91-60-1Relevant articles and documents
Integration of a Four-Step Reaction into One-Pot under the Coexistence of Silica-Gel-Supported Acid and Base Reagents: Synthesis of Benzo- and Naphthothiophenes Using NaHSO 4 /SiO 2 and Na 2 CO 3 /SiO 2
Aoyama, Tadashi,Hayakawa, Mamiko,Kosuge, Masayuki,Nakaoka, Kyohei,Ouchi, Akihiko
, p. 2572 - 2578 (2019/06/08)
A four-step synthesis of benzo- and naphthothiophenes that have biological importance and application in material science was integrated into a one-pot reaction by using silica gel-supported acid and base reagents, NaHSO 4 /SiO 2 and Na 2 CO 3 /SiO 2. The supported reagents provided acid and base environments on the surface of the supports without neutralization and worked separately in the same medium. The four-step reaction comprises (i) deacetylation of 3-halo-2,4-pentanediones to α-halo ketones, (ii) deacetylation of S -aryl thioacetates to arenethiols, (iii) coupling of α-halo ketones and arenethiols to give α-sulfanyl ketones, and (iv) cyclization of sulfanyl ketones to benzo- and naphthothiophenes. The steps (i) and (iii) proceeded by Na 2 CO 3 /SiO 2, and (ii) and (iv) by NaHSO 4 /SiO 2. The four-step reaction proceeded efficiently by introduction of starting materials and reagents in a single reaction vessel. The starting materials were very easy to handle and unpleasant smell of aryl thiols that were used in conventional methods could be avoided. Novel thirty-nine benzo- and naphthothiophenes were synthesized by this method in excellent to fair yields.
Metal–organic framework MOF-199-catalyzed direct and one-pot synthesis of thiols, sulfides and disulfides from aryl halides in wet polyethylene glycols (PEG 400)
Soleiman-Beigi, Mohammad,Sadeghizadeh, Fatemeh,Basereh, Ali
, p. 572 - 583 (2017/09/27)
A highly porous metal–organic frame work Cu3 BTC2 (copper(II)-benzene-1,3,5-tricarboxylate) that is known as MOF-199 was synthesized from the reaction of 1,3,5-benzenetricarboxylic acid and Cu(OAc)2·H2O by a solvothermal method and characterized by several techniques including FT-IR, XRD, EDX and scanning electron microscopy. The MOF-199 used as an efficient catalyst for one-pot synthesis of thiols by domino reactions of aryl halides and thiourea, and subsequently conversion to aryl alkyl sulfides and diaryl disulfides in polyethylene glycols (PEGs). A variety of aryl alkyl sulfides can be obtained in good to excellent yields in a relatively short reaction time and in the presence of the trace amount of catalyst. Also, the catalyst can be separated from the reaction mixture by decanting, and be reused without significant degradation in catalytic activity.
SINGLE-STEP SYNTHESIS METHOD OF ARYL THIOL AND APPLICATION THEREOF
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Paragraph 0032; 0033; 0063; 0067; 0068; 0070, (2017/09/02)
The present invention relates to a single-step synthesis method of aryl thiol, and more specifically, to a method of synthesizing aryl thiol in a single-step by making aryl halide react with alkane dithiol in the presence of a transition metal catalyst. According to the present invention, a single-step synthesis method using the transition metal catalyst, the synthesis method which is capable of synthesizing aryl thiol from aryl halide at a high yield, can be provided. Various aryl halides may be applied to the synthesis method. Further, the synthesis method has advantages that an easily usable reagent may be used, operations are simple, and reactions can be performed under mild conditions. In addition, the synthesized aryl thiol may be used in the synthesis of advanced molecules such as diaryl sulfides and benzothiophenes.COPYRIGHT KIPO 2017
Copper(II)-Catalyzed Single-Step Synthesis of Aryl Thiols from Aryl Halides and 1,2-Ethanedithiol
Liu, Yajun,Kim, Jihye,Seo, Heesun,Park, Sunghyouk,Chae, Junghyun
supporting information, p. 2205 - 2212 (2015/07/27)
A highly efficient transition metal-catalyzed single-step synthesis of aryl thiols from aryl halides has been developed employing copper(II) catalyst and 1,2-ethanedithiol. The key features are use of readily available reagents, a simple operation, and relatively mild reaction conditions. This new protocol shows a broad substrate scope with excellent functional group compatibility. A variety of aryl thiols are directly prepared from aryl halides in high yields. Furthermore, the aryl thiols are used in situ for the synthesis of more advanced molecules such as diaryl sulfides and benzothiophenes.
Structural characterization and function determination of a nonspecific carboxylate esterase from the amidohydrolase superfamily with a promiscuous ability to hydrolyze methylphosphonate esters
Xiang, Dao Feng,Kumaran, Desigan,Swaminathan, Subramanyam,Raushel, Frank M.
, p. 3476 - 3485 (2014/06/23)
The uncharacterized protein Rsp3690 from Rhodobacter sphaeroides is a member of the amidohydrolase superfamily of enzymes. In this investigation the gene for Rsp3690 was expressed in Escherichia coli and purified to homogeneity, and the three-dimensional structure was determined to a resolution of 1.8 ? The protein folds as a distorted (β/α)8-barrel, and the subunits associate as a homotetramer. The active site is localized to the C-terminal end of the β-barrel and is highlighted by the formation of a binuclear metal center with two manganese ions that are bridged by Glu-175 and hydroxide. The remaining ligands to the metal center include His-32, His-34, His-207, His-236, and Asp-302. Rsp3690 was shown to catalyze the hydrolysis of a wide variety of carboxylate esters, in addition to organophosphate and organophosphonate esters. The best carboxylate ester substrates identified for Rsp3690 included 2-naphthyl acetate (kcat/Km = 1.0 × 105 M-1 s-1), 2-naphthyl propionate (k cat/Km = 1.5 × 105 M-1 s -1), 1-naphthyl acetate (kcat/Km = 7.5 × 103 M-1 s-1), 4-methylumbelliferyl acetate (kcat/Km = 2.7 × 103 M-1 s-1), 4-nitrophenyl acetate (kcat/Km = 2.3 × 105 M-1 s-1), and 4-nitrophenyl butyrate (kcat/Km = 8.8 × 105 M -1 s-1). The best organophosphonate ester substrates included ethyl 4-nitrophenyl methylphosphonate (kcat/Km = 3.8 × 105 M-1 s-1) and isobutyl 4-nitrophenyl methylphosphonate (kcat/Km = 1.1 × 104 M-1 s-1). The (SP)-enantiomer of isobutyl 4-nitrophenyl methylphosphonate was hydrolyzed 10 times faster than the less toxic (RP)-enantiomer. The high inherent catalytic activity of Rsp3690 for the hydrolysis of the toxic enantiomer of methylphosphonate esters make this enzyme an attractive target for directed evolution investigations.
Catalytic enantioselective oxidation of bulky alkyl aryl thioethers with H2O2 over titanium-salan catalysts
Bryliakov, Konstantin P.,Talsi, Evgenii P.
experimental part, p. 4693 - 4698 (2011/10/03)
A simple and efficient catalytic procedure for the oxidation of bulky (preferably aryl benzyl substituted) thioethers with hydrogen peroxide in good to high yields and enantioselectivities (up to 98.5%ee) is reported. The high optical yields are achieved in a tandem stereoconvergent enantioselective oxidation and kinetic resolution process. A reasonable balance between the sulfoxide yield and enantioselectivity could be found by varying the concentration and temperature. An improved synthesis of the titanium-salan catalysts for the preparation of a more stereoselective catalyst is reported.
Palladium catalyzed synthesis of aryl thiols: Sodium thiosulfate as a cheap and nontoxic mercapto surrogate
Yi, Jun,Fu, Yao,Xiao, Bin,Cui, Wei-Chen,Guo, Qing-Xiang
experimental part, p. 205 - 208 (2011/02/26)
A Pd-catalyzed coupling reaction of ArBr/ArCl/ArOTf with sodium thiosulfate takes place in presence of Cs2CO3 at 80 °C. The reaction mixture is directly treated with Zn/HCl to afford aryl thiols in good to excellent yields.
[[(tert-Butyl)dimethylsilyl]oxy]-methylGroup for sulfur protection
Wang, Lihong,Clive, Derrick L. J.
supporting information; experimental part, p. 1734 - 1737 (2011/06/09)
Aromatic and aliphatic thiols can be protected by reaction with t-BuMe 2SiOCH2Cl in DMF in the presence of a base (2,6-lutidine or proton sponge); the resulting t-BuMe2SiOCH2SR or t-BuMe2SiOCH2SAr are deprotected by sequential treatment with Bu4NF and I2 to give symmetrical disulfides. Another mode of deprotection involves reaction with a sulfenyl chloride; this process gives an unsymmetrical disulfide and was examined with Me(CH2) 11SCH2OSiMe2Bu-t and three sulfenyl chlorides.
Thiol radical cations and thiyl radicals as direct products of the free electron transfer from aromatic thiols to n-butyl chloride radical cations
Hermann, Ralf,Dey, Ghasi Ram,Naumov, Sergej,Brede, Ortwin
, p. 1213 - 1220 (2007/10/03)
Radical and ionic reactions were observed in the pulse radiolysis of thiophenols (ArSH = thiophenol, o-, m- and p-thiocresol or 2-thionaphthol) in n-butyl chloride solution. The main source of aromatic thiyl radicals is the reaction of butyl radicals with the thiols, which proceeds at 1.0-5.6 x 108 dm3 mol-1 s-1. This radical generation path is completely quenched in the presence of oxygen. Under these conditions, only the electron transfer reaction between n-butyl chloride parent ions and the thiophenols remains and could be well analyzed. It takes place at a rate constant of about 1.5 x 1010 dm3 mol-1 s-1 and takes two parallel paths-common electron transfer yielding thiophenol radical cations and a more complex ionic reaction resulting directly in thiyl radicals. The latter is thought to proceed via an encounter complex geometry, ArSH···ClBu.+, in which electron transfer is directly followed by immediate deprotonation. The thiyl radicals and the thiol radical cations are characterized by their optical absorption spectra and their kinetic properties. Quantum chemical calculations underpin our mechanistic interpretation and provide information about the charge distribution and reactivity of the thiol radical cations.
Photochemistry of benzyl β-naphthyl sulfoxide and characterization of the β-naphthylsulfinyl radical
Guo, Yushen,Darmanyan, Alexandre P.,Jenks, William S.
, p. 8619 - 8622 (2007/10/03)
Photolysis of benzyl β-naphthyl sulfoxide results mainly in α-cleavage. The isomeric sulfenic ester is the major product. Because the triplet energies of both the sulfoxide and sulfenic ester are below that of acetone, in contrast to the previously studied phenyl and tolyl cases, interpretation of sensitization experiments is straightforward. The sulfinyl radical is characterized by transient absorption and a model is proposed to account for its reactivity with nitroxide radicals.
