Sulfur—oxygen bonds reactions with

Reaction of Thiols with Sulfur-Oxygen Bonds of Bis(Alkoxy)Sulfanes... 

An example of cleavage ol the sulfur-oxygen bond in trifluoromethane-sulfonic ester has been reported Tnfluororaethyl triflate reacts with neutral or anionic nucleophiles with elimination of carbonyl difluoride and formation of trifluoromethanesulfonyl fluoride [57] (equation 32) The mechanism of this reaction involves elimination of fluoride ion, which is a chain carrier in the substitution of fluorine for the trifluoromethoxy group... 

Notice in the list of Lewis bases just given that some compounds, such as carboxylic acids, esters, and amides, have more than one atom ivith a lone pair of electrons and can therefore react at more than one site. Acetic acid, for example, can be protonated either on the doubly bonded oxygen atom or on the singly bonded oxygen atom. Reaction normally occurs only once in such instances, and the more stable of the two possible protonation products is formed. For acetic add, protonation by reaction with sulfuric acid occurs on... 

Because of certain misconceptions with regard to the choice of solvent and the occurrence of sulfur-oxygen bond fission in hydroxylic solvents - , it is important to emphasize that one can greatly reduce the rate of this competing process by the use of weak bases. In systems which can undergo facile C—O as well as S—O bond fission, it is possible to control the type of bond cleavage by choosing the appropriate base . A remarkable illustration of this behavior is found in the ethanolysis of sulfinate 6a. In anhydrous ethanol at 90.0° with acetate ion as the added base, 6a yielded ethyl 2, 6-dimethylbenzenesulfinate plus a trace of sulfone 7a. Under the same conditions but with 2,6-lutidine the reaction was slower and sulfone 7a was the only detectable reaction product . ... 

According to kinetic measurements (21), this reaction proceeds as a nucleophilic substitution reaction with sulfur acting as EPD and apparently involves an electron shift from the more negative to the more positive part of the hypochlorite ion. Formation of a coordinate bond between sulfur and oxygen has been demonstrated using relabeled 0C1-. 

Sulfinate esters (18) are isomeric with sulfones, but have very different properties. Cyclic sulfinate esters (sultines) (21) can be conveniently prepared by the action of sulfuryl chloride on t-2 butyl hydroxyalkyl sulfoxides (20) (Scheme 13). The most common reaction of sulfinate esters is nucleophilic substitution at sulfur with consequent sulfur-oxygen bond cleavage (Scheme 13). 

This observation clearly indicated that the substitution reaction followed the bimolecular (Sn2) mechanism. Nucleophilic attack on sulfonate esters may occur via two possible pathways either with carbon-oxygen bond cleavage (Equation 17) or by cleavage of the sulfur-oxygen bond (Equation 18). 

Metal carbonyl derivatives with metal-oxygen bonds are not common. Flash photolysis of oxygen-iron pentacarbonyl mixtures produces a substance believed to be [Fc202(C0)] 226). Sulfur trioxide and iron pentacarbonyl afford an unisolable material thought to be the pyrophosphate Fe[0(S03)2](C0)3 141). However, the reaction between sulfur dioxide and enneacarbonyldiiron gives a substance [Fe2(C0)gS02], for which... 

Alkyl hydrogen sulfates can be converted to alcohols by heating them with water This IS called hydrolysis, because a bond is cleaved by reaction with water It is the oxygen-sulfur bond that is broken when an alkyl hydrogen sulfate undergoes hydrolysis... 

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