Cleavage of the Carbon-Sulfur Bond in Divalent Sulfur Compounds.

Tarbell, D. S.; Harnish, Donald P.

doi:10.1021/cr60152a001

Cited by 153 publications

(47 citation statements)

References 229 publications

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“…refs. [4][5][6][7][8][9][10][11][12][13][14][15][16] and a limited amount of work using thionoesters has been reported (17)(18)(19)(20). However, only three reports, none of which contain kinetic analyses, could be found concerning the base catalysed hydrolysis of dithioesters (2 1-23), According to Sakurada (21), the action of aqueous alkali on ethyl dithioacetate leads to the production of dithioacetic acid, however, two other studies (22,23) report that thiol acids are produced by dithioester hydrolysis.…”

Section: Introductionmentioning

confidence: 99%

An investigation of the biphasic kinetics observed during the hydroxide ion-catalyzed hydrolysis of alkyl dithioesters

Storer¹

1983

Can. J. Chem.

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Kinetic evidence is presented for the establishment of an equilibrium, in dilute aqueous alkaline solutions, between alkyl dithioesters and a species I. The species I is formed cither by the extraction of a proton from, or by the addition of an hydroxide ion to, the dithioester. In the former case I would be an anion (probably an enethiolate) formed by the removal of a proton from the α-carbon atom, and in the latter case I would be a stabilized tetrahedral intermediate formed by the addition of an hydroxide ion to the thiocarbonyl carbon atom. It has not been possible, using kinetic evidence alone, to distinguish conclusively between these two possibilities. However, using the available evidence, arguments are presented in favor of I being an enethiolate anion.

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Section: Introductionmentioning

confidence: 99%

An investigation of the biphasic kinetics observed during the hydroxide ion-catalyzed hydrolysis of alkyl dithioesters

Storer¹

1983

Can. J. Chem.

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“…A common feature of square-planar Pd II and Pt II complexes in the solid state is long interactions in the axial positions so as to form pseudo-octahedral structures. [29] The thiocyanate group is relatively reactive and the cleavage of the carbon-sulfur bond can occur in both acidic and basic media [30] such that the resulting mercaptan anion can potentially coordinate to a metal centre. Accordingly, the reaction of 1a or 1c with PdCl 2 in 20 % HNO 3 solution slowly affords orange-red crystals, which were characterised as [PdCl 2 {C 1 Smim}] 2 (3) by X-ray crystallographic analysis.…”

Section: Resultsmentioning

confidence: 99%

Thiocyanate Functionalised Ionic Liquids: Synthesis, Characterisation and Reactivity

et al. 2007

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The reaction of chloromethyl thiocyanate with 1‐methylimidazole affords the imidazolium salt, 1‐thiocyanomethyl‐3‐methylimidazolium chloride, [C1SCNmim]Cl (1a). Exchange of the chloride anion in 1a by [PF6]–, [BF4]–, [Tf2N]– or [AuCl4]– affords salts 1b, 1c, 1d and 1e, respectively. Salts [C1SCNmim][BF4] (1c) and [C1SCNmim][Tf2N] (1d) melt below 100 °C and can therefore be classified as ionic liquids. The reaction of 1a with PdCl2 affords [C1SCNmim]2[PdCl4] (2a), whereas 1c reacts with PdCl2 to form the complex [PdCl2{C1SCNmim}2][BF4]2 (2c). In the presence of HNO3 both 1a and 1c react with PdCl2 with the loss of HCN to form a sulfide‐bridged palladium dimer [PdCl2{C1Smim}]2 (3). The structures of 1a, 1e, 2a and 3 have been determined in the solid state by single‐crystal X‐ray diffraction. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

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“…This elementary step of the enzymic catalysis may be relevant to the alkaline hydrolysis of simple alkyl esters or thiol esters when the hydroxyl ion is the nucleophile. In these model reactions no significant difference can be observed between the rate of the hydrolysis of an oxygen ester and that of the corresponding thiol ester (18).…”

Section: Reactivity Of Hydroxyl and Sulfhydryl Groups In Simple Orgmentioning

confidence: 90%

Simulated Mutation at the Active Site of Biologically Active Proteins

Polgár

Bender

1970

Advances in Enzymology - And Related Areas of Molecular Biology

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Cleavage of the Carbon-Sulfur Bond in Divalent Sulfur Compounds.

Cited by 153 publications

References 229 publications

An investigation of the biphasic kinetics observed during the hydroxide ion-catalyzed hydrolysis of alkyl dithioesters

An investigation of the biphasic kinetics observed during the hydroxide ion-catalyzed hydrolysis of alkyl dithioesters

Thiocyanate Functionalised Ionic Liquids: Synthesis, Characterisation and Reactivity

Simulated Mutation at the Active Site of Biologically Active Proteins

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