- FLUORENONE KETYL ANIONS GENERATED IN HYDROCARBON MEDIA BY PHASE TRANSFER CATALYSIS
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Fluorenone ketyl anions with the counterions Bun3S(1+), Bun4N(1+) and (n-C12H25)3(CH3)N(1+) have been generated in benzene by decomposing fluorenopinacol with the relevant alkylammonium or alkylsulphonium base, under phase-transfer catalytic conditions.The recorded ESR spectra in the hydrocarbon medium exhibit a marked cation dependence.The phenomenon is interpreted on the basis of spin density transfer from the anion to the magnetic nuclei of the cation.The implications to the phase transfer catalysis are discussed.
- Cazianis, Constantine T.,Screttas, Constantinos G.
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Read Online
- Synthesis, IR/Raman, and quantum-chemical structural analysis of new octathiotetraphosphetane ammonium salts
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New octathiotetraphosphetane ammonium salts are obtained based on the reaction of white phosphorus (P4) and elemental sulfur with aliphatic mercaptans in the presence of amines (morpholine, methylmorpholine, pyrrolidine, and N,N-dimethylbenzylamine). Both the salts and novel Cu(I) chloride complex with the pyperidinium salt of octathiotetraphosphetane are characterized by IR/Raman spectroscopy in combination with DFT methods. The comparative spectral analysis reveals clear spectral features, characteristic for a P4S 84- anion, which are present in IR and Raman spectra of all the compounds obtained.
- Badeeva, Elena K.,Platova, Elena V.,Batyeva, Elvira S.,Kursheva, Lidiya I.,Zvereva, Elena E.,Vandyukov, Aleksander E.,Katsyuba, Sergey A.,Kovalenko, Valeryi I.,Sinyashin, Oleg G.
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Read Online
- Catalytic dehydrogenation of amines to imines and the in-situ reduction of sulfoxides into sulfides
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The catalytic acceptorless dehydrogenation of primary amines into imines and H2 represents one of the most important organic transformations, and the in-situ utilization of the generated H2 for chemical reduction reactions has never
- Li, Bo,Liu, Bing,Liu, Xixi,Wang, Wei,Wang, Yanxin,Xiang, Nian,Zhang, Zehui
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- Thioether preparation method
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The invention provides a thioether preparation method. The thioether is prepared according to the reaction formula of a formula (1) or a formula (2), wherein the A1-R1-X1 and the A2-R2-X2 are arylhalostannyl derivatives, no transition metal catalysts are needed in the reaction, heavy metal pollution is avoided, the used sulfur sources (sulfide and elementary substance sulfur) are cheap and easy to obtain, operation is simple and efficient, the reaction condition is mild, the cost is low, safety is high, and the thioether preparation method is suitable for industrial production.
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Paragraph 0063; 0064
(2017/02/28)
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- Cd(II)-MOF-IM: Post-synthesis functionalization of a Cd(II)-MOF as a triphase transfer catalyst
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A robust and porous Cd(ii)-MOF based on a bent imidazole-bridged ligand was synthesized and post-synthetically functionalized with linear alkyl chains to afford imidazolium salt (IM)-type triphase transfer catalysts for organic transformations. The imidazolium salt decorated Cd(ii)-MOF-IM exhibits typical solid phase transfer catalytic behavior for the azidation and thiolation of bromoalkane between aqueous/organic phases. Moreover, they can be easily recovered and reused under the PTC conditions. Cd(ii)-MOF-IM herein created a versatile family of solid phase transfer catalysts for promoting a broad scope of reactions carried out in a biphasic mixture of two immiscible solvents.
- Wang, Jian-Cheng,Ma, Jian-Ping,Liu, Qi-Kui,Hu, Yu-Hong,Dong, Yu-Bin
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supporting information
p. 6989 - 6992
(2016/06/09)
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- One-Pot Intermolecular C–S Self-Coupling of Dimethyl Sulfoxide Promoted by Molybdenum Pentachloride
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The reactions between MoCl5and 1–2 equiv. of a selection of sulfoxides at room temperature in dichloromethane as solvent were studied. The 1:1 molar reaction between MoCl5and dimethyl sulfoxide (DMSO) afforded the C–S coupling product [Me2SCH2SMe][MoOCl4] (1), which was isolated in 46 % yield and characterized by analytical and spectroscopic methods and by X-ray diffraction. MoOCl3, SMe2and HCl were identified as side products. The reactions between MoCl5and tetrahydrothiophene 1-oxide, nBu2SO, MePhSO or (PhCH2)2SO yielded the corresponding sulfides and, in the cases of (PhCH2)2SO and MePhSO, also C–S activation compounds. According to DFT calculations, the unusual formation of 1 is the consequence of thermodynamically feasible Cl/O interchange between MoCl5and DMSO, this being a prerequisite for successive C–H bond activation.
- Bortoluzzi, Marco,Ferretti, Eleonora,Hayatifar, Mohammad,Marchetti, Fabio,Pampaloni, Guido,Zacchini, Stefano
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p. 3838 - 3845
(2016/08/19)
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- Oxidation and halogenation of divinyl selenide. first synthesis of divinyl selenoxide
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Efficient procedure was developed for the preparation of divinyl selenoxide in 92% yield by oxidation of divinyl selenide with sodium periodate. At the action of S-nucleophiles on the divinyl selenoxide it is reduced to divinyl selenide. The reaction of divinyl selenide with an equimolar amount of sulfuryl chloride or bromine led to halogenation products at the selenium atom: divinylselenium dichloride and divinylselenium dibromide. A rearrangement was discovered of divinylselenium dibromide into vinyl(1,2-dibromoethyl)-selenide. The hydrolysis of divinylselenium dichloride results in divinyl selenide.
- Kurkutov,Potapov,Amosova
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p. 624 - 627
(2016/07/06)
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- Reaction mechanisms of thioetherification for mercaptans and olefins over sulfided Mo-Ni/Al2O3 catalysts
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The thioetherification reaction of 1-butanethiol and 1-hexene dissolved in n-hexane was investigatedover sulfided Mo-Ni/Al2O3catalysts. The experimental results showed the catalysts have good cat-alytic performance for thioetherification reaction, but the isomerization and hydrogenation reactions of olefins over the catalysts can inhibit thioetherification reaction. As reaction temperature increases,the isomerization and hydrogenation reactions of olefins increase rapidly, however, the inhibition of thioetherification reaction also increases. The sulfur distribution and molecular structures of sulfurcompounds in the products were analyzed by the gas chromatograph with sulfur chemiluminescencedetector (GC-SCD) and the gas chromatograph/mass spectra spectrometry (GC/MS). Two possible routesof thioetherification reaction could be observed. At low temperature, the major pathway involves a directaddition of 1-butanethiol to the terminal carbon of double bond of 1-hexene. In this mechanism, the mainproduct is anti-Markovnikov adduct. At a higher temperature, the C S bond of 1-butanethiol can be sub-sequently cleaved, and the adsorbed -SH species can be formed on the catalysts. On the same time,abundant 1-hexene can be absorbed on the catalysts, as well. Therefore, the adsorbed SH species canthen recombine with adsorbed 1-hexene to form new hexyl-mercaptans, which can continue to produceanother kind of thioether (di-hexyl sulfide) with adsorbed 1-hexene. Similar with the first reaction route,the thioether of the anti-Markonikov adduct still dominates in the product.
- Shen, Zhibing,Ke, Ming,Yu, Pei,Hu, Haiqiang,Song, Zhaozheng,Jiang, Qingzhe
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p. 120 - 127
(2015/02/02)
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- Unexpected reaction of 2-chloro-1-propen-3-yl isothiuronium chloride with potassium ditelluride: the first example of vicinal elimination of chlorine and sulfur-bearing moieties
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2-Chloro-1-propen-3-yl isothiuronium chloride reacts with potassium ditelluride in hydrazine hydrate to afford elemental tellurium and allene. The latter is formed due to the vicinal elimination of chlorine and a sulfur-bearing moiety.
- Levanova, Ekaterina P.,Grabelnykh, Valentina A.,Elaev, Alexander V.,Albanov, Alexander I.,Klyba, Lyudmila V.,Russavskaya, Natalia V.,Tarasova, Olga A.,Rozentsveig, Igor B.,Korchevin, Nikolai A.
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p. 505 - 511,7
(2020/09/16)
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- Aliphatic thioethers by s-alkylation of thiols via trialkyl borates
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A simple and convenient one-pot procedure is described for the synthesis of thioethers via boron esters. This procedure involves in-situ generation of alkyl sulfates by reaction of trialkyl borates with concentrated sulfuric acid and subsequent reaction with thiols in the presence of pyridine. The reactions with boron esters of primary or secondary alcohols proceed cleanly at 100C and afford aliphatic thioethers in reasonable yields (59-93%) within 24 h. Interestingly, the 1H NMR spectra of the products showed no sign of positional isomerisms. The method fails however with thiophenol and does not yield aromatic thioethers, due to electrophilic substitution at the phenyl ring. Copyright Taylor & Francis Group, LLC.
- Gunes, Deniz,Sirkecioglu, Okan,Bicak, Niyazi
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experimental part
p. 1685 - 1690
(2010/09/17)
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- An improved and green preparation of 3-(alkylthio)propionic acids
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An efficient, facile microwave-assisted synthesis has been developed for the preparation of unsymmetrical sulfide derivatives from 3-mercaptopropionic acid and a wide variety of alkyl, allyl or aryl chlorides or bromides. The synthesis performed in ethanol at 80 or 120 °C using sodium hydroxide as a base, selectively without an offensive smell, generates 3-(alkylthio)propionic acids in good yields. Effects of reaction components, temperature, and the heating technique on the formation of the product and side-products were studied.
- Vaismaa, Matti J. P.,Yliniemel?, Sanna M.,Lajunen, Marja K.
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p. 1317 - 1323
(2008/10/09)
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- KF/Al2O3-mediated N-alkylation of amines and nitrogen heterocycles and S-alkylation of thiols
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KF/Al2O3 efficiently catalyzes N-alkylation of heterocyclic, primary, and secondary amines and S-alkylation of thiols with a variety of alkyl halides. The N-alkylation and S-alkylation adducts were produced in good to excellent yields and in short times. Copyright Taylor & Francis Group, LLC.
- Moghaddam, Firouz Matloubi,DokhtTaimoory, Seyedeh Maryam,Ismaili, Hossein,Bardajee, Ghasem Rezanejade
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p. 3599 - 3607
(2007/10/03)
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- A mild and highly convenient chemoselective alkylation of thiols using Cs2CO3-TBAI
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A mild and improved method for the synthesis of thioethers has been developed. In the presence of cesium carbonate, tetrabutylammonium iodide, and DMF, various alkyl and aryl thiols underwent S-alkylation to afford structurally diverse sulfides in high yield. Unprotected mercaptoalcohols and thioamines reacted chemoselectively at the sulfur moiety exclusively. An example of a one-pot, solid-phase synthesis of a thioether is also described.
- Salvatore, Ralph Nicholas,Smith, Robert A.,Nischwitz, Adam K.,Gavin, Terrence
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p. 8931 - 8935
(2007/10/03)
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- Reductive cleavage of S-S bond by Zn/AlCl3 system: A novel method for the synthesis of sulfides from alkyl tosylates and disulfides
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Alkyl and aryl disulfides are reduced by zinc powder in the presence of AlCl3 in aqueous media to yield zinc thiolates. These thiolate anion species then react with alkyl tosylates to give sulfides in high to excellent yields.
- Movassagh, Barahman,Mossadegh, Amir
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p. 2337 - 2343
(2007/10/03)
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- Reductive cleavage of S-S bond by Zn/AlCl3 system: A novel method for the synthesis of sulfides from alkyl tosylates and disulfides
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Alkyl and aryl disulfides are reduced by zinc powder in the presence of AlCl3 in aqueous media to yield zinc thiolates. This thiolate anion species then react with alkyl tosylates to give sulfides in high execellent yields.
- Movassagh, Barahman,Mossadegh, Amir
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p. 1685 - 1690
(2007/10/03)
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- Synthesis of organic sulfides via Zn/AlCl3 system in aqueous media
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An efficient procedure for preparation of various sulfides has been introduced through a simple reaction of disulfides with suitable alkyl or aryl halides which is promoted by commercial zinc powder in the presence of AlCl3 in aqueous media at 65°C.
- Lakouraj,Movassagh,Fadaei
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p. 1237 - 1242
(2007/10/03)
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- Highly Efficient Solvents and Reagents for Elemental Sulfur
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Elemental sulfur is easily activated in the hydrazine hydrate-alkali system with formation of polysulfide anions. The procedure is developed for yielding highly concentrated solutions of alkali metal polysulfides. The latter compounds are readily alkylated with alkyl halides to form dialkyl polysulfides. The alkylation using higher alkyl halides (C7-C9) yields dialkyl sulfides that are difficult to prepare by other methods.
- Deryagina,Kozlov,Vershal',Babkin
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p. 1240 - 1243
(2007/10/03)
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- Reaction of Triphenylsulfonium Salt with Organolithium Reagents
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The reaction of triphenylsulfonium trifluoromethanesulfonate with various nucleophilic, organolithium reagents gave ligand coupling products and the corresponding diaryl or di-heteroaryl sulfides. Moreover, ligand exchange reaction did not give any noticeable product in each reaction. Therefore, it was found that only the ligand coupling reaction proceeds in this reaction system.
- Oae,Ishihara,Yoshihara
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p. 265 - 269
(2007/10/03)
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- Studies on the Reaction of Iron Sulphide with Butan-1-ol in the Vapour Phase
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A new reaction of iron sulphide with butan-1-ol in the vapour phase a 359-500 deg producing mainly 1,1'-thiobis(butane) and 1,1-dibutoxybutane is reported.Iron sulphide (FeS) catalyses the formation of 1,1-dibutoxybutane and decomposition of 1-butane thiol.
- D'Souza, Ita M.,Banerjee, Anil C.
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p. 739 - 742
(2007/10/03)
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- Single electron transfer catalyzed simultaneous cleavage of C-S and S-S bonds
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Since the S-S bond of polysulfides plays a vital role in biological processes, the chemistry of the S-S bond has attracted considerable attention.The reaction of bis-(trifluoromethyl) trisulfide with organolithium reagents at -78 deg C has now been found to cause simultaneous scissions of the C-S and S-S bonds and to furnish mixed monosulfides, disulfides and trisulfides containing the trifluoromethyl moiety.The formation of the various products has been rationalized on the basis of the involvement of the single electron transfer process.
- Munavalli, S.,Rossman, D. I.,Rohrbaugh, D. K.,Ferguson, C. P.,Banks, H. D.
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- Catalytic Thioether and Thioacetal Formation using Bis(diphenylphosphino)methane Complexes of Platinum (II)
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Bis(dihenylphosphino)methane complexes of platinum (II) catalyze the formation of thioethers from thiols and alkyl halides and of thioacetals from thiols or dithiols and geminal dihalides.
- Page, Philip C. Bulman,Klair, Sukhbinder S.,Brown, Michael P.,Smith, Christopher S.,Maginn, Stephen J.,Mulley, Suzanne
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p. 5933 - 5940
(2007/10/02)
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- Acid-Catalyzed Photoreduction of Dialkyl Sulfoxides by an Acid-Stable NADH Analogue
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Photoreduction of dialkyl sulfoxides by an acid-stable NADH analogue, 9,10-dihydro-10-methylacridine (AcrH2), proceeds in the presence of perchloric acid in acetonitrile via photoinduced electron transfer from the singlet excited state of AcrH2 to protonated sulfoxides to yield the corresponding dialkyl sulfides.
- Fukuzumi, Shunichi,Tokuda, Yoshihiro
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p. 897 - 900
(2007/10/02)
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- Electrochemical Alkylation of Thiols
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Synthesis of functionally substituted sulfides by alkylation of electrochemically generated thiolate on platinum or glassy carbon cathodes with organohalides of various structures is reported.
- Petrosyan, V. A.,Niyazymbetov, M. E.,Konyushkin, L. D.,Litvinov, V. P.
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p. 841 - 842
(2007/10/02)
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- ELECTROCHEMICAL SYNTHESIS OF FUNCTIONALLY SUBSTITUTED SULFIDES
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A method of synthesis of functionally substituted sulfides by cathode electrolysis of thiols on platinum or carbon glass electrodes in the presence of organyl halides was developed.The method of the rotating disk electrode with ring showed that this process passes through the intermediate formation of a thiolate anion on the cathode, and its reaction with the organyl halide results in a high yield of sulfides.
- Niyazymbetov, M. E.,Petrosyan, V. A.,Konyushkin, L. D.,Litvinov, V. P.
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p. 1454 - 1457
(2007/10/02)
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- HIGH-TEMPERATURE ORGANIC SYNTHESIS. XXXIV. THERMOLYSIS OF DIBUTYL POLYSULFIDES
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The main liquid product from the thermolysis of dibutyl polysulfides (C4H9)2Sn at 500-550 deg C is thiophene (maximum yield 43 percent with n = 3).The most thermally labile is dibutyl tetrasulfide, which decomposes even at 250 deg C.Above 350 deg C the tetrasulfide is also converted into 5-methyl-1,2-dithiole-3-thione, the yield of which amounts to 5-6percent.During the thermolysis of dibutyl disulfide in the presence of acetylene even at 400 deg C thiophene is formed with a yield of 70percent but in a mixture with benzene (yield 25 percent).
- Sukhomazova, E. N.,Turchaninova, L. P.,Korchevin, N. A.,Deryagina, E. N.,Voronkov, M. G.
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p. 1059 - 1062
(2007/10/02)
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- REACTIONS OF EPISULPHOXIDES AND EPISULPHIDES WITH ORGANOLITHIUM REAGENTS
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Reactions of aryl-substituted episulphoxides and episulphides with butyl- and phenyllithium, lithium di-isopropyl amide and lithium dimethylcuprate have been examined.The following reaction paths could be observed: a) attack at sulphur leading to olefins with complete retention of configuration at the carbon skeleton; b) attack at proton leading to a vinyl sulphenate in the case of episulphoxides, or to a thiolate anion, in the case of episulphides, trapped as methyl vinyl sulphoxide or methyl vinyl sulphide, respectively; c) attack at carbon, observed only in thereaction of styrene episulphoxide with lithium dimethylcuprate, leading to a saturated sulphenate anion trapped as alkyl methyl sulphoxide.Mechanisms and stereochemistry of these processes are discussed.
- Bonini, Bianca F.,Maccagnani, Gaetano,Mazzanti, Germana,Zani, Paolo
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p. 115 - 121
(2007/10/02)
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- Rapid and Mild Deoxygenation of Organoheteroatom Oxides with the Efficient Electron Transfer System SmI2-Tetrahydrofuran-Hexamethylphosphoric Triamide
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A variety of organoheteroatom oxides such as sulphoxides, sulphones, N-oxides, a phosphine oxide, and an organo tin oxide were rapidly deoxigenated at room temperature by using a stoicheiometric amount of SmI2 in tetrahydrofuran-hexamethylphosphoric triamide.
- Handa, Yuichi,Inanaga, Junji,Yamaguchi, Masaru
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p. 298 - 299
(2007/10/02)
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- Electronic and steric effects in the dissociative displacement of thioethers from mixed phenyl(thioether)platinum(II) complexes
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A series of compounds of the type cis-[PtPh2L2], where L encompasses a wide range of thioethers of different steric and electron-donating characteristics, have been prepared and characterized. Most of these monomeric compounds exist in solution in equilibrium with the sulfur-bridged dimer [Pt2Ph4(μ-L)2] and the free thioether. Addition of small amounts of ligand in solution allows the stabilization of the monomeric form. Kinetic studies of the displacement of the thioethers with 2,2′-bipyridine (bpy) to yield [PtPh2(bpy)] in CH2Cl2 at 298.16 K, carried out in the presence of sufficient excess of [L] and [bpy] to ensure pseudo-first-order conditions, showed that the reactions follow a bivariate nonlinear rate law kobsd = a[bpy]/(b[L] + [bpy]) + c[bpy], which has the same form as that of similar systems for which a dissociative mechanism has been proposed. The reactivity decreases linearly with increasing σ-donor ability of the leaving thioether, with bulky substituents on sulfur playing an accelerating role. The relative sensitivities of the dissociative and associative processes to the inductive effects of the leaving group are compared and related to the degree of lengthening and weakening of the bond with the metal produced by the trans-activating group.
- Alibrandi, Giuseppe,Minniti, Domenico,Scolaro, Luigi Monsù,Romeo, Raffaello
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p. 1939 - 1943
(2008/10/08)
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- CARBON-SULPHUR BOND FORMATION CATALYSED BY BIS(DIPHENYLPHOSPHINO)-METHANE COMPLEXES OF PLATINUM(II)
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Thiols react with alkylhalides in the presence of sodium carbonate and a catalytic quantity of (dppm)PtCl2 to give thioethers.Of especial interest is the succesful application to thioacetal formation using 1,1-dihalides which, does not require the use of strong bases or the intermediacy of thiolate anions.
- Page, Philip C. Bulman,Klair, Sukhbinder S.,Brown, Michael P.,Harding, Marjoire M.,Smith, Christopher S.,et al.
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p. 4477 - 4480
(2007/10/02)
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- Pentaborane(9) as a source for higher boron hydride systems. a new synthesis of nido-5,6-(CH3)2-5,6-C2B8H 10
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Pentaborane(9), B5H9, is shown to be a useful source for the production of higher boron hydride systems. Investigation of the reaction of B5H9 with sodium hydride or potassium hydride in THF or glyme to produce the tetradecahydrononaborate(1-) anion, [B9H14]-, is reported in detail, and evidence is given for reaction pathways. This anion is also obtained from the reaction of NaI with B5H9. When generated in situ from B5H9, [B9H14]- is an intermediate in the syntheses of a number of other higher boron hydride systems: B9H13·L ligand adducts, n-B18H22, B10H14, nido-5,6-C2B8H12, and nido-5,6-(CH3)2-5,6-C2B8H 10. The synthesis of B10H14 reported here is an improved procedure over the earlier reported preparation from B5H9, and the preparations of nido-5,6-(CH3)2-5,6-C2B8H 10 and nido-5,6-C2B8H12 are new syntheses.
- Lawrence, Steven H.,Wermer, Joseph R.,Boocock, Simon K.,Banks, Michael A.,Keller, Phillip C.,Shore, Sheldon G.
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p. 367 - 372
(2008/10/08)
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- PHOTOCHEMICAL REDUCTION OF N-TOSYLSULFILIMINES WITH THIOLATE ANION
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The reaction between N-tosyldiarylsulfilimines and p-toluenethiolate anion did not take place in the dark even upon heating up to 62o but proceeded smoothly upon irradiation with visible light in DMF at room temperature, affording S-N bond cleavage products.
- Fujimori, K.,Togo, H.,Pelchers, Y.,Nagata, T.,Furukawa, N.,Oae, S.
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p. 775 - 778
(2007/10/02)
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- THIOETHER PROTECTION VIA SELECTIVELY CLEAVABLE SULFONIUM SALTS
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There are few protecting groups available for the thioether functionality.The selective cleavage of 4-phthalimidobutyl- and p-methoxybenzylsulfonium salts make these derivatives ideal for thioether protection.
- Doi, Joyce Takahashi,Luehr, Gary W.
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p. 6143 - 6146
(2007/10/02)
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- Nucleophilic Substitution of Alkyl Halides by Zinc Salts: Part 4-Synthesis of Thioethers and Thiolesters
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A variety of alkyl halides including tertiary alkyl halides react smoothly with the zinc salts of thiols and thiolcarboxylic acids yielding thioethers and thiolesters.
- Rajanikanth, B.,Ravindranath, B.
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p. 1043 - 1045
(2007/10/02)
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- Ion-pair extraction of thiocyanate from plasma and its gas chromatographic determination using on-column alkylation
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Tributylsulfonium thiocyanate may be extracted from aqueous solutions with organic solvents. Injection into the heated injection port of a gas chromatograph results in conversion to the volatile derivative butyl thiocyanate. Tributylsulfonium selenocyanate undergoes analogous extraction and thermal conversion to the butyl derivative. A procedure has been developed for the extraction of thiocyanate from human plasma and gas chromatographic determination using selenocyanate as an internal standard. The method has good sensitivity and precision and has been applied to behavioral and pharmacologic studies of smokers.
- Jacob III,Savanapridi,Yu,et al.
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p. 1692 - 1695
(2007/10/02)
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- REACTIONS OF TRIORGANOSILYLSULFENYL HALIDES WITH SOME NUCLEOPHILES
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The reaction of triorganosilylsulfenyl halides R3SiSX (R=Ph, Et; X=Cl, Br) with carbon-carbon double bonds, trialkyl phosphites, and organometallic reagents have been studied.With the first two nucleophiles the course of the reactions differed from that with organosulfenyl chlorides because of nucleophilic attack of halide ion on silyl group.
- Kowalski, J.,Chojnowski, J.,Michalski, J.
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- REACTION OF DIMETHYL SULFITE WITH PHENYLLITHIUM. FORMATION OF BIPHENYL AND DIPHENYL SULFIDE VIA SULFURANE
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Dimethyl sulfite reacted an excess of phenyllithium yielding biphenyl and diphenyl sulfide in good yield.Other dialkyl sulfites also reacted giving identical yields of biphenyl and diphenyl sulfide irrespective of the structure of the aryl groups, indicating that dialkyl sulfites can be used for the reaction with aryllithiums in place of diaryl sulfoxides.The mechanism of the reaction of diaryl sulfoxides with aryllithium is discussed on the the basis of the isomer distribution of bitolyls, the effect of additives, and the ratio of the benzyne and sulfonium salt pathways.Sulfurane 1 is formed in an initial stage of the reaction of diaryl sulfoxide with aryllithium followed by its competitive collapse by way of benzyne and sulfonium salt pathways.
- Hara, Yoshinori,Matsuda, Minoru
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p. 211 - 222
(2007/10/02)
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- POLYMER SUPPORTED REAGENTS. THE USE OF ANION-EXCHANGERS IN THE SYNTHESIS OF SULPHIDES AND DISULPHIDES
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The macroreticular anion-exchanger Amberlyst A-26, in thiolate and disulphide form, reacts under mild conditions, with primary and secondary alkyl halides and tosylates to give good yields of sulphides and disulphides, respectively.The reaction seems to be of general applicability and is particularly useful in the synthesis of disulphides as no thiol is needed as starting material.The exhausted polymeric reagent is easily regenerable.
- Cainelli, Gianfranco,Contento, Michele,Manescalchi, Francesco,Plessi, Laura
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p. 461 - 464
(2007/10/02)
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- Reactions of bis(acetoxymethyl) ether and several of its aryloxy analogues
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Displacement of acetoxy groups from bis(acetoxymethyl) ether by a varietyof phenols is demonstrated.The effect of various catalysts of the reaction is documented, and a possible role of the catalyst is discussed.Several (aryloxy)methyl ethers are used for the preparation of (alkylthio)methyl ethers.
- Wadsworth, Donald H.,Vinal Richard S.,Cleveland, James P.
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p. 1623 - 1626
(2007/10/02)
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- Chemical Conversions using Sheet Silicates: Novel Intermolecular Eliminations of Hydrogen Sulphide from Thiols
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Aliphatic primary and secondary thiols react in the interlamellar layers of ion-exchanged montmorillonite catalysts to produce dialkyl sulphides via intermolecular elimination of hydrogen sulphide; similar processes result in the production of diphenyl sulphide from benzenethiol and poly(phenylenemethylene) from α-toluenethiol.
- Ballantine, James A.,Galvin, Robert P.,O'Neil, Robert M.,Purnell, Howard,Rayanakorn, Mongkon,Thomas, John M.
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p. 695 - 696
(2007/10/02)
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