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Oleg A. Rakitin - One of the best experts on this subject based on the ideXlab platform.
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Reactivity of 1,2-Dithioles
Russian Chemical Reviews, 2012Co-Authors: V A Ogurtsov, Oleg A. RakitinAbstract:Available data concerning the chemistry of 1,2-Dithioles published over the past 15 years have been summarized and systematized. Different transformations of these compounds have been considered, including reactions with participation of substituents in the Dithiole ring. The bibliography includes 96 references.
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Unexpected and Rich Chemistry of 4,5-Dichloro-1,2-Dithiole-3-thione
Phosphorus Sulfur and Silicon and The Related Elements, 2011Co-Authors: V A Ogurtsov, Alexey A Smolentsev, Yuri V. Karpychev, Oleg A. RakitinAbstract:Abstract 4,5-Dichloro-1,2-Dithiole-3-thione was found to undergo 1,3-dipolar cycloaddition reactions with internal and terminal alkynes. The combination of these reactions together with new transformations afforded versatile heterocyclic systems including 1,3-Dithioles, imino-1,3-dithietanes, 2-iminothiophen-3-ones, thienothiopyranthiones, and others.
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a novel transformation of 1 2 Dithiole 3 thiones into 1 3 thiazine 4 thiones
Russian Chemical Bulletin, 2008Co-Authors: V A Ogurtsov, Yu V Karpychev, Oleg A. RakitinAbstract:1,2 Dithiole 3 thiones 1 exhibit a variety of reactivi ties.1 1,3 Dipolar cycloaddition of these compounds is best studied: the reaction involves ring opening with participation of the thione group. Transformations with retention of the thione group are much more uncommon. 1,2 Dithiole 3 thiones have been reported to react with α,β unsaturated nitriles to give thiopyran thiones2 and with amines to give 1,2 thiazole 3 thiones or 1,2 isothiazole 5 thiones.3 We discovered a novel transformation of the Dithiole ring. In reactions of 1,2 Dithiole 3 thiones 1a—d with 3,4 dihydropyrrolo[1,2 a]pyrazine (2), the imine frag ment of compound 2 is inserted into the 1,2 Dithiole ring with extrusion of the S atom (the latter was isolated as elemental sulfur in a nearly quantitative yield) to give fused 1,3 thiazine 4 thiones 3a—d in high yields (Scheme 1). The transformation is possible for both fused (1a—c) and monocyclic 1,2 Dithioles (1d). Such reactions in volving the insertion of nitrogen containing fragments into the 1,2 Dithiole ring give wide scope for the synthesis of novel heterocyclic systems. The structures of 1,4 thiazine 4 thiones 3a—d were fully confirmed by elemental analysis data and 1H and 13C NMR, IR, and mass spectra. Some of the spectral Scheme 1
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selective synthesis of bis 1 2 dithiolo 1 4 thiazines from 4 isopropylamino 5 chloro 1 2 Dithiole 3 ones
Tetrahedron Letters, 2007Co-Authors: Lidia S Konstantinova, Andrej A Berezin, Kirill A Lysov, Oleg A. RakitinAbstract:Abstract Reaction of 4-isopropylamino-5-chloro-1,2-Dithiole-3-ones 3 and S 2 Cl 2 in acetonitrile gave selectively 3-oxo-bis[1,2]dithiolo[1,4]thiazine-5-thiones 1 by the addition of triethylamine and bis[1,2]dithiolo[1,4]thiazine-3,5-diones 5 under the action of formic acid. 3,5-Diones 5 were also obtained by intramolecular cyclization of N , N -bis(5-chloro-3-oxo[1,2]dithiol-4-yl)amines 6 with S 2 Cl 2 in the presence of Et 3 N.
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synthesis of 5 mercapto 1 2 Dithiole 3 thiones and their transformation into 5 chloro 1 2 dithiol 3 ones
Russian Chemical Bulletin, 2006Co-Authors: Lidia S Konstantinova, Andrej A Berezin, Kirill A Lysov, Oleg A. RakitinAbstract:A number of 4-dialkylamino-5-mercapto-1,2-Dithiole-3-thiones were synthesized by reactions of alkyl(diisopropyl)amines with S2Cl2. Their reactions with S2Cl2—DABCO unexpectedly gave 5-chloro-4-dialkylamino-1,2-dithiol-3-ones.
Deqing Zhang - One of the best experts on this subject based on the ideXlab platform.
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an hg2 gated chiral molecular switch created by using binaphthalene molecules with two anthracene units and two 1 3 Dithiole 2 thione 1 3 Dithiole 2 one units
Chemistry: A European Journal, 2008Co-Authors: Cheng Wang, Deqing Zhang, Guanxin Zhang, Junfeng XiangAbstract:By integrating the features of anthracene, 1,3-Dithiole-2-thione, and binaphthalene units, (S)-1 and its analogue (S)-2, which contains two 1,3-Dithiole-2-one units instead of 1,3-Dithiole-2-thione, were studied for creating a new molecular regulation system and building a gated chiral molecular switch. The results show that the photodimerization is controlled by the remote functional-group transformation of C=S into C=O, thus providing an elegant example of molecular regulation. The photodimerization of two anthracene units induces circular dichroism (CD) spectral variation. Overall, the CD spectrum can be remotely modulated by Hg 2+ in (S)-1, which leads to an Hg 2+ -gated chiral molecular switch.
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An Hg2+‐Gated Chiral Molecular Switch Created by Using Binaphthalene Molecules with Two Anthracene Units and Two 1,3‐Dithiole‐2‐thione (1,3‐Dithiole‐2‐one) Units
Chemistry: A European Journal, 2008Co-Authors: Cheng Wang, Deqing Zhang, Guanxin Zhang, Junfeng XiangAbstract:By integrating the features of anthracene, 1,3-Dithiole-2-thione, and binaphthalene units, (S)-1 and its analogue (S)-2, which contains two 1,3-Dithiole-2-one units instead of 1,3-Dithiole-2-thione, were studied for creating a new molecular regulation system and building a gated chiral molecular switch. The results show that the photodimerization is controlled by the remote functional-group transformation of C=S into C=O, thus providing an elegant example of molecular regulation. The photodimerization of two anthracene units induces circular dichroism (CD) spectral variation. Overall, the CD spectrum can be remotely modulated by Hg 2+ in (S)-1, which leads to an Hg 2+ -gated chiral molecular switch.
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1 3 Dithiole 2 thione derivatives featuring an anthracene unit new selective chemodosimeters for hg ii ion
Chemical Communications, 2005Co-Authors: Guanxin Zhang, Deqing Zhang, Xiaodi Yang, Zhigang ShuaiAbstract:New selective chemodosimeters for Hg(II) ion based on 1,3-Dithiole-2-thione derivatives containing an anthracene unit are described.
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a new approach to 4 alkylthio 1 3 Dithiole 2 thione an unusual reaction of a zinc complex of 1 3 dithole 2 thione 4 5 dithiolate
Organic Letters, 2001Co-Authors: Deqing Zhang, And Wei XuAbstract:A new and facile approach to 4-alkylthio-1,3-Dithiole-2-thione starting from easily accessible reactants was described. This approach was based on the unusual reaction of a zinc complex of 1,3-Dithiole-2-thione-4,5-dithiolate with electrophilic reagents in the presence of 3-picolyl chloride hydrochloride/or 4-picolyl chloride hydrochloride/or pyridine hydrochloride.
Junfeng Xiang - One of the best experts on this subject based on the ideXlab platform.
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an hg2 gated chiral molecular switch created by using binaphthalene molecules with two anthracene units and two 1 3 Dithiole 2 thione 1 3 Dithiole 2 one units
Chemistry: A European Journal, 2008Co-Authors: Cheng Wang, Deqing Zhang, Guanxin Zhang, Junfeng XiangAbstract:By integrating the features of anthracene, 1,3-Dithiole-2-thione, and binaphthalene units, (S)-1 and its analogue (S)-2, which contains two 1,3-Dithiole-2-one units instead of 1,3-Dithiole-2-thione, were studied for creating a new molecular regulation system and building a gated chiral molecular switch. The results show that the photodimerization is controlled by the remote functional-group transformation of C=S into C=O, thus providing an elegant example of molecular regulation. The photodimerization of two anthracene units induces circular dichroism (CD) spectral variation. Overall, the CD spectrum can be remotely modulated by Hg 2+ in (S)-1, which leads to an Hg 2+ -gated chiral molecular switch.
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An Hg2+‐Gated Chiral Molecular Switch Created by Using Binaphthalene Molecules with Two Anthracene Units and Two 1,3‐Dithiole‐2‐thione (1,3‐Dithiole‐2‐one) Units
Chemistry: A European Journal, 2008Co-Authors: Cheng Wang, Deqing Zhang, Guanxin Zhang, Junfeng XiangAbstract:By integrating the features of anthracene, 1,3-Dithiole-2-thione, and binaphthalene units, (S)-1 and its analogue (S)-2, which contains two 1,3-Dithiole-2-one units instead of 1,3-Dithiole-2-thione, were studied for creating a new molecular regulation system and building a gated chiral molecular switch. The results show that the photodimerization is controlled by the remote functional-group transformation of C=S into C=O, thus providing an elegant example of molecular regulation. The photodimerization of two anthracene units induces circular dichroism (CD) spectral variation. Overall, the CD spectrum can be remotely modulated by Hg 2+ in (S)-1, which leads to an Hg 2+ -gated chiral molecular switch.
Jeanlouis Burgot - One of the best experts on this subject based on the ideXlab platform.
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Substituent effects of 1,2-Dithiole groups on the electrochemical oxidation of some ferrocenyl-1,2-Dithiole compounds
Journal of Organometallic Chemistry, 2020Co-Authors: Marie-laurence Abasq, Jeanlouis Burgot, Mokhtar Saidi, André DarchenAbstract:Abstract New ferrocenyl compounds substituted by sulfur containing groups were synthesized leading to ferrocenyl-3H-1,2-Dithiole-3-thiones and related compounds. The substituent of the ferrocene was a [3-thioxo-3H-1,2-dithiol]-4 or 5-yl, a [3-oxo-3H-1,2-dithiol]-4 or 5- yl or a [3-methylsulfanyl-3H-1,2-dithiolium]-4 or 5-yl cation group. Their anodic behavior was studied by cyclic voltammetry at a Pt electrode in aprotic solvent. All synthesized ferrocenes exhibited a one-electron reversible oxidation leading to the corresponding ferricinium cation. At low potential scan, the irreversible oxidation of 5 -ferrocenyl-3H-1,2-Dithiole-3-thione was observed and attributed to a dimerization involving the Dithiolethione group. Redox potential of the reversible oxidation allowed the determination of the electronic effect of the 1,2-Dithiole groups. The Hammett σ p constants of the Dithiole substituents were obtained from linear correlation between oxidation potentials and electronic effects. The results showed that the [3-thioxo-3H-1,2-dithiol]-5-yl and the [3-methylsulfanyl-3H-1,2-dithiolium]-5-yl cation groups were strong inductive electron withdrawing substituents characterized by σ p values of 0.55 and 0.97, respectively.
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Synthesis of 5-Formyl and 5-Acyl-1,2-Dithiole-3-ones
Phosphorus Sulfur and Silicon and The Related Elements, 2003Co-Authors: Sylvain Gargadennec, Beatrice Legouin, Jeanlouis BurgotAbstract:The preparation of new 5-formyl-, 5-acetyl- and 5-propionyl-1,2-Dithiole-3-ones by oxidation of the corresponding 1,2-Dithiole-3-thiones with mercuric acetate is described.
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Cathodic behaviour of some 5-nitrophenyl-1,2-Dithiole-3-thiones and 5-nitrophenyl-1,2-Dithiole-3-ones
Electrochimica Acta, 2002Co-Authors: Jeanlouis Burgot, André Darchen, Mokhtar SaidiAbstract:Abstract The electrochemical behaviour of 5-(nitrophenyl)-1,2-Dithiole-3-thiones and 5-(nitrophenyl)-1,2-Dithiole-3-ones was studied by cyclic voltammetry in DMF. The standard reduction potentials of 5-( p -nitrophenyl)-Dithiolethione and 5-( p -nitrophenyl)-dithiolone entered into a linear correlation involving standard reduction potentials of substituted nitrobenzenes and known electronic constants of several substituents. This correlation allowed the determination of the electronic effects of [3-thioxo-1,2-Dithiole]-5-yl and [3-oxo-1,2-diothiole]-5-yl groups which were, respectively, σ p − =1.14 and σ p − =0.86, comparable with those of nitro or cyano substituents.
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improvement in solubility and dissolution rate of 1 2 Dithiole 3 thiones upon complexation with β cyclodextrin and its hydroxypropyl and sulfobutyl ether 7 derivatives
Journal of Pharmaceutical Sciences, 1999Co-Authors: Gilles Dollo, Marylene Chollet, Jeanlouis Burgot, Pascal Le Corre, Francois Chevanne, M Bertault, Roger Le VergeAbstract:Inclusion complexes between β‐cyclodextrin derivatives and 1,2‐dithione‐3‐thiones were studied in aqueous solution and in the solid state. Phase solubility study was used to evaluate the complexation in solution, at 37 °C, of three cyclodextrins, i.e., β‐cyclodextrin (βCD), hydroxypropyl‐β‐cyclodextrin (HPβCD), sulfobutyl ether‐7‐β‐cyclodextrin (SBE7βCD), and four 1,2‐Dithiole‐3‐thiones, i.e., the parent compound Dithiolethione (DTT), dimethylDithiolethione (DMDTT), 5‐phenylDithiolethione (5PDTT), and anetholetrithione (ATT). Stability constants of the DTT complexes with HPβCD and SBE7βCD were also determined spectrophotometrically using a nonlinear least‐squares methodology. Differential scanning calorimetry (DSC) and scanning electronic microscopy (SEM) were used to characterize spray‐dried complexes formed between 5PDTT and SBE7βCD, ATT and SBE7βCD. Dissolution studies using the USP paddle method were carried out in water at 37 °C for both ATT and 5PDTT binary systems with HPβCD and SBE7βCD. Solubility enhancements were much greater with the more lipophilic ATT and 5PDTT compared to DTT and DMDTT, whatever the cyclodextrin used, in the rank order SBE7βCD > HPβCD ≫ βCD. Stability constants obtained (between 120 and 12800 mol−1) were also the highest for the more lipophilic drugs and in the same rank order SBE7βCD > HPβCD ≫ βCD. Results obtained by UV spectrophotometry were in good agreement with those obtained by phase‐solubility study. DSC thermograms of spray‐dried complexes of ATT and 5PDTT with HPβCD and SBE7βCD lacked the endothermal peak of pure drug peak which was found for the physical mixtures (107 °C and 125 °C for ATT and 5PDTT, respectively). Finally, dissolution profiles of spray‐dried inclusion complexes studied displayed a faster dissolution rate compared to physical mixtures and pure drugs. The present study showed that complexation of 1,2‐Dithiole‐3‐thiones with β‐cyclodextrin derivatives resulted in an increase in solubility, allowing intravenous formulation for bioavailability and metabolism studies and an increase in the dissolution rate of the drugs, which shoud be of interest for oral absorption of these lipophilic compounds.
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assessment of the substituent constants of the 3 thioxo 1 2 dithiol 4 and 5 yl groups through pka values measurements of 4 and 5 hydroxy or amino phenyl 1 2 Dithiole 3 thiones in water at 298 k
Journal of The Chemical Society-perkin Transactions 1, 1998Co-Authors: Marylene Chollet, Beatrice Legouin, Jeanlouis BurgotAbstract:The UV–VIS spectrophotometric assessment of the electronic substituent constants of the 3-thioxo-1,2-dithiol-4- and -5-yl and 3-oxo-1,2-dithiol-4- and -5-yl groups through pKa measurements in water of 4 and 5-(hydroxy or amino-phenyl)-1,2-Dithiole-3-thiones and corresponding dithiolones has been performed. Linear free-enthalpy relationships based on pKa values of phenols and anilinium ions indicated a strong withdrawing effect for the 3-thioxo-1,2-dithiol-5-yl group by both an inductive and a resonance effect [σp– = 0.76, σm = 0.44 (anilinium ions relationship) and σp– = 0.97, σm = 0.45 (phenols relationship)]. The corresponding 3-oxo group was slightly less attractive than the 3-thioxo one [σp– = 0.64 (anilinium ions) and σp– = 0.78 (phenols)]. The 3-thioxo-1,2-dithiol-4-yl group and also its oxo analogue had only a weak withdrawing effect by an inductive effect (σp ≊ σp– ≊ 0.2) indicating a lack of conjugation between the Dithiole and phenyl nuclei in 4-phenylDithiolethiones. The original 1,2-Dithiole-3-thiones and 1,2-dithiol-3-ones used in correlations are described.
Guanxin Zhang - One of the best experts on this subject based on the ideXlab platform.
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an hg2 gated chiral molecular switch created by using binaphthalene molecules with two anthracene units and two 1 3 Dithiole 2 thione 1 3 Dithiole 2 one units
Chemistry: A European Journal, 2008Co-Authors: Cheng Wang, Deqing Zhang, Guanxin Zhang, Junfeng XiangAbstract:By integrating the features of anthracene, 1,3-Dithiole-2-thione, and binaphthalene units, (S)-1 and its analogue (S)-2, which contains two 1,3-Dithiole-2-one units instead of 1,3-Dithiole-2-thione, were studied for creating a new molecular regulation system and building a gated chiral molecular switch. The results show that the photodimerization is controlled by the remote functional-group transformation of C=S into C=O, thus providing an elegant example of molecular regulation. The photodimerization of two anthracene units induces circular dichroism (CD) spectral variation. Overall, the CD spectrum can be remotely modulated by Hg 2+ in (S)-1, which leads to an Hg 2+ -gated chiral molecular switch.
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An Hg2+‐Gated Chiral Molecular Switch Created by Using Binaphthalene Molecules with Two Anthracene Units and Two 1,3‐Dithiole‐2‐thione (1,3‐Dithiole‐2‐one) Units
Chemistry: A European Journal, 2008Co-Authors: Cheng Wang, Deqing Zhang, Guanxin Zhang, Junfeng XiangAbstract:By integrating the features of anthracene, 1,3-Dithiole-2-thione, and binaphthalene units, (S)-1 and its analogue (S)-2, which contains two 1,3-Dithiole-2-one units instead of 1,3-Dithiole-2-thione, were studied for creating a new molecular regulation system and building a gated chiral molecular switch. The results show that the photodimerization is controlled by the remote functional-group transformation of C=S into C=O, thus providing an elegant example of molecular regulation. The photodimerization of two anthracene units induces circular dichroism (CD) spectral variation. Overall, the CD spectrum can be remotely modulated by Hg 2+ in (S)-1, which leads to an Hg 2+ -gated chiral molecular switch.
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1 3 Dithiole 2 thione derivatives featuring an anthracene unit new selective chemodosimeters for hg ii ion
Chemical Communications, 2005Co-Authors: Guanxin Zhang, Deqing Zhang, Xiaodi Yang, Zhigang ShuaiAbstract:New selective chemodosimeters for Hg(II) ion based on 1,3-Dithiole-2-thione derivatives containing an anthracene unit are described.
