cas 20277-69-4, Sodium methanesulphinate | Articles data

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Direct α-Acylation of Alkenes via N-Heterocyclic Carbene, Sulfinate, and Photoredox Cooperative Triple Catalysis
N-Heterocyclic carbene (NHC) catalysis has emerged as a versatile tool in modern synthetic chemistry. Further increasing the complexity, several processes have been introduced that proceed via dual catalysis, where the NHC organocatalyst operates in concert with a second catalytic moiety, significantly enlarging the reaction scope. In biological transformations, multiple catalysis is generally used to access complex natural products. Guided by that strategy, triple catalysis has been studied recently, where three different catalytic modes are merged in a single process. In this Communication, direct α-C-H acylation of various alkenes with aroyl fluorides using NHC, sulfinate, and photoredox cooperative triple catalysis is reported. The method allows the preparation of α-substituted vinyl ketones in moderate to high yields with excellent functional group tolerance. Mechanistic studies reveal that these cascades proceed through a sequential radical addition/coupling/elimination process. In contrast to known triple catalysis processes that operate via two sets of interwoven catalysis cycles, in the introduced process, all three cycles are interwoven.
Liu, Kun,Studer, Armido
supporting information
p. 4903 - 4909
(2021/05/04)

Visible-Light-Driven Sulfonation of α-Trifluoromethylstyrenes: Access to Densely Functionalized CF3-Substituted Tertiary Alcohol
Reported herein is a visible-light-induced sulfonation of α-trifluoromethylstyrenes with sodium sulfinates, which provides a series of α-trifluoromethyl-β-sulfonyl tertiary alcohols. This new synthetic protocol is enabled by a charge-transfer complex between oxygen and sulfinates, featuring broad substrate scope and scalability. Excellent functional group compatibility and chemoselectivity render this method suitable for sulfonation of pharmaceutically relevant molecules. In the presence of D2O, deuteriotrifluorinated products were also obtained, further demonstrating the flexibility and synthetic potentials of this strategy.
Chen, Yi-Xuan,Wang, Zhu-Jun,Xiao, Jun-An,Chen, Kai,Xiang, Hao-Yue,Yang, Hua
supporting information
p. 6558 - 6562
(2021/08/23)

Preparation method of substituted sulfinate
The invention discloses a preparation method of substituted sulfinate, which comprises the following steps: by using substituted sulfonyl chloride as a raw material, carrying out hydrolysis reductionreaction on the substituted sulfonyl chloride in water in the presence of a reducing agent and an acid-binding agent to generate the corresponding substituted sulfinate. The method is a novel method which is easy to implement and suitable for industrial scale production and is used for preparing sulfinate and derivatives thereof. The method is simple in technological process, high in product purity and safe and environment-friendly, wherein the waste gas, solid and liquid are easy to treat.
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Paragraph 0023-0029

(2020/12/30)

Synthesis of β-ketosulfone derivatives as new non-cytotoxic urease inhibitors in vitro
Background: Peptic ulcer and urolithiasis are largely due to infection caused by urease-producing bacteria. Therefore, the discovery of urease inhibitors is an important area of medicinal chemistry research. Objective: The main aim of the work was to identify novel urease inhibitors with no cytotoxicity. Method: During the current study, a series of β-ketosulfones 1-26 was synthesized in two steps and evaluated for their in vitro urease inhibition potential. Results: Out of twenty-six compounds, seventeen have shown good to significant urease inhibitory activity with IC50 values ranging between 49.93-351.46 μM, in comparison to standard thiourea (IC50 = 21 ± 0.11 μM). Moreover, all compounds found to be non-cytotoxic against normal 3T3 cell line. Conclusion: This study has identified β-ketosulfones as novel and non-cytotoxic urease inhibitors.
Iqbal Choudhary, M.,Iqbal, Sarosh,Khan, Ajmal,Khan, Khalid Mohammed,Kiran, Shumaila,Nazir, Rashid,Perveen, Shahnaz
p. 244 - 255
(2020/03/10)

Metal-Free Chemoselective Reaction of Sulfoxonium Ylides and Thiosulfonates: Diverse Synthesis of 1,4-Diketones, Aryl Sulfursulfoxonium Ylides, and β-Keto Thiosulfones Derivatives
A diverse chemoselective insertion reaction of sulfoxonium ylides and thiosulfonates under transition-metal-free conditions is developed, which successfully affords 1,4-diketone compounds, arylthiosulfoxide-ylides, and β-keto thiosulfones, respectively. The nucleophilic addition of two molecular sulfoxonium ylides to construct sulfone-substituted 1,4-dione compounds is the highlight of this work.
Wang, Fei,Liu, Bo-Xi,Rao, Weidong,Wang, Shun-Yi
supporting information
p. 6600 - 6604
(2020/09/02)

Direct sulfonylation of BODIPY dyes with sodium sulfinates through oxidative radical hydrogen substitution at the α-position
An efficient and convenient protocol for the direct sulfonylation of BODIPY dyes with sodium sulfinates via a radical process is described for the first time. This transformation presented wide substrate scope and high regioselectivity, providing a series of α-sulfonylated BODIPYs. Meaningfully, the sulfonyl group, as a good leaving group, allowed the facile introduction of a variety of functionalities on the BODIPY core. Moreover, a 2,4-dinitrobenzenesulfonyl (DBS) group substituted BODIPY showed dramatically quenched fluorescence via the photoinduced electron transfer (PET) pathway, and was demonstrated as a new fluorescent probe for selective biothiol detection. This journal is
Lv, Fan,Guo, Xing,Wu, Hao,Li, Heng,Tang, Bing,Yu, Changjiang,Hao, Erhong,Jiao, Lijuan
supporting information
p. 15577 - 15580
(2020/12/30)

Switching of Sulfonylation Selectivity by Nature of Solvent and Temperature: The Reaction of β-Dicarbonyl Compounds with Sodium Sulfinates under the Action of Iron-Based Oxidants
Selectivity of sulfonylation of β-keto esters with sodium sulfinates under the action of iron(III) salts as oxidants can be regulated by the type of solvent used and the reaction temperature. α-Sulfonyl β-keto esters are obtained when the process is conducted in THF/H2O solution at 40 °C. The change of the solvent to iPrOH/H2O and refluxing of a reaction mixture provides α-sulfonyl esters – the products of successive sulfonylation-deacylation. When β-diketones are applied as starting materials, only α-sulfonyl ketones are formed. The reaction pathway includes sulfonylation of dicabonyl compounds under the action of Fe(III) to form α-sulfonylated dicarbonyl compounds, which are then attacked by a solvent as the nucleophile, resulting in the products of successive sulfonylation-deacylation. Participation of the solvent in the reaction pathway determines the products structure.
Mulina, Olga M.,Pirgach, Dmitry A.,Nikishin, Gennady I.,Terent'ev, Alexander O.
supporting information
p. 4179 - 4188
(2019/05/08)

A Convenient Synthesis of Sulfones via Light Promoted Coupling of Sodium Sulfinates and Aryl Halides
A convenient and e?cient synthesis of sulfones from sulfinates and aryl halides was developed. The reaction occurred under UV irradiation without transition metal catalyst or photocatalyst. A radical pathway via single-electron transfer (SET) of electron donor-acceptor (EDA) complex was proposed based on UV-vis spectroscopy, radical inhibiting and trapping experiments. (Figure presented.).
Chen, Lei,Liang, Jie,Chen, Zhen-yu,Chen, Jie,Yan, Ming,Zhang, Xue-jing
supporting information
p. 956 - 960
(2019/01/25)

Copper-catalyzed redox coupling of nitroarenes with sodium sulfinates
A simple copper-catalyzed redox coupling of sodium sulfinates and nitroarenes is described. In this process, abundant and stable nitroarenes serve as both the nitrogen sources and oxidants, and sodium sulfinates act as both reactants and reductants. A variety of aromatic sulfonamides were obtained in moderate to good yields with broad substrate scope. No external additive is employed for this kind of transformation.
Liu, Saiwen,Chen, Ru,Zhang, Jin
(2019/05/02)

α-Diazo-β-oxosulfones as Partners in the Wolff 1,2,3-Triazole Synthesis and the Wolff Rearrangement in the Presence of Aromatic Amines
The readily available α-diazo-β-oxosulfones have been employed, for the first time, in the Wolff cyclocondensation with aromatic amines promoted by 1.5-fold excess of TiCl4. The reaction was found to be general (as illustrated by 15 product examples) and resulted in moderate yields of medicinally relevant sulfonyl 1,2,3-triazoles. Excluding the Lewis acid promoter resulted in a clean and high-yielding formation of α-sulfonyl acetanilides resulting from the thermal Wolff rearrangement and trapping of the ketene intermediate with an aniline molecule.
Safrygin, Alexander,Dar'in, Dmitry,Kantin, Grigory,Krasavin, Mikhail
supporting information
p. 4721 - 4724
(2019/08/01)

Switchable regioselection of C-H thiolation of indoles using different TMS counterions
A switchable regioselectivity in C-H thiolation reaction by simply swapping the counteranions of TMS is reported here for the first time. An exclusive C3-H thiolation of indoles with sodium arylsulfinates was achieved in the presence of TMSCl as a promoter. In contrast, with the use of TMSOTf instead of TMSCl under otherwise identical conditions, a regiospecific C2-H thiolation of indoles was realized with the same set of substrates.
Ji, Yuan-Zhao,Li, Hui-Jing,Zhang, Jin-Yu,Wu, Yan-Chao
p. 11864 - 11867
(2019/10/11)

Regio- and Enantioselective Preparation of Chiral Allylic Sulfones Featuring Elusive Quaternary Stereocenters
We describe here the first general asymmetric synthesis of sterically encumbered α,α-disubstituted allylic sulfones via Pd-catalyzed allylic substitution. The design and application of a new and highly efficient phosphoramidite ligand (L10) proved to be crucial, and a wide variety of challenging allylic sulfones featuring quaternary stereocenters could be obtained in good yields and with good to excellent levels of regio- and enantioselectivities under attractive process conditions. The developed methodology employs easily accessible chemical feedstock including racemic allylic precursors and sodium sulfinates. The utility of the method is further demonstrated by the synthesis of the sesquiterpene (?)-Agelasidine A.
Cai, Aijie,Kleij, Arjan W.
supporting information
p. 14944 - 14949
(2019/11/05)

Methanesulfonyl Iodide
Methanesulfonyl iodide is produced in aqueous solutions from the reaction of triiodide with methanesulfinate. Dichroic crystals of (CH3SO2I)4·KI3·2I2 are formed from KI/I2 solutions with high concentrations of CH3SO2-, while dichroic crystals of (CH3SO2I)2·RbI3 are formed from RbI/I2 solutions. X-ray crystallography of these two compounds shows that the CH3SO2I molecules coordinate through their oxygen atoms to the metal cations and that the S-I bond length is 2.44 ?. At low concentrations of CH3SO2-, the solutions remain homogeneous and the sulfonyl iodide is formed in a rapid equilibrium: CH3SO2- + I3- ? CH3SO2I + 2I-, KMSI = 1.07 ± 0.01 M at 25 °C (μ = 0.1 M, NaClO4). The sulfonyl iodide solutions display an absorbance maximum at 309 nm with a molar absorptivity of 667 M-1 cm-1. Stopped-flow studies reveal that the equilibrium is established within the dead time of the instrument (～2 ms). Solutions of CH3SO2I decompose slowly to form the sulfonate: CH3SO2I + H2O → CH3SO3- + I- + 2H+, khyd. In dilute phosphate buffer, this decomposition occurs with khyd = 2.0 × 10-4 s-1 the decomposition rate shows an inverse-squared dependence on [I-] because of the KMSI equilibrium.
Rajakaruna, Pradeepa,Gorden, John D.,Stanbury, David M.
supporting information
p. 14752 - 14759
(2019/11/11)

Direct Substitution of Secondary and Tertiary Alcohols to Generate Sulfones under Catalyst- and Additive-Free Conditions
An environmentally benign protocol that affords propargylic sulfones containing highly congested carbon centers from easily accessible alcohols and sulfinic acids with water as the only byproduct is reported. The reaction proceeded via an in situ dehydrative cross-coupling process by taking advantage of the synergetic actions of multiple hydrogen bonds rather than relying on an external catalyst and/or additives to achieve high product distribution.
Liu, Yanan,Xie, Peizhong,Sun, Zuolian,Wo, Xiangyang,Gao, Cuiqing,Fu, Weishan,Loh, Teck-Peng
supporting information
p. 5353 - 5356
(2018/09/13)

Design, synthesis and biological evaluation of novel 2-sulfonylindoles as potential anti-inflammatory therapeutic agents for treatment of acute lung injury
Acute lung injury (ALI) is primarily driven by inflammation that severely impacts lung function. Novel 2-sulfonylindoles were recently shown to exhibit anti-inflammatory activity through the inhibition of tumor necrosis factor-α (TNF-α) and interleukin-6 (IL-6) production. Here, we synthesized 31 compounds which contained 2-sulfonylindole structure. The compounds 8a, 9g, 9h and 9k exhibited dose-dependent anti-inflammatory activity in vitro. Structural-activity relationship analysis revealed that the introduction of sulfonyl group in indole nucleus may be successful to obtain new anti-inflammatory structures and leads. The compounds 9h and 9k also decreased liposaccharide (LPS)-induced IL-6, IL-1β and vascular cell adhesion molecule-1 (VCAM-1) mRNA expression, both in vitro and in an in vivo model of ALI. Furthermore, the compounds 9h and 9k at a high dose (20 mg/kg) significantly protected against LPS-induced ALI in mice. These results show that compounds 9h and 9k could be a promising lead structure for the treatment of ALI.
Xia, Qinqin,Bao, Xiaodong,Sun, Chuchu,Wu, Di,Rong, Xiaona,Liu, Zhiguo,Gu, Yugui,Zhou, Jianmin,Liang, Guang
p. 120 - 132
(2018/10/21)

Copper-mediated oxysulfonylation of alkenyl oximes with sodium sulfinates: a facile synthesis of isoxazolines featuring a sulfone substituent
A novel and efficient Cu(OAc)2-mediated oxysulfonylation of alkenyl oximes with sodium sulfonates was developed. The reactions are easy to conduct, occur under mild conditions, and form a broad range of sulfone-substituted isoxazolines in good yields.
Wang, Li-Jing,Chen, Manman,Qi, Lin,Xu, Zhidong,Li, Wei
supporting information
p. 2056 - 2059
(2017/02/15)

Iodine/TBHP-Promoted One-Pot Deoxygenation and Direct 2-Sulfonylation of Quinoline N-Oxides with Sodium Sulfinates: Facile and Regioselective Synthesis of 2-Sulfonylquinolines
A highly efficient iodine/TBHP-mediated one-pot deoxygenative and regioselective 2-sulfonylation of quinoline N-oxides with sodium sulfinate salts has been developed. This metal-, base-, and phosphorus-free protocol employs readily accessible and easy-to-handle reagents and can be conveniently carried out at room temperature under mild conditions, providing an alternative access to a series of 2-sulfonylquinolines and other related heteroaryl sulfone products in moderate-to-excellent yields within a short reaction time.
Sumunnee, Ladawan,Buathongjan, Chonchanok,Pimpasri, Chaleena,Yotphan, Sirilata
supporting information
p. 1025 - 1032
(2017/02/15)

Regioselectivity of the thermal van Alphen–Hüttel rearrangement of 4- and 5-mono- and 4,5-disubstituted 3,3-diphenyl-3H-pyrazoles
Thermal van Alphen–Hüttel rearrangement of methyl 3,3-diphenyl-3H-pyrazole-4-carboxylate, 3,3-diphenyl-3H-pyrazole-4-carbonitrile, and methyl 5-methyl-3,3-diphenyl-3H-pyrazole-4-carboxylate involves completely regioselective migration of one phenyl group from the 3-position to N2with formation of aromatic 1H-pyrazole system. Thermal rearrangement of methyl 3,3-diphenyl-3H-pyrazole-5-carboxylate leads to the formation of methyl 4,5-diphenyl-1H-pyrazole-3-carboxylate as a result of migration of the 3-phenyl group exclusively to the C4atom and subsequent prototropic isomerization. Under analogous conditions, methyl 4-methyl-3,3-diphenyl-3H-pyrazole-5-carboxylate, methyl 5-(methanesulfonyl)-3,3-diphenyl-3H-pyrazole-4-carboxylate, methyl 5-(benzenesulfonyl)-3,3-diphenyl-3H-pyrazole-4-carboxylate, and dimethyl 3,3-diphenyl-3H-pyrazole-4,5-dicarboxylate have been regioselectively converted into the corresponding 4H-pyrazoles. Thermolysis of 5-(4-methylbenzenesulfonyl)-3,3-diphenyl-3H-pyrazole-4-carbonitrile gives rise to a mixture of 1H- and 4H-pyrazoles, the former considerably prevailing, whereas the corresponding 1H-pyrazoles are formed as the only product from 5-(methanesulfonyl)- and 5-(benzenesulfonyl)-3,3-diphenyl-3H-pyrazole-4-carbonitriles.
Vasin,Razin,Bezrukova,Petrov
p. 862 - 872
(2016/07/30)

Cu-Catalyzed Deoxygenative C2-Sulfonylation Reaction of Quinoline N-Oxides with Sodium Sulfinate
An unexpected Cu-catalyzed deoxygenative C2-sulfonylation reaction of quinoline N-oxides in the presence of radical initiator K2S2O8 was developed that used sodium sulfinate as a sulfonyl coupling partner. The mechanism studies indicate that the reaction proceeds via Minisci-like radical coupling step to give sulfonylated quinoline with good chemical yields.
Du, Bingnan,Qian, Ping,Wang, Yang,Mei, Haibo,Han, Jianlin,Pan, Yi
supporting information
p. 4144 - 4147
(2016/08/30)

Synthesis and promising in Vitro antiproliferative activity of sulfones of a 5-nitrothiazole series
The synthesis in water of new sulfone derivatives under microwave irradiation is described. This eco-friendly process leads to the expected products in good yields by reaction of various substituted sulfinates (commercially available or obtained by reduction of the corresponding sulfonyl chlorides) with 4-chloromethyl-2-methyl-5-nitro-1,3- thiazole. In order to evaluate the antiproliferative effect of these compounds, several sulfone derivatives are also dichlorinated on the Ca next to the sulfonyl group. An evaluation on different cancer cell lines reveals promising selective in vitro antiproliferative activity toward HepG2 human cell lines by dihydrogenated sulfones, suggesting further research should be to explore their anticancer potential in the treatment of liver cancer.
Cohen, Anita,Crozet, Maxime D.,Rathelot, Pascal,Azas, Nadine,Vanelle, Patrice
p. 97 - 113
(2013/04/10)

METHOD FOR PRODUCING PYRIDAZINONE COMPOUNDS AND INTERMEDIATE THEREOF
The present invention relates to a novel method for producing a pyridazinone compound and an intermediate thereof as shown in the following scheme: wherein the symbols are as defined in the specification.
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(2012/03/27)

Process for the preparation of sulfinates poor in extraneous salts
A method for the production of sulfinates (I) with a low content of extraneous salt involves the reduction of dithionite salts (II) of alkali metals, alkaline earth metals or ammonium with carbonyl compounds or imines (III) at a pH of more than 6, preferably 8-13, especially 9-11.
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(2008/06/13)

Design and synthesis of aminopropyl tetrahydroindole-based indolin-2-ones as selective and potent inhibitors of Src and Yes tyrosine kinase
A novel series of substituted 3-[3-(aminopropyl)-4,5,6,7-tetrahydro-1H- indol-2-ylmethylene]-1,3-dihydro-indole-2-ones was discovered as potent inhibitors of the non-receptor tyrosine kinase Src and Yes. A structure-activity relationship was developed in order to optimize their potency and selectivity. Syntheses of these compounds are also described herein.
Guan, Huiping,Laird, A. Douglas,Blake, Robert A.,Tang, Cho,Liang, Chris
p. 187 - 190
(2007/10/03)

Synthesis, enantiomeric conformations, and stereodynamics of aromatic ortho-substituted disulfones
Aromatic ortho-disulfone derivatives are readily accessible from diiodide precursors by CuI-mediated reaction with sodium sulfinate salts (DMF, 110°). The sulfonyl substituents adopt in solution and in the solid state two enantiomeric conformations (λ and δ) as evidenced by 31P- and IH-NMR data of the chiral D3-symmetric tris{4,5-bis[(4-methylphenyl)sulfonyl]benzene-1,2-diolato(2-)- κO,κO′}phosphate(v) anion (3a) and 1,2-bis(camphor-10-sulfonyl)-4,5-dimethoxybenzene((=1, 2-bis{{[(1S,4R)-7,7-dimethyl-2-oxobicyclo[2.2.1]- hept-1-y1]methyl}sulfonyl}-4,5-dimethoxybenzene; 6c). X-Ray structure analysis of 1,2-dimethoxy-4,5-bis(methylsulfonyl)benzene (6a) and 1,2-dimethoxy-4,5-bis(4-methylphenyl)sulfonyl]benzene (6b) confirmed in the solid state the preferred chiral orientation of the sulfonyl groups. Dynamic conformational isomerism was detected for 6c in its IH-NMR in the temperature range of 110°, the corresponding free energy being 19.8 kcal mol-1.
Lacour, Jerome,Monchaud, David,Mareda, Jiri,Favarger, France,Bernardinelli, Gerald
p. 65 - 81
(2007/10/03)

Studies on the metabolic activation of disulfiram in rat. Evidence for electrophilic S-oxygenated metabolites as inhibitors of aldehyde dehydrogenase and precursors of urinary N-acetylcysteine conjugates
Recent studies on the mechanism by which disulfiram inhibits aldehyde dehydrogenase have provided evidence for the formation of reactive intermediates that are thought to carbamoylate, and thereby inactivate the enzyme. In our study, rats were dosed with either disulfiram (0.25 mmol kg- 1 i.p.) or its reduced metabolite diethyldithiocarbamate (DDTC; 0.5 mmol kg-1 i.p.) and urine was collected for the analysis of metabolites derived from putative reactive intermediates. By means of ionspray LC-MS/MS, two novel N-acetylcysteine (NAC) conjugates, i.e., N-acetyl-S-(N, N- diethylcarbamoyl)cysteine and N-acetyl-S-(N, N- diethylthiocarbamoyl)cysteine, were identified in urine specimens. Quantitative analyses indicated that, over the 0- to 24-hr period after drug administration, urinary excretion of N-acetyl-S-(N, N- diethylcarbamoyl)cysteine accounted for 7.5 ± 4.0 and 6.2 ± 1.0%, respectively, of the dose of disulfiram and diethyidithiocarbamate, while the corresponding thiocarbamoyl conjugate, N-acetyl-S-(N, N- diethylthiocarbamoyl)cysteine, accounted for a further 0.5 ± 0.3 and 0.3 ± 0.1%, respectively, of the dose. These conjugates are believed to derive from reactive sulfoxide and sulfone metabolites of disulfiram, namely S-methyl-N, N-diethylthiocarbamate sulfoxide (DETC-MeSO), S-methyl-N, N- diethyithiocarbamate sulfone (DETC-MeSO2), S-methyl-N, N- diethyldithiocarbamate sulfoxide (DDTC-MeSO) and S-methyl-N, N- diethyldithiocarbamate sulfone (DDTC-MeSO2), which were found to carbamoylate N-acetylcysteine in vitro with the following rank order of reactivity: DDTC-MeSO2 > DETC-MeSO2 > DDTC-MeSO > DETC-MeSO. In vitro experiments with aldehyde dehydrogenase showed that all four S-oxygenated metabolites inhibited the enzyme effectively. Furthermore, inclusion of NAC in incubation media attenuated significantly the inhibition by DDTC-MeSO2, DETC-MeSO2 and DDTC-MeSO, but had little effect on that by DETC-MeSO. Our results are consistent with the hypothesis that disulfiram and diethyldithiocarbamate undergo activation by a sequence of metabolic reactions leading to the formation of electrophilic S-methyl sulfoxides and sulfones that carbamoylate, and thereby inhibit, aldehyde dehydrogenase and possibly other enzymes.
Hu, Pei,Jin, Lixia,Baillie, Thomas A.
p. 611 - 617
(2007/10/03)

Hydrolysis of Di- and Trimesylhydroxylamines and their Methylated Derivatives
The mesylhydroxylamines (CH3SO2)2NOH, (CH3SO2)2NOCH3, CH3SO2N(H)OSO2CH3, CH3SO2N(CH3)OSO2CH3 (1-4) and (CH3SO2)2NOSO2CH3 (5) were treated with basic, neutral, and acidic aqueous solutions.The reaction products were identified.Possible decomposition mechanisms were discussed.
Brink, Klaus,Mattes, Rainer
p. 351 - 354
(2007/10/02)

A CONVENIENT AND GENERAL SYNTHESIS OF ALKANE SULFINIC ACIDS
2-(Alkylsulfonyl)benzothiazoles are reduced with sodium tetrahydroborate to give alkane sulfinic acids in good yield.
Ueno, Yoshio,Kojima, Akihiko,Okawara, Makoto
p. 2125 - 2128
(2007/10/02)

Substitution Reactions of Alkanesulfonyl Derivatives: Direct Substitution vs. Elimination-Addition Mechanisms in Substitution Reactions of Alkyl α-Disulfones
The reactions of a series of alkyl and aralkyl α-sulfones, RSO2SO2R ( R = Me, n-Bu, i-Pr, ArCH2) with a variety of nucleophiles in aqueous dioxane have been examined.Both rates of reaction and whether a given reaction takes place by an elimination-addition (sulfene intermediate) or a direct substitution (attack of nucleophile on SO2 group of α-sulphone) mechanism have been determined.The great majority of substitution reactions of alkyl α-disulfones take place via an elimination-addition mechanism (eq 3a), with formation of a sulphene from the α-disulphone being rate determining.Only when nucleophile is one, like azide ion, that is weakly basic while still being a good nucleophile is a direct substitution the preferred pathway.Even with azide the reaction pathway changes to elimination-addition when the acidity of the hydrogens on the carbon adjacent to the sulfonyl group is increased sufficiently, as in (PhCH2SO2)2.Comparison of rates of elimination of α-disulphones (R'CH2SO2)2 with rates of base-catalyzed hydrogen exchange of the corresponding trifluoromethyl sulfones R'CH2SO2CF3 indicates that formation of sulfenes from α-disulfones involves either an irreversible E1cB or a very E1cB-like E2 mechanism, a conclusion that is also supported by the observed variation of the rate of elimination of RR'CHSO2SO2R'' with changes in R and R'.Comparison of the behavior of an alkyl α-disulfone with that of the corresponding alkanesulfonyl chloride reveals that changing Y in RCH2SO2Y from RSO2 to Cl causes direct substitution to be able to compete much more effectively with elimination-addition.Kinetic studies show that this arises because, for a given nucleophile, (a) elimination-addition is 5-10 times slower for the alkanesulfonyl chloride than for the α-disulfone while (b) the rate of direct substitution is 5-10 times faster for the sulfonyl chloride.The origin of these rate differences is discussed and explained.
Fang, Lieh-pao O.,Kice, John L.
p. 1137 - 1145
(2007/10/02)

Aminecarbotrithioates
A thiolsulfonate is reacted with an aminecarbodithioate salt to give an aminecarbotrithioate product. The products of this invention have biological activity, particularly in controlling microorganisms and other pests.
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(2008/06/13)