40. Aspects of stereochemistry. Part III. Acidic and basic hydrolysis of some diol cyclic sulphates and related compounds

Brimacombe, J. S.; Foster, A. B.; Hancock, E. B.; Overend, W. G.; Stacey, M.

doi:10.1039/jr9600000201

Cited by 35 publications

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“…In other words, chloride ion may be reducing the rate of 1 + 2 by sequestering part of the starting material in a less reactive form ( l l ) , thereby lowering the concentration(s) of the reactive species (9) and (or) (10).…”

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The mechanism of hydrolysis of 2-hydroxyethanesulfonyl chloride: the intermediacy of 1,2-oxathietane 2,2-dioxide (β-sultone)

King¹,

Khemani²

1989

Can. J. Chem.

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JAMES FREDERICK KING and KISHAN CHAND KHEMANI. Can. J. Chem. 67, 2162 (1989). The hydrolysis of 2-hydroxyethanesulfonyl chloride (1) has been investigated with the aid of kinetic and product analysis studies. .The results are quantitatively consistent with the mechanism of hydrolysis shown in Scheme 1, the chief features of which are (a) formation of p-sultone (2) and its rapid further reaction (the major pathway), together with (b) a minor direct hydrolysis route. The kinetics of both the p-sultone formation and the direct hydrolysis shows two terms, one first order in 1 alone, and the other first order in hydroxide as well; the rates of the first-and second-order reactions are lowered by added sodium chloride. It is suggested (a) that the unimolecular p-sultone formation involves 1 in a complex with water (as in 9) and that the water acts as a general base in the cyclization to 2, and (b) the hydroxide-promoted reaction proceeds by cyclization of the conjugate base of 1 (i.e., 10). The unimolecular direct hydrolysis is regarded as a conventional hydrolysis of a sulfonyl chloride with attack of the water with general base assistance from a second water molecule. The hydroxide-promoted direct reaction in D20 leads to no uptake of deuterium, showing that the reaction does not go by way of the sulfene, and a reaction by way of a six-membered cyclic transition state is tentatively proposed. Evidence is presented that the chloride ion rate suppression is not primarily due to reaction of p-sultone with C1-to give back 1; the possible origins of the effect are discussed.Key words: sulfonyl chlorides, 2-hydroxyethanesulfonyl chloride, p-sultone, kinetics of sulfonyl chloride hydrolysis, mechanisms of sulfonyl chloride hydrolysis. La cinCtique de la formation de la p-sultone ainsi que de I'hydrolyse directe prCsente A chaque fois deux termes : I'un du premier ordre uniquement en composC 1 et I'autre qui est en plus du premier ordre en ion hydroxyde; les vitesses des rkactions du premier et du deuxikme ordre sont abaissCes par l'addition de chlorure de sodium. On sugghe : (a) que la formation unimolCculaire de la p-sultone implique que le compost5 1 est complexC dans I'eau (comme dans 9) et que I'eau agit comme base gCntrale dans la cyclisation conduisant au compost 2 et (b) que la rCaction catalysCe par I'ion hydroxyde se produit par le biais d'une cyclisation de la base conjuguCe du composC 1 (soit 10). On considkre I'hydrolyse unimolCculaire directe comme une hydrolyse conventionnelle d'un chlorure de sulfonyle impliquant une attaque de I'eau avec l'assistance d'une seconde molCcule d'eau agissant comme base gCnCrale. L'hydrolyse directe, dans le D 2 0 et sous I'influence d'ions hydroxydes, ne provoque aucune incorporation de deuttrium; ce rCsultat dCmontre que la reaction ne se produit pas par le biais du sulfene et on propose provisoirement que la rCaction se produit via un Ctat de transition cyclique A six chalnons. On prksente des donntes dCmontrant que le ralentissement de la reaction sous I'iduence d'ions chloru...

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The mechanism of hydrolysis of 2-hydroxyethanesulfonyl chloride: the intermediacy of 1,2-oxathietane 2,2-dioxide (β-sultone)

King¹,

Khemani²

1989

Can. J. Chem.

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“…[14] + SOCI 2 After the addition the reaction mixture is allowed to stand at 10°C for \ hr, refluxed for \ hr, separated from the warm syrupy layer of pyridine hydrochloride, concentrated, and the residue distilled to afford 41 gm (97%), b.p.…”

Section: -3 Preparation Of the Cyclic Sulfite Of Catecholmentioning

confidence: 99%

Sulfites

1971

Organic Chemistry: A Series of Monographs

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“…The first step in the hydrolysis of five-membered cyclic sulphate diesters involves O-S cleavage in alkali, but in acid solution C-O cleavage is the rule. The product monoesters exhibit the opposite behaviour, with C-O cleavage in alkali and O-S cleavage in acid (Garner & Lucas, 1950;Brimacombe et al, 1960;Kaiser et al, 1963). Several simple alkyl sulphates also exhibit C-O bond fission in alkali and O-S bond fission in acid (Burwell, 1952;Kursanov & Kudryartsev, 1956;Kaiser et al, 1963;Batts, 1966).…”

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A novel mechanism of enzymic ester hydrolysis. Inversion of configuration and carbon-oxygen bond cleavage by secondary alkylsulphohydrolases from detergent-degrading micro-organisms

Bartholomew¹,

Dodgson²,

Matcham³

et al. 1977

Biochemical Journal

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The hydrolysis was studied of potassium (+)-octan-2-yl sulphate by two analogous, optically stereospecific, secondary alkylsulphohydrolases purified from two detergent-degrading micro-organisms, Comamonas terrigena and Pseudomonas C12B. Polarimetry studies have shown that (+)-octan-2-yl sulphate prepared from (+)-octan-2-ol is hydrolysed by both enzymes to yield (-)-octan-2-ol. This inversion of configuration implies that the enzymes are catalysing the scission of the C-O bond of the C-O-S linkage, a type of bond scission apparently not hitherto encountered among hydrolytic enzymes acting on ester bonds. Enzymic hydrolysis of potassium (+)-octan-2-yl sulphate in the presence of H218O and analysis of hydrolysis products for the presence of 18O has confirmed that C-O bond scission (and not O-S bond scission) occurs with both enzymes.

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40. Aspects of stereochemistry. Part III. Acidic and basic hydrolysis of some diol cyclic sulphates and related compounds

Cited by 35 publications

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The mechanism of hydrolysis of 2-hydroxyethanesulfonyl chloride: the intermediacy of 1,2-oxathietane 2,2-dioxide (β-sultone)

The mechanism of hydrolysis of 2-hydroxyethanesulfonyl chloride: the intermediacy of 1,2-oxathietane 2,2-dioxide (β-sultone)

Sulfites

A novel mechanism of enzymic ester hydrolysis. Inversion of configuration and carbon-oxygen bond cleavage by secondary alkylsulphohydrolases from detergent-degrading micro-organisms

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