) sulfide arsenic(III) sulfide tin(II) sulfide tin(IV) sulfide). When heated to decomposition it emits toxic fumes of Cd and Cr. See also CHLORATES. 

Very early in the study of sulfide mineral biodegradation, it was discerned that microbially-regenerated ferric ions constituted a very potent reagent for indirect attack (for literature, see Kuznetsov et al., 1963 Silverman and Ehrlich, 1964 Zajic, 1969). The ubiquitous occurrence of iron in natural situations and the wide range of reactions with sulfide minerals that can occur, combine to make the ferric ion, either as such or in complex form, the most important chemical species involved in indirect attack mechanisms. The general reaction, known to be applicable to a number of sulfide minerals under aerobic conditions (Bryner et al., 1954 Ivanov et al., 1961), may be expressed as ... 

This includes reactions of the polymer groups with metallic sites on the particle surface that may result in the formation of stable or insoluble compounds through covalent, ionic or coordination bonding. Carboxyl flocculants such as polyacrylic acid and carboxyl-methyl cellulose can chemisorb on the surface of calcite and sphalerite which have calcium or zinc sites on them. Certain flocculants, such as cellulose and starch with xanthate and polyacrylamide with dithiocarbamate with high chemically active groups, have been found to exhibit selective reaction with sulfide minerals. Such complexing polymers have been investigated for their use in selective flocculation processes. 

Mid-ocean ridge hydrothermal processes provide an ideal application for geochemical reaction path modeling, involving temperature dependent reactions, fluid mixing, reaction with sulfide products, and reaction with seafloor basalts (5). The solution and solid compositions are well characterized, including that of sulfur isotopes (10.11). However, measured fractionations between solution and solid samples can not be the result of simple equilibrium processes f 10-121. The ability to track reactions involving seawater sulfate = 21 per mil) and hydrother-... 

Disulfides do not appear to be capable of reducing Fe(III) Lb to Fe(II) Lb (135). Reaction with sulfide itself appears to be different and gives rise to a Fe(III) Lb-sulfide complex rather than reduction or nucleophilic attack (135). The complex is, however, susceptible to reduction by strong reducing agents such as dithionite and ascorbic acid. 

Primary alcohols in admixture with acids can act as alkylating agents, their reaction with sulfides leading to loss of water and formation of sulfonium salts ... 

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