Sulphonyl transfer reactions: solvolysis of arenesulphonyl chlorides in aqueous trifluoroethanol

Forbes, Rowena M.; Maskill, Howard

doi:10.1039/c39910000854

Cited by 19 publications

(23 citation statements)

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“…As chemical probe we used the hydrolysis of the 4-methoxybenzenesulfonil chloride (MBSC), a molecule whose geometry and polarity is suitable for complex formation with b-CD and whose basic hydrolysis has been previously studied in water and water:organic solvent 0009-2614/$ -see front matter Ó 2010 Elsevier B.V. All rights reserved. doi:10.1016/j.cplett.2010.09.017 mixtures [10]. The results obtained confirm that, contrary to the expectations, the percentage of uncomplexed CD decreases with the number of carbons of the chain, meaning that the percentage of uncomplexed CD decreases with the hydrophobic character of the surfactant.…”

Section: Introductioncontrasting

confidence: 80%

Cyclodextrin-surfactant binding constant as driven force for uncomplexed cyclodextrin in equilibrium with micellar systems

Cepeda

Daviña

García‐Río

et al. 2010

Chemical Physics Letters

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Section: Introductioncontrasting

confidence: 80%

Cyclodextrin-surfactant binding constant as driven force for uncomplexed cyclodextrin in equilibrium with micellar systems

Cepeda

Daviña

García‐Río

et al. 2010

Chemical Physics Letters

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“…The importance of kinetic order in solvent and associated mass law effects is strongly supported by the selectivities obtained in 90-99% alcohol-water [eqn. (15) , Fig. 31, which leads to independent values of the third-order rate constants ( Table 5).…”

Section: Discussionmentioning

confidence: 94%

Stoichiometric solvation effects. Part 2. A new product–rate correlation for solvolyses of p-nitrobenzenesulfonyl chloride in alcohol–water mixtures

Bentley¹,

Jones²,

Koo³

1994

J. Chem. Soc., Perkin Trans. 2

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For reactions involving nucleophilic attack in alcohol-water mixtures, a linear relationship between the reciprocal of product selectivities (S) and the molar ratios of alcohol and water solvents can be derived, if it is assumed that the reactions are second-order in protic solvent (e.g., w i t h one molecule of solvent acting as a nucleophile and the other as a general base). The relationship {1/S = (slope) ([alcohol] /[water]) + intercept} fits the products of solvolyses of p-nitrobenzenesulfonyl chloride in aqueous ethanol and methanol at 25 "C (determined by refrigerated RP-HPLC) within the range from water t o 80% v/v alcohol-water. From the slopes and intercepts of these product plots and the one observed rate constant for hydrolysis in pure water, the observed first-order rate constants in alcohol-water mixtures up to 90% (v/v) can be calculated satisfactorily, further supporting the validity of the derived linear relationship; the kinetic model includes three third-order rate constants: k , , where water acts as both nucleophile and general base; k,,, water acts as a nucleophile and alcohol acts as a general base; k,,, alcohol acts as a nucleophile and water acts as a general base. Inclusion of a fourth rate constant, k,,, where the alcohol acts as a nucleophile and a second molecule of alcohol acts as a general base, is necessary t o account for solvolyses in 90-99% alcohol-water; k,, can be calculated from the observed first-order rate constants in pure alcohols. Independent values of k,, and k,, can be obtained from k,, and the slopes and intercepts of linear relationships between S and the molar solvent ratio [water]/ [alcohol] within the range 90-99% alcohol-water. The dominant effect of solvent stoichiometry and the absence of other substantial medium effects is confirmed by the approximately constant third-order rate constants, calculated from the observed first-order rate constants in acetonitrile-, acetone-and dioxane-water m i xt u res.Competing nucleophilic substitution reactions in alcohol-water mixtures are interpreted in terms of product selectivities (S), defined from molar ratios of products and of solvents [eqn (l)]. If these reactions simply involved competition between attack by one molecule of water or one molecule of alcohol, S values would be independent of the solvent. However, many reactions show solvent-dependent S values,' for which, until recently, no convincing explanation had been given. Contrary to the reactivity-selectivity principle,' S often increases in more aqueous media when reactivity also increases. S = [alcoholysis prod][water solv]/ [hydrolysis prod][alcohol solv] (1) 1 IS = (slope)([alcohol solv]/[water solv]) + (intercept) (2)We recently reported a new eqn.(2), accounting for the solvent dependence of product selectivities in alcohol-water mixtures; eqn. (2) is successful both for the product-forming step of reactions of free cations3'4 and also for concerted nucleophilic substitution r e a c t i o n~.~*~,~ In the latter case, from the derivation given below, it i...

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“…Thus, Hall and Robertson assumed the hydrolysis of N,N‐dimetylsulfamoyl chloride is a unimolecular process, based on the small solvent kinetic isotope effect (SKIE) (k H2O /k D2O = 1.33) and low sensitivity of the studied substrates to nucleophile changes in aqueous 1,4‐dioxane solutions (86.1/13.9% V /V) ([Piperidine] = 0.0231 M, k = 4.6 s −1 ; [NaOH] = 0.0138 M, k = 4.9 s −1 ; [NaClO 4 ] = 0.0068 M, k = 5.09 s −1 ). Maskill, based on data on solvolysis in 2,2,2‐trifluoroethanol, concluded the solvolysis of 4‐N,N‐(dimethylamino)benzenesulfonyl chloride takes place through an S N 2 mechanism, where bond breaking significantly prevails over bond formation at the TS . This was later confirmed by results on the solvolysis of this compound in 80 % aqueous acetic acid and hydrolysis at different pH values …”

Section: Introductionmentioning

confidence: 79%

“…Nucleophilic substitution reactions near sulfonyl sulfur have been thoroughly studied. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15] However, the available literature is often contradictory and occasionally related to rather limited sets of substrates.…”

Section: Introductionmentioning

confidence: 99%

Propanolysis of arenesulfonyl chlorides: Nucleophilic substitution at sulfonyl sulfur

Iazykov

Canle

Santaballa

et al. 2017

J of Physical Organic Chem

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We have studied the mechanism of solvolysis of arenesulfonyl chlorides by propan‐1‐ol and propan‐2‐ol at 303‐323 K. Kinetic profiles were appropriately fit by first‐order kinetics. Reactivity increases with electron‐donating substituents. Ortho‐alkyl substituted derivatives of arenesulfonyl chlorides show increased reactivity, but the origin of this “positive” ortho‐effect remains unclear. Likely, ortho‐methyl groups restrict rotation around the C‐S bond, facilitating the attack of the nucleophile. No relevant reactivity changes have been found with propan‐1‐ol and propan‐2‐ol in terms of nucleophile steric effect. The existence of isokinetic relationships for all substrates suggests a single mechanism for the series. Solvolysis reactions of all substrates in both alcohols show isokinetic temperatures (Tiso) close to the working temperature range, which is an evidence of the process being influenced by secondary reactivity factors, likely of steric nature in the TS. Solvation plays a relevant role in this reaction, modulating the reactivity. In some cases, the presence of t‐Bu instead of Me in para‐ position leads to changes in the first solvation shell, increasing the energy of the reaction (ca. 1 kJ·mol−1). The obtained results suggest the same kinetic mechanism of solvolysis of arenesulfonyl chlorides for propan‐1‐ol and propan‐2‐ol, as in MeOH and EtOH, where bimolecular nucleophilic substitution (SN2) takes place with nucleophilic solvent assistance of one alcohol molecule and the participation of the solvent network involving solvent molecules of the first solvation shell.

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Sulphonyl transfer reactions: solvolysis of arenesulphonyl chlorides in aqueous trifluoroethanol

Abstract: Activation parameters for the solvolysis in aqueous trifluoroethanol of arenesulphonyl chlorides with electron-supplying substituents have been determined; the results are not in accord with earlier proposals that such compounds react by an SNI mechanism.

Cited by 19 publications

References 14 publications

Cyclodextrin-surfactant binding constant as driven force for uncomplexed cyclodextrin in equilibrium with micellar systems

Cyclodextrin-surfactant binding constant as driven force for uncomplexed cyclodextrin in equilibrium with micellar systems

Stoichiometric solvation effects. Part 2. A new product–rate correlation for solvolyses of p-nitrobenzenesulfonyl chloride in alcohol–water mixtures

Propanolysis of arenesulfonyl chlorides: Nucleophilic substitution at sulfonyl sulfur

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