- Redox-active proligands from the direct connection of 1,3-dithiol-2-one to tetrathiafulvalene (TTF): Syntheses, characterizations and metal complexation
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In the search for novel tetrathiafulvalene-substituted dithiolene ligands, two tetrathiafulvalene (TTF) molecules directly connected to 1,3-dithiol-2-one fragments have been synthesized and characterized by single crystal X-ray diffraction, electrochemical and spectroscopic analyses. TTF1 was obtained, in moderate yield, by the cross-coupling of 4,5-bis(methylthio)-1,3-dithiole-2-one with 4,4′-bis(1,3-dithiole-2-one) in triethylphosphite, whereas for TTF2, the 1,3-dithiol-2-one fragment was introduced, in high yield, by an original reaction of the alkyne group of an ethynyl TTF (Me3TTF-CCH) with xanthogen in the presence of a radical initiator. Opening of the 1,3-dithiol-2-one fragments with sodium methanolate leads to the formation of two new 1,2-dithiolate ligands functionalized with redox-active TTF moieties, which can efficiently coordinate metals. As an illustration, two original heteroleptic bis(cyclopentadienyl)dithiolene titanium complexes were isolated and characterized.
- Camerel, Franck,Jeannin, Olivier,Yzambart, Gilles,Fabre, Bruno,Lorcy, Dominique,Fourmigué, Marc
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- Optical spectroscopy of perfluorothiophenyl, perfluorothionaphthyl, xanthate and dithiophosphinate radicals
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Laser flash photolysis has been used to record the optical spectra of sulfur-containing radicals forming from photodissociation of diphenyl disulfide, perfluorodiphenyl disulfide, perfluoro-2,2′-dinaphthyl disulfide, diisopropyldixantogene and bis(diisobutylthio-phosphoryl-disulfane). The extinction coefficients of absorption bands were determined from the reaction of S-radicals with a stable nitroxyl radical. The rate constant of this reaction was for all radicals close to 109 M-1 s-1 and successfully competes with the reaction of recombination. The presence of a narrow and strong absorption band in the optical spectrum of a nitroxyl radical and the absence of absorption in the reaction products allows one to accurately determine the extinction coefficients of the absorption bands of S-radicals.
- Plyusnin,Ivanov, Yu.V.,Grivin,Vorobjev, D.Yu.,Larionov,Maksimov,Platonov,Tkachenko,Lemmetyinen
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- A two-trisulfide isopropyl xanthate preparation method (by machine translation)
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The present invention discloses a two-trisulfide isopropyl xanthate preparation method, in order to isopropanol, solid alkali, carbon bisulfide and chlorine as raw materials, the materials are added into the reactor, and then each raw material in shear dispersion under reaction, make the disulfide isopropyl xanthate. The invention oxidant chlorine, thereby avoiding the introduction of water, meets the isopropyl alcohol with carbon disulfide reaction needs anhydrous conditions, will be isopropyl xanthate and oxidation of the generation of the two-step reaction "combined", the "one-step" process for preparing disulfide isopropyl xanthate. At the same time, through the isopropanol is used as the dispersion medium, controls the oxidant chlorine access time, access time and other reaction conditions, the product of the invention yield and purity are higher, with the use of sodium hypochlorite as oxidizing agent compared with the "two-step" process, simplifying the process, the amount of raw material is reduced, thereby reducing the waste of the emissions, ensuring the product yield. (by machine translation)
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Paragraph 0036
(2017/06/28)
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- Carbon tetrabromide promoted reaction of amines with carbon disulfide: Facile and efficient synthesis of thioureas and thiuram disulfides
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A novel carbon tetrabromide promoted one-pot reaction of amines and carbon disulfide under mild conditions has been developed, which provides a straightforward and efficient access to thioureas and thiuram disufides, depending on the nature of the amines employed. The promotion effect is explained as the transient formation of a sulfenyl bromide intermediate from dithiocarbamate and carbon tetrabromide during the reaction. Georg Thieme Verlag Stuttgart · New York.
- Liang, Fushun,Tan, Jing,Piao, Chengri,Liu, Qun
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experimental part
p. 3579 - 3584
(2009/07/04)
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- Photochemical and Thermal Transformations of O-Alkyl-S-phthalylalanyl Xanthates
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The reaction of phthalylalanyl chloride with different potassium O-alkylxanthates (R = Et, n-pr, iso-pr, n-Bu, iso-Bu) around 0 deg C in ether solution gave rise to the corresponding O-alkyl-S-phthalylalanyl xanthates.Irradiation of the latter in benzene solution gave xanthic acid disulphide, phthalylalanine and thioanhydride of phthalylalanine in addition to some other products.Thermal decomposition of these acylxanthates around 150 - 60 deg C for 15 - 20 min yielded the corresponding esters and carbon disulphide.
- Darji, R. R.,Shah, A.
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p. 104 - 106
(2007/10/02)
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- Redox Reactions in Non-aqueous Media. Determination of Xanthates and Organotrithiocarbonates (Thioxanthates) with Iron(III) in Acetonitrile
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The use of iron(III) perchlorate (in acetonitrile) for the visual, potentiometric and spectrophotometric determination of xanthates and organotrithiocarbonates (thioxanthates) in acetonitrile medium is described.The proposed methods are simple, accurate and reliable and show the promise of wide applicability.
- Verma, B. C.,Sharma, Neelam,Sud, Anila,Sharma, Usha,Sud, Anita
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p. 625 - 626
(2007/10/02)
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- Novel Symmetrical and Mixed Carbamoyl and Amino Polysulfanes by Reactions of (Alkoxydichloromethyl)polysulfanyl Substrates with N-Methylaniline
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Reactions of (alkoxydichloromethyl)polysulfanes with N-methylaniline can be rationalized by a "carbamoyl" route where the alkoxydichloromethyl group behaves via loss of alkyl chloride as a "masked" acid chloride or by a "sulfenyl" route which reflects fragmentation of the (alkoxydichloromethyl)polysulfanyl functionality into the corresponding alkoxy(thiocarbonyl) and sulfenyl components (cf.Scheme I).Application of this and related chemistry to bifunctional substrates arising from partial or complete chlorination of 2Sm, R = Me, Et, i-Pr, and m = 1-4, has led to Ph(Me)N(C=O)Sn(C=O)N(Me)Ph, n = 2-12; Ph(Me)N(C=O)SnN(Me)Ph, n = 1-6; Ph(Me)NSnN(Me)Ph, n = 1-10; RO(C=S)Sn(C=O)N(Me)Ph, n = 2, 3; and RO(C=S)SnN(Me)Ph, n = 1-5.These families allowed a test of reversed-phase high-pressure liquid chromatography for evaluating homologies in polysulfane series.Treatment of bis sulfide (27c) with sulfuryl chloride in the presence of calcium carbonate conveniently gave distillable bis(chlorocarbonyl)trisulfane (14), whereas the same procedure with SO2Cl2 alone gave directly (chlorocarbonyl)disulfanyl chloride (12) (see Scheme VII).Higher Cl(C=O)SmCl, m = 3-5, were indicated but could not be isolated in the course of studies generalizing results on 14 to the preparation of higher Cl(C=O)Sn(C=O)Cl, n = 4-6.The new bis(carbamoyl) monosulfide 61 was obtained by the relatively slow triphenylphosphine or cyanide promoted desulfurization of bis(methylphenylcarbamoyl)disulfane (4) (eq. 1 and 4); cyanide treatment of the higher polysulfanes Ph(Me)N(C=O)Sn(C=O)N(Me)Ph for n > 3 rapidly gave disulfane directly (eq 5).
- Schroll, Alayne L.,Barany, George
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p. 1866 - 1881
(2007/10/02)
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