- Copper(I) and Copper(II) Chelates containing Imidazole and Thioether Groups; Synthesis of the Ligand 1,2-Bis(benzimidazol-2'-ylmethylthio)-benzene (bbtb) and the X-Ray Crystal Structure at -52 deg C of 2*5EtOH
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Stable copper(I) and copper(II) complexes of the title ligand (bbtb) have been prepared.The design of the ligand prevents planar four-co-ordination of CuII.The X-ray structure of 2*5EtOH shows that the co-ordination geometry around the metal ion is trigonal bipyramidal.Two benzimidazole nitrogen atoms occupy axial positions, the equatorial positions being occupied by the two thioether sulphur atoms and an oxygen atom of a co-ordinated water molecule.The structure is compared with recently solved structures of closely related imidazole-thioether chelates.The compound crystallizes in the monoclinic space group P21/n with a=18.865(3), b=12.652(2), c=17.902(7) Angstroem, β=101.99(2) deg, and Z=4.The intensities of 5 095 independent reflections were measured on an automatic diffractometer at -52 deg C (to prevent decomposition).The structure was solved by direct methods and refined using full-matrix least-squares techniques to a residual R of 0.069 for 2 869 reflections with l>2δ(l).The e.s.r. spectrum of the solid compound 2*2H2O is 'exchange narrowed' and shows only one signal.The ligand-field spectrum is consistent with a trigonal-bipyramidal geometry.The e.s.r. and ligand-field data indicate a co-ordination geometry in solution which is different from the solid state, and in which the unpaired electron is mainly in a dx2-Y2 orbital.
- Rietmeijer, Frederik J.,Birker, Paul J. M. W. L.,Gorter, Syb,Reedijk, Jan
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- New Selective Synthesis of Dithiaboroles as a Viable Pathway to Functionalized Benzenedithiolenes and Their Complexes
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A synthetic protocol to synthesize 2-bromobenzo-1,3,2-dithiaboroles in one step from easily accessible benzene bis(isopropyl thioether)s has been developed. The reaction is remarkably specific in converting substrates with two adjacent iPrS moieties while leaving isolated thioether functions and other functional groups intact. On the basis of the spectroscopic detection or isolation of reaction intermediates, a mechanistic explanation involving a neighbor-group-Assisted dealkylation as a key step is proposed. The resulting products featuring one or two dithiaborole units were isolated in good yields and fully characterized. Subsequent methanolysis, which was carried out either as a separate reaction step or in the manner of a one-pot reaction, gave rise to functionally substituted benzenedithiols. The feasibility of a methylphosphoryl-substituted benzenedithiol to act as a dianionic S,S-chelating ligand was demonstrated with the formation of paramagnetic Ni(III) and Co(III) complexes. Selective reduction of the phosphoryl group afforded a rare example of a phosphino dithiol which was shown to act as a monoanionic P,S-bidentate ligand toward Pd(II). All complexes were characterized by spectral data and X-ray diffraction studies, and the paramagnetic ones also by superconducting quantum interference device magnetometry.
- Schlindwein, Simon H.,Bader, Katharina,Sibold, Carlo,Frey, Wolfgang,Neugebauer, Petr,Orlita, Milan,Slageren, Joris Van,Gudat, Dietrich
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- An efficient one-pot synthesis of 1,2-benzenedithiol from benzenethiol
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1,2-Benzenedithiol (3) can be prepared on a molar scale and isolated in 96% yield by a convenient one-pot procedure starting from benzenethiol. This method utilizes recent discoveries on the formation of dilithium 1,2-benzenedithiolate (2) via directed ortho-lithiation of lithium benzenethiolate.
- Giolando,Kirschbaum
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- The preparation and characterisation of rhodium(III) and Iridium(III) half sandwich complexes with napthalene-1,8-dithiolate, acenaphthene-5,6-dithiolate and biphenyl-2,2′-dithiolate
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The synthesis of rhodium(III) and iridium (III) half sandwich complexes [Cp?M(PEt3) (S-R-S)], M = Rh, Ir; S-R-S = naphthalene-1,8-dithiolate (NaphthS2, a), acenaphthene-5,6-dithiolate (AcenapS2, b) and biphenyl-2,2′-dithiolate (BiphenS2, c) is reported. We also describe the isolation of a new compound acenaphthene-1,8-dithiol. All complexes have been fully characterised using multinuclear NMR spectroscopy and single crystal X-ray diffraction. The ligands naphthalene-1,8-dithiol (H2a), acenaphthene-1,8-dithiol (H2b), 1,1′-biphenyl-2,2′-dithiol (H2c) and benzene-1,2-dithiol (H2d) have also been characterised by single crystal X-ray diffraction.
- Nejman, Phillip S.,Morton-Fernandez, Brian,Black, Nicholas,Cordes, David B.,Slawin, Alexandra M.Z.,Kilian, Petr,Woollins, J. Derek
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- Photochemical studies on bis-sulfide and -sulfone tethered polyenic derivatives
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This study focusses on the [2 + 2]-photocycloaddition of a symmetric polyenic system tethered by an aryl bis-sulfide or sulfone platform. Using direct irradiation or photosensitization, no expected ladderane product was isolated. In most cases, only tricyclic products including a single cyclobutane moiety were formed. Irradiation of bis-acrylic precursors in water with encapsulation by a host (cyclodextrin or cucurbituril) provided a stereoselective access to valuable cyclobutyl adducts.
- Guélen, Simon,Blazejak, Max,Chamoreau, Lise-Marie,Huguet, Arnaud,Derenne, Sylvie,Volatron, Fran?ois,Mouriès-Mansuy, Virginie,Fensterbank, Louis
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- A method for preparing phthalic of the dithiol
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The invention provides a method for preparing benzene-1,2-dithiol. The method includes the steps that metal sodium, ethyl mercaptan and 1,2-dichlorobenzene serve as starting raw materials, two halogen atoms of the 1,2-dichlorobenzene are completely substituted in polar solvents N,N-dimethyl formamide by controlling the molecular proportion of the reactants through the high nucleophilic substitution capacity of sodium thioethylate, 1,2-2 ethyl petrol phenyl sulfide is obtained with the high yield, then sulphur atom deprotection is carried out under the reducing action of the metal sodium and naphthalene, and the target product benzene-1,2-dithiol is produced in an almost-quantitative mode after acidizing is carried out through hydrochloric acid. The preparing method is simple, convenient to operate, low in price and high in yield, and has the broad application prospects in the fine chemical engineering and the pharmaceutical industry.
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Paragraph 0044-0049
(2020/05/05)
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- 2-FLUORO-1,3-BENZODITHIOL 1,1,3,3-TETRAOXIDE DERIVATIVE, PRODUCTION METHOD THEREOF, AND PRODUCTION METHOD OF MONOFLUOROMETHYL GROUP-CONTAINING COMPOUND USING THE SAME
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A 2-fluoro-1,3-benzodithiol 1,1,3,3-tetraoxide derivative as a monofluoromethyl group introduction agent that is effective as an intermediate in pharmaceutical and agrochemical synthesis, a production method thereof, and a production method of a monofluoromethyl group-containing compound using this 2-fluoro-1,3-benzodithiol 1,1,3,3-tetraoxide derivative are provided. The 2-fluoro-1,3-benzodithiol 1,1,3,3-tetraoxide derivative represented by the following general formula (1) (wherein R1, R2, R3, and R4 each independently represent a hydrogen atom, a straight-chain or branched alkyl group having 1 to 4 carbon atoms, a straight-chain or branched alkyloxy group having 1 to 4 carbon atoms, a halogen atom, a nitro group, or a cyano group), the production method thereof, and various monofluoromethyl group-containing compounds are manufactured using this 2-fluoro-1,3-benzodithiol 1,1,3,3-tetraoxide derivative as a monofluoromethylating agent.
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Page/Page column 11
(2012/01/13)
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- An Effective and Selective Synthesis of Sterically Crowded Benzotrithioles from Benzodithiastannoles via Benzotrithiole 2-Oxides
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Sterically crowded benzotrithioles were efficiently and selectively prepared by the reduction of corresponding benzotrithiole 2-oxides which were readily obtained on treatment of benzodithiastannoles, synthetic equivalents of benzenedithiols, with thionyl chloride.
- Ogawa, Satoshi,Yomoji, Naoki,Chida, Shin-ichi,Sato, Ryu
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p. 507 - 510
(2007/10/02)
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- ELEMENTORGANISCHE VERBINDUNGEN MIT o-PHENYLENSUBSTITUENTEN, XX. 2,3,7,8-TETRA(METHYLTHIO)THIANTHREN
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Starting from thiophenol (3) the sequence 1,2-di(methylthio)benzene (4) -> 1-bromo-3,4-di(methylthio)benzene (5) -> bissulfide (6) -> bissulfide (7) finally leads to the title compound 2.The 1H- and 13C-NMR, and the MS data of 2 are reported.The 1H-NMR data of compounds 5-7 are also given.
- Doetze, Marc,Klar, Guenter
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p. 217 - 222
(2007/10/02)
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- CONVERSION OF CYCLIC TRITHIOCARBONATES TO THIOACETALS, INCLUDING 1,3-DITHIANE, BY REDUCTION WITH DIISOBUTYLALUMINIUM HYDRIDE (DIBAL)
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Cyclic trithiocarbonates can be desulfurized with diisobutylaluminium hydride (DIBAL) to form the corresponding thioacetals.This new synthetic pathway was exploited for the preparation of several Umpolung reagents, including 1,3-dithiane.An efficient isolation of sodium trithocarbonate is described.
- Jordis, Ulrich,Rudolf, Manfred
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p. 279 - 284
(2007/10/02)
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- Oxidation of Thiols by Superoxide Ion
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Superoxide ion oxidizes aromatic thiols to disulfides or sulfonic acids.Benzene-1,2-dithiol and its 4-methyl analogue formed the cyclic disulfides dibenzotetrathiocins.Aliphatic thiols gave disulfides, and ethane-1,2-dithiol and propane-1,3-dithiol formed the cyclic disulfides 1,2,5,6- tetrathiocan and 1,2,6,7-tetrathiecan respectively.Butane-1,4-dithiol underwent an intramolecular cyclization to 1,2-dithian.Cysteine was oxidized by O2 anion radical to cysteic acid.
- Crank, George,Makin, Mohammad I. H.
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p. 2331 - 2337
(2007/10/02)
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- Oxidations with Lead Tetraacetate. IV. Oxidations of 1,3-Benzodithioles
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Oxidations of 2,2-dialkyl and spiro with lead tetraacetate gave mainly sulfoxides and disulfoxides.The stereochemistry of these products was elucidated by n.m.r. spectroscopy.Oxidation of 2-methyl-2-aryl derivatives gave sulfoxides as minor products; here the main products were derived from attack on the methyl group forming acetoxy, diacetoxy, formyl and carboxylic acid derivatives and ring cleavage products. 2,2-Diaryl derivatives also formed small amounts of sulfoxides but ring cleavage products were predominant.Monosubstituted benzodithioles were very reactive and produced a variety of oxidation products, mostly unidentified.
- Aromdee, Chantana,Cole, Edward R.,Crank, George
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p. 2499 - 2509
(2007/10/02)
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- Fragmentation of Aryl Alkyl Sulfides. A Simple, One-Pot Synthesis of Polymercaptobenzenes from Polychlorobenzenes
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A simple procedure is described which allows one to prepare polymercaptobenzenes starting from chlorobenzenes.The reactions of all the possible chlorobenzenes with Me2CHSNa in HMPA give the corresponding (isopropylthio)benzenes which can be cleaved by adding sodium to the reaction mixtures to give the arenethiolates in good yields.In some cases the polymercaptobenzenes were isolated after treatment with acid; in other cases methyl iodide was added to the reaction mixture and poly(methylthio)benzenes were obtained.It is suggested that the (isopropylthio)benzenes react with sodium to give the corresponding radical anions which fragment at the sulfur-alkyl bond to give the arenethiolates.
- Maiolo, Filippo,Testaferri, Lorenzo,Tiecco, Marcello,Tingoli, Marco
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p. 3070 - 3073
(2007/10/02)
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- Ethylenic silicon compounds and thermoplastic elastomers obtained therefrom
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The invention provides organosilicon compounds of the formula: STR1 in which: N IS 1, 2 OR 3; Each R, which may be identical or different, is a monovalent organic group which contains a carbon-carbon double bond and from 2 to 10 carbon atoms; Each R1, which may be identical or different, is a straight or branched alkyl radical optionally substituted by one or more halogen atoms or cyano groups; an aryl radical or an alkylaryl radical optionally substituted by one or more halogen atoms; R2 is a straight or branched divalent alkylene or alkylidene radical possessing up to 4 carbon atoms; X is a divalent radical consisting of, or containing, at least one hetero-atom selected from oxygen, sulphur and nitrogen atoms, the radical being attached to the radical R2 via a said hetero-atom; G is an organic radical of valency (m+ l) possess from 1 to 30 carbon atoms; m is 1, 2 or 3; And each Y, which may be identical or different, is a functional group selected from: --NO2, STR2 --COOM (where M represents a sodium, potassium or lithium atom); --COOR4 ; STR3 --COCl; --OH; --OR4 ; STR4 --SH; --SR4 ; STR5 --CONH2 ; --CSNH2 ; --CN; --CH2 --NH2 ; --CHO; STR6 --NCO; STR7 wherein R3 represents a hydrogen atom or a straight or branched alkyl radical possessing up to 6 carbon atoms and R4 represents an alkyl radical possessing up to 4 carbon atoms, with the proviso that two Y groups can together constitute an imide group STR8 wherein R5 represents a hydrogen atom or a straight or branched alkyl radical possessing up to 4 carbon atoms. These are useful intermediates in the preparation of disilanes and silicon polymers, in particular of polyethylenic silicon compounds which can be polymerized with an α, ω-dihydrogenopolysiloxane to give thermoplastic elastomers.
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