Sulfur-oxygen compounds

2-Cyclic sulfites (320) have been shown to react with sodium acetoacetate (321  

The specific rates of solvolysis of benzyl p-toluenesulfonate and nine benzylic-ring-substituted derivatives (324) have been satisfactorily correlated using Aij and Tots scales within the extended Grunwald-Winstein equation. The reactions of Z-phenylethyl X-benzenesulfonates (325) with Y-pyridines (326) in acetonitrile at 60 °C have been studied at high pressures. The results indicated that the mechanism of the reaction moves from a dissociative 5)vr2 to an early-type concerted 5)vr2 with increasing pressure. 

In strongly alkaline solution, 2,4-dinitrophenyl 4-hydroxy-/3-styrenesulfonate (327) hydrolyses via a dissociation E cB) mechanism with the probable intervention of an extended sulfoquinone intermediate (328).  

Tris(fluorosulfuroyl)fluoromethane (329) reacted with bis(diethylamido)benzyl phosphite to yield an intermediate (330) which extruded a molecule of SO2 to give as final product the bis(fluorosulfonyl) compound (331). The kinetics and mechanism of the reaction of fluorinated tricoordinate phosphorus compounds (332) and aryl 2,2,2-trifluoroethyl sulfenates (333) have been reviewed.  

Ab initio SCRF/MO methods have been applied to the hydrolysis and methanol-ysis of methanesulfonyl chloride (334). ° The aminolysis by aromatic amines of sulfonyl and acyl chlorides has been examined in terms of solvent parameters, the former being the more solvent-dependent process.Solvent effects on the reactions of dansyl chloride (335) with substituted pyridines in MeOH-MeCN were studied using two parameters of Taft s solvatochromatic correlation and four parameters of the Kirkwood-Onsager, Parker, Marcus and Hildebrand equations. MeCN solvent molecules accelerate charge separation of the reactants and stabilize the transition 

General base (J mlc = 0.19) and nucleophilic catalysis mechanisms have been established for the hydrolysis of benzenesulfonyl chloride. Two-parameter LFERs were found for each route and electronic effects were seen to be greater than steric.272 

Methanolysis of the sulfonates (175)141 and the reaction of the sulfonate ester (102) with hydroxylamine (103)88 were looked at earlier. Yoh and co-workers have looked at the reactions of (Z)-phenylethyl (X)-benzenesulfonates with (Y)-pyridines in acetonitrile under pressure and the structure-reactivity relationships established show that as the pressure is increased the mechanism moves from a dissociative, S 2 to early-type concerted 5n2.276 In other studies also under pressure the same group found that a mechanistic change from associative 5k2 to late-type 5n2 occurs as the pressure is increased in the reaction of (Z)-phenacyl (X)-benzenesulfonates with (Y)-pyridines in acetone.277 

Lee s group has published extensive results on aminolysis of sulfonates.278-281 Thus the reactions of anilines with 2-cyano-2-propyl and 1-cyanocyclooctylarenesulfonates in acetonitrile have been studied.278 A dissociative 5 2 mechanism with a loose TS is supported from the usual LFERs. An 5n2 mechanism is also found for the reaction in acetone of (Z)-benzyl (X)-benzenesulfonates with (Y)-pyridines.279 Nucleophilic substitutions with the cycloalkylmethylsulfonates (306) and anilines in MeOH were also studied.280 Finally the reaction of thiopheneethyl arenesulfonates (307) with anilines and /V, /V- d i m c th y I an i I i nc s in MeCN has been reported on.281 Frontside-attack in an 5n2 mechanism with a four-centre TS is supported. 

King and Gill have been studying the reaction of alkyl 2,2,2-trifluoroethanesulfonate esters (tresylates) (308) in aqueous base (pH 9) in the presence of a primary or secondary amine.282 Reaction with hydroxide is found to be a reversible ElcB process and reaction with water is the normal sulfonic ester hydrolysis. 

The hydrolysis/alcoholysis of (309 R = Pr , Bu, allyl, propargyl) with various alcohols and water caused only a slight difference in the heat of activation for R but, for a fixed R the variation was much greater. The kinetics could be described by a Taft-Pavelich equation.283 

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Calcium carbonate is finding increasing use in flue gas desulfurization. This appHcation by a variety of engineering processes traps the sulfur—oxygen compounds produced in the combustion of coal (qv) (see Coal conversion process Exhaust contdol, industrial Sulfurremoval and recovery). 

Sulfur-Oxygen Compounds. Due to its 3s23p4 electron configuration sulfur, like oxygen, forms many divalent compounds with two covalent bonds and two lone electron pairs, but d-hybridization is quite common, to form compounds with oxidation of 4+ and 6+. 

The Nitrogen and Sulfur Analysis of Defined Fractions. Nitrogen and sulfur analysis for the subfractions are given in Table IX. For the acid fractions, the nitrogen is concentrated in the weak acids. This is consistent with the infrared analysis that showed these fractions to contain predominantly amides and carbazoles. The sulfur in the acid concentrates is randomly distributed and is probably of a thiophene or sulfide type. There is no evidence for the presence of appreciable quantities of sulfur-oxygen compounds such as sulfoxides, sulfones, or sulfonic acids in the acid concentrates. 

Sulfuryl fluoride has been prepared by a number of methods. Most of these consist of the fluorination of a sulfur-oxygen compound, as in the direct reaction of elemental fluorine with sulfur dioxide,1 a metal sulfate, or a metal thiosulfate.2 A well-known exception to this general method is the pyrolysis of barium fluorosulfate 3... 

Silicon is one of the most oxophilic elements (see Silicon Organosilicon Chemistry). Therefore, organosilicon sulfides react with certain sulfur oxygen compounds, as shown in equations (39) and (40). ... 

Sulfur-Oxygen Compounds (Thiosulfonates, Bunte Salts, Dimethyl Sulfate)... 

Sulfane oxides are compounds of type R2S Om ( > 1, m = 1, 2, 3...) with the oxygen atoms present as sulfoxide or sulfone groups. For the nomenclature of organic sulfur-oxygen compounds see Table 2 for reviews on oxidized sulfur chains and rings, see Steudel. Disulfane 1-oxides, RS(0)-SR, are also known as thiosulfinates and the 1,1-dioxides are usually termed as thiosulfonates. Trisulfane 1-oxides and 1,3-dioxides, as well as tetrasulfane 1-oxides and 1,4-dioxides, have been obtained by stepwise oxidation of the corresponding sulfanes by peroxy acids (equations 151 153) 67,101,123,127,262 26s... 

Previous methods for the preparation of sulfuryl fluoride have involved either the reaction of elemental fluorine with a variety of sulfur-oxygen compounds or the reaction of silver fluoride with sulfur dioxide. A very simple procedure for the preparation of sulfuryl fluoride in good yield involves the reaction of potassium fluorosulfite with chlorine gas. ... 

As expected, when comparing vibrational spectra of sulfur and selenium compounds, the absorptions due to bonds to selenium occur at lower frequencies than the corresponding sulfur modes. This frequency shift is normally 50-150 cm" but may be more for selenium-oxygen compounds when compared to sulfur-oxygen compounds ... 

Sulfates (sulfur-oxygen compounds) absorbed by plant roots... 

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