- Visible light induced decomposition of sulfonyl hydrazides using Pd/ZrO2nanocomposite photocatalyst
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A new approach to synthesis of thiosulfonates has been developed under mild conditions without any oxidants and promoting reagents through a Pd/ZrO2nanocomposite photocatalyst catalyzed decomposition of sulfonyl hydrazides. This protocol gave the products in moderate yields, comparable to the best results reported so far. Finally, a plausible reaction mechanism was proposed.
- Li, Xiaoji,Zhou, Chao,Diao, Pinhui,Ge, Yanqin,Guo, Cheng
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Read Online
- Copper-Catalyzed Aerobic Formation of Unstable Sulfinyl Radicals for the Synthesis of Sulfinates and Thiosulfonates
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Copper-catalyzed aerobic coupling of thiols and alcohols affords sulfinates and thiosulfonates. These products are assumed to form via sulfinyl radicals which are not commonly found in oxidative coupling reactions of thiols. A reaction mechanism involving sulfinyl radicals is proposed, and mass and electron paramagnetic resonance (EPR) experimental results are provided.
- Shyam, Pranab K.,Kim, Yu Kwon,Lee, Chan,Jang, Hye-Young
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Read Online
- Oxidation of disulfides with Selectfluor: Concise syntheses of thiosulfonates and sulfonyl fluorides
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The reaction of aromatic or benzylic disulfides with 2.5 equiv of Selectfluor in acetonitrile/water (10:1) at room temperature efficiently produced the corresponding thiosulfonates. On the other hand, the reaction of disulfides with 6.5 equiv of Selectfluor in refluxing acetonitrile/water (10:1) provided sulfonyl fluoride in high yields.
- Kirihara, Masayuki,Naito, Sayuri,Ishizuka, Yuki,Hanai, Honoka,Noguchi, Takuya
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- Zinc dichromate trihydrate (ZnCrmiddot;3H) as an efficient reagent for the one-pot synthesis of thiosulfonates from thiols
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ZnCrH is a readily available and efficient reagent for the one-pot synthesis of a variety of thiosulfonates by chemoselective oxidation of thiols. Georg Thieme Verlag Stuttgart New York.
- Sobhani, Sara,Aryanejad, Sima,Maleki, Mahdi Faal
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- TCCA-promoted solvent-free chemoselective synthesis of thiosulfonates on grinding
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Trichloroisocyanuric acid (TCCA) is an inexpensive and efficient reagent for solvent-free chemoselective synthesis of thiosulfonates by grinding, providing a metal-free new methodology for the oxidation of disulfides. The important features of this method are that it is reasonably fast, very clean, high yielding, has a simple workup and is environmentally benign.
- Xu, Yali,Peng, Yong,Sun, Junhui,Chen, Jiuxi,Ding, Jinchang,Wu, Huayue
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- Synthesis of Symmetrical Thiosulfonates via Cu(OTf)2-Catalyzed Reductive Homocoupling of Arenesulfonyl Chlorides
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A variety of symmetrical thiosulfonates are synthesized via Cu-catalyzed reductive homocoupling of aryl sulfonyl chlorides. This protocol uses organic amine acting as a mild reductant and low-cost copper as an effective catalyst. Such a reductive coupling process features a broad substrate scope and good functional group tolerance. Related thiosulfonate products can also be converted into diverse functional molecules.
- Liu, Lixia,Luo, Bo,Wang, Chengming
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supporting information
p. 5880 - 5883
(2021/11/27)
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- Dual Roles of Rongalite: Reductive Coupling Reaction to Construct Thiosulfonates Using Sulfonyl Hydrazides
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A tunable and practical transformation of structurally diverse sulfonyl hydrazides into thiosulfonates in the presence of Rongalite (NaHSO 2·CH 2O) was developed. Transition-metal-free conditions, operational simplicity, and readily available reagents are the striking features of this protocol. It is the first example for the synthesis of thiosulfonates using sulfonyl hydrazides with the assistance of reductant. Additionally, the mechanistic studies revealed that this transformation probably undergoes via a reducing-coupling pathway.
- Zhang, Guofu,Fan, Qiankun,Zhao, Yiyong,Wang, Huimin,Ding, Chengrong
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- Synthesis of symmetrical / unsymmetrical thiosulfonates through the disproportionate coupling reaction of sulfonyl hydrazide mediated by phosphomolybdic acid
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Phosphomolybdic acid (H3PMo12O40) is reported as a green low-cost catalyst for the synthesis of symmetrical / unsymmetrical thiosulfonates via the disproportionate coupling reaction of sulfonyl hydrazide. The attributes of this reported catalytic system include low catalyst loadings (1 mol%), efficient turnover, and high yields (up to 94%). Additionally, this reaction mechanism involves the formation of a thiyl radical and sulfonyl radical via sulfinyl radical disproportionation.
- Lv, Mengting,Liu, Yufeng,Li, Ke,Yang, Guoping
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- The organocatalytic synthesis of perfluorophenylsulfides: Via the thiolation of trimethyl(perfluorophenyl)silanes and thiosulfonates
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The organic superbase t-Bu-P4-catalyzed direct thiolation of trimethyl(perfluorophenyl)silanes and thiosulfonates was developed. Yields of perfluorophenylsulfides of up to 97% under catalysis of 5 mol% t-Bu-P4 were achieved. This method was shown to provide an efficient way to construct the perfluorophenyl-sulfur bond under mild metal-free reaction conditions. This journal is
- Cai, Zhihua,Du, Guangfen,He, Lin,Lin, Muze,Luo, Jinyun,Wu, Leifang
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supporting information
p. 9237 - 9241
(2021/11/13)
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- Metal-Free Radical Annulation of Oxygen-Containing 1,7-Enynes: Configuration-Selective Synthesis of (E)-3-((Arylsulfonyl)methyl)-4-Substituted Arylidenechromene Derivatives
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A novel strategy for the synthesis of (E)-3-((arylsulfonyl)methyl)-4-substituted benzylidenechromene derivatives via a metal-free radical annulation reaction of oxygen-containing 1,7-enynes with thiosulfonates has been developed. The reaction shows broad substrate scope, wide functional group tolerance, and moderate to excellent yields. Moreover, thiosulfonates were well driven to achieve the bifunctionalization reaction of oxo-1,7-enynes which derived from aliphatic alkynes. In addition, the (E)-configuration of the products was highly controlled by the structure of 1,7-enyne.
- Bian, Mouwang,Dai, Lei,Mao, Kaimin,Rong, Liangce,Wang, Chang,Yu, Qiuyu,Zhang, Jinghang
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supporting information
p. 218 - 224
(2021/01/13)
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- Direct conversion of sulfinamides to thiosulfonates without the use of additional redox agents under metal-free conditions
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Direct conversion of sulfinamides to thiosulfonates is described. Without the use of additional redox agents, the reaction proceeds smoothly in the presence of TFA under metal-free conditions. This protocol possesses many advantages such as odourless and stable starting materials, broad substrate scope, selective synthesis, and mild reaction conditions. This journal is
- Ji, Yuan-Zhao,Li, Hui-Jing,Wang, Jun-Hu,Wu, Yan-Chao,Zhang, Chi
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p. 9291 - 9298
(2021/11/13)
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- Electrochemical metal- And oxidant-free synthesis of S-thiocarbamates
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An expeditious synthetic strategy to access functionalized S-thiocarbamates was developed in good to excellent yields and with high current efficiencies. Readily available isocyanides and thiols were used as the starting materials under simple metal- and oxidant-free reaction conditions avoiding an inert atmosphere. The practical application of the present methodology was achieved by electrochemical synthesis of the herbicides prosulfocarb and pebulate. Furthermore, continuous electrochemical flow conditions using a graphite/Pt flow cell were used to obtain S-thiocarbamate compounds on a gram scale within a residence time of 35 min. This journal is
- Malviya, Bhanwar Kumar,Sharma, Siddharth,Verma, Ved Prakash
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p. 9491 - 9500
(2021/11/17)
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- Transition-Metal-Free Synthesis of Aryl Trifluoromethyl Thioethers through Indirect Trifluoromethylthiolation of Sodium Arylsulfinate with TMSCF3
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Herein, we report an indirect trifluoromethylthiolation of sodium arylsulfinates. This transition-metal-free reaction significantly provides an environmentally friendly and practical synthetic method for aryl trifluoromethyl thioethers using commercial Ruppert-Prakash reagent TMSCF3. This approach is also a potential alternative to the current industrial production method owing to facile substrates, excellent functional group compatibility, and operational simplicity.
- Zheng, Changge,Jiang, Chao,Huang, Shuai,Zhao, Kui,Fu, Yingying,Ma, Mingyu,Hong, Jianquan
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supporting information
p. 6982 - 6986
(2021/09/08)
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- Electrochemical cross-coupling reactions of sodium arenesulfinates with thiophenols and phenols
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A green electrochemical oxidative cross-coupling protocol for the generation of thiosulfonates and sulfonate esters using sodium arenesulfinates and thiophenols/phenols is disclosed. The protocol involves using inorganic and non-toxic NaI as both redox catalyst and supporting electrolyte at room temperature without oxidant and base. The reactions provide good yields of products and tolerate broad substrate scope. The mechanistic studies revealed that the reactions proceed via a radical pathway for the formation of SO2–S and SO2–O bonds.
- Ma, Jinfeng,Xu, Pan,Zhong, Zijian,Zhou, Aihua
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supporting information
(2021/10/26)
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- H4SiW12O40-catalyzed cyclization of epoxides/aldehydes and sulfonyl hydrazides: An efficient synthesis of 3,4-disubstituted 1H-pyrazoles
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A simple and efficient method for the synthesis of pyrazoles through a silicotungstic acid (H4SiW12O40)-catalyzed cyclization of epoxides/aldehydes and sulfonyl hydrazides has been developed. Various epoxides/aldehydes were smoothly reacted with sulfonyl hydrazides to furnish regioselectivity 3,4-disubstituted 1H-pyrazoles. The application of such an earth-abundant, readily accessible, and nontoxic catalyst provides a green approach for the construction of 3,4-disubstituted 1H-pyrazoles. A plausible reaction mechanism has been proposed on the basis of control experiments, GC-MS and DFT calculations.
- Cheng, Mengyuan,Cheng, Yuanyuan,Gao, Xiaofei,Li, Ke,Lin, Xiaoling,Liu, Yufeng,Xie, Xuanjie,Yang, Guoping
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supporting information
(2021/09/06)
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- Diaryl disulfides and thiosulfonates as combretastatin A-4 analogues: Synthesis, cytotoxicity and antitubulin activity
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Diaryl disulfides and diaryl thiosulfonates were synthesized with the two phenyl rings of all compounds bearing identical halide substituents. Because of structural similarity to the potent antimitotic natural product combretastatin A-4 (CA-4), the compounds were examined for inhibition of tubulin polymerization, and the thiosulfonates were more active than the disulfides. The nine thiosulfonates had IC50 values ranging from 1.2 to 9.1 μM, as compared with 1.3 μM obtained with CA-4. The compounds thus ranged from equipotent with CA-4 to 7-fold less active. The nine disulfides had IC50 values ranging from 1.2 to 5.1 μM, as compared with 0.54 μM obtained with CA-4. The compounds thus ranged from less than half as active as CA-4 to over 9-fold less active. The most active members of each group, 2 g and 3c, in the assembly assay were modeled into the colchicine site. Compound 3c had significant hydrophobic interactions with β-tubulin residues CYS 241 and ALA 250, and its thiosulfonate bridge made a hydrogen bond with β-tubulin residue ASN 258. Compound 2 g had hydrophobic interactions with β-tubulin residues ALA 250, CYS 241 and ALA 254, but there was no significant interaction of the disulfide bridge with tubulin.
- Bai, Ruoli,Barbosa, Euzébio Guimar?es,Beatriz, Adilson,Hamel, Ernest,Khodyuk, Rejane Gon?alves Diniz,Louren?o, Estela Mariana Guimar?es,de Lima, Dênis Pires,dos Santos, Edson dos Anjos
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- Perfluoroalkylation of Thiosulfonates: Synthesis of Perfluoroalkyl Sulfides
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A practical synthesis of perfluoroalkyl sulfides is described. The method employs stable and readily accessible thiosulfonates as new electrophiles with commercial nucleophilic perfluoroalkylating reagents. The mild reaction conditions allow access to a wide variety of both aryl- and alkyl-substituted perfluoroalkyl sulfides amenable to pharmaceutical development. Furthermore, the reaction operation is straightforward, odorless, does not produce toxic wastes, and, therefore should appeal to practitioners in industrial-scale productions.
- Luo, Ziwei,Yang, Xinkan,Tsui, Gavin Chit
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supporting information
p. 6155 - 6159
(2020/07/30)
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- CuCl2-promoted decomposition of sulfonyl hydrazides for the synthesis of thiosulfonates
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Sulfonyl hydrazides recently received much attention as reagents for the introduction of sulfur-containing functional groups into organic compounds, because both sulfonyl and sulfenyl sources could be generated by the oxidation and decomposition of the sulfonyl hydrazides, respectively. However, the transformations of sulfonyl hydrazides into thiosulfonates, which could be produced by the reaction between sulfonyl and sulfenyl sources, have been less investigated. In this manuscript, we describe CuCl2-promoted selective synthesis of thiosulfonates from sulfonyl hydrazides. A variety of thiosulfonates were produced in moderate to good yields. The mechanism involving radical intermediates such as sulfonyl radical and thiyl radical was proposed on the basis of the previously reported references and mechanistic investigations. In addition, quantum chemical simulations revealed that Cu-promoted decomposition of sulfonyl hydrazides is thermodynamically viable in the developed conditions.
- Kim, Junsu,Park, Sanggil,Kim, Hyungjun,Kim, Jinho
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- Cs2CO3-Mediated Vicinal Thiosulfonylation of 1,1-Dibromo-1-Alkenes with Thiosulfonates: An Expedient Synthesis of (E)-1,2-Thiosulfonylethenes
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A new and highly efficient vicinal thiosulfonylation of 1,1-dibromo-1-alkenes with thiosulfonates in the presence of cesium carbonate has been developed. The metal-free diheterofunctionalization is an operationally simple to access a wide range of (E)-1,2-thiosulfonylethenes (α-aryl-β-thioarylvinyl sulfones) in moderate to high yields with high levels of stereoselectivities. Further, scalable reactions have been demonstrated for this transformation, thus illustrating its efficiency and practicality. (Figure presented.).
- Reddy, Raju Jannapu,Kumari, Arram Haritha,Kumar, Jangam Jagadesh,Nanubolu, Jagadeesh Babu
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supporting information
p. 1587 - 1591
(2019/02/16)
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- Unprecedented Reactivity of β-Iodovinyl Sulfones: An Efficient Synthesis of β-Keto Sulfones and β-Keto Thiosulfones
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An unprecedented reactivity of (E)-β-iodovinyl sulfones in the presence of NaOAc is reported. The (E)-β-iodovinyl sulfones were treated with NaOAc in DMSO/H2O to yield β-keto sulfones in moderate to high yields. A novel oxidative difunctionalization of β-iodovinyl sulfones with thiosulfonates and NaOAc in DMF has been developed. This metal-free oxosulfenylation is an operationally simple to access a wide range of β-keto thiosulfones (α-thioaryl-β-keto sulfones) in moderate to high yields. The transformations were reliable at gram-scale, thus illustrating its efficiency and practicality. A plausible mechanism for the protocol is also proposed.
- Reddy, Raju Jannapu,Kumar, Jangam Jagadesh,Kumari, Arram Haritha
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supporting information
p. 3771 - 3775
(2019/06/24)
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- External Oxidant-Free Oxidative Tandem Cyclization: NaI-Catalyzed Thiolation for the Synthesis of 3-Thiosubstituted Pyrroles
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A simple method for the synthesis of 3-thiosubstituted pyrroles from homopropargylic amines and thiosulfonates via a tandem sulfenylation/cyclization has been developed. The thiosulfonates are used both as substrates and oxidants in this transformation. This procedure exhibits good functional group tolerance and a series of 3-thiosubstituted pyrrole derivatives was obtained in moderate to good yields. (Figure presented.).
- Yuan, Bingxiang,Jiang, Yong,Qi, Zhenjie,Guan, Xin,Wang, Ting,Yan, Rulong
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supporting information
p. 5112 - 5117
(2019/11/11)
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- Visible-light mediated sulfonylation of thiols via insertion of sulfur dioxide
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A simple and efficient visible-light mediated synthesis of thiosulfonates via a radical-radical coupling of sulfenyl radicals and arylsulfonyl radicals was developed. The reaction of thiols, aryldiazonium tetrafluoroborates and DABSO proceeded at room temperature using 5 mol% eosin Y. The reaction displayed wide functional group tolerance and delivered the unsymmetrical thiosulfonates in good to excellent yields.
- Nair, Akshay M.,Kumar, Shreemoyee,Halder, Indranil,Volla, Chandra M. R.
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supporting information
p. 5897 - 5901
(2019/06/24)
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- A S - aryl sulfur [...] compound synthesis method (by machine translation)
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The invention discloses a S - aryl sulfur [...] compound synthesis method, the method through in the organic solvent, phenyl four boron fluoride diazonium salt with thiourea to form phenyl isothiourea salt after the addition, thiophenol anion obtained, under the light source is illuminated, excited state of Rodamin 6 G will thiophenol anion thiophenol free radical oxidation; phenyl four boron fluoride diazonium salt with low valence state of Rodamin 6 G generating single electron transfer by the phenyl radical, phenyl radical with a solid substitute of the sulfur dioxide is obtained by combining the benzenesulfonyl radical; thiophenol radical with a benzenesulfonyl radical-radical coupling, to obtain the corresponding target product. The method of the invention mild condition, simple and efficient, the reaction yield is high, good product purity, facilitates separation of the purification, it has very good application value. (by machine translation)
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Paragraph 0031; 0032; 0034
(2019/01/23)
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- Preparation method of thiosulfonate compounds in aqueous phase
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The invention relates to a preparation method of thiosulfonate compounds in an aqueous phase. The preparation method comprises adding sulfonyl hydrazide, an accelerant, an oxidant and solvent water into a Schlenk reaction bottle, stirring to allow to react under certain temperature and air atmosphere, and carrying out free radical coupling reaction to obtain the thiosulfonate compounds.
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Paragraph 0060-0062
(2019/06/27)
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- Disproportionate Coupling Reaction of Sodium Sulfinates Mediated by BF3·OEt2: An Approach to Symmetrical/Unsymmetrical Thiosulfonates
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The BF3·OEt2-mediated disproportionate coupling reaction of sodium sulfinates was found for the first time. In this reaction, various S-S(O)2 bonds can be formed, efficiently giving thiosulfonates in moderate to excellent yields. As a convenient protocol for the synthesis of symmetrical and unsymmetrical thiosulfonates, its reaction mechanism involves the formation of a thiyl radical and sulfonyl radical via a sulfinyl radical disproportionation. What is more, this transformation can also be applied practically as a gram-scale reaction and to the two-step synthesis of sulfone and sulfonamide in one pot in situ using thiosulfonate as an intermediate.
- Cao, Liang,Luo, Shi-He,Jiang, Kai,Hao, Zhi-Feng,Wang, Bo-Wen,Pang, Chu-Ming,Wang, Zhao-Yang
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supporting information
p. 4754 - 4758
(2018/08/24)
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- Transition-Metal-Free Synthesis of Thiosulfonates through Radical Coupling Reaction
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An efficient and practical transition-metal-free radical coupling reaction of sulfonyl hydrazides mediated by NIS/K 2 S 2 O 8 has been developed to afford a variety of biological activity thiosulfonates in moderate to excellent yields. Compared to a known approach for the synthesis of thiosulfonates from sulfonyl hydrazides, this strategy features high yields, mild reaction conditions, and broad substrate scope. The mechanistic studies revealed that the procedure undergoes via a radical cross-coupling process for the construction of S-S bonds.
- Zhou, Guodong,Xu, Xu-Dong,Chen, Gan-Ping,Wei, Wen-Ting,Guo, Zhiyong
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supporting information
p. 2076 - 2080
(2018/09/18)
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- Selective oxidation method of disulfide
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The invention relates to a selective oxidation method of disulfide, and discloses a novel synthesis method of a single sulfone compound shown as a formula (I). According to the invention, disulfide shown in a formula (II) is taken as a raw material, under existence of tert-butyl hydroperoxide, an oxidation reaction is carried out in a solvent, after the reaction is completed, and through post-treatment, the single sulfone compound shown as the formula (I) is obtained. Compared with the prior art, an oxidizing agent tert-butyl hydroperoxide which is friendly to environment is employed, usage ofa metal catalyst is avoided, the reaction condition is mild, selectivity is high, the operation is simple, the applicability is wide, and the reaction yield is high.
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Paragraph 0040; 0041; 0042
(2018/09/26)
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- Preparation method of S-(4-chlorophenyl)-4-chlorobenzenesulfothioate
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The invention relates to a preparation method of S-(4-chlorophenyl)-4-chlorobenzenesulfothioate. The preparation method comprises the following steps: adding 4-chlorophenylthiophenol and an oxidant into a solvent and reacting for 2h-6h under a condition t
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Paragraph 0027; 0029; 0030; 0031; 0032; 0033-0050
(2017/05/13)
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- Tunable and Practical Synthesis of Thiosulfonates and Disulfides from Sulfonyl Chlorides in the Presence of Tetrabutylammonium Iodide
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A tunable and practical synthesis of electrophilic sulfenylating reagents, thiosulfonates and disulfides, from inexpensive and easily available sulfonyl chlorides, has been developed. By appropriate choice of solvents, the reaction of sulfonyl chlorides and tetrabutylammonium iodide gave the target products in good to excellent yields, respectively. These transformations probably proceed through a reducing–coupling pathway. (Figure presented.).
- Zheng, Yong,Qing, Feng-Ling,Huang, Yangen,Xu, Xiu-Hua
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supporting information
p. 3477 - 3481
(2016/11/13)
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- Iron(III)-Catalyzed Radical Cross-Coupling of Thiols with Sodium Sulfinates: A Facile Access to Thiosulfonates
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A convenient and efficient synthesis of symmetrical and asymmetric thiosulfonates from thiols and sodium sulfinates is reported. The protocol involves iron(III)-catalyzed formation of sulfenyl and sulfonyl radicals in situ under aerobic conditions and their subsequent cross-coupling to afford thiosulfonates in 83-96% yield. The utilization of readily available, nontoxic, and inexpensive iron(III) as a catalyst and atmospheric oxygen as an oxidant is within the confines of green and sustainable chemistry.
- Keshari, Twinkle,Kapoorr, Ritu,Yadav, Lal Dhar S.
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p. 1878 - 1882
(2016/07/16)
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- Facile synthesis of symmetric thiosulfonates by oxidation of disulfide with oxone/MX (MX = KBr, KCl, NaBr and NaCl)
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Abstract A new method is described for the oxidation of aliphatic- and aromatic disulfides containing electron-donating and electron-withdrawing groups to their corresponding thiosulfonates using oxone in combination with the MX (MX = KBr, KCl, NaBr and NaCl). No obvious electronic effects influence the yields of thiosulfonates. Avoiding the usage of toxic and unstable reagents, mild reaction conditions, short reaction times and cost-effectiveness are advantages of this methodology when likened to known methods for thiosulfonates syntheses.
- Natarajan, Palani
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p. 4131 - 4134
(2015/08/03)
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- A mild and facile synthesis of aryl and alkenyl sulfides via copper-catalyzed deborylthiolation of organoborons with thiosulfonates
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An efficient deborylthiolation of aryl- and alkenylborons with thiosulfonates has been achieved under mild conditions using a copper catalyst. All steps of the experimental process were free from unpleasant odors. The mild reaction conditions as well as ready availability of boron compounds and thiosulfonates enabled easy access to an array of sulfides, including those bearing sensitive functional groups.
- Yoshida, Suguru,Sugimura, Yasuyuki,Hazama, Yuki,Nishiyama, Yoshitake,Yano, Takahisa,Shimizu, Shigeomi,Hosoya, Takamitsu
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supporting information
p. 16613 - 16616
(2015/11/25)
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- Silver-mediated oxidative vinylic C-H bond sulfenylation of enamides with disulfides
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A silver-mediated oxidative vinylic C-H bond sulfenylation of enamides was developed. This method is compatible with diaryl and dialkyl disulfides to deliver biologically precious chalcogenated olefins efficiently. A plausible non-chain radical mechanism
- Yang, Luo,Wen, Qing,Xiao, Fuhong,Deng, Guo-Jun
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p. 9519 - 9523
(2015/02/19)
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- Oxidation of disulfides with electrophilic halogenating reagents: Concise methods for preparation of thiosulfonates and sulfonyl halides
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The reaction of aromatic or benzylic disulfides with 2.5 equiv of Selectfluor in acetonitrile/water (10:1) at room temperature efficiently produced the corresponding thiosulfonates. Conversely, the reaction of disulfides with 6.5 equiv of Selectfluor or thiosulfonates with 4.5 equiv of Selectfluor in refluxing acetonitrile/water (10:1) provided sulfonyl fluorides in high yields. Accufluor and FP-T300 are also effective in preparing sulfonyl fluorides from disulfides under the similar reaction conditions. Sulfonyl chlorides or sulfonyl bromides were effectively obtained from the reaction of disulfides with 6 equiv of either N-chlorosuccinimide or N-bromosuccinimide in acetonitrile/water (10:1) at room temperature. Some other electrophilic chlorinating or brominating reagents are also able to be used instead of N-chlorosuccinimide or N-bromosuccinimide for the syntheses of sulfonyl halides from disulfides. These reactions of disulfides with electrophilic halogenating reagents are convenient methods to prepare thiosulfonates and sulfonyl halides.
- Kirihara, Masayuki,Naito, Sayuri,Nishimura, Yuki,Ishizuka, Yuki,Iwai, Toshiaki,Takeuchi, Haruka,Ogata, Tomomi,Hanai, Honoka,Kinoshita, Yukari,Kishida, Mari,Yamazaki, Kento,Noguchi, Takuya,Yamashoji, Shiro
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p. 2464 - 2471
(2014/04/03)
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- Investigations on the Lewis-acids-catalysed electrophilic aromatic substitution reactions of thionyl chloride and selenyl chloride, the substituent effects, and the reaction mechanisms
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The previously established aluminium-chloride-(AlCl3)-catalysed electrophilic aromatic substitution (EAS) of benzene (PhH) with thionyl chloride (SOCl2) has been extended to toluene (PhCH3), chlorobenzene (PhCl), and phenol (PhOH). -CH3 was found to be mainly a para-director with a minor ortho-directing effect on the EAS reactions giving diaryl sulfoxides (Ar2SO). -Cl was found to be exclusively a para-director for formation of Ar2SO. All the -CH3, -Cl, and -OH groups were shown to be exclusive para-directors for formation of diaryl sulfides (Ar2S) from the EAS reactions. Although the reactions of PhH and PhCH3 with SOCl2 in the presence of AlCl 3 gave the major Ar2SO and minor Ar2S at ambient temperature, the phenol (PhOH) reaction was shown to give only the reduced sulfide (p-HOC6H4)2S with no sulfoxide (p-HOC6H4)2SO formed. The mixed diaryl sulfoxides ArSOAr′ (Ar, Ar′=C6H5, p-CH 3C6H4; C6H5, o-CH 3C6H4; and C6H5, p-ClC6H4) were produced in the AlCl3-catalysed reactions of SOCl2 with molar 1:1 PhH-PhX mixtures (X=CH3 and Cl). Efforts to enhance the yield of S-aryl arenesulfonothioates ArSO 2SAr (Ar=Ph, p-CH3C6H4, and p-ClC6H4) from the AlCl3-catalysed EAS reactions of SOCl2 were made, showing that decreasing the molar ratios of ArH/SOCl2 or lowering the temperature resulted in an increase in the product yield. A detailed mechanism has been proposed to account for the formation of ArSO2SAr. The Lewis-acid-MCl3-(M=Al and Fe)-catalysed EAS reactions of PhH with selenyl chloride (SeOCl2) were demonstrated to give the reduced diphenyl selenide (Ph2Se) and diphenyl diselenide (PhSeSePh) via novel auto-redox processes in selenium of the key EAS intermediates.
- Sun, Xiaoping,Haas, David,McWilliams, Samantha,Smith, Benjamin,Leaptrot, Katrina
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p. 736 - 744
(2014/01/23)
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- Synthesis of S-Aryl arenethiosulfonates from N,N-Di(arenesulfonyl) hydrazines: Reduction of sulfonyl chlorides with an organic reagent
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N,N-Di(arenesulfonyl)-N′,N′-dimethyl-hydrazines, readily prepared from arenesulfonyl chlorides and N,N-dimethylhydrazine, were heated at 120°C in chlorobenzene to give S-aryl arenethiosulfonates, ArSSO 2Ar, in good yields.
- Iwata, Satoshi,Senoo, Masato,Hata, Takeshi,Urabe, Hirokazu
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p. 336 - 344
(2013/08/23)
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- Synthesis of sulfonyl chlorides and thiosulfonates from H2O 2-TiCl4
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A new method is described for the oxidative chlorination of thiols to sulfonyl chlorides using titanium tetrachloride in combination with the oxidant hydrogen peroxide. Direct conversion of thiols into their corresponding thiosulfonates is also reported. Good to excellent yields, short reaction times, high efficiencies, cost-effectiveness, and, facile isolation of the desired products make the present methodology a practical alternative.
- Bahrami, Kiumars,Khodaei, Mohammad M.,Khaledian, Donya
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experimental part
p. 354 - 358
(2012/01/19)
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- NBS-promoted sulfenylation of sulfinates with disulfides leading to unsymmetrical or symmetrical thiosulfonates
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A highly practical method to access unsymmetrical and symmetrical thiosulfonates in moderate to excellent yields has been developed through NBS-promoted sulfenylation of sulfinates with disulfides. The present process enables the use of two RS in RSSR and shows broad functional group tolerance, which represents an atom-economical and practical procedure for the synthesis of thiosulfonates. A plausible mechanism for the role of NBS as a promoter for the cleavage of disulfides generating N-(organothio)succinimide that then undergos facile sulenylation with sulfinates is proposed. Copyright
- Liang, Gaigai,Liu, Miaochang,Chen, Jiuxi,Ding, Jinchang,Gao, Wenxia,Wu, Huayue
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experimental part
p. 1611 - 1616
(2012/09/07)
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- CAN/I2-catalyzed chemoselective synthesis of thiosulfonates by oxidation of disulfides or thiols
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sCAN/I2 promoted synthesis of thiosulfonates by oxidation of disulfides and thiols with high chemoselectivity and excellent yields in wet poly(ethylene glycol) (PEG-400). The overall process is simple, practical, and it provides convenient access to thiosulfonates.
- Cai, Ming-Tiao,Lv, Guang-Shu,Chen, Jiu-Xi,Gao, Wen-Xia,Ding, Jin-Chang,Wu, Hua-Yue
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supporting information; experimental part
p. 368 - 369
(2010/07/06)
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- Temperature-controlled selective reduction of arenesulfonyl chlorides promoted by samarium metal in DMF
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Promoted by samarium in DMF, arenesulfonyl chlorides can be selectively reduced to diaryldisulfones, diarylthiosulfonates and diaryldisulfides in good to excellent yields by reaction temperature control without the need to pretreat or activate the metallic samarium.
- Liu, Yongjun,Zhang, Yongmin
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p. 4291 - 4294
(2007/10/03)
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- 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)
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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.
- Xia, Min,Chen, Zhen-Chu
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p. 1301 - 1308
(2007/10/03)
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- REACTIVITY OF PHENYLIODONIUM BIS(ARYLSULPHONYL)METHYLIDES TOWARDS ALKENES AND ALKYNES: CRYSTAL STRUCTURE OF 9-PHENYLSULPHONYL-1,2,3,4,4a,9a-HEXAHYDRO-1,4-METHANOFLUORENE
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Thermal or photochemical reactions of phenyliodonium bis(arylsulphonyl)methylides with alkenes lead normally to gem-(arylsulphonyl)cyclopropanes.Norbornene and trans-stilbene, however, afford 1-(phenylsulphonyl)indane derivatives.The crystal structure of the title compound /= 3.0>> confirmed the identity of the product with norbornene.Diarylacetylenes give 1-(arylsulphonyl)indenes.Thermal decomposition of the ylides involves a new rearrangement, with formation of aryl arenethiosulphonates.
- Hatjiarapoglou, Lazaros,Varvoglis, Anastassios,Alcock, Nathaniel W.,Pike, Graham A.
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p. 2839 - 2846
(2007/10/02)
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- PREPARATION AND SPECTRAL PROPERTIES OF SYMMETRICAL S-ARYL ARENESULFONOTHIOATES (THIOSULFONATES)
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Arenesulfinyl chlorides (4-XC6H4S(O)Cl; X = H, CH3, F, Cl, Br) react with activated zerovalent zinc in benzene at 6 to 8 deg C to give symmetrical S-aryl arenesulfonothioates (thiosulfonates) in good to excellent yields. 2- and 3-substituted arenesulfinyl chlorides (X=Cl, CH3) give a mixture of products (disulfide, thiosulfinate, and/or thiosulfonate). 2,4,6-Triisopropylbenzenesulfinyl chloride reacts with zinc in 1,2-dimethoxyethane to give S-(2,4,6-triisopropylphenyl) 2,4,6-triisopropylbenzenesulfinothioate and bis(2,4,6-triisopropylphenyl) disulfide.Possible mechanisms for the reaction, the 1H and 13C NMR spectra and the chemical ionization and electron impact mass spectra of the thiosulfonates are discussed.The para carbon substituent chemical shifts (Cp-SCS) for the thiosulfonates and for symmetrical diaryl disulfides have been subjected to several dual substituent parameter (DSP) correlations. Key Words: S-aryl-arenesulfonothioates (thiosulfonates); arenesulfinyl chlorides; 1H and 13C NMR; mass spectrometry; substituent shift parameters.
- Freeman, Fillmore,Bartosik, Lisa G.,Bui, Nghe Van,Keindl, Monica C.,Nelson, Eric L.
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p. 375 - 386
(2007/10/02)
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- REACTION OF ARENESULFENYL CHLORIDES WITH N-CHLOROCARBONIMIDIC AND N-CHLOROBENZENECARBOXIMIDIC ESTERS. N-(ETHOXYCARBONYL)- AND N-BENZOYLARENESULFINIMIDOYL CHLORIDES
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In the reaction of arenesulfonyl chlorides with diethyl N-chlorocarbonimidate or N-chlorobenzenecarboximidic esters at 20 deg C 1:1 adducts are formed, and they probably have the structure of tetracoordinated compounds of sulfur.The latter are also formed during the chlorination of N-(arylthio)carbonimidic or N-(arylthio)benzenecarboximidic esters.The obtained compounds are dechlorinated by the action of bases with the formation of N-(arylthio)carbonimidic or N-(arylthio)benzenecarboximidic esters.During acidolysis they split into arenesulfenyl chlorides and the salts of the corresponding carbonimidic and benzenecarboximidic esters.During thermolysis they eliminate alkyl chlorides and are converted into N-(ethoxycarbonyl)- or N-benzoylarenesulfinimidoyl chlorides.
- Levchenko, E. S.,Dubinina, T. N.,Budnik, L. V.,Romanenko, E. A.
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p. 1166 - 1171
(2007/10/02)
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- STRUCTURE AND CONFORMATION OF SYMMETRIC ARYL THIOSULPHONIC ESTERS
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The symmetric thiosulphonic esters R-SO2-S-R (R = CH3, C6H5, p-CH3-C6H4, p-CH3O-C6H4, p-Cl-C6H4, 2,4,6-(CH3)3-C6H2, 2,4,6-(i-C3H7)3-C6H2) have been prepared by a one-step synthesis partially reducing the sulphonyl chlorides with KI in the presence of catalytic amounts of pyridine.The crystal structures of the aryl derivatives X-C6H4-SO2-S-C6H4-X (X = H, CH3, Cl) have been determined using single crystal X-ray diffractometric data: C6H5-SO2-S-C6H5 (MoKα): P2/n, a = 12.413(4), b = 8.537(2), c = 12.649(5) Angstroem, β = 116.50(2) deg, Z = 4, final R = 0.0485; CH3-C6H4-SO2-S-C6H4-CH3 (CuKα): P21/n, a = 13.932(6), b = 12.076(6), c = 8.326(4) Angstroem, β = 93.40(6) deg, Z = 4, final R = 0.0425; Cl-C6H4-SO2-S-C6H4-Cl (MoKα): P21/n, a = 13.716(9), b = 11.932(8), c = 8.206(4) Angstroem, β = 92.47(2) deg, Z = 4, final R = 0.0493.The three structures are strictly similar with a conformation of the thiosulphonyl system essentially determined by the tendency of the non bonding electron pairs of S(II) to assume synclinal and antiperiplanar conformation with respect to the S(VI)-O bonds.The repulsion exerted by these pairs on the S(II)-C and S(II)-S(VI) bonding pairs justifies the narrowing of the S(VI)-S(II)-C angle with respect to the tetrahedral value.Electronic effects due to the para substituents in the phenyl rings superimpose that repulsion producing a different narrowing in the three derivatives.These effects influence also the S(VI)-S(II) distance which is shorter in the case of X = H, where the angle S(VI)-S(II)-C is larger.The angular deformations of the environment of S(VI) make the two oxygen atoms non equivalent, so that S(VI) is chiral.
- Caputo, Romualdo,Palumbo, Giovanni,Nardelli, Mario,Pelizzi, Giancarlo
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p. 421 - 430
(2007/10/02)
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- Reactions of Arenesulfonyl Chlorides with Olefins Catalyzed by a Ruthenium(II) Complex
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Arenesulfonyl chlorides react with vinylarenes in the presence of dichlorotris(triphenylphosphine)ruthenium(II) catalyst and 1 molar equiv of a tertiary amine to form α,β-unsaturated sulfones 2.Only the E isomers of the sulfones are formed.In reactions of arenesulfonyl chlorides containing an electron-withdrawing Cl or NO2 substituent with α-methylstyrenes, 2-aryl-3-(arylsulfonyl)propenes (5) are also formed.Mechanisms for these reactions are proposed.
- Kamigata, Nobumasa,Sawada, Hideo,Kobayashi, Michio
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p. 3793 - 3796
(2007/10/02)
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- SULFENYL CHLORIDES, XIII; A NEW PROCEDURE FOR THE SYNTHESIS OF SULFONIC ACID THIOL ESTERS FROM THIOLS
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Chlorination of thiols in alkali carbonate media yielded symmetrically substituted alkyl- and arylsulfonic acid thiol esters (thiosulfonates).The procedure is simple, intermediates need not be isolated.
- Pintye, J.,Stajer, G.
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p. 155 - 157
(2007/10/02)
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- Physical Properties and Various Reactions of Thionitrites and Related Substances
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Several new sulfenyl or sulfonyl derivatives, thionitrates (RSNO2), sulfonyl nitrites (RSO2NO), were successfully isolated by treating corresponding thiols and sulfinic acids with dinitrogen tetraoxide (N2O4).Spectroscopic data of both stable and many rather unstable compounds were determined and compared with those of corresponding alkyl nitrites (RONO) or alkyl nitrates (RONO2).Chemical reactivities of these uncommon, novel S-nitroso and S-nitro compounds were investigated.
- Oae, Shigeru,Shinhama, Koichi,Fujimori, Ken,Kim, Yong Hae
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p. 775 - 784
(2007/10/02)
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