Synthesis of Novel Arylthio Derivatives of Mucochloric Acid

Kurbangalieva, Almira; Devyatova, N. F.; Bogdanov, A. V.; Бердников, Е. А.; Mannafov, T. G.; Krivolapov, Dmitry B.; Литвинов, И. А.; Чмутова, Г. А.

doi:10.1080/10426500601015989

Cited by 29 publications

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“…The syntheses of sulfides 2-23 were described in literature. [5][6][7] The synthesis of sulfoxide 24 by treatment of sulfide 3 with m chloroperbenzoic acid will be described in a separate paper devoted to the results of chemical oxidation of sulfides derived from mucochloric acid to the corresponding sulfoxides and sulfones.…”

Section: Methodsmentioning

confidence: 99%

Electron transfer and subsequent reactions during electrochemical oxidation of aryl- and alkylthio derivatives of mucochloric acid

et al. 2009

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The electrochemical oxidation of aryl and alkylthio derivatives of mucochloric acid (3,4 dichloro 5 hydroxyfuran 2(5H) one) in MeCN-Bu 4 NBF 4 (0.1 mol L -1 ) was investi gated. It was shown that all sulfides are electrochemically active, from one to five oxidation steps of sulfur containing groups were observed for them. The ease and direction of oxida tion of the thio group depend on its nature and position in the furanone ring. 3 Substituted 2(5H) furanones possess the lowest oxidation potential. 4 Substituted 2(5H) furanones are predominantly oxidized to sulfoxides, 5 aryl and alkylthio derivatives undergo fragmentation to give mucochloric acid, and 3 arylthio derivative gives complex unidentified mixture of products. In the case of 3,4 bis(4 methylphenylthio) derivative, the oxidation product of the arylthio group at the 3 position to the corresponding sulfoxide was isolated. Based on the data from cyclic voltammetry with different concentrations of a substrate and water added, the results of preparative electrolysis and quantum chemical calculations, possible mechanisms of electrochemical oxidation of mucochloric acid derived sulfides are discussed. The initial common step is a reversible single electron transfer from the substrate molecule to form highly reactive radical cation.Aromatic and aliphatic sulfides have been well studied by electrochemical methods. Both reduction and oxida tion processes of these compounds were investigated in detail. 1,2 At the same time, the current interest in this class of compounds does not wane due to the synthesis of new sulfides and, therefrom, sulfoxides and sulfones with practically useful properties. It appears that the structures combining a heterocyclic fragment and a sulfinyl or sulfonyl group will be particularly promising. Also, of great inter est are optically active sulfoxides widely used in the enantioselective syntheses. 3,4In recent years, we have synthesized a variety of sul fides based on mucochloric acid, 3,4 dichloro 5 hydroxy furan 2(5Н) one (1a). 5-7 This stimulated our search for the selective oxidation reactions of the obtained sulfides by chemical and electrochemical methods. In the present communication, the results of the experimental and theoretical studies on the processes of electrochemical oxidation (ECO) of sulfides 2-23 in MeCN by cyclic voltammetry, preparative electrolysis and quantum chemical simulation are presented. The pathways of for mation of their oxidation products including sulfoxides 24, 25 are discussed. ExperimentalCyclic voltammograms (CV curves) were recorded using a PI 50 1 potentiostat connected to an N 307/2 XY recorder. The working electrode was a glassy carbon disk electrode (d = 2 mm) pressed fitted into a fluoroplastic casing. Prior to each measurement, the electrode was mechanically polished. Potentials were measured relative to the standard potential of the redox system ferrocene/ferrocenium cation (Fc/Fc + ) (internal standard) using a silver reference electrode Ag/AgNO 3 (0.01 mol L -1 ) in MeCN. Dissolved oxygen w...

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confidence: 99%

Electron transfer and subsequent reactions during electrochemical oxidation of aryl- and alkylthio derivatives of mucochloric acid

et al. 2009

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“…11 The use of sulfur containing binucleophilic reagents (ethane 1,2 dithiol 12 and 2 mercaptoethanol 13 ) furnished nucleophilic substitution products including mono and bicyclic and unexpectedly acyclic ones.…”

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“…Previously, 9,11 it was shown that in the presence of basic substances, 3,4 dichloro 2(5H) furanones react with S nucleophiles with substitution of chlorine in position 4 of the lactone ring. The reactions of mucochloric acid 1 and its alkoxy derivatives 2-4 with 2 mercaptoacetic acid in the presence of triethylamine in acetone follow a similar route resulting in the products of replacement of chlorine at the С(4) atom in the lactone ring 8-11 (Scheme 2).…”

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“…1 A large number of publications are devoted to reactions of 2(5H) furanones with N , С , О , and Р nucleophiles; however, among reactions with S nucleophiles, only those with thiols were described. [5][6][7][8][9][10][11] Our recent studies of reactions of mucochloric acid with various sulfur containing nucleophiles 11-13 were * Dedicated to Academician A. I. Konovalov on his 75th birthday. mainly aimed at elucidating the conditions for selective thiolation, preparation of sulfides of different structural types, investigation of their spatial and electronic struc tures, and the possibilities to be involved in intermole cular contacts.…”

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“…1, Table 1), the five membered ring is planar (within 0.009(4) Å), which is typical of both the proper mucochloric acid 16 and the products of its reactions with thiophenols. 11 The molecules of 6 in the crystal occur in a "coiled" confor mation in which the terminal carbonyl group C(7)=O (7) and the endocyclic bond O(1)-C(2) are spatially proxi mate. The structure has short contacts, С(7)...O(1) (3.071(4) Å) and С(2)...O(7) (3.032(5) Å) (the sum of the van der Waals radii of oxygen and carbon is 3.22 Å).…”

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Reactions of 2-mercaptoacetic acid with mucochloric acid and its derivatives

Kurbangalieva¹,

Devyatova²,

Kosolapova³

et al. 2009

Russ Chem Bull

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The stable products of reactions of mucochloric acid and some of its ethers with 2 mer captoacetic acid were synthesized and characterized. The variation of experimental conditions allowed targeted introduction of a sulfur containing fragment into particular position of the heterocycle: the reaction in aqueous potassium hydroxide gives 3 substituted 2(5H) furanone, the triethylamine additive in nonaqueous solvents facilitates the formation of 4 substituted products, and acid catalysis results in the replacement of the hydroxy (methoxy) group at С(5).(3,4 Dichloro 2 oxo 2,5 dihydrofuran 5 ylthio)ethanoic acid and (3 chloro 5 hydroxy 2 oxo 2,5 dihydrofuran 4 ylthio)ethanoic acid were characterized by X ray diffraction; their crystal and gas phase structures were discussed. The 5 monosubstituted product crystallizes as a racemate, while 4 monosubstituted product, as a conglomerate.

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Modular synthesis of pyrrolo[2,1‐b]thiazoles and related monocyclic pyrrolo structures

O'Dwyer

Mullane

Smyth

2010

Journal of Heterocyclic Chem

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A modular synthesis of selectively-substituted pyrrolo[2,1-b]thiazoles (D 6 isomeric form) has been implemented, involving a distinctive bicyclization reaction of a mucobromic acid derivative followed by a Suzuki-Miyaura coupling. A novel process of D 6 to D 7 isomerization of the pyrrolothiazole structure was uncovered that appears to involve a 1,4-addition-1,2-elimination mechanism. Preparation of 1,5-dihydropyrrol-2-one structures, selectively substituted at the 3-and 4-positions, was also achieved using the mucobromic acid synthon in a reductive amination process.

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Synthesis of Novel Arylthio Derivatives of Mucochloric Acid

Cited by 29 publications

References 14 publications

Electron transfer and subsequent reactions during electrochemical oxidation of aryl- and alkylthio derivatives of mucochloric acid

Electron transfer and subsequent reactions during electrochemical oxidation of aryl- and alkylthio derivatives of mucochloric acid

Reactions of 2-mercaptoacetic acid with mucochloric acid and its derivatives

Modular synthesis of pyrrolo[2,1‐b]thiazoles and related monocyclic pyrrolo structures

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