cas 98-66-8, 4-Chlorobenzenesulfonic acid | Articles data

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Cornforth and Corey-Suggs reagents as efficient catalysts for sulfonation of aromatic and heteroaromatic compounds using NaHSO3 under solvent free and microwave conditions
Cornforth and Corey-Suggs reagents Pyridinium Dichromate (PDC) and Pyridinium Chlorochromate (PCC) were explored as efficient catalysts for sulfonation of aromatic and heteroaromatic compounds using NaHSO3 in aqueous acetonitrile medium at room temperature within 1–4 h, while microwave assisted reactions took place within 1–4 min under solvent-free conditions. These observations indicate significant rate accelerations in microwave assisted reactions. which were explained due to the bulk activation of molecules induced by insitu generated high temperatures and pressures when microwaves are transmitted through reaction medium.
Fatima, Touheeth,Duguta, Govardhan,Purugula, Venkanna,Yelike, Hemanth Sriram,Kamatala, Chinna Rajanna
p. 1001 - 1006
(2020/07/27)

Sustainable access to sulfonic acids from halides and thiourea dioxide with air
A sustainable and mild one-step strategy is explored for the synthesis of aryl and alkyl sulfonic acids using a facile combination of halides and sulfur dioxide surrogates under air. The cheap industrial material thiourea dioxide was employed as an eco-friendly and easy-handling sulfur dioxide surrogate, while air was used as a green oxidant. Both aryl and alkyl sulfonic acids were obtained under transition metal-catalyzed or transition metal-free conditions. Mechanistic studies demonstrated that sulfinate was involved as an intermediate in this transformation. Notably, this protocol has been applied to the late-stage sulfonation of the drugs naproxen, isoxepac and ibuprofen.
Zhang, Hui,Wang, Ming,Jiang, Xuefeng
supporting information
p. 8238 - 8242
(2020/12/29)

Aryl and alkyl sulfonic acid compounds as well as construction method adopting inorganic sulfur salt and application
The invention discloses aryl and alkyl sulfonic acid compounds as shown in a formula (1) and a synthesis method thereof. The method comprises the following step: aromatic iodine and an inorganic sulfur source or alkyl bromide and an inorganic sulfur source as reaction raw materials react in a solvent under the action of alkali, a catalyst or an additive to obtain a series of aryl and alkyl sulfonic acid compounds. According to the method, the aryl and alkyl sulfonic acid compounds are constructed in one step by taking an inorganic sulfur reagent as a sulfur source, so that the defect of the mode in which the aryl and alkyl sulfonic acid compounds are synthesized by taking concentrated sulfuric acid, chlorosulfonic acid or sulfur dioxide gas and the like as sulfonating reagents in the priorart is avoided. The aryl and alkyl sulfonic acid compounds developed by the invention can be used for synthesizing aryl and alkyl sulfonic acid drug analogues.
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Paragraph 0046-0049; 0072-0075

(2020/09/16)

Regioselective Sulfonation of Aromatic Compounds over 1,3-Disulfonic Acid Imidazolium Chloride under Aqueous Media
1,3-Disulfonic acid imidazolium chloride ([Dsim]Cl), as a Bronsted acidic ionic liquid, is introduced for the sulfonation of aromatic compounds by in situ generation of sulfuric acid at 50 °C under mild conditions and in aqueous medium.
Moosavi-Zare, Ahmad Reza,Zolfigol, Mohammad Ali,Noroozizadeh, Ehsan
p. 1682 - 1684
(2016/07/06)

Nucleophilic Substitution Reactions of 2,4-Dinitrophenyl X-Substituted-Benzenesulfonates and Y-Substituted-Phenyl 4-Nitrobenzenesulfonates with Azide Ion: Regioselectivity and Reaction Mechanism
The second-order rate constants for reactions of 2,4-dinitrophenyl X-substituted-benzenesulfonates (4a-4f) and Y-substituted-phenyl-4-nitrobenzenesulfonates (5a-5f) with N3- ion have been measured spectrophotometrically. The reactions of 4a-4f proceed through S-O and C-O bond fission pathways competitively. Fraction of the S-O bond fission decreases rapidly as the substituent X in the benzenesulfonyl moiety changes from an electron-withdrawing group to an electron-donating group. The Hammett plots for reactions of 4a-4f are linear with ρX=1.87 and 0.56 for the S-O and C-O bond fission, respectively. The fact that the substituent X is further away from the reaction site of the C-O bond fission than that of the S-O bond fission is one reason for the smaller ρX value. The nature of the reaction mechanism (i.e., a stepwise mechanism in which expulsion of the leaving group occurs after the rate-determining step) is also responsible for the smaller ρX value obtained from the C-O bond fission. The Bronsted-type plot for the reactions of 5a-5f is linear with βlg=-0.63, which is typical for reactions reported previously to proceed through a concerted mechanism. Effects of substituents X and Y on regioselectivity and reaction mechanism are discussed in detail.
Moon, Ji-Hyun,Kim, Min-Young,Han, So-Yeop,Um, Ik-Hwan
p. 1360 - 1365
(2015/07/15)

A PROCESS FOR MANUFACTURING HALOARYL COMPOUNDS FROM MIXTURES OF ISOMERS OF DIHALODIARYLSULFONES
A process for the manufacture of a haloaryl compound which comprises contacting a mixture of dihalodiarylsulfone isomers [mixture (M)] with sulfuric acid to provide a mixture of haloarylsulfonic acid isomers [mixture (M1)] and reacting mixture (M1) in the presence of water. The process is independent on the manufacturing process of mixture (M) and is advantageous in that the obtained haloaryl compound can be recycled to the first step of a dihalodiarylsulfone manufacturing process.
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Page/Page column 18; 19

(2013/07/05)

Synthesis of sulfonyl chlorides and sulfonic acids in SDS micelles
H2O2/POCl3 is found to be a reactive reagent system that can be used in sodium dodecyl sulfate (SDS) micellar solution in aqueous media for the direct oxidative chlorination of thiol and di-sulfide derivatives to give the desired sulfonyl chlorides. The oxidation of thiols and disulfides to sulfonic acids with this system is also reported. In most cases, these reactions are highly selective, simple, and clean, affording products in excellent yields and high purity. Georg Thieme Verlag Stuttgart · New York.
Bahrami, Kiumars,Khodaei, Mohammad M.,Abbasi, Jamshid
experimental part
p. 316 - 322
(2012/03/26)

PROCESS FOR PREPARING 4,4'-DICHLORODIPHENYL SULFONE
The invention relates to a process for preparing 4,4′-dichlorodiphenyl sulfone, comprising the reaction of monochlorobenzene and liquid sulfur trioxide, wherein the liquid sulfur trioxide used has a boron content of at most 100 ppm based on the total weight of the sulfur trioxide used, including all secondary components.
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(2011/11/06)

PROCESS FOR PREPARING 4,4'-DICHLORODIPHENYL SULFONE
The invention relates to a process for preparing 4,4′-dichlorodiphenyl sulfone proceeding from monochlorobenzene, wherein the content in the monochlorobenzene used of hydrocarbons having from 5 to 8 carbon atoms is at most 100 ppm; based on the total weight of the monochlorobenzene used, including the secondary components. The present invention further relates to the use of monochlorobenzene with the properties mentioned for preparation of 4,4′-dichlorodiphenyl sulfone.
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Page/Page column 4

(2011/11/06)

The mechanisms of acid-catalyzed hydrolysis of n-(4-substituted arylthio) phthalimides
The acid-catalyzed hydrolysis of N-(4-substitutedarylthio)phthalimides was studied in aqueous solutions of sulfuric, perchloric, and hydrochloric acids at 40.0 ±0.1° C. Analysis of the data by the excess acidity method, activation parameters, and substituent effects indicates hydrolysis by an A-2 mechanism at low acidity. At higher acidities, a changeover to an A-1 mechanism is observed.
Kutuk, Halil,Yakan, Hasan
experimental part
p. 1460 - 1469
(2011/10/05)

PROCESSES FOR PREPARING 4-CHLOROBENZENESULFONIC ACID AND 4,4'-DICHLORODIPHENYL SULFONE
The invention relates to a process for preparing 4-chlorobenzenesulfonic acid from 2-chlorobenzenesulfonic acid and/or 3-chlorobenzenesulfonic acid, comprising the conversion of 2-chlorobenzenesulfonic acid and/or 3-chlorobenzenesulfonic acid to 4-chlorobenzenesulfonic acid in the presence of sulfuric acid at a temperature of 100 to 300° C. The present invention further relates to a process for preparing 4,4′-dichlorodiphenyl sulfone, comprising said process for preparing 4-chlorobenzenesulfonic acid.
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Page/Page column 4

(2011/10/02)

The SN3-SN2 spectrum. Rate constants and product selectivities for solvolyses of benzenesulfonyl chlorides in aqueous alcohols
Rate constants for a wide range of binary aqueous mixtures and product selectivities (S) in ethanol - Water (EW) and methanol-water (MW) mixtures, are reported at 25 °C for solvolyses of benzenesulfonyl chloride and the 4-chloro - Derivative. S is defined as follows using molar concentrations: S =([ester product]/[acid product]) × ([water solvent]/[alcohol solvent]). Additional selectivity data are reported for solvolyses of 4-Z-substituted sulfonyl chlorides (Z - OMe, Me, H, Cl and NO2) in 2, 2, 2-trifluoroethanol-water. To explain these results and previously published data on kinetic solvent isotope effects (KSIEs) and on other solvolyses of 4-nitro and 4-methoxybenzenesulfonyl chloride, a mechanistic spectrum involving a change from third order to second order is proposed. The molecularity of these reactions is discussed, along with new term 'SN3-SN2 spectrum' and its connection with the better established term 'S N2-SN1 spectrum'. Copyright
Bentley, T. William,Jones, Robert O,Kang, Dae Ho,Koo, Sun
scheme or table
p. 799 - 806
(2010/06/16)

Selective and mild oxidation of thiols to sulfonic acids by hydrogen peroxide catalyzed by methyltrioxorhenium
Aromatic and aliphatic thiols are oxidized in acetonitrile at 20 °C by hydrogen peroxide in the presence of methyltrioxorhenium as the catalyst to yield the corresponding sulfonic acids in high isolated yields (85-94%).
Ballistreri, Francesco P.,Tomaselli, Gaetano A.,Toscano, Rosa M.
p. 3291 - 3293
(2008/09/20)

A novel method for sulfonation of aromatic rings with silica sulfuric acid
Direct and chemoselective sulfonation of aromatic compounds with silica sulfuric acid in 1,2-dichloeoethane or under solvent-free conditions.
Hajipour, Abdol R.,Mirjalili, Bi Bi F.,Zarei, Amin,Khazdooz, Leila,Ruoho
p. 6607 - 6609
(2007/10/03)

Effect of Amine Nature on Reaction Rate and Mechanism in Nucleophilic Substitution Reactions of 2,4-Dinitrophenyl X-Substituted Benzenesulfonates with Alicyclic Secondary Amines
Second-order rate constants have been measured for reactions of 2,4-dinitrophenyl X-substituted benzenesulfonates with a series of alicyclic secondary amines. The reaction proceeds through S-O and C-O bond fission pathways competitively. The S-O bond fission occurs more dominantly as the amine basicity increases and the substituent X in the sulfonyl moiety becomes more strongly electron withdrawing, indicating that the regioselectivity is governed by the amine basicity as well as the electronic nature of the substituent X. The S-O bond fission proceeds through an addition intermediate with a change in the rate-determining step at pKa° = 9.1. The secondary amines are more reactive than primary amines of similar basicity for the S-O bond fission. The k1 value has been determined to be larger for reactions with secondary amines than with primary amines of similar basicity, which fully accounts for their higher reactivity. The second-order rate constants for the S-O bond fission result in linear Yukawa-Tsuno plots while those for the C-O bond fission exhibit poor correlation with the electronic nature of the substituent X. The distance effect and the nature of reaction mechanism have been suggested to be responsible for the poor correlation for the C-O bond fission pathway.
Um, Ik-Hwan,Chun, Sun-Mee,Chae, Ok-Mi,Fujio, Mizue,Tsuno, Yuho
p. 3166 - 3172
(2007/10/03)

Clean-chemistry sulfonation of aromatics
A solution of TFAA/H2SO4 is an atom-efficient liquid-phase system for rapid sulfonation of aromatic structures; H2SO4 is consumed stoichiometrically and the spent trifluoroacetic anhydride (TFAA) is readily recovered as trifluoroacetic acid (TFA) which can be recycled to TFAA.
Corby, Brian W.,Gray, Anthony D.,Meaney, Padraig J.,Falvey, Michael J.,Lawrence, Gregory P.,Smyth, Timothy P.
p. 326 - 327
(2007/10/03)

Competitive Reaction Pathways in the Nucleophilic Substitution Reactions of Aryl Benzenesulfonates with Benzylamines in Acetonitrile
The reactions of aryl benzenesulfonates (YC6H4SO2OC6H4Z) with benzylamines (XC6H4CH2NH2) in acetonitrile at 65.0 deg C have been studied. The reactons proceed competitevely by S-O (kS-O) and C-O (kC-O) bond scission, but the former provides the major reaction pathway. On the basis of analysis of the Hammet and Broensted coefficients together with the cross-interaction constants ρXY, ρYZ, and ρXZ, stepwise mechanisms are proposed in which the S-O bond cleavage proceeds by rate-limiting formation of a trigonal-bipyramidal pentacoordinate (TBP-5C) intermediate, whereas the C-O bond scission takes place by rate-limiting expulsion of the sulfonate anion (YC6H4SO3-) from a Meisenheimer-type complex.
Choi, Jin Heui,Lee, Byung Choon,Lee, Hai Whang,Lee, Ikchoon
p. 1277 - 1281
(2007/10/03)

Oxidative hydrolysis of phosphorus(V) esters of thiols by peroxymonosulfate ion. Reactions of peroxymonosulfate ion with phosphorus(V) esters of thiols
Peroxymonosulfate ion, HSO5-, as Oxone, readily converts phosphorus(V) esters of thiols into the phosphorus(V) and sulfonic acids. The esters were Ph2PO·SC6H4R(p) with R=MeO (1a), Me (1b), H (1c), Cl (1d) and NO2 (1e), (EtO)2PO·SPh (2), Ph2OI·SEt (3) and PhPO(OEt)SEt (4). Reactions are first order in each reactant and second-order rate constants, k2, for 1a-e fit the Hammett equation with ρ=-0.46. The rate constants increase markedly with increasing water content of H2O-MeCN, the activation enthalpies are low and the entropies are negative. Despite the low value of -ρ, these esters are much less reactive than thiol ethers, but the rate constants of reactions of these compounds and acyl thiols qualitatively follow the ionization potentials of the ethers and the esters.
Blasko, Andrei,Bunton, Clifford A.,Kumar, Anurag
p. 427 - 434
(2007/10/03)

Kinetics and mechanism of the aminolysis of cycloalkylmethyl arenesulfonates
Nucleophilic substitution reactions of cycloalkylmethyl arenesulfonates (CmH2n-1 CH2OSO2C6H4Z) with anilines (XC6H4NH2) in methanol at 65.0 °C were studied. The reactivity order (n=4>6>7>5) reflects largely the order of steric effect of the ring size (SEs term) except for n=5, which exhibits the least reactivity. This reversal of the order for n=5 is considered to result from large rate retardation due to polar effect of the ρ*σ* term. Application of the Taft equation to the rate data for n=5 and 6 gives ρ=17·4 and 5=2·3 with correlation coefficient of 0·90. The σ* values for n=4 and 7 are estimated to be - 0·23 and - 0·11, respectively. The positive ρxz values of ca 0·3 are consistent with previous results for the reactions at primary reaction centers.
Oh, Hyuck Keun,Song, Se Jeong,Jo, Dong-Soo,Lee, Ikchoon
p. 91 - 96
(2007/10/03)

Sulfide Oxidation and Oxidative Hydrolysis of Thioesters by Peroxymonosulfate Ion
Peroxymonosulfate ion, HSO5-, as OXONE, in aqueous MeCN readily converts aryl thiobenzoates, XC6H4CO*SC6H4Z (X = p-OMe, p-Me, H, p-Cl, p-CN; Z = p-OMe, p-Me, H, m-OMe, p-Cl, m-Cl, p-NO2) into carboxylic and sulfonic acids.Reactions are second order and have small substituent effects, with ρ ca. -0.6 based on ?m and ?p substituent parameters, but rates increase markedly with increasing water content in aqueous MeCN and entropies of activation are negative.The initial step is very similar to the oxidation of methyl aryl sulfides by HSO5- which has similar solvent and substituent effects.Enthalpies of activation are much lower for oxidation of the sulfides than of the corresponding esters but entropies of activation are similar.
Bunton, Clifford A.,Foroudian, Houshang J.,Kumar, Anurag
p. 33 - 40
(2007/10/02)

Solvolysis of α-t-Butylbenzyl arenesulphonates: A Prototypical SN1 Process.
Solvolyses of α-t-butylbenzyl arenesulphonates are studied with a view to correlating the magnitude of the cross-interaction constants, ρxy, ρxz and ρyz (where X, Y, and Z denote nucleophile, substrate and leaving group, respectively), with the SN1 transition state (TS) structure.As postulated for a limiting SN1 process, ρxy and ρxz vanish whereas the ρyz value is exceptionally large.Moreover, the solvent dependence of ρyz indicates an earlier TS along the reaction coordinate as the ion-pair intermediate is stabilized, in accordance with theBEP principle.The large magnitude of the kinetic response, m, to the solvent ionizing power, YoTs, and the ρy' values are within the ranges of values reported for SN1 reactions.The results of kinetic solvent isotope effect studies and the activation parameters, ΔH* and ΔS*, determined are also in line with those expected from a typical SN1 mechanism.
Lee, Ikchoon,Choi, Myung Soo,Lee, Hai Whang
p. 568 - 587
(2007/10/02)

Solvolysis Mechanism of Indan-2-yl Arenesulfonates
The solvolysis rates of 5-(Y)-substituted indan-2-yl (Z)-benzenesulfonates were determined in a variety of protic solvents at 45.0, 55.0 and 65.0 deg C.Application of an extended Grunwald-Winstein equation indicates that kinetic responses to both solvent ionizing power, YOTs, and solvent nucleophilicity, NOTs, are relatively low but increase in parallel with increasing leaving ability, m = 0.39-0.46 and I=0.32-0.41 for Z=p-Me p-NO2.The magnitude of cross-interaction constant, ρYZ, is also relatively small (0.16-0.32), which is, however, much more dependent on the nucleophilicity rather than the ionizing power of the solvent.These are consistent with the typical SN2 mechanism proceeding through a transition state in which solvent participates in both bond-making and -breaking processes.
Lee, Ikchoon,Lee, Young Sook,Lee, Bon-Su,Lee, Hai Whang
p. 1441 - 1445
(2007/10/02)

Photooxidation of Thiols in Self-Assembled Monolayers on Gold
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Huang, Jingyu,Hemminger, John C.
p. 3342 - 3343
(2007/10/02)

Cross-interaction Constants as a Measure of the Transition State Structure. Part 11. Solvolyses of 1-Phenyl-2-propyl Benzenesulphonates
The solvolyses of 1-phenyl-2-propyl benzenesulphonates (PPBs) have been investigated in methanol-acetonitrile mixtures and in hexafluoropropan-2-ol (HFIP).The transition state structure has been discussed using various selectivity parameters, especially with the cross-interaction constants, ρYZ and λYZ, between substituents in the substrate (Y) and in the leaving group (Z).It has been found that the solvolysis proceeds by the solvent-assisted pathway, ks, in methanol, whereas in HFIP PPBs solvolyse via the aryl-assisted pathway, kΔ.The only exception was the p-MeO substituent, which deviates positively in methanol from the log ks vs. ? plot due to participation of the aryl-assisted path and negatively in HFIP from the log kΔ vs. ?(neophyl) plot due to deactivation by hydrogen bonding of the methoxy oxygen in the acidic solvent.The two distinctive high values of ρYZ provided evidence for the strongly bound transition states in the two processes, ks and kΔ, with a relatively low degree of bond breaking.
Lee, Ikchoon,Lee, Won Heui,Lee, Hai Whang,Lee, Byung Choon
p. 785 - 791
(2007/10/02)

FACILE CONVERSION OF AMIDES TO THE ACIDS AND/OR ANHYDRIDES USING DINITROGEN TETROXIDE
Carboxamides and sulfonamides were reacted with dinitrogen tetroxide to give the corresponding acids, while such as N-bromoamides and hydroxamic acids were also converted to the corresponding acids together with their anhydrides.
Kim, Yong Hae,Kim, Kweon,Park, Young Jun
p. 3893 - 3894
(2007/10/02)

Cross Interaction Constants As a Measure of Transition State structure. Part 7. Aminolysis of Alkyl Benzenesulphonates
Kinetic studies of the reactions of methyl and ethyl benzenesulphonates with anilines and benzylamines in methanol and acetonitrile at 65.0 deg C have been reported.The magnitudes of cross-interaction constants between substituents in the nucleophile (X) and the leaving group (Z),ρxz and βxz, were found to be greater for the ethyl series which indicates a tighter transition state for ethyl rather than methyl derivatives.This unexpected trend has been rationalized by making the assumption that the small electron-donating polar effect, of the α-methyl substituent in the ethyl compounds, requires a tighter transition-state structure in addition to the major effect of steric repulsion on the activation barrier which is present in all SN2 reactions taking place at a carbon centre.
Lee, Ikchoon,Choi, Young Hoon,Rhyu, Keun Woo,Shim, Chang Sub
p. 1881 - 1886
(2007/10/02)

Multiple Structure-Reactivity Relationships for a Menschutkin-type SN2 Reaction
The mechanism of nucleophilic displacement was studied by using three variable systems of ρX, ρY and ρZ obtained from the change of substituents X, Y and Z for the reaction of (Z)-substituted benzyl (X)-benzenesulphonates with (Y)-substituted N,N-dimethylanilines in aceton at 35 deg C.The coefficient of the interaction term, ρXY, has a value of 0.21 which means that bond-making and -breaking are concerted in the SN2 transition state.In the range Z = H to p-NO2, in which the SN2 mechanism is predicted to be dominant, the ρZY value is very large, 0.5, which means that the interaction between Z and Y is very large. ρZX is ca. 0.06 which means that the interaction is small between X and Z.In contrast, in the range Z = H to p-Me, in which the SN1 mechanism is dominant, the ρZY value is nearly zero, indicating no interaction between Z and Y.Changes of substituent effect and interaction terms, ρXY, ρYZ and ρZX are useful tools for distinguishing wrong reaction mechanisms.
Yoh, Soo-Dong,Tsuno, Yuho,Fujio, Mizue,Sawada, Masami,Yukawa, Yasuhide
p. 7 - 14
(2007/10/02)

Kinetics and Mechanism of Reactions between 2-Phenylethyl Benzenesulphonates and Anilines in Methanol
Kinetics of reactions between 2-phenylethyl benzenesulphonates and anilines in methanol at 65.0 deg C have been studied; the mechanism is discussed on the basis of cross interaction constants, ρij.The overall reaction was found to proceed by a dissociative SN2 mechanism with a relatively small degree of aryl participation.The fraction of the phenonium ion intermediate captured by the nucleophile, aniline, in the aryl-assisted pathway has been shown to increase with a stronger nucleophile, and a four-centre transition state in an intermolecular SNi mechanism is suggested for the aryl-unassisted pathway.
Lee, Ikchoon,Choi, Yong Hoon,Lee, Hai Whang,Lee, Byung Choon
p. 1537 - 1540
(2007/10/02)

KINETICS AND MECHANISM OF HYDROLYSIS OF AROMATIC SULFONYL CHLORIDES IN AQUEOUS SULFURIC ACID SOLUTIONS
The kinetics of the hydrolysis of 12 aromatic sulfonyl chlorides were studied by a spectrophotometric method in water and aqueous sulfuric acid solutions ( 1.0 - 60.5 wt.percent ) at 25 deg C and in 50percent sulfuric acid at several temperatures.It was shown that the reaction obeys the single-parameter equation log keff = log k0 + m'X, in which keff and k0 are the first-order rate constants in a solution with "excess acidity" X and in water respectively.The coefficient m' depends on the substituent in the ring and is equal to -0.85 to -0.38.The activity of the water does not enter into the equation for the calculation of keff.For the hydrolysis of nine substituted sulfonyl chlorides in 50percent sulfuric acid a satisfactory correlation is observed between log keff and the Σ?0.Palm induction constants ( ρ = -1.85 +/- 0.12 ).A reaction mechanism is proposed in which the rate-determining stage in the hydrolysis of the ArSO2Cl is the transformation of the complex H2O...SO2(Cl)Ar, in the form of which all the sulfonyl chloride dissolved in the water is present, into the reaction products.
Gnedin, B. G.,Ivanov, S. N.,Shchukina, M. V.
p. 731 - 737
(2007/10/02)

Kinetics of hydrolysis of aromatic mono- and disulfonyl chlorides
A continuous polarografic method of recording instantaneous concentrations of - SO2Cl groups in an aqueous acetic acid system containing CH3CO2Na has been elaborated.Ten model monosulfonyl chlorides underwent hydrolysis according to pseudo-first order kinetics (20percent H2O, 80percent v.v.CH3CO2H, 0.5 mol/dm3 CH3CO2Na).Plots of hydrolysis for seven disulfonyl dichlorides with different number of - CH3 groups have been determined.Pseudo-first order rate constants for two consecutive reactions of hydrolysis (k1 and k2) have been computed and the influence of -SO2Cl and -SO3- groups on the reactivity of the second group - SO2Cl has been discussed.The mechanism of nucleophilic substitution has also been discussed.
Sanecki, Przemyslaw,Rokaszewski, Edward
p. 2263 - 2267
(2007/10/02)

Solvolysis of Allyl Arenesulfonates. Cautionary Comments concerning the NOTs Scale of Solvent Nucleophilicities
The rates of solvolysis of five allyl arenesulfonates are analysed in terms of the extended Grunwald-Winstein equation.The l values are constant but the m values decrease slightly as the nucleofugality of the leaving group increases.The solvent nucleophilicity (NOTs) values presently available in the literature are based upon a m value for methyl p-toluenesulfonate (tosylate) solvolysis of 0.3; it is demonstrated that a value of 0.55 is more appropriate.The previously reported l values and correlation coefficients for tosylate ester solvolyses are accurate and the "ap parent" sensitivities to solvent ionizing power (m values) are easily corrected.However, for use in conjunction with solvent ionizing power scales for other leaving groups, NTs values based on the appropriate m value or, alternatively, NEt3O+%& values (based on triethyloxonium ion solvolysis) are required.
Kevill, Dennis N.,Rissmann, Thomas J.
p. 3062 - 3064
(2007/10/02)

Crystalline benzenesulfonate salts of sultamicillin
Novel benzenesulfonic acid addition salts of sultamicillin of the formula STR1 and hydrated forms thereof, where X is hydrogen or chloro, especially the crystalline dihydrate salts, having advantages over the prior art forms of sultamicillin in pharmaceutical dosage forms, most particularly those for use in pediatric medicine, method for their use and pharmaceutical compositions thereof.
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(2008/06/13)

KINETICS AND MECHANISM OF THE SOLVOLYSIS OF METHYL ESTERS OF AROMATIC SULFONIC ACIDS IN CONCENTRATED SULFURIC ACID AND WEAK OLEUM
The effect rate constants for the solvolysis of methyl benzenesulfonate in 99.03-100.2percent sulfuric acid, methyl p-toluenesulfonate in 99.81-100percent sulfuric acid, and methyl p-chlorobenzenesulfonate in 100percent sulfuric acid were determined at 25 deg C by GLC.In the investigated range of sulfuric acid concentrations a linear relation is observed between lof keff and log aH2S2O7 with a slope close to unity against the abscissa axis.It is assumed that the rate-determining stage of the process is the decomposition of a complex formed by the molecules of the sulfonic ester and pyrosulfonic acid.The reaction takes place with cleavage of the S-O bond in the molecule of the sulfonic ester.In the transition state of the rate-determining stage the order of the S-OMe bond is lower than the order of the S-O bond.
Gnedin, B. G.,Karmanova, T. V.,Chumakova, M. V.,Ivanov, S. N.
p. 503 - 507
(2007/10/02)

HYDROLYSIS OF AROMATIC SULFONIC ACIDS UNDER THERMODYNAMIC CONTROL OF THE REACTION
Linear mathematical models which describe the hydrolysis of alkyl- and halobenzenesulfonyl acids under the conditions for their isomerization in sulfuric acid have been obtained by the method of mathematical experiment planning.The value of the effective rate constants of hydrolysis calculated according to the models for comparative conditions (150 deg C, 3 moles of 85percent sulfuric acid) were used to obtain the correlation between log kh and the ? constants of the substituents.The correlation corresponds the electrophilic nature of the hydrolysis process (ρ = -4.69).The strong influence of the electronic effects of the substituents on the rate of hydrolysis is an indication of the development of a considerable positive charge on the reaction center in the transition state.
Krylov, E. N.,Volgina, L. V.,Isaeva, G. Yu.
p. 1129 - 1133
(2007/10/02)

COMPARISON OF THE MECHANISMS OF SOLVOLYSIS OF ARENESULFONIC ESTERS OF BEZOIN IN METHANOL AND FORMIC ACID ON THE BASIS OF THE HAMMOND POSTULATE
The kinetic of the methanolysis of the arenesulfonic esters of substituted benzoins p-XC6H4C(O)CH(OSO2C6H4Y)C6H5 (X = CH3O, H, Cl; Y = p-CH3O, p-CH3, H, p-Cl, m-Cl) at 30-50 deg C were studied, and it was established that unlike the previously investigated formolysis of these substrates (ρ+X o and ρY is opposite in character, which agrees with the Hammond postulate.The given contradiction is explained by the fact that the experimental temperature range is higher than the isoselectivity temperature.
Dement'eva, L. P.,Semenova, S. N.,Karavan, V. S.
p. 654 - 657
(2007/10/02)

EFFECT OF STRUCTURE ON THE KINETICS AND MECHANISM OF THE ACID-CATALYZED DECOMPOSITION OF N-ALKYL-N-NITROBENZENESULFONAMIDES
The decomposition rate of a series of meta- and para-substituted N-alkyl-N-nitrobenzenesufonamides was determined by a spectrophotometric method in aqueous sulfuric acid.It was shown that the decomposition of the compounds takes place both by denitration and by cleavage of the N-S bond with the formation fo primary aliphatic N-nitrosamines.Electron-withdrawing substituents in the aromatic ring shift the process toward denitration.
Drozdova, O. A.,Astrat'ev, A. A.,Kuznetsov, L. L.,Selivanov, V. F.
p. 671 - 675
(2007/10/02)

Hydrolysis of aromatic sulfonic acids under conditions of thermodynamic control of the sulfonation reaction
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Krylov, E. N.,Savel'eva, G. M.
p. 833 - 836
(2007/10/02)

EFFECT OF STRUCTURE ON THE KINETICS AND MECHANISM OF THE ACID-CATALYZED DECOMPOSITION OF N-NITROBENZENESULFONAMIDES
The decomposition rate of a series of ring-substituted N-nitrobenzenesulfonamides in aqueous sulfuric acid was measure by a spectrophotometric method.Decomposition of the compounds takes place both by the cleavage of the N-S bond to form the corresponding sulfonic acid, nitrous oxide, and water and by denitration.In crease in the electronegativity of the substituent in the aromatic ring promotes the denitration reaction.
Drozdova, O. A.,Astrat'ev, A. A.,Kuznetsov, L. L.,Selivanov, V. F.
p. 2063 - 2067
(2007/10/02)

STUDIEN ZUM VORGANG DER WASSERSTOFFUEBERTRAGUNG.61. Chemische Reaktivitaet und Halbstufenpotential Vergleichende Versuche am Beispiel einiger Arylsulfonsaeurederivate
In arylsulfonyl halides, the half-wave potentials of the corresponding chlorides and fluorides differ by more than 1000 mV, the fluoride being more negative; the influence of para-substituents is small for the chlorides, large for the fluorides.In agreement with the half-wave potentials, arylsulfonyl chlorides are considerably more reactive chemically than the corresponding fluorides.The O-selectivity found for P(O)F compounds is not observed in arylsulfonyl fluorides.Studies of competitive ester formation using primary and secondary alcohols and various arylsulfonyl chlorides yielded no clear analogy to the half-wave potentials.The primary alcohol is always sulfonated in preference to the secondary alcohol, whether the hydroxy functions are present in different molecules or the same molecule.In the latter case, the secondary hydroxyl function is then attacked in a further step by a second, different, arylsulfonyl chloride, giving the compounds 4-8.The further electroreduction of these diesters may be carried out in high yields, giving selective fission of one ester linkage only (that with the more positive potential) provided the difference in the half-wave potentials of the different ester linkages is sufficiently large.In the electroreductive fission the monosulfinic acid and the corresponding alcohol are liberated (see table II).In the competition reaction between phenol and 1:1 mixtures of tosyl chloride (A) and p-carboxyethyl-benzenesulfonyl chloride (B), the chloride with the more positive potential (B), E1/2=72 mV reacts quicker by a factor of 2.5.In competitive Finkelstein reactions, the selectivity was 1:11 at a difference in half-wave potentials of 760 mV (table IV).Arylsulfonates with free secondary alcohol functions may be oxidized smoothly and in high yield to the corresponding ketone using Na2Cr2O7 (3), without effecting the sulfonate linkage.The alkali hydrolysis of n-hexyl para-substituted arylsulfonates follows the Hammett relation but shows a lesser selectivity than was observed in the electroreductive fission of the same esters at the required potentials.Tables VI, VII and VIII concentrate on the preparative importance of the potential-controlled electroreductive fission of aliphatic and aromatic arylsulfonates.The corresponding hydroxy compounds are liberated in yields of up to over 90percent: N-alkyl- and N-aryl arylsulfonamides give analogous results. (table IX)
Horner, Leopold,Schmitt, Rolf-Erhard
p. 189 - 212
(2007/10/02)