- Photooxidation of Sulfenic Acid Derivatives. 5. The Reaction of Singlet Oxygen with Ethyl Phenyl Sulfenate
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The reaction of ethyl phenylsulfenate ester with singlet oxygen was investigated.The total rate of disappearance of singlet oxygen induced by the sulfenate ester, kT, was measured by monitoring the quenching of the emission of singlet oxygen at 1270 nm.This result coupled with a measurement of the rate of product formation reveals that ethyl phenylsulfenate ester does not physically quench singlet oxygen.Quantitative trapping studies with Ph2S and Ph2SO suggest that only one intermediate is kinetically required on the reaction surface.This is in dramatic contrast to sulfides and sulfenamides which require two intermediates.The implications of these results are discussed.
- Clennan, Edward L.,Chen, Ming-Fang
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- Direct synthesis of sulfinic esters via ultrasound accelerated tandem reaction of thiols and alcohols with N-bromosuccinimide
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The direct transformation of various thiols and simple alcohols with N-bromosuccinimide into sulfinic esters has been investigated by using different categories of base/acidic catalysts as well as co-solvents under varied reaction conditions. The reaction was found out to afford the sulfinic esters with high yields in the absence of catalysts, especially within the shorter time under the acceleration of ultrasonic irradiation than under the longer-lasting conventional stirring conditions.
- Nguyen, Lan-Anh Thi,Le, Tri-Nghia,Duong, Cong-Thang,Vo, Chi-Tam,Duus, Fritz,Luu, Thi Xuan Thi
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p. 519 - 528
(2021/05/27)
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- NaHSO3-Mediated Direct Synthesis of Sulfinic Esters from Sulfonyl Hydrazides under Transition-Metal-Free Conditions
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We have developed a protocol for the NaHSO3-promoted esterification of sulfonyl hydrazides with alcohols for the synthesis of sulfinic esters. Various sulfonyl hydrazides could be converted to the corresponding sulfinic esters in good to high yields. The merits of this protocol include mild transition-metal-free reaction conditions, an inexpensive and available reagent, and operational simplicity. Controlled experiments reveal that this transformation probably undergoes via a radical pathway. (Figure presented.).
- Zhang, Guofu,Fan, Qiankun,Wang, Huimin,Zhao, Yiyong,Ding, Chengrong
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p. 833 - 837
(2020/12/07)
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- Preparation method of sulfinate compound
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The invention relates to a preparation method of a sulfinate compound shown as a formula (III), which comprises the following steps: by using a sulfonyl hydrazine compound shown as a formula (I) and alcohol shown as a formula (II) as raw materials, adding
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Paragraph 0059-0062
(2021/02/13)
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- Sulfoxide-Promoted Chlorination of Indoles and Electron-Rich Arenes with Chlorine as Nucleophile
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An efficient chlorination of indoles and electron-rich arenes with chlorine anion as nucleophile is described. With the use of ethyl phenyl sulfoxide as the promoter, the reaction went smoothly under metal-free and mild conditions. Various indoles and electron-rich arenes are converted into the corresponding chlorinated compounds in moderate to excellent yields. A plausible interrupted Pummerer reaction mechanism was proposed without the oxidation of chloride anion. In addition, the byproduct thioether could be easily converted to the starting material sulfoxide just by a simple oxidation reaction. (Figure presented.).
- Ji, Yuan-Zhao,Li, Hui-Jing,Wang, Yi-Ruo,Wu, Yan-Chao,Zhang, Zheng-Yan
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supporting information
(2020/02/05)
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- Electrochemical synthesis of sulfinic esters from alcohols and thiophenols
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Electrochemical oxidative couplings between S[sbnd]H and O[sbnd]H bonds are achieved herein directly from readily-available alcohols and thiophenols, affording a series of diverse sulfinic esters. This strategy can take advantage of 6 equivalents of alcohol, relative to thiophenol, to achieve moderate to good yields, without the assistance of any metallic catalysts, bases, and additional oxidants.
- He, Yang,Zhang, Jinli,Xu, Liang,Wei, Yu
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supporting information
(2020/01/31)
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- Metal- And oxidant-free electrochemical synthesis of sulfinic esters from thiols and alcohols
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An efficient and eco-friendly electrochemical synthesis of various sulfinic esters from thiols and alcohols via sequential S-H/S bond cleavage and double S-O bond formation under mild reaction conditions has been developed. Stoichiometric oxidants, metal catalysts, activating agents and even added bases were avoided in this method, and the only by-product generated from this reaction was dihydrogen gas which could serve as a green source of energy. Various functional groups are compatible with this green protocol which can be easily conducted on a gram-scale.
- Ai, Chongren,Shen, Haiwei,Song, Dingguo,Li, Yujin,Yi, Xiao,Wang, Ze,Ling, Fei,Zhong, Weihui
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supporting information
p. 5528 - 5531
(2019/10/22)
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- Sodium Arenesulfinates-Involved Sulfinate Synthesis Revisited: Improved Synthesis and Revised Reaction Mechanism
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Reaction of alcohols with sodium arenesulfinates could afford either sulfones or sulfinates, and O-attack of sulfinate anions onto the in situ generated carbocation intermediates from alcohols was the previous proposed reaction mechanism in many syntheses of sulfinates. This concept, which is often used consciously or unconsciously, was revised herein by using isotopic labeling experiments and development of an improved sulfinate synthesis. The improved sulfinate synthetic protocol possesses many advantages such as a high sulfinate/sulfone selectivity, a broad substrate scope, metal-free, and mild reaction conditions. The revised reaction mechanism necessitates revision of many previous proposed reaction mechanisms in literatures.
- Ji, Yuan-Zhao,Li, Hui-Jing,Zhang, Jin-Yu,Wu, Yan-Chao
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p. 1846 - 1855
(2019/02/14)
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- Catalyst-free sulfenylation of indoles with sulfinic esters in ethanol
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A novel catalyst-free method for the synthesis of structurally diverse indole thioethers in moderate to excellent yields has been developed. In this reaction, sulfinic esters serve as new sulfur electrophiles.
- Yang, Xiuqin,Bao, Yishu,Dai, Zonghao,Zhou, Qingfa,Yang, Fulai
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supporting information
p. 3727 - 3731
(2018/08/21)
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- Copper-Catalyzed Oxidative Reaction of β-Keto Sulfones with Alcohols via C?S Bond Cleavage: Reaction Development and Mechanism Study
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A Cu-catalyzed cascade oxidative radical process of β-keto sulfones with alcohols has been achieved by using oxygen as an oxidant. In this reaction, β-keto sulfones were converted into sulfinate esters under the oxidative conditions via cleavage of C?S bond. Experimental and computational studies demonstrate that a new pathway is involved in this reaction, which proceeds through the formation of the key four-coordinated CuII intermediate, O?O bond homolysis induced C?S bond cleavage and Cu-catalyzed esterification to form the final products. This reaction provides a new strategy to sulfonate esters and enriches the research content of C?S bond cleavage and transformations.
- Du, Bingnan,Wang, Wenmin,Wang, Yang,Qi, Zhenghang,Tian, Jiaqi,Zhou, Jie,Wang, Xiaochen,Han, Jianlin,Ma, Jing,Pan, Yi
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supporting information
p. 404 - 408
(2018/02/21)
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- Non-expensive, open-flask and selective catalytic systems for the synthesis of sulfinate esters and thiosulfonates
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Two simple and efficient methods for the synthesis of sulfinate esters and thiosulfonates from sodium salts of sulfinic acids are described. Different alcohols were converted into the corresponding sulfinate esters in good yields and purity in an open flask. By the adjustment of the reaction conditions thiosulfonates could also be obtained in a very short reaction time.
- Tranquilino, Arisson,Andrade, Silvia R.C.P.,da Silva, Ana Paula M.,Menezes, Paulo H.,Oliveira, Roberta A.
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supporting information
p. 1265 - 1268
(2017/03/10)
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- Direct sulfenylation of imidazoheterocycles with disulfides in an iodine-hydrogen peroxide system
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Imidazoheterocycles undergo efficient and regioselective sulfenylation with disulfides using the iodine/hydrogen peroxide system in ethanol at 25 °C. This green strategy tolerates a wide range of functional groups to afford diverse sulfenylated imidazoheterocycles in high yields. Moreover, the fipronil (a pesticide) skeleton can be readily attached to imidazoheterocycles using this strategy, which is significant in drug development.
- Ji, Xiao-Ming,Zhou, Shu-Juan,Chen, Fan,Zhang, Xing-Guo,Tang, Ri-Yuan
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p. 659 - 671
(2015/05/04)
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- The synthesis of sulfinylphthalimides and their reactions with some nucleophiles in dioxane
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In this study, some N-(p-substituted-arylsulfinyl)phthalimides (1a-1e) were synthesized. The synthesized compounds were examined with respect to their substitution reactions with sodium ethoxide, sodium methoxide, methylamine, and t-butylamine in dioxane.
- Bozkurt, Yasemin Soydas,Kutuk, Halil
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p. 2250 - 2257
(2012/03/27)
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- The first effective procedure for the direct esterification and thiolysis of sulfinic acids
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Alkyl arenesulfinates and S-thiosulfinates are readily accessible in good yields by the reaction of sulfinic acids and alcohols or thiols, respectively, in the presence of lanthanide(III) triflates as catalysts. Georg Thieme Verlag Stuttgart · New York.
- Drabowicz, Jozef,Kwiatkowska, Malgorzata,Kielbasinski, Piotr
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experimental part
p. 3563 - 3564
(2009/06/18)
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- Hammett Correlations in the Photosensitized Oxidation of 4-Substituted Thioanisoles
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Singlet oxygen is quenched by a series of 4-substituted thioanisoles (methoxy to nitro), with rate constant kt = 7 × 104 to 7 × 106 M-1 s-1, close to the value observed for the myoglobin-catalyzed sulfoxidation of the same sulfides. Correlations with σ (ρ = -1.97) and with Eox (slope -3.9 V-1) are evidence for an electrophilic mechanism. In methanol sulfoxides are formed (85%) via an intermediate quenched by diphenyl sulfoxide; competing minor paths lead to arylthiols, arylsulfenic acid, and aryl sulfoxides. In aprotic solvents, the sulfoxidation is quite sluggish, but carboxylic acids (mostly ≤0.1 M) enhance the rate by a factor of > 100. The protonated persulfoxide is formed in this case and acts as an electrophile with sulfides, again with a rate constant correlating with σ (ρ = -1.78).
- Bonesi, Sergio M.,Fagnoni, Maurizio,Albini, Angelo
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p. 928 - 935
(2007/10/03)
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- A new reaction of 2-(phenylsulfonyl)-3-phenyloxaziridine (davis reagent): Oxidation of thiolates to sulfinates. Application to the synthesis of sulfones
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(Matrix Presented) The first efficient and general method for the generation of sulfinate anions by oxidation of the corresponding thiolates is described. The oxidizing agent employed is the classical 2-(phenylsulfonyl)-3-phenyloxaziridine, commonly known as the Davis reagent. Subsequent S-alkylation of the sulfinates under phase-transfer catalysis affords sulfones 6 in 71-91% isolated yields (10 examples).
- Sandrinelli, Franck,Perrio, Stephane,Beslin, Pierre
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p. 1177 - 1180
(2008/02/09)
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- Hypervalent iodine in synthesis. XXIV: A facile method for the preparation of arylsulfinic esters: Oxidation of disulfides or thiophenols by phenyliodine(III) bis(trifluoroacetate) in the presence of alcohols
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Arylsulfinic esters were prepared by the oxidation of diaryl disulfides or thiophenols with phenyliodine(III) bis(trifluoroacetate) in the presence of alcohols.
- Xia,Chen
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p. 1321 - 1326
(2007/10/03)
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- Reactions of benzyl aryl sulfides with excess active halogen reagents
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1,2,3-Tribromopyrrolo[1,2-b][1,2]benzothiazin-10-one (2) is produced from 2-[2-(benzylthio)benzoyl]-pyrrole (1) when treated with excess (5 equiv) NBS in CHCl3. With NCS, a mixture is obtained in which di- and trichloropyrrolo[1,2-b][1,2]benzothiazin-10-ones are present. If ethanol is present in the NCS reaction, compound 4 is formed as the major product. Further, compound 3 is also formed by the reaction of compound 1 or the corresponding disulfide with excess SOCl2. A novel route to alkyl arenesulfinic esters is also reported. Treatment of a benzyl aryl sulfide with excess (5 equiv) NCS in the presence of an n-alkyl alcohol (7 equiv) produces an n-alkyl arenesulfinic ester in good yield. An arenesulfonyl chloride is the major product in the presence of benzyl alcohol.
- Xia, Mingde,Chen, Shaowu,Bates, Dallas K.
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p. 9289 - 9292
(2007/10/03)
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- Sulfinate esters from methoxymethyl sulfides
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Several benzene (or phenylmethane) sulfinate esters were synthesized in 53-98% yields from the corresponding methoxymethyl (MOM) sulfides employing NBS as oxidant.
- Ko,Koo,Kim,Kim
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p. 2871 - 2876
(2007/10/02)
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- NMR of Terminal Oxygen, 6 - 17O NMR of the S-O 'Double Bond': Derivatives of Arylsulphinic and Arylsulphonic Acids
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The 17O NMR spectra of terminal oxygen atoms in esters, anions and amides of substituted arenesulphinic acids and in esters and amides of substituted arenesulphonic acids were measured.The signals of the terminal O appear close to those of the bridge O.Co
- Dahn, Hans,Toan, Vien Van,Ung-Truong, My-Ngoc
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p. 897 - 903
(2007/10/02)
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- ORGANOSULPHUR COMPOUNDS XLVII ALKYLATION OF SULPHINIC ACIDS BY O-ALKYLISOUREAS: O-VERSUS S-REACTIVITY AND ASYMMETRIC SYNTHESIS OF ALKYL SULPHINATES
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The reaction of O-alkylisoureas with sulphinic acids was found to produce the corresponding sulphones and sulphinates, the latter being predominantly formed.The sulphinate to sulphone ratio is strongly influenced by the kind of alkyl groups in the O-alkylisourea and appeared to be also dependent on the solvent used.A few optically active sulphinates (e.e. up to 8.1percent) were prepared in the reaction between benzenesulphinic acid and a series of O-alkylisoureas bearing optically active substituents at the nitrogen atom.A possible reaction mechanism is discussed.
- Kielbasinski, Piotr,Zurawinski, Remigiusz,Drabowitz, Jozef,Mikolajczyk, Marian
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p. 6687 - 6692
(2007/10/02)
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- N-BROMOSUCCINIMIDE-CATALYSED TRANSESTERIFICATION AND RACEMIZATION OF SULPHINATES
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Both aliphatic and aromatic sulphonates undergo transesterification reaction in the presence of N-bromosuccinimide.Isopropanolysis of optically active alkyl arenesulphinates was found to give racemic isopropyl p-toluenesulphinates.The rate of racemization of optically active isopropyl p-toluenesulphinate was found to be first order with respect of both N-bromosuccinimide and isopropyl alcohol, suggesting that the reaction is a bimolecular nucleophilic substitution at the sulfur atom.The para electrodonating substituents in the aromatic ring accelerate slightly the rate of racemization.At the same time the rate of racemization was found to be retarded by the increase of steric requirements of the substituent at the sulphinyl sulphur atom suggesting that the initial formation of bromoxonium salt is the rate-determining step.Completely nonstereospecific isopropanolysis of optically active alkyl p-toluenesulphinates suggests that a sulphurane is formed as an intermediate in the exchange step of the reaction.
- Drabowicz, Jozef
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p. 123 - 132
(2007/10/02)
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- The reactions of some α-halo-β-ketosulfones with hard and soft nucleophiles. A preparation of sulfinate esters
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The α-halo-β-ketosulfonyl functionality was attacked by ethanethiolate at the halogen which, in the presence of a proton source, usually resulted in reduction to the β-ketosulfone.A range of other soft nucleophiles did not react, whereas hard nucleophiles invariably attacked at the carbonyl, with subsequent cleavage to α-halosulfones.Ambident arylsulfinate anions usually attacked at halogen to form the sulfonyl halide, which reacted with excess sulfinate to give an intermediate that is readily attacked by alcohols.This reaction resulted in the formation of alkyl arylsulfinate esters in reasonable yields.The same reaction occurred when sulfonyl chlorides were reacted with sulfinate salts and it was rationalized by using HSAB principles.Spectral properties of some sulfinate esters are presented.
- Grossert, J. Stuart,Dubey, Pramod K.,Elwood, Tom
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p. 1263 - 1267
(2007/10/02)
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- The Mechanism of the Reactions of Alkoxy- and Aryloxytrimethylsilanes with Sulfinyl Chlorides. A Doubt about 4-Center Mechanism for the Bimolecula IVb-VIb Bond Cleavages
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Kinetic studies have been conducted for the reactions of ethoxytrimethylsilane with benzenesulfinyl chloride and aryloxytrimethylsilane with methanesulfinyl chloride.Both the reactions were found to obey second order rate equation.A clear negative ρ value was observed for the reaction of aryloxytrimethylsilane.The solvent effects suggested that both the two reactions were quite similar in their mechanisms.Nucleophilic addition of silyl-oxygen atom to sulfinyl group has been suggested for these two reactions.
- Kozuka, Seizi,Higashino, Tetsuji
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p. 1183 - 1185
(2007/10/02)
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- A CONVENIENT PREPARATION OF SULPHINIC ESTERS FROM SULPHINYL CHLORIDES AND CHLOROSULPHITES USING HEXAMETHYLDISILOXANE AS CHLORIDE ANION ACCEPTOR
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Sulphinic esters can be obtained in high yields by the reaction of sulphinyl chlorides with chlorosulphites in the presence of hexamethyldisiloxane and catalytic amount of dimethyl sulphoxide.
- Drabowicz, Jozef
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p. 1753 - 1754
(2007/10/02)
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- Selective Oxidation of Unsymmetrical Thiosulfinic S-Esters to the Corresponding Thiosulfonic S-Esters with NaIO4
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Unsymmetrical thiosulfinic S-esters were oxidized with sodium metaperiodate in aqueous media to the corresponding unsymmetrical thiosulfonic S-esters nearly quantitatively.The oxidation was accelerated by addition of a catalytic amount of inorganic and organic acids or halogen.Sulfinic esters were produced competitively along with the thiosulfonic S-esters in the oxidation of thiosulfinic S-esters in aqueous alcohol.However, unsymmetrical disulfides were not oxidized selectively to the corresponding unsymmetrical thiosufonic S-esters but a mixture of the both symmetrical and unsymmetrical thiosulfonic S-esters was obtained.
- Takata, Toshikazu,Kim, Yong Hae,Oae, Shigeru
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p. 1443 - 1447
(2007/10/02)
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- MODE OF OXIDATIONS OF ORGANOSULFUR COMPOUNDS: EXAMPLE OF NUCLEOPHILIC OXYGENATIONS OF THIOLSULFINATES
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Two types of oxygenative oxidations ( Nucleophilic and Electrophilic Oxidations) of sulfur atom are proposed and a typical mode of nucleophilic oxidation is shown with a few unsymmetrical thiolsulfinates.
- Oae, Shigeru,Takata, Toshikazu
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p. 3213 - 3216
(2007/10/02)
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