104-15-4Relevant articles and documents
The mechanisms of acid-catalyzed hydrolysis of n-(4-substituted arylthio) phthalimides
Kutuk, Halil,Yakan, Hasan
, p. 1460 - 1469 (2011)
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.
Evidence for complexes of different stoichiometries between organic solvents and cyclodextrins
Garcia-Rio,Herves,Leis,Mejuto,Perez-Juste,Rodriguez-Dafonte
, p. 1038 - 1048 (2006)
The influence of the organic solvent on the acid and basic hydrolysis of N-methyl-N-nitroso-p-toluenesulfonamide (MNTS) in the presence of α- and β-cyclodextrins has been studied. The observed rate constant was found to decrease through the formation of an unreactive complex between MNTS and the cyclodextrins. In the presence of dioxane, acetonitrile or DMSO, the inhibitory effect of β-CD decreased on increasing the proportion of organic cosolvent as a result of a competitive reaction involving the formation of an inclusion complex between β-CD and the cosolvent. The disparate size of the organic solvent molecules resulted in stoichiometric differences between the complexes; the β-CD-dioxane and β-CD-DMSO complexes were 1: 1 whereas the β-CD-acetonitrile complex was 1: 2. The basic and acid hydrolysis of MNTS in the presence of α-CD showed a different behavior; thus, the reaction gave both 1: 1 and 2: 1 α-CD-MNTS complexes, of which only the former was reactive. This result was due to the smaller cavity size of α-CD and the consequent decreased penetration of MNTS into the cavity in comparison to β-CD. The acid hydrolysis of MNTS in the presence of α-CD also revealed decreased penetration of MNTS into the cyclodextrin cavity, as evidenced by the bound substrate undergoing acid hydrolysis. In addition, the acid hydrolysis of MNTS in the presence of acetonitrile containing α-CD gave 1: 1 α-CD-acetonitrile inclusion complexes, which is consistent with a both a reduced cavity size and previously reported data. The Royal Society of Chemistry 2006.
ESR study of free radical decomposition of N,N-bis(arylsulfonyl)hydroxylamines in organic solution
Balakirev, Maxim Yu.,Khramtsov, Valery V.
, p. 7263 - 7269 (1996)
Decomposition of N,N-bis(p-tolylsulfonyl)hydroxylamine (BTH) in chloroform and benzene solutions has been studied and was found to involve the formation of several radical intermediates. This process has been found to be accelerated by oxygen, resulting in the formation of p-toluenesulfonic acid and N,N,O-tris(p-tolylsulfonyl)hydroxylamine (TTH) as the main decay products. In addition, a small amount of p-toluenesulfonyl chloride has been isolated from chloroform solution, suggesting the chlorine abstraction from solvent. The formation of nitric oxide (NO) from BTH has been shown by mass spectrometry in gaseous phase and using nitronyl nitroxide as an NO trap in solution. It was proposed that liberation of NO proceeds through the homolytic cleavage of the S-N bond of p-tolylsulfonyl nitrite existing in equilibrium with BTH in solution. The formation of p-tolylsulfonyl radicals has been proved by spin trapping using 2-methyl-2-nitrosopropane (MNP) and 5,5-dimethyl-1-pyrroline N-oxide (DMPO). The rate of NO production in the presence of nitronyl nitroxide and the rate of oxygen consumption revealed linear plots in BTH concentration with the rate constants 0.0044 s-1 and 0.0016 s-1, respectively. It was found also that nitrogen dioxide formed during NO oxidation reacts readily with BTH to produce the organic analog of Fremy's radical. This radical recombines with p-tolylsulfonyl radical yielding N,N,O-trisubstituted hydroxylamine TTH.
Investigation of micellar media containing ?2-cyclodextrins by means of reaction kinetics: Basic hydrolysis of N-methyl-N-nitroso-p-toluenesulfonamide
Garciì?a-Riì?o,Leis,Mejuto,Peì?rez-Juste
, p. 7383 - 7389 (1997)
The kinetics of the basic hydrolysis of N-methyl-N-nitroso-p-toluenesulfonamide were studied in media containing sodium dodecyl sulfate (SDS) or tetradecyltrimethylammonium bromide (TTABr) micelles and ?2-cyclodextrin (CD). Under the experimental conditions, [NaOH] = 0.17 M, all CD will have been deprotonated; thus, binding constants apply to the CD anion. The results have been interpreted in terms of a pseudophase model that takes into account the formation of both CD - surfactant and CD - substrate complexes and also, for TTABr systems, the exchange of Br- and OH- ions between the micellar and aqueous pseudophases. The presence of CD has no effect on existing SDS or TTABr micelles but raises the cmc: complexation of surfactant by cyclodextrin makes the cmc dependent on CD concentration because the cmc is now the sum of the concentrations of free and complexed surfactant when micelles begin to form; increasing [CD] reduces the former quantity but increases the latter to a greater extent. At surfactant concentrations above the cmc, competition between the micellization and complexation processes leads to the existence of a significant concentration of free cyclodextrin.
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Lee et al.
, p. 206,212 (1959)
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Influence of colloid suspensions of humic acids on the alkaline hydrolysis of N-methyl-N-nitroso-p-toluene sulfonamide
Astray,Garcia-Rio,Lodeiro,Mejuto,Moldes,Morales,Moyano
, p. 316 - 322 (2010)
The influence of humic substances (HSs) upon the alkaline hydrolysis of N-methyl-N-nitroso-p-toluene sulfonamide has been studied. Important inhibition of hydrolysis reaction has been reported. This inhibition has been explained in terms of association of reactants to the humic substances. Kinetic results have been modeled using the micellar pseudophase model.
Hypervalent iodine in synthesis. XXI: A facile method for the preparation of thiosulfonic S-esters by the oxidation of diaryl disulfides or thiophenols with phenyliodine(III) bis(trifluoroacetate)
Xia, Min,Chen, Zhen-Chu
, p. 1301 - 1308 (1997)
Phenyliodine(III) bis(trifluoroacetate) can be used to readily oxidize diaryl disulfides or thiophenols to corresponding thiosulfonic S-esters with good yields under very mild conditions.
Competitive electron transfers from a tyrosyl side-chain and peptide bond in the photodegradation of N-tosyl α-aminomethylamides: An insight into photosynthesis and photodamage in the biological oxidation of water?
Hill, Roger R.,Moore, Sharon A.,Roberts, David R.
, p. 2838 - 2839 (2003)
Photo-excited N-tosyl derivatives of phenylalanyl- and, more particularly, O-methyltyrosylmethylamides undergo electron transfer from aryl to tosyl groups whereas the photo-degradation of aliphatic analogues is initiated by electron transfer from the peptide bond, suggesting the latter as one possible reason for the rapid turnover of the D1 protein in biological water oxidation when the essential mediating role of tyrosine 116 in the PSII complex is inhibited.
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Thomas,Anzilotti,Hennion
, p. 408 (1940)
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Palladium nanoparticles as reusable catalyst for the synthesis of N-aryl sulfonamides under mild reaction conditions
Khalaj, Mehdi,Ghazanfarpour-Darjani, Majid,Talei Bavil Olyai, Mohamad Reza,Shamami, Sakineh Faraji
, p. 211 - 221 (2016)
An efficient palladium nanoparticles-catalyzed N-arylation of sulfonamides and sulfonyl azides is described. This procedure serves as an active protocol for intermolecular C-N bond formation using Pd(OAc)2 in PEG-400 under air. Aryl bromides and triflates react at 35°C, while aryl chlorides require heating to 50°C and give the desired products only in low yields. This reaction proceeds smoothly in acceptable yields using low catalyst loading.
Experimental and molecular modelling studies on aromatic sulfonation
Morley, John O.,Roberts, David W.,Watson, Simon P.
, p. 538 - 544 (2002)
The mechanism of the sulfonation of toluene has been explored both experimentally and theoretically using molecular orbital methods. Sulfonation with sulfur trioxide is proposed to proceed initially via the formation of a toluene-S2O6 π-complex (3) which rearranges to form a Wheland pyrosulfonate intermediate (5) which in turn undergoes a facile prototropic rearrangement involving the transfer of the ring hydrogen at the sp3 carbon to the sulfonate oxygen atom to form toluenepyrosulfonic acid (7). Once formed, this acid is thought to attack toluene to form two equivalents of toluenesulfonic acid (6) which preferentially react with sulfur trioxide to re-form the pyrosulfonic acid (7). Experimentally, sulfonation using either acetylsulfonic acid (9), trifluoroacetylsulfonic acid (10), or trimethylacetylsulfonic acid (11), as models for pyrosulfonic acid (7), appears to show second order kinetics at room temperature. The reaction with acetylsulfonic acid (9) shows no significant kinetic isotope effect when 4deuterotoluene is used as the substrate, suggesting that sulfonation proceeds via attack of the π-electrons of the toluene ring at the sulfur atom, S8, of acetylsulfonic acid or toluenepyrosulfonic acid with simultaneous cleavage of the O7-S8 bond, where the displaced acetate or toluenesulfonate anion respectively can facilitate the removal of the ring proton at the sp3 carbon.
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Schenk et al.
, p. 907,911 (1950)
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Regioselective Sulfonation of Aromatic Compounds over 1,3-Disulfonic Acid Imidazolium Chloride under Aqueous Media
Moosavi-Zare, Ahmad Reza,Zolfigol, Mohammad Ali,Noroozizadeh, Ehsan
, p. 1682 - 1684 (2016)
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.
A Novel Concept of Acid Proliferation. Autocatalytic Fragmentation of an Acetoacetate Derivative as an Acid Amplifier
Ichimura, Kunihiro,Arimitsu, Koji,Kudo, Kazuaki
, p. 551 - 552 (1995)
tert-Butyl 2-methyl-2-(p-toluenesulfonyloxymethyl)acetoacetate was designed to be subjected to the acid-catalyzed fragmentation to liberate p-toluenesulfonic acid which can act as the autocatalyst to lead to the increment of the acid concentration in geometric progression.
Cholesteryl Tosylate: A Solvolytic Investigation
Roberts, Donald D.
, p. 1269 - 1272 (1993)
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Bis Sulfate as an Organosilicon Synthon
Voronkov, M. G.,Roman, V. K.,Maletina, E. A.
, p. 277 - 280 (1982)
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Neighboring group competition revisited: Relative abilities of cyclobutyl/cyclopentyl/phenyl groups to stabilize an electron-deficient carbon
Roberts
, p. 1341 - 1343 (1999)
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Importance of repulsion of lone electron pairs in the enhanced reactivity of 1,8-naphthyridine and the large α-effect of hydrazine in the aminolyses of p-toluenesulfonyl chloride
Oae, Shigeru,Kadoma, Yoshihito
, p. 1184 - 1188 (1986)
The rates of aminolyses of p-toluenesulfonyl chloride with primary and tertiary amines have been determined both in acetonitrile and in ethanol.The Broensted plots of log krel again pKa' values fo amines (except hydrazine and 1,8-naphthyridine in acetonitrile) gave a good correlation when the aminolyses were carried out in acetonitrile.In ethanol, however, although Broensted plots with all tertiary amines show a good correlation, less basic hydrazine shows a higher reactivity than n-butylamine.The abnormal rate enhancement found with hydrazine is undoubtedly due to the α-effect, while with 1,8-naphthyridine in acetonitrile is considered to be due to the repulsion of two lone electron pairs on the two nitrogen atoms in 1,8-naphthyridine.
A kinetic study of acid-catalyzed hydrolysis of some arylsulfonyl phthalimides
Kutuk, Halil,Ozturk, Seyhan
, p. 332 - 340 (2009)
The acid-catalyzed hydrolysis of arylsulfonyl phthalimides was studied in aqueous solutions of sulfuric, perchloric, and hydrochloric acid at 35.0 ± 0.1C. Analysis of the data by the excess acidity method and activation parameters, as well as substituent and solvent isotope effects, indicate hydrolysis by an A-2 mechanism at low acidity. At higher acidities, a changeover to an A-1 mechanism is observed.
Extremely mild and selective method for hydrolysis of tosyl esters by photo-sensitized single electron transfer reactions
Nishida,Hamada,Yonemitsu
, p. 2977 - 2980 (1990)
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Photocleavage of o-nitrobenzyl ether derivatives for rapid biomedical release applications
Kim, Moon Suk,Diamond, Scott L.
, p. 4007 - 4010 (2006)
The externally controlled cleavage of covalently linked prodrugs, proteins, or solid-phase formulation vehicles offers potential advantages for controlled drug or gene delivery. A series of o-nitrobenzyl ester compounds (1-8) were synthesized to allow a systematic study of photolability. The o-nitrobenzyl ester was strictly required for photolability, while imido esters were not photolabile. The degradation kinetics of 1-o-phenylethyl ester was an order of magnitude faster than that of o-nitrobenzyl ester. Tosylate, phosphate, and benzoate derivatives of 1-o-nitrophenylethyl displayed similar photolability (>80% decomposition within 10 min at 3.5 mW/cm2 at 365 nm). O-o-Nitrobenzyl O′,O″-diethyl phosphate displayed the fastest decomposition at photoirradiation condition (3.5 mW/cm2, 365 nm) suitable for biological systems. We report the synthesis and photo-decomposition of 1-o-nitrophenylethyl derivatives amenable for the creation of photolabile prodrugs or formulation particles for drug depots, DNA condensation, or tissue engineering applications.
BRANCHED AMINO ACID SURFACTANTS FOR AGRICULTURAL PRODUCTS
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, (2022/01/23)
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BRANCHED AMINO ACID SURFACTANTS FOR PERSONAL CARE AND COSMETIC PRODUCTS
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, (2022/01/24)
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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
Fatima, Touheeth,Duguta, Govardhan,Purugula, Venkanna,Yelike, Hemanth Sriram,Kamatala, Chinna Rajanna
, p. 1001 - 1006 (2020/07/27)
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.
