Mechanisms of the Hydrolysis of Aromatic Sulphonyl Chlorides and of Alkyl and Aryl Arenesulphonates

Vizgert, R. V.

doi:10.1070/rc1963v032n01abeh001289

Cited by 23 publications

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“…In this place, it is necessary to mention that the claims in the early literature [18][19][20][21][22][23][24] that sulfamoyl and sulfonyl chlorides undergo solvolysis by the dissociative SN1-type process were shown to be wrong and have been corrected [25][26][27]. However, in the course of these early studies Vizgert [22][23][24] found that 2,4,6-trimethylbenzenesulfonyl chloride, (2,4,6-Me3)-1 (Scheme 4), as well as other ortho-alkyl substituted sulfonyl chlorides, (R)-1 [28], are hydrolyzed faster than benzenesulfonyl chloride 1. At the same time Bunnett and Bassett [29] came to the conclusion that the two orthomethyls provide no detectable steric hindrance of nucleophilic substitution at the sulfonate sulfur.…”

Section: Introductionmentioning

confidence: 99%

“…Moreover, to gain a comprehensive understanding of the reactivity of arenesulfonyl chlorides 1 in the above reaction and to solve a question of its mechanism (SN2-S or A-E) the computational studies of this identity reaction were carried out. In this context, it is necessary to mention that Lee In this place, it is necessary to mention that the claims in the early literature [18][19][20][21][22][23][24] that sulfamoyl and sulfonyl chlorides undergo solvolysis by the dissociative S N 1-type process were shown to be wrong and have been corrected [25][26][27]. However, in the course of these early studies Vizgert [22][23][24] found that 2,4,6-trimethylbenzenesulfonyl chloride, (2,4,6-Me 3 )-1 (Scheme 4), as well as other ortho-alkyl substituted sulfonyl chlorides, (R)-1 [28], are hydrolyzed faster than benzenesulfonyl chloride 1.…”

Section: Introductionmentioning

confidence: 99%

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Nucleophilic Substitution at Tetracoordinate Sulfur. Kinetics and Mechanism of the Chloride-Chloride Exchange Reaction in Arenesulfonyl Chlorides: Counterintuitive Acceleration of Substitution at Sulfonyl Sulfur by ortho-Alkyl Groups and Its Origin

et al. 2020

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The chloride-chloride exchange reaction in arenesulfonyl chlorides was investigated experimentally and theoretically by density functional theory (DFT) calculations. The second order rate constants and activation parameters of this identity reaction were determined for 22 variously substituted arenesulfonyl chlorides using radio-labeled Et4N36Cl. The chloride exchange rates of 11 sulfonyl chlorides bearing para-and meta-substituents (σ constants from −0.66 to +0.43) in the aromatic ring followed the Hammett equation with a ρ-value of +2.02. The mono- and di-ortho-alkyl substituted sulfonyl chlorides exhibit an enhanced reactivity although both inductive and steric effects lower the reaction rate. The DFT calculations of their structures together with X-ray data showed that an increased reactivity is mainly due to a peculiar, rigid, strongly compressed and sterically congested structure. The DFT studies of the title reaction revealed that it proceeds via a single transition state according to the SN2 mechanism. The analogous fluoride exchange reaction occurs according to the addition–elimination mechanism (A–E) and formation of a difluorosulfurandioxide intermediate. The reliability of the calculations performed was supported by the fact that the calculated relative rate constants and activation parameters correlate well with the experimental kinetic data.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Nucleophilic Substitution at Tetracoordinate Sulfur. Kinetics and Mechanism of the Chloride-Chloride Exchange Reaction in Arenesulfonyl Chlorides: Counterintuitive Acceleration of Substitution at Sulfonyl Sulfur by ortho-Alkyl Groups and Its Origin

et al. 2020

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“…Algumas comparações entre as reatividades dos carbonos: aromático e saturado, carbonílico e saturado, aromático e carbonílico, aromático, heteroaromático e sistema tropílico, carbonílico e imidoílico, e de arenos coordenados e não-coordenados são descritas na literatura [6][7][8][9][10][11][12][13][14][15] . Todavia, muito pouco é conhecido acerca da reatividade do enxofre como centro eletrofílico, embora haja uma quantidade razoável de trabalhos sobre centros sulfonílicos 16 e pouco sobre centros sulfenílicos.…”

Section: Introductionunclassified

Reatividade Relativa em Solvólise Nucleofílica de Cloretos de Arilsulfenila, Arilcarbonila, Arilsulfonila, Arilmetila e de Arila

1997

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The experimental results for the 2-propanolysis of benzoyl, benzyl, benzene sulphenyl and benzene sulphonyl chlorides obtained by conductimetric technique were compared with estimates for chlorobenzene which is extremely unreactive as an electrophile. We thus obtained the following reactivity sequence: PhSCl>PhCOCl>PhSO 2 Cl>PhCH 2 Cl>PhCl with rate-coefficiente ratios (in the same order): 9.5 x 10 4 : 1: 7.14 x 10 -2 : 4.7 x 10 -3 : about 10 -26 . We have discussed these results in specific terms and with the aid of general conclusions which stem from our own classification of electrophiles.Keywords: 2-propanolysis; electrophilic carbon and sulphur centres; solvolysis mechanism. ARTIGO INTRODUÇÃONo campo da substituição nucleofílica, as pesquisas relativas às reatividades de substratos que têm como centro eletrofílico o carbono saturado 1,2 , o carbono carbonílico 3,4 e o carbono aromá-tico 5 têm recebido muita atenção; entretanto, estudos comparativos entre si são raros. Algumas comparações entre as reatividades dos carbonos: aromático e saturado, carbonílico e saturado, aromático e carbonílico, aromático, heteroaromático e sistema tropílico, carbonílico e imidoílico, e de arenos coordenados e não-coordenados são descritas na literatura [6][7][8][9][10][11][12][13][14][15] . Todavia, muito pouco é conhecido acerca da reatividade do enxofre como centro eletrofílico, embora haja uma quantidade razoável de trabalhos sobre centros sulfonílicos 16 e pouco sobre centros sulfenílicos.Estudos comparativos das reatividades relativas de compostos com carbono e enxofre como centros eletrofílicos, em solvólise nucleofílica, são, ainda, desconhecidos. Assim, no presente trabalho dispensou-se atenção aos cloretos de benzenossulfenila em reações de solvólise com 2-propanol e, para comparação, foram relacionadas reações de substituição nucleofílica nos grupos carbonila e sulfonila e nos carbonos saturado e aromático.A escolha do 2-propanol para o estudo da solvólise nucleofí-lica foi baseada na facilidade para seguir as reações usando uma técnica convencional (condutimetria), no nível conveniente de velocidade de reação, na escassez de dados de sua solvólise nucleofílica e no desejo de comparar os diferentes sistemas, sem as complicações introduzidas se algum deles reagisse por um mecanismo unimolecular (S N 1). Julgou-se que isso não ocorre em 2-propanol anidro para os compostos não substituídos e muito menos para os que possuem substituintes receptores de elé-trons no anel benzênico. Julgou-se, também, que entre as classes de compostos estudados, aquelas que oferecem maiores chances de operar por um mecanismo unimolecular são os sistemas benzílico e benzoílico. Entretanto, é muito relevante o fato de ter-se constatado que, mesmo na metanólise, nem cloreto de benzila e nem de benzoíla reagiu por um mecanismo S N 1 11,17 . Escolheram-se sistemas arílicos por conveniência e porque planejou-se estender os estudos cinéticos para incluir arenos eletrofí-licos. A escolha do cloreto como nucleófugo se deveu ao fato de ele se consti...

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“…[6]. Since ethoxide can in principle react with both free and metal-complexed substrates as well as in the form of an ion pair, as illustrated below, the observed rate law would be eq.…”

Section: Catalysis By Preassociation Of Metal Ion With Substratementioning

confidence: 99%

“…The alkaline hydrolysis reactions of benzenesulfonate and tosylate esters have been studied in a number of different media: water (3), aqueous ethanol (4), aqueous DMSO (4), aqueous acetonitrile (5), aqueous DME ( 5 ) , aqueous dioxane (6), and aqueous acetone (6). However, no studies have used single solvent systems other than water.…”

Section: Introductionmentioning

confidence: 99%

Metal ion catalysis in nucleophilic displacement reactions at carbon, phosphorus, and sulfur centers. III. Catalysis vs. inhibition by metal ions in the reaction of p-nitrophenyl benzenesulfonate with ethoxide

Pregel¹,

Dunn²,

Buncel³

1990

Can. J. Chem.

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Thispaper is dedicated to Professor Ross Stewart on the occasion of his 65th birthday MARKO J. PREGEL, EDWARD J. DUNN, and ERWIN BUNCEL. Can. J. Chem. 68, 1846 (1990). The rate of the nucleophilic displacement reaction of p-nitrophenyl benzenesulfonate (I) with alkali metal ethoxides in ethanol at 25°C has been studied by spectrophotometric techniques. For lithium ethoxide, sodium ethoxide, potassium ethoxide, and cesium ethoxide, the observed rate constants increase in the order LiOEt < NaOEt < CsOEt < KOEt. The effect of added crown ether and cryptand complexing agents was also investigated. Addition of complexing agent to the reaction of KOEt results in the rate decreasing to a minimum value corresponding to the reaction of free ethoxide. Conversely, addition of complexing agent to the reaction of LiOEt results in the rate increasing to a maximum value that is identical to the minimum value seen in the reaction of KOEt in the presence of excess complexing agent. In complementary experiments, alkali metal ions were added in the form of umeactive salts. Addition of a K' salt to the reaction of KOEt increases the reaction rate, while addition of a ~i + salt to the reaction of LiOEt decreases the rate. The involvement of metal ions in the reaction of 1 is proposed to occur via reactive alkali metal -ethoxide ion pairs. The kinetic data are analyzed in terms of an ion pairing treatment that allows the calculation of second-order rate constants for free ethoxide and metal-ethoxide ion pairs; the rate constants increase in the order LiOEt < EtO-< NaOEt < CsOEt < KOEt. Thus, ~i ' is an inhibitor of the reaction of ethoxide with 1 , while the other metals ions studied are all catalysts. Equilibrium constants for the association of the various metal ions with the transition state are calculated using a thermodynamic cycle, and are compared to association constants in the ground state. Consistent with the observed kinetic results, Li+ is found to stabilize the ground state more than the transition state, while Na', K + , and Cs' all stabilize the transition state more than the ground state. The trend in the magnitude of the transition state stabilization is interpreted in terms of interactions of the transition state with bare or solvated metal ions. It is concluded that the transition state for the reaction of 1 with ethoxide forms solvent separated ion pairs with alkali metal ions. Analogous data were available for the reaction of p-nitrophenyl diphenylphosphinate (2) with ethoxides, where Li', Na+, K' , and Cs+ all function as catalysts, and the results are analyzed as above. In contrast to the sulfonate system, it is proposed that the phosphinate transition state forms contact ion pairs with alkali metal ions. The difference is attributed to a greater localization of negative charge in the phosphinate transition state, leading to stronger interactions with metal ions, which overcome metal ion -solvent interactions.Key words: nucleophilic substitution at sulfur, alkali metal ion catalysis.MARKO J. PREGEL, EDWARD J. D...

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Mechanisms of the Hydrolysis of Aromatic Sulphonyl Chlorides and of Alkyl and Aryl Arenesulphonates

Cited by 23 publications

References 0 publications

Nucleophilic Substitution at Tetracoordinate Sulfur. Kinetics and Mechanism of the Chloride-Chloride Exchange Reaction in Arenesulfonyl Chlorides: Counterintuitive Acceleration of Substitution at Sulfonyl Sulfur by ortho-Alkyl Groups and Its Origin

Nucleophilic Substitution at Tetracoordinate Sulfur. Kinetics and Mechanism of the Chloride-Chloride Exchange Reaction in Arenesulfonyl Chlorides: Counterintuitive Acceleration of Substitution at Sulfonyl Sulfur by ortho-Alkyl Groups and Its Origin

Reatividade Relativa em Solvólise Nucleofílica de Cloretos de Arilsulfenila, Arilcarbonila, Arilsulfonila, Arilmetila e de Arila

Metal ion catalysis in nucleophilic displacement reactions at carbon, phosphorus, and sulfur centers. III. Catalysis vs. inhibition by metal ions in the reaction of p-nitrophenyl benzenesulfonate with ethoxide

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