- Practical Electro-Oxidative Sulfonylation of Phenols with Sodium Arenesulfinates Generating Arylsulfonate Esters
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A practical and sustainable synthesis of arylsulfonate esters has been developed through electro-oxidation. This reaction employed the stable and readily available phenols and sodium arenesulfinates as the starting materials and took place under mild reaction conditions without additional oxidants. A wide range of arylsulfonate esters including those bearing functional groups were produced in good to excellent yields. This reaction could also be conducted at a gram scale without a decrease of reaction efficiency. Those results well demonstrated the potential synthetic value of this reaction in organic synthesis.
- Tian, Zhibin,Gong, Qihang,Huang, Tianzeng,Liu, Long,Chen, Tieqiao
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p. 15914 - 15926
(2021/05/04)
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- Quantum Dot-Catalyzed Photoreductive Removal of Sulfonyl-Based Protecting Groups
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This Communication describes the use of CuInS2/ZnS quantum dots (QDs) as photocatalysts for the reductive deprotection of aryl sulfonyl-protected phenols. For a series of aryl sulfonates with electron-withdrawing substituents, the rate of deprotection for the corresponding phenyl aryl sulfonates increases with decreasing electrochemical potential for the two electron transfers within the catalytic cycle. The rate of deprotection for a substrate that contains a carboxylic acid, a known QD-binding group, is accelerated by more than a factor of ten from that expected from the electrochemical potential for the transformation, a result that suggests that formation of metastable electron donor–acceptor complexes provides a significant kinetic advantage. This deprotection method does not perturb the common NHBoc or toluenesulfonyl protecting groups and, as demonstrated with an estrone substrate, does not perturb proximate ketones, which are generally vulnerable to many chemical reduction methods used for this class of reactions.
- Perez, Kaitlyn A.,Rogers, Cameron R.,Weiss, Emily A.
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p. 14091 - 14095
(2020/06/08)
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- Sulfonyl Fluoride Synthesis through Electrochemical Oxidative Coupling of Thiols and Potassium Fluoride
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Sulfonyl fluorides are valuable synthetic motifs for a variety of applications, among which sulfur(VI) fluoride exchange-based "click chemistry" is currently the most prominent. Consequently, the development of novel and efficient synthetic methods to access these functional groups is of great interest. Herein, we report a mild and environmentally benign electrochemical approach to prepare sulfonyl fluorides using thiols or disulfides, as widely available starting materials, in combination with KF, as an inexpensive, abundant and safe fluoride source. No additional oxidants nor additional catalysts are required and, due to mild reaction conditions, the reaction displays a broad substrate scope, including a variety of alkyl, benzyl, aryl and heteroaryl thiols or disulfides.
- Laudadio, Gabriele,Bartolomeu, Aloisio De A.,Verwijlen, Lucas M. H. M.,Cao, Yiran,De Oliveira, Kleber T.,No?l, Timothy
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p. 11832 - 11836
(2019/08/26)
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- Deprotection of durable benzenesulfonyl protection for phenols — efficient synthesis of polyphenols
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A robust protection method for phenol was demonstrated by the use of durable benzenesulfonyl group, which survives various harsh reaction conditions using Grignard reagent, organolithium reagent, metal alkoxide, phosgene, mineral, and Lewis acids. A facile deprotection condition utilizing pulverized KOH (5 equiv) and t-BuOH (10 equiv) in hot toluene makes this protocol as a practical method, which can be applied to the multistep synthesis of biologically and medicinally important polyphenol compounds.
- Alam, Mohammad Shariful,Koo, Sangho
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supporting information
p. 247 - 254
(2018/01/08)
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- Synthetic method of benzenesulfonate derivative
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The invention relates to a synthetic method of a benzenesulfonate derivative and belongs to the technical field of synthesis of compounds. A compound (described in the specification) is taken as raw materials, and reaction is carried out with ethylene glycol or R2-OH to generate a compound (described in the specification), wherein R1 is selected from alkyl, H or F, and R2 is selected from allyl, propargyl or benzene. The synthetic method provided by the invention comprises the following concrete operations: adding ethylene glycol or R2-OH and dichloromethane into a reactor, adding organic alkali while stirring, then cooling to the temperature below 15 DEG C, starting to dropwise add a substance (described in the specification), after the substance is dropwise added, returning to room temperature and further stirring for 0.5-1 hour, then heating and carrying out reflux reaction for 1-2 hours, after the reflux reaction is complete, carrying out ice thawing treatment, layering, drying, and concentrating, so that the benzenesulfonate derivative product is obtained. The synthetic method provided by the invention is simple, reaction process is mild and stable, yield is high, and the obtained product is high in purity.
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Paragraph 0020; 0021; 0023
(2018/05/03)
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- Benzenesulfonylation reagent as well as preparation method and application thereof
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The invention discloses a benzenesulfonylation reagent. The structure of the benzenesulfonylation reagent is shown as formula I in the specification, wherein R is a benzene ring connected with 0-5 substituents, and the substituents on the benzene ring are chlorine atoms, fluorine atoms, methyl groups or tert-butyl groups independently. The invention further discloses a preparation method and an application of the benzenesulfonylation reagent. The benzenesulfonylation reagent is prepared from methoxyamine hydrochloride and benzenesulfonyl chloride or a benzenesulfonyl chloride derivative through two steps of reactions, raw materials are cheap, a preparation process is simple, reaction conditions are mild, few side effects are produced, only extraction and simple column chromatographic purification are needed for aftertreatment, and the yield is high. The benzenesulfonylation reagent has higher benzenesulfonylation activity, benzenesulfonylation reaction conditions are mild, a reaction substrate range is wider, compounds such as alcohol, phenol, naphthol, thiophenol and the like can be subjected to a benzenesulfonylation reaction in presence of acetonitrile neutralized potassium carbonate, and -C1 does not exist on the benzenesulfonylation reagent, so that HCl gas with pungent odor cannot be emitted during application.
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- Dimerization of Aryl Sulfonates by in situ Generated Nickel(0)
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A mild and user-friendly nickel-catalyzed method for the reductive homocoupling of aromatic tosylates is presented. The reaction proceeds between room temperature and 60 °C, with stable substrates (ArOTs) easily prepared from inexpensive and commercially available phenols or naphthols. It relies on a catalytic amount (10 mol%) of a robust catalyst (NiBr2bipy) that does not require the preparation of sensitive organometallic intermediates. Yields are good to excellent.
- Maddaluno, Jacques,Durandetti, Muriel
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supporting information
p. 2385 - 2388
(2015/10/19)
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- Kinetic and computational evidence for an intermediate in the hydrolysis of sulfonate esters
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The hydrolytic reactions of sulfonate esters have previously been considered to occur by concerted mechanisms. We now report the observation of a break in a Bronsted correlation for the alkaline hydrolysis of aryl benzenesulfonates. On either side of a break-point, β leaving group values of -0.27 (pKa a > 8.5) are measured. These data are consistent with a two-step mechanism involving a pentavalent intermediate that is also supported by QM/MM calculations. The emerging scenario can be explained by the combined effect of a strong nucleophile with a poor leaving group that compel a usually concerted reaction to favour a stepwise process.
- Babtie, Ann C.,Lima, Marcelo F.,Hollfelder, Florian,Kirby, Anthony J.
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p. 8095 - 8101,7
(2012/12/11)
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- Highly efficient Pd-catalyzed cyanation of aryl chlorides and arenesulfonates with potassium ferrocyanide in aqueous media
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A highly improved Pd-catalyzed cyanation of aryl chlorides to corresponding benzonitriles was demonstrated in aqueous media. Moreover, Pd-catalyzed cyanation of aryl tosylates and benzenesulfonates with K4[Fe(CN) 6] was developed under the similar conditions, which extended application scope of the cyanation. Graphical Abstract: [Figure not available: see fulltext.]
- Zhang, Junli,Chen, Xiaorong,Hu, Tongjie,Zhang, Yuan,Xu, Kunling,Yu, Yanpeng,Huang, Jun
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experimental part
p. 56 - 60
(2011/01/12)
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- A new preparative method of aryl sulfonate esters by using cyclic organobismuth reagents
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A new method for the preparation of aryl sulfonate esters by using a cyclic pentavalent bismuth is described. Aryl sulfonate esters are formed in good to high yields by treating 10-arylphenothiabismine 5,5-dioxides, m-chloroperoxybenzoicacid (m-CPBA)and various sulfonic acids in dichloromethane.
- Sakurai, Naoto,Mukaiyama, Teruaki
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p. 771 - 790
(2008/09/18)
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- Facile N-arylation of amines and sulfonamides and O-arylation of phenols and arenecarboxylic acids
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An efficient, transition-metal-free procedure for the N-arylation of amines, sulfonamides, and carbamates and O-arylation of phenols and carboxylic acids has been achieved by allowing these substrates to react with a variety of o-silylaryl inflates in the presence of CsF. Good to excellent yields of arylated products are obtained under very mild reaction conditions. This chemistry readily tolerates a variety of functional groups.
- Liu, Zhijian,Larock, Richard C.
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p. 3198 - 3209
(2007/10/03)
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- Unprecedented observation of sulfonamides in the transesterification of N-unsubstituted carbamates with sulfonyl chlorides
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Sulfonamides have been identified as by-products in the base-mediated transesterification of N-unsubstituted carbamates with sulfonyl chlorides to give the corresponding sulfonates. A proposed mechanism and the synthesis of hindered 2,6-disubstituted arylsulfonates via this method are also reported.
- Dauvergne, Jér?me,Wellington, Kevin,Chibale, Kelly
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- 'Latent' ultraviolet light absorbers
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We have synthesized and characterized photo-labile and acid-labile esters of 2-hydroxybenzophenone and 2-hydroxybenzotriazoles, which, upon appropriate treatment, release classical UV absorbers. Two concepts of 'latent' UV absorbers are presented, namely,
- Kocher, Christoph,Weder, Christoph,Smith, Paul
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- Competitive Reaction Pathways in the Nucleophilic Substitution Reactions of Aryl Benzenesulfonates with Benzylamines in Acetonitrile
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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
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p. 1277 - 1281
(2007/10/03)
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- Reactivity of sterically hindered aromatic sulfonic acid derivatives: VIII. * General mathematical model for catalytic sulfonylation of phenol
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A general mathematical model is proposed for interpretation and prediction of the reactivity of sterically hindered arenesulfonyl chlorides in the catalytic sulfonylation of phenol. Some specific features of transition states in the catalytic and noncatal
- Rubleva,Maksimenko
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p. 1298 - 1300
(2007/10/03)
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- Bismuth(III) halides: Remarkable doping agents for triflic acid in the catalytic sulfonylation of arenes
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The catalytic activity of triflic acid has been dramatically increased by the addition of a catalytic amount of bismuth(III) chloride. Thus, the catalytic sulfonylation of arenes using the new system BiCl3-triflic acid has been successfully carried out while both components of this catalytic system are poorly active or inactive alone, which suggests a synergy between BiCl3 and triflic acid. Other bismuth halide-triflic acid systems proved to be active.
- Repichet,Le Roux,Dubac
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p. 9233 - 9234
(2007/10/03)
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- Solvolysis of benzenesulfonyl chloride. Base and nucleophilic catalysis mechanisms with tertiary amines
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Competing pathways in the phenolysis and methanolysis of benzenesulfonyl chloride in acetonitrile, catalyzed by tertiary amines, have been distinguished. The rate of the reaction pathway, where nucleophilic catalysis is operative, is strongly sensitive to inductive and steric effects of substituents in the tertiary amine and almost insensitive to the nature of the nucleophile. The rate of the general base catalysis pathway is very sensitive to nucleophilic power of the amine and nucleophile and almost insensitive to steric accessibility of the catalyst. 1996 MAEe Cyrillic signΚ Hayκa/Interperiodica Publishing.
- Bezrodnyi,Kiprya,Skrypnik
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p. 519 - 523
(2007/10/03)
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- Solvent Independent Transition-state Structures. Part III. Sulfonyl Transfer Reactions
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A kinetic spectrophotometric study has been performed on the reactions of p-nitrophenyl benzenesulfonate (PNPBS) with m-chlorophenoxide, p-chlorophenoxide, phenoxide, p-methylphenoxide and p-methoxyphenoxide ions in DMSO-H2O mixtures at 25.0 deg C.Systema
- Tarkka, Richard M.,Park, William K. C.,Liu, Ping,Buncel, Erwin,Hoz, Shmaryahu
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p. 2439 - 2444
(2007/10/02)
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- REACTIVITY OF STERICALLY HINDERED DERIVATIVES OF AROMATIC SULFONIC ACIDS. III. EFFECT OF THE STRUCTURE OF ARENESULFONYL CHLORIDES ON THE KINETICS OF CATALYTIC SULFONYLATION OF PHENOL
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The kinetics of the catalytic sulfonylation of phenol by benzenesulfonyl chlorides XArSO2Cl in benzene in the presence o
- Maksimenko, N. N.,Rubleva, L. I.
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p. 694 - 697
(2007/10/02)
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- Metal ion catalysis in nucleophilic displacement reactions at carbon, phosphorus, and sulfur centers.1 4. Mechanism of the reaction of aryl benzenesulfonates with alkali-metal ethoxides: Catalysis and inhibition by alkali-metal ions
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The rates of the nucleophilic displacement reactions of aryl benzenesulfonates (1a-f) with alkali-metal ethoxides (LiOEt, KOEt, and KOEt in the presence of completing agents) in anhydrous ethanol at 25 °C have been studied by spectrophotometric techniques. For all esters studied, the order of reactivity is LiOEt - +) and inhibition (Li+) are proposed to occur via reactive alkali-metal ethoxide ion pairs. Second-order rate constants for free ethoxide and metal-ethoxide ion pairs are calculated. Hammett treatment of leaving-group effects results in correlation of rate data with σ0 substituent constants and large ρ values of 3.0 (KOEt), 3.1 (LiOEt), and 3.4 (EtO-). A rate-determining transition state having well-advanced EtO-S bond formation but little S-OAr bond breakage is proposed. The similarity of the ρ values for KOEt, LiOEt, and EtO- implies that alkali-metal ions do not significantly alter the extent of S-OAr bond breakage in the transition state. However, metal ions do stabilize the transition state to differing degrees. Equilibrium constants for association of K+ and Li+ with the transition state are calculated, and it is concluded from the relative magnitudes of these values (Li+ +) that solvated metal ions interact with the transition state, rather than bare metal ions. Hammett plots of the free energy of association of metal ions with the transition state indicate that leaving-group substituent effects on metal ion binding in the transition state are small (ρ = -0.39 (K+) and -0.23 (Li+)) and lead to the conclusion that more electron-rich transition states bind metal ions more strongly.
- Pregel, Marko J.,Dunn, Edward J.,Buncel, Erwin
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p. 3545 - 3550
(2007/10/02)
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- CATALYTIC EFFECT OF TRIETHYLAMINE IN THE HYDROLYSIS AND PHENOLYSIS OF BENZENESULFONYL CHLORIDE
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Investigation of the hydrolysis and phenolysis of benzenesulfonyl chloride in dioxane and acetonitrile with triethylamine as catalyst by GLC and potentiometric titration showed that in both cases the reaction is of first order in the sulfonyl chloride and the catalyst and of first order in the phenol.The catalytic effect is more than 106 for phenolysis and 12 for hydrolysis in dioxane and 40.5 for hydrolysis in acetonitrile.
- Skrypnik, Yu. G.,Bezrodnyi, V. P.,Gilenson, M. M.
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p. 697 - 700
(2007/10/02)
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- CATALYTIC SULFONYLATION OF PHENOL BY STERICALLY HINDERED SULFONYL CHLORIDES
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The sulfonylation of phenol by substituted arenesulfonyl chlorides XArSO2Cl in the presence of triethylamine in benzene was studied by potentiometric titration.A linear relation was obtained between the logaritmhs of the catalytic rate constants and the steric constants Eso of the substituents in the sulfonyl chloride.The contribution from the induction and steric effects of the substituents at position2 to the kinetics of the process was assessed.It was concluded that the steric effect plays a predominant role over the induction and resonance effects.
- Vizgert, R.V.,Maksimenko, N.N.,Rubleva, L.I.
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p. 2144 - 2146
(2007/10/02)
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- SULFONYLATION OF PHENOLS IN THE PRESENCE OF PYRIDINE BASES
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The sulfonylation of phenols by aromatic sulfonyl chlorides in the presence of pyridine bases in nitrobenzene was studied by potentiometric titration.A linear dependence was found between the logarithms of the catalytic constants and the ?-Hammett constan
- Viggert, R. V.,Maksimenko, N. N.,Rubleva, L. I.,Derevyanko, S. V.
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p. 1295 - 1298
(2007/10/02)
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- KINETICS OF SULFONYLATION OF SUBSTITUTED PHENOLS IN THE PRESENCE OF TRIETHYLAMINE
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The rate constants for the sulfonation of meta- and para-substituted phenols by benzenesulfonyl chloride in the presence of triethylamine in benzene were determined.The dependence of the rate constants on the Hammett ? constants has a V-shaped form.The effect of the leaving group was investigated, and the kinetic isotope effect was determined.The possibility of reaction by two catalytic paths (nucleophilic and general base catalysis) is discussed, and proposals were made about the reaction mechanism.
- Vizgert, R. V.,Maksimenko, N. N.,Krut'ko, I. N.
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p. 1247 - 1252
(2007/10/02)
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