- 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
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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.
- Aoyama, Tadashi,Hayakawa, Mamiko,Kosuge, Masayuki,Nakaoka, Kyohei,Ouchi, Akihiko
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p. 2572 - 2578
(2019/06/08)
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- SINGLE-STEP SYNTHESIS METHOD OF ARYL THIOL AND APPLICATION THEREOF
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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
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Paragraph 0032; 0033; 0063; 0067; 0068; 0070
(2017/09/02)
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- 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)
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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.
- Soleiman-Beigi, Mohammad,Sadeghizadeh, Fatemeh,Basereh, Ali
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p. 572 - 583
(2017/09/27)
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- Copper(II)-Catalyzed Single-Step Synthesis of Aryl Thiols from Aryl Halides and 1,2-Ethanedithiol
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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.
- Liu, Yajun,Kim, Jihye,Seo, Heesun,Park, Sunghyouk,Chae, Junghyun
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supporting information
p. 2205 - 2212
(2015/07/27)
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- Structural characterization and function determination of a nonspecific carboxylate esterase from the amidohydrolase superfamily with a promiscuous ability to hydrolyze methylphosphonate esters
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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.
- Xiang, Dao Feng,Kumaran, Desigan,Swaminathan, Subramanyam,Raushel, Frank M.
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p. 3476 - 3485
(2014/06/23)
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- Catalytic enantioselective oxidation of bulky alkyl aryl thioethers with H2O2 over titanium-salan catalysts
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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.
- Bryliakov, Konstantin P.,Talsi, Evgenii P.
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experimental part
p. 4693 - 4698
(2011/10/03)
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- Palladium catalyzed synthesis of aryl thiols: Sodium thiosulfate as a cheap and nontoxic mercapto surrogate
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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.
- Yi, Jun,Fu, Yao,Xiao, Bin,Cui, Wei-Chen,Guo, Qing-Xiang
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experimental part
p. 205 - 208
(2011/02/26)
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- [[(tert-Butyl)dimethylsilyl]oxy]-methylGroup for sulfur protection
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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.
- Wang, Lihong,Clive, Derrick L. J.
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supporting information; experimental part
p. 1734 - 1737
(2011/06/09)
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- Thiol radical cations and thiyl radicals as direct products of the free electron transfer from aromatic thiols to n-butyl chloride radical cations
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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.
- Hermann, Ralf,Dey, Ghasi Ram,Naumov, Sergej,Brede, Ortwin
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p. 1213 - 1220
(2007/10/03)
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- Photochemistry of benzyl β-naphthyl sulfoxide and characterization of the β-naphthylsulfinyl radical
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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.
- Guo, Yushen,Darmanyan, Alexandre P.,Jenks, William S.
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p. 8619 - 8622
(2007/10/03)
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- Potassium fluoride on alumina: Synthesis of O-aryl N,N-dimethylthiocarbamates and their rearrangement into S-aryl N,N-dimethylthiocarbamates under microwave irradiation
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A series of O-aryl N,N-dimethyl thiocarbamates have been prepared by the reaction of dimethylthiocarbamoyl chloride with phenols absorbed on potassium fluoride on alumina. The rearrangement of O-aryl N,N-dimethylthiocarbamate into S-aryl N,N-dimethylthiocarbamate under microwave irradiation was also studied. The use of conductive support like graphite or silicon carbide allow these rearrangements although the O-aryl N,N-dimethylthiocarbamates have very low dielectric lost.
- Villemin, Didier,Hachemi, Messaoud,Lalaoui, Mekki
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p. 2461 - 2471
(2007/10/03)
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- Convenient synthesis of aromatic thiols from phenols
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Aromatic thiols were synthesised from phenols in good yield and under mild conditions by reaction of the corresponding triflates with sodium triisopropylsilanethiolate (NaSTIPS) and subsequent deprotection.
- Arnould, Jean Claude,Didelot, Myriam,Cadilhac, Caroline,Pasquet, Marie Jeanne
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p. 4523 - 4524
(2007/10/03)
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- Cyclizations and Rearrangements of Samarium Diiodide-Generated Vinyl Radicals
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Vinyl bromides 1, 5, 15, 20, 23, 27, 33a,b, 41a-c, 44a-c, 46a,b, 52a,b, 55a, 56a,b, and 60a,b react with samarium diiodide in THF and/or acetonitrile to give the corresponding vinyl radicals.Radicals 3, 7, and 16 afforded products deriving from cyclization on the adjacent triple bond in a 5-(?-exo)exo, 6-(?-endo)exo, and 6-(?-exo)exo mode, respectively.Radical 7 undergoes competitive 1,5-hydrogen translocation.Vinyl radicals 21 and 24 readily cyclize on the proximal double bond, leading to 5- and 6-membered rings, respectively.Thienyl-substituted radical 28 leads to a product deriving from 5-exo cyclization on the thiophene ring and subsequent β-fission of the C-S bond, whereas thienyl-substituted radicals 34a,b undergo almost exclusively 1,5-hydrogen translocation.Aryl-substituted radicals obtained from vinyl bromides 41, 44, 46, 52, and 55 do not form any products deriving from 5-exo or 6-exo cyclization (or ipso cyclization).Finally, naphthyl-substituted radicals 57a and 61a give only direct reduction products, whereas the radical 61b affords, in addition to the direct reduction product, a rearranged product deriving from a 1,3-radical migration of the naphthylthio group.Evidence is reported for the reduction of EWG-substituted benzene rings and thio-substituted naphthalene rings to radical anions, which can fragment on the side chain with the elimination of allyl radicals. α-Oxy(and α-thio)-substituted radicals deriving from 1,5-shift rearrange to alcohols (and thiols) through a Wittig rearrangement or a cyclization/fragmentation process.
- Capella, Laura,Montevecchi, Pier Carlo,Navacchia, Maria Luisa
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p. 7424 - 7432
(2007/10/03)
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- Thiazole o-quinodimethanes: The generation, electrocyclisation and Diels-Alder reactions of phenyl substituted derivatives
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α-(2-Phenyl-4-methylthiazol-5-yl)-α-phenylmethyl acetate 2 undergoes thermal elimination of acetic acid to give the o-quinodimethane 3. In solution this can be intercepted in Diels-Alder reactions but under flash pyrolytic conditions naphthalene-2-thiol is formed by electrocyclisation and fragmentation.
- Potter, Andrew J.,Storr, Richard C.
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p. 5293 - 5296
(2007/10/02)
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- RADIKALIONEN 89. EINELEKTRONEN-OXIDATIONEN VON DIARYLDISULFIDEN MIT AlCl3/H2CCl2
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The single electron oxidation of 14 alkyl and alkoxy substituted diaryldisulfides by AlCl3/H2CCl2 has been investigated by ESR/ENDOR spectroscopy.The radical cations observed prove the following skeletal rearrangements: Those with ring hydrogens in ortho positions to the disulfide bridge preferentially form thianthrene derivatives.The isomeric dinaphthyl disulfides react differently, the 2,2'-isomer yielding the dibenzothianthrene radical cation and the 1,1'-isomer the well-known naphthalene-1,8-disulfide radical cation.For all diaryl disulfides with completely alkyl- or methoxy-blocked ortho positions, oxidative desulfuration is observed.As substantiated by additional (2)D and (33)S isotope marking, the bis(2,5-dimethoxyphenyl)disulfide reacts both to the corresponding thianthrene derivative as well as via desulfuration to the radical cation of the monosulfide.Accompanying cyclovoltammetric and photoelectron spectroscopic measurements prove that all ESR spectroscopically detected radical cations result from compounds Ar-S-Ar, Ar-SS-Ar and Ar(S)2Ar with rather low oxidation or ionisation potentials and thus suggest that each the most easily oxidized paramagnetic species is observed in the rather complex product mixtures, which form on AlCl3/H2CCl2 oxidation of diaryldisulfides. Key words: Diaryl disulfides; one-electron oxidation; radical cations; ESR/ENDOR spectra.
- Bock, Hans,Rittmeyer, Peter
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p. 261 - 292
(2007/10/02)
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- THERMOLYSIS AND PHOTOLYSIS OF SOME SELECTED ARYL THIOESTERS
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Aryl thioesters I and II were prepared and pyrolyzed in the absence of promotors either alone or in isoquinoline as solvent.Thermolysis of β-naphthyl thiobenzoate (I) on heating in air at 250 deg C gives benzil, benzophenone, benzoic acid, biphenyl, thio β-naphthol, 2,2'-binaphthyl, diphenyl sulfide, thianthrene, thiophenol, phenyl β-naphthyl sulfide and 2,2'-binaphthyl sulfide.Similar results were also obtained on heating p-tolyl thiobenzoate (II) under the same conditions in addition to thio p-cresol, p-bitolyl, p-ditolyl sulfide and phenyl p-tolyl sulfone.H2S and CO are also produced in all cases.Thermolysis of I and II in the presence of isoquinoline affords in addition to the above products, 1-phenylisoquinoline.Photolysis of I and II in acetone gives similar products to those of the thermolysis.From these results a free radical mechanism has been postulated to take place through the initial homolysis of C-S bond.No isomer redistribution proceeds the coupling reactions.Key words: Thermolysis, photolysis, aryl thioesters.
- El-Aal, Abd,Gaber, M.
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p. 211 - 217
(2007/10/02)
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- NEW SYNTHESIS OF 1,2,5-SELENADIAZOLES
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A new synthesis of 1,2,5-selenadiazoles which starts from unsubstituted or monosubstituted 1,2,5-thiadiazoles and Grignard reagents is described and the mechanism of the reaction discussed.
- Bertini, Vincenzo,Munno, Angela De,Picci, Nevio,Lucchesini, Francesco,Pocci, Marco
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p. 2153 - 2158
(2007/10/02)
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- Reactions of Sodium Borohydride. IV. Reduction of Aromatic Sulfonyl Chlorides with Sodium Borohydride
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Aromatic sulfonyl chlorides were reduced with sodium borohydride in tetrahydrofuran at 0 deg C to the corresponding sulfinic acids in good yields.Further reduction proceeded when the reaction was carried out under reflux in tetrahydrofuran to give disulfide and thiophenol derivatives via sulfinic acid.Furthermore, sulfonamides were reduced with sodium borohydride by heating directly to give sulfide, disulfide and thiophenol derivatives, and diphenyl sulfone was reduced under similar conditions to give thiophenol and biphenyl.Keywords---reduction; sodium borohydride;aromatic sulfonyl chloride; sulfonamide; sulfone; aromatic sulfinic acid disulfide; sulfide; thiophenol
- Nose, Atsuko,Kudo, Tadahiro
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p. 1770 - 1776
(2007/10/02)
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- REDUCTION OF SULFONIC ACIDS WITH TRIPHENYLPHOSPHINE-DIARYL DISULFIDE SYSTEM.
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Diaryl disulfides are effective catalysts to reduce arenesulfonic acids with triphenylphosphine to the corresponding arenethiols in good yields, while alkanesulfonic acids are transferred into the corresponding alkyl aryl sulfides. Arenesulfonic acids bearing electron-donating substituents can be reduced more readily than those having electron-withdrawing substituents, while diaryl disulfides bearing electron-withdrawing substituents are more effective catalysts than diaryl disulfides with electron-donating ring substituents.
- Oae,Togo
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p. 232 - 236
(2007/10/02)
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- Reduction of Sulfonic Acids and Related Organosulfur Compounds with Triphenylphosphine-Iodine System
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Arenesulfonic acids, their sodium salts, and alkyl arenesulfonates can be reduced readily to the corresponding arenethiols quantitatively by treatment with a mixture of triphenylphosphine and a catalytic amount of iodine, while alkanesulfonic acids, sulfinic acids, disulfides, thiosulfonic S-esters, and sulfonates are also readily reduced to the corresponding thiols similarly.Upon treatment with a mixture of triphenylphosphine and excess iodine, however, these aliphatic sulfur compounds are converted eventually to the corresponding alkyl iodides.The relative reactivities of these sulfonyl derivatives in the reaction with the triphenylphosphine-iodine system are the following.Aromatic series: ArSO2Cl, ArSO2SAr' > ArSO2H > ArSO3R > ArSO3-HNBu3+ (or PyH+) > ArSO3H > ArSO2SO2Ar >> ArSO2CH2C(CH3)3, ArSO3Ar'.Aliphatic series: RSO2Cl, RSO2SR', RSO2-HNBu3+ > RSO3-HNBu3+ > RSSR, RSO2H > RSO3H > RSH > RSO3R'.In these reactions, the arenesulfonic acids bearing electron-donating substituents can be reduced more readily than those having electron-withdrawing substituents.
- Oae, Shigeru,Togo, Hideo
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p. 3802 - 3812
(2007/10/02)
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- REDUCTION OF SULFONIC ACIDS WITH PHOSPHORUS PENTASULFIDE
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Arene, and alkanesulfonic acids are easily reduced to the corresponding polysulfides R-(S)n-R (n= 2.9 3.3) by treatment with phosphorus pentasulfide.In this reaction, the formation of both P-O-S and P-S-H linkages is considered to be involved in the key step of the reduction.
- Oae, Shigeru,Togo, Hideo
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p. 4701 - 4704
(2007/10/02)
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- A NEW SYNTHESIS OF AROMATIC THIOLS
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Benzenoid and heterocyclic lithio derivatives react smoothly with tetraisopropylthiuram disulfide to give highly crystalline and readily purified S-aryl-N,N-diisopropyldithiocarbamates, which yield aromatic thiols on alkaline hydrolysis.
- Jen, Kwan-Yue,Cava, Michael P.
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p. 2001 - 2004
(2007/10/02)
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- IODINE CATALYZED REDUCTION OF ARENESULFONIC ACID TO THE ARENETHIOL WITH TRIPHENYLPHOSPHINE
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Arenesulfonic acids, its sodium salts, and alkyl arenesulfonates were reduced readily to the corresponding arenethiols quantitatively with triphenylphosphine in the presence of iodine.
- Fujimori, Ken,Togo, Hideo,Oae, Shigeru
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p. 4921 - 4924
(2007/10/02)
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- A CONVENIENT SYNTHESIS OF AROMATIC THIOLS FROM UNACTIVATED ARYL HALIDES
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Aromatic thiols are obtained in good yields from unactivated aryl halides and excess MeSNa in HMPA.
- Testaferri, L.,Tingoli, M.,Tiecco, M.
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p. 3099 - 3100
(2007/10/02)
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