622-20-8Relevant articles and documents
Nucleophilic Cleavage of the Ether Bond of Chlorex in the Chalcogenation with Diphenyl Dichalcogenides in the System Hydrazine Hydrate–KOH
Albanov, A. I.,Bogdanova, I. N.,Grabel?nykh, V. A.,Istomina, N. V.,Korchevin, N. A.,Nikonova, V. S.,Rozentsveig, I. B.,Russavskaya, N. V.,Sosnovskaya, N. G.
, p. 1760 - 1762 (2020/10/15)
Abstract: The synthesis of unsymmetrical pincer ligands by reactions of diphenyl disulfide and diphenyl diselenide with bis(2-chloroethyl) ether in the system hydrazine hydrate–KOH was accompanied by the formation of 1,2-bis(phenylsulfanyl)ethane, 1,2-bis(phenylselanyl)ethane, and 1-(phenylselanyl)-2-(phenylsulfanyl)ethane as by-products with an overall yield of 23% as a result of nucleophilic cleavage of the C–O–C bond in the initial ether.
Synthesis and characterization of dithioethers, and their RuII and RuIII complexes
Cheu, Elizabeth L.S.,Yapp, Donald T.T.,Patrick, Brian O.,James, Brian R.
, p. 49 - 54 (2019/05/24)
The syntheses of nine, new dithioethers of the type RS(CH2)xSR, where x = 2 or 3 and R is an alkyl chain, as well as the known x = 2, R = phenyl or cyclohexyl compounds, are reported. The known dithioethers react with RuCl3·3H2O to form trans-RuCl2(dithioether)2 complexes 1 (R = Ph) and 2 (R = C6H11), whereas from the other dithioethers RuCl2[RS(CH2)xSR]2(μ-Cl)2 complexes have been isolated, where x = 3, and R = Et (complex 3), nPr (complex 4), nBu (complex 5), and R = npentyl (complex 6). The complexes are well characterized, including X-ray structures for complexes 1–4. The interest in these compounds stems from oxidation of the dithioethers to the corresponding disulfoxides and their Ru complexes.
A Bulky Disulfoxide Ligand for Pd-Catalyzed Oxidative Allylic C-H Amination with 2,2,2-Trichloroethyl Tosyl Carbamate
Li, You-Gui,Li, Li,Yang, Ming-Yue,He, Gang,Kantchev, Eric Assen B.
, p. 4907 - 4917 (2017/05/12)
Challenging substrates and conditions in homogeneous catalysis pose stringent demands on the ligands used. A novel, bulky, 1-adamantyl-substituted disulfoxide ligand designed after a systematic evaluation of the electronic and steric properties of disulfoxide substituents permits the allylic oxidative C-N coupling reaction to proceed at lower catalyst loading while requiring a smaller excess of reagents. Additionally, this ligand improves the yields when TsNHCOOCH2CCl3, a novel reagent that permits deprotection of the products under both acidic and basic conditions, is used.
A highly efficient heterogeneous rhodium(I)-catalyzed C-S coupling reaction of thiols with polychloroalkanes or alkyl halides under mild conditions
Xia, Jianhui,Yao, Ruiya,Cai, Mingzhong
, p. 221 - 225 (2015/03/30)
Heterogeneous C-S coupling reaction of thiols with polychloroalkanes or alkyl halides was achieved at 30 or 80 °C in the presence of 5 mol% of an MCM-41-immobilized bidentate phosphine rhodium complex (MCM-41-2P-RhCl(PPh3)) and triethylamine, yielding a variety of formaldehyde dithioacetals, ethylenedithioethers and unsymmetric thioethers in good to excellent yields. This heterogeneous rhodium catalyst can be easily recovered and recycled by simple filtration of the reaction solution and used for at least 10 consecutive trials without significant loss of activity.
Palladium(ii)-1-phenylthio-2-arylchalcogenoethane complexes: Palladium phosphide nano-peanut and ribbon formation controlled by chalcogen and Suzuki coupling activation
Kumar Rao, Gyandshwar,Kumar, Arun,Saleem, Fariha,Singh, Mahabir P.,Kumar, Satyendra,Kumar, Bharat,Mukherjee, Goutam,Singh, Ajai K.
, p. 6600 - 6612 (2015/04/14)
The ligands PhSCH2CH2EAr (L1-L3; E = S, Se or Te) and their Pd-complexes [PdLCl2] (1-3) have been synthesized and authenticated with their 1H, 13C{1H}, 77Se{1H} and 125Te{1H} NMR spectra. Single crystal structures of 1 and 3 reveal the geometry of donor atoms around palladium as nearly square planar. Thermolysis of all three complexes in trioctylphosphine (TOP) at 350, 320 and 280 °C, respectively, results in a single phase of crystalline PdP2. The morphology of the phase varies with 'E' to some extent. The nanopeanuts (size ～30 and ～35 nm) were formed with 1 and 2 as precursor complexes. On using complex 3 as a precursor nanoribbons are formed. The preferential growth in the (202) plane in the case of all the three precursor complexes has been rationalized in terms of texture coefficient and average crystallite size. All three complexes and PdP2 NPs have been explored for Suzuki-Miyaura coupling of several aryl halides. Complexes 1 and 2 show good catalytic activity but complex 3 does not. The activity appears to result due to in situ generated palladium containing nanoparticles (NPs) in the case of 1 and 2. The formation of inactive large Pd aggregates in the case of 3 appears to be responsible for the difference. The PdP2 NPs have been found to show good catalytic activity and recyclability up to six reaction cycles. The results of the three phase test suggest the involvement of both homogeneous and heterogeneous pathways in the activation of Suzuki coupling. DFT based free energy calculations are consistent with the results of catalysis via Pd(0) protected with the ligand. This palladium may also be released from in situ generated NPs. In the case of 3, negligible reactivity may be due to non-release of Pd. This journal is
(η5-Cp)Rh(III)/Ir(III) complexes with bis(chalcogenoethers) (E, E′ Ligands: E = S/Se; E′ = S/Se): Synthesis, structure, and applications in catalytic oppenauer-type oxidation and transfer hydrogenation
Prakash, Om,Sharma, Kamal Nayan,Joshi, Hemant,Gupta, Pancham L.,Singh, Ajai K.
, p. 983 - 993 (2014/03/21)
The air- and moisture-insensitive half-sandwich complexes [(η5-Cp)Rh(L)Cl][PF6] (1-3) and [(η5- Cp)Ir(L)Cl][PF6] (4-6) have been prepared by reacting L = L1-L3 (1,2-bis(phenylthio)ethane (L1), 1-(phenylseleno)-2-(phenylthio)ethane (L2) and 1,2-bis(phenylseleno)ethane (L3)) with [(η5-Cp)RhCl(μ-Cl)] 2 and [(η5-Cp)IrCl(μ-Cl)]2, respectively, at room temperature followed by treatment with NH 4PF6. Their HR-MS and 1H, 13C{ 1H}, and 77Se{1H} NMR spectra have authenticated them. The single-crystal structures of 1-6 have been established by X-ray crystallography. Complexes 1-6 have been explored for catalytic Oppenauer-type oxidation of alcohols and transfer hydrogenation of ketones with 2-propanol. 3 and 6 were the most efficient in the two catalytic reactions (TON values up to 9.9 × 102 and 9.8 × 103, respectively) and were therefore investigated in detail. 3 is the first example of a Rh(III) species explored for Oppenauer-type oxidation. The catalysis appears to be homogeneous. In transfer hydrogenation it appears that one of the catalytic species is without a Cp* ring. DFT calculations indicate higher reactivity for Rh complexes in comparison to Ir complexes. This order has also been found for the two catalytic reactions experimentally. The calculated bond lengths/angles by DFT are generally consistent with the experimental values.
Silica-promoted facile synthesis of thioesters and thioethers: A highly efficient, reusable and environmentally safe solid support
Basu, Basudeb,Paul, Susmita,Nanda, Ashis K.
experimental part, p. 767 - 771 (2010/09/05)
An efficient, mild and rapid procedure for the acylation and alkylation of aromatic and aliphatic thiols mediated on a silica gel surface at room temperature is described. The protocol allows the protection of thiols under neutral heterogeneous conditions without requiring any bases or Lewis acids, and the silica gel used as the promoter can be recycled for several runs without any loss of activity.
A highly efficient carbon-sulfur bond formation reaction via microwave-assisted nucleophilic substitution of thiols to polychloroalkanes without a transition-metal catalyst
Cao, Yi-Ju,Lai, Yuan-Yuan,Cao, Hong,Xing, Xiao-Ning,Wang, Xiang,Xiao, Wen-Jing
, p. 1529 - 1533 (2007/10/03)
An efficient carbon-sulfur bond formation reaction has been developed under microwave irradiation. This reaction affords a novel and rapid synthesis of thioacetals and sulfides under mild conditions. This method is particularly noteworthy given its experimental simplicity and high generality, and no transition-metal catalysts were needed under our conditions.
Unexpected Hofmann elimination in the benzophenone-(phenylthio)acetic tetrabutylammonium salt photoredox system
Wrzyszczynski, Andrzej,Pietrzak, Marek,Bartoszewicz, Jarogniew,Kozubek, Halina,Hug, Gordon L.,Marciniak, Bronislaw,Paczkowski, Jerzy
, p. 11182 - 11183 (2007/10/03)
The triplet state of benzophenone was quenched by the tetrabutylammonium salt of (phenylthio)acetic acid in acetonitrile solutions. The quenching event, following laser flash photolysis, resulted in the formation of a transient ion pair consisting of the benzophenone radical anion and the tetrabutylammonium cation. Subsequently this ion pair decays with the quaternary ammonium cation undergoing a Hofmann elimination to form butane-1 and tributylamine, which were detected in steady-state irradiation. This appears to be the first report of an ion pair consisting of a benzophenone radical anion and an organic cation (nonradical), in addition to the first report of a photoinduced Hofmann elimination in quaternary ammonium ions. Copyright
New preparative procedure for the synthesis of chloroalkyl sulfides
Russavskaya,Korchevin,Alekminskaya,Sukhomazova,Levanova,Deryagina
, p. 1445 - 1448 (2007/10/03)
Reaction of thiols with dihaloalkanes in the system hydrazine hydrate-base leads to alkyl(chloroalkyl) sulfides with different positions of the chlorine atom with respect to sulfur. The developed one-step procedure for the synthesis of such unsymmetrical sulfides is most suitable for arenethiols and alkanethiols having a long polymethylene chain. The reaction mechanism is discussed.
