Of sulfonate esters

The hydrolysis of sulfonate esters of 2 octanol is stereospecific and proceeds with complete inversion of configuration Write a structural formula that shows the stereochemistry of the 2 octanol formed by hydrolysis of an opti cally pure sample of (S) (+) 1 methylheptyl p toluenesulfonate identify the prod uct as / or S and deduce its specific rotation... 

PyrogaUol has been cited for use in photosensitive compositions. It is used in the form of sulfonate esters of quinonediazides which hydrolyze when exposed to actinic light to Hberate the acid which, in turn, catalyzes further reaction of novolak resins (60). 

Only one of these methods, namely the reaction of halides with lithium aluminum deuteride, is a true displacement reaction, following the same course as the previously discussed displacement of sulfonate esters (section Vl-A). Thus, lithium aluminum deuteride treatment of 7a- and 7jS-bromo-3 -benzoyloxy-5a-cholestanes (195) and (196) gives the corresponding deuterium labeled cholestanols (197) and (198) respectively." ... 

Reactions of Organic Fluorine Compounds Table 13. Reactions of Sulfonate Esters with Nucleophiles... 

The Preparation of Halodeoxy Sugars by Displacement of Sulfonate Esters... 

Another deviation from the normal displacement reaction of primary tosylates occurs in nucleoside derivatives (39, 81) where cyclonucleosides and anhydronucleosides are formed by participation of a nitrogen atom (as in purine nucleosides) and oxygen atom (as in pyrimidine nucleosides ), respectively. Iodonucleosides can result from these reactions only if these cyclic compounds are prone to attack by iodide ion. Several new examples of unexpected reactions during the solvolysis of sulfonate esters in sugar derivatives have been recorded in the past few years (2, 4,5,7,15,44,62,63,94). 

C-6 with sulfuryl chloride. 181 Solvolysis of sulfonate esters,... 

Similarly, the presence of sulfonate esters also indicates incomplete hydrolysis. Residual saponifiable material in a final AOS product is then a measure of the quality of the surfactant. In practice, such material can be extracted, subjected to drastic conditions of saponification, and the quantity of residual saponifiable material calculated. Methods have been developed which can be used for the determination of 10 or more ppm of saponifiable material in the neutral oil of AOS. Unfortunately, the procedures outlined below are now of historic interest only, since they give unrealistically high values for residual saponifiable material content. Methods listed in the sultones section are now the analyses of choice. 

Two types of sulfonate esters can be formed in the production of AOS. Neutral esters are formed by the addition of alkenesulfonic acid to alkene (Fig. 29). Acid esters are formed by the dimerization of two alkene mono- or disulfonic acids (Fig. 30). These would normally be expected to hydrolyze in the saponification stage of the process. 

Trifluoromethanesulfonates of alkyl and allylic alcohols can be prepared by reaction with trifluoromethanesulfonic anhydride in halogenated solvents in the presence of pyridine.3 Since the preparation of sulfonate esters does not disturb the C—O bond, problems of rearrangement or racemization do not arise in the ester formation step. However, sensitive sulfonate esters, such as allylic systems, may be subject to reversible ionization reactions, so appropriate precautions must be taken to ensure structural and stereochemical integrity. Tertiary alkyl sulfonates are neither as easily prepared nor as stable as those from primary and secondary alcohols. Under the standard preparative conditions, tertiary alcohols are likely to be converted to the corresponding alkene. 

The importance of reactions with complex, metal hydrides in carbohydrate chemistry is well documented by a vast number of publications that deal mainly with reduction of carbonyl groups, N- and O-acyl functions, lactones, azides, and epoxides, as well as with reactions of sulfonic esters. With rare exceptions, lithium aluminum hydride and lithium, sodium, or potassium borohydride are the... 

Elimination of sulfonic esters on anomeric acetal derivatives... 

Another example of the fact that primary displacement of sulfonic esters is not always facile101,103-105 is the discovery that vigorous conditions were required for fluorination of l,2 3,5-di-0-isopropylidene-6-0-(methylsulfony])-a-D-galactofuranose with potassium fluoride dihydrate in methanol,85,88 and a comparatively long reaction-time was necessary for the fluorination of the 6-O-p-tolylsulfonyl derivative with tetrabutylammonium fluoride in acetonitrile.106... 

An alternative procedure for the introduction of the fluorine substituent in secondary positions of carbohydrates consists in nucleophilic displacement of sulfonic esters. Walden inversion always accompanies such displacements, and the success of this method may be attributed to two factors. 

Secondly, the factors controlling nucleophilic displacements of sulfonic esters had already been determined to a considerable extent, and have been described in reviews in this Series103,104 and, in addition, the steric and polar factors governing such displacements have been summarized qualitatively,101 and will therefore not be discussed here in any detail. This accumulated knowledge made possible the prediction of the course of such fluoride displacements. 

Some 40 research articles resulted from Tipson s 18 years at the Mellon Institute, and they demonstrate that he was able to sustain some of his interest in carbohydrate chemistry, and he continued to study the reactions of sulfonic esters with sodium iodide. In 1945 he compiled his published work into a senior thesis for the D.Sc. degree that was awarded by the University of Birmingham. However, a considerable proportion of the research at the Mellon Institute was never published because of patent restrictions. This was particularly true for his work on carbohydrates and other organic compounds conducted after July 1952, when he was assigned to the Parke, Davis and Company Fellowship in Medicinal Chemistry to synthesize potential antiviral and anticancer agents. 

In addition to these physical studies at the Bureau, Tipson was able to return to his synthetic interests, both alone and in collaboration with other staff members. He was especially pleased to prepare D-talose in crystalline form, an accomplishment that had eluded Emil Fischer. Pursuing his longstanding interest in the reaction of sulfonic esters with iodide and following an earlier observation that the tetratosyl ester of erythritol is converted into butadiene by the action of sodium iodide and zinc, he demonstrated (with A. Cohen) that nonterminal unsaturation may be conveniently introduced into alditol derivatives by reaction of contiguous secondary sulfonates with sodium iodide and zinc dust in boiling A.A-dimethylformamide. This Tipson-Cohen reaction subsequently proved of great utility in other hands for the conversion of more complex carbohydrate structures into vicinal dideoxy derivatives. 

Oxidation of triazine herbicides with chlorine and chlorine dioxide has been widely studied [105-108]. In the case of sulfur-containing triazines, oxidation occurs mainly via cleavage of the weakened R-S-CH3 bond rather than by addition of chlorine. Reactions of S-triazines with chlorine are faster than with chlorine dioxide, and form sulfoxide, sulfone, and a sulfone hydrolysis product. Chlorination with chlorine dioxide only produced sulfoxide [108]. Lopez et al. identified the formation of sulfonate esters during the chlorination of ametryn and terbutryn [106, 107]. Triazine DBFs identified by Brix et al. exhibited higher toxicities than the parent compounds [105]. Similar to triazines, clethodim, a cyclohexanedione herbicide, is oxidized by hypochlorite and chloramines to clethodim sulfoxide and then to sulfone [109]. 

Displacement of sulfonate esters with nitrate anion... 

It is often possible to predict the reactivity of a chlorosulfonyloxy group by a consideration of the steric and polar factors affecting the formation of the transition state,27-28 as indicated in Section 11,1 (see p. 227) for nucleophilic-replacement reactions of sulfonic esters of carbohydrate derivatives. Thus, it has been found that the presence of a vicinal, axial substituent or of a (3-trans-axial substituent on a pyranoid ring inhibits replacement of a chlorosulfonyloxy group also, a chlorosulfate group at C-2 has been observed to be deactivated to nucleophilic substitution by chloride ion. 

Deoxyhalogeno sugars are susceptible to nucleophilic attack, leading either to displacement, elimination, or anhydro-ring formation. The ease of displacement decreases in the order I > Br> Cl > F the iodo and bromo derivatives have, therefore, been especially utilized in such reactions, although several reactions with chlorodeoxy sugars have now been reported as a result of the increased availability of these compounds. The approach delineated in Section 11,1 (see p. 227) for predicting the reactivity of sulfonic esters can be expected also to be applicable, in an approximate and qualitative way,... 

Sulfonic acids, R(Ar)S03H, form derivatives similar to those of carboxylic acids (see Table 16-3). These are sulfonyl chlorides, sulfonates (esters), and sulfonamides. The transsulfonylation reactions are similar to the transacylation reactions, except that the ester and amide cannot be made directly from the acid. See Problem 13.17 for preparation of sulfonyl chlorides and esters and Problem 13.18 for use of sulfonate esters as substrates in S l and S,42 reactions. 

Bimolecular, nucleophilic-displacement reactions of sulfonic esters of carbohydrates have been reviewed.77,78... 

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