- Nucleophilic Cleavage of the Ether Bond of Chlorex in the Chalcogenation with Diphenyl Dichalcogenides in the System Hydrazine Hydrate–KOH
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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.
- 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.
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p. 1760 - 1762
(2020/10/15)
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- Synthesis and characterization of dithioethers, and their RuII and RuIII complexes
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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.
- Cheu, Elizabeth L.S.,Yapp, Donald T.T.,Patrick, Brian O.,James, Brian R.
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- A Bulky Disulfoxide Ligand for Pd-Catalyzed Oxidative Allylic C-H Amination with 2,2,2-Trichloroethyl Tosyl Carbamate
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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.
- Li, You-Gui,Li, Li,Yang, Ming-Yue,He, Gang,Kantchev, Eric Assen B.
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p. 4907 - 4917
(2017/05/12)
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- Palladium(ii)-1-phenylthio-2-arylchalcogenoethane complexes: Palladium phosphide nano-peanut and ribbon formation controlled by chalcogen and Suzuki coupling activation
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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
- Kumar Rao, Gyandshwar,Kumar, Arun,Saleem, Fariha,Singh, Mahabir P.,Kumar, Satyendra,Kumar, Bharat,Mukherjee, Goutam,Singh, Ajai K.
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p. 6600 - 6612
(2015/04/14)
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- A highly efficient heterogeneous rhodium(I)-catalyzed C-S coupling reaction of thiols with polychloroalkanes or alkyl halides under mild conditions
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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.
- Xia, Jianhui,Yao, Ruiya,Cai, Mingzhong
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p. 221 - 225
(2015/03/30)
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- (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
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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.
- Prakash, Om,Sharma, Kamal Nayan,Joshi, Hemant,Gupta, Pancham L.,Singh, Ajai K.
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p. 983 - 993
(2014/03/21)
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- Silica-promoted facile synthesis of thioesters and thioethers: A highly efficient, reusable and environmentally safe solid support
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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.
- Basu, Basudeb,Paul, Susmita,Nanda, Ashis K.
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experimental part
p. 767 - 771
(2010/09/05)
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- A highly efficient carbon-sulfur bond formation reaction via microwave-assisted nucleophilic substitution of thiols to polychloroalkanes without a transition-metal catalyst
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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.
- Cao, Yi-Ju,Lai, Yuan-Yuan,Cao, Hong,Xing, Xiao-Ning,Wang, Xiang,Xiao, Wen-Jing
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p. 1529 - 1533
(2007/10/03)
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- Unexpected Hofmann elimination in the benzophenone-(phenylthio)acetic tetrabutylammonium salt photoredox system
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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
- Wrzyszczynski, Andrzej,Pietrzak, Marek,Bartoszewicz, Jarogniew,Kozubek, Halina,Hug, Gordon L.,Marciniak, Bronislaw,Paczkowski, Jerzy
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p. 11182 - 11183
(2007/10/03)
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- New preparative procedure for the synthesis of chloroalkyl sulfides
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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.
- Russavskaya,Korchevin,Alekminskaya,Sukhomazova,Levanova,Deryagina
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p. 1445 - 1448
(2007/10/03)
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- Reactions of diorganyl disulfides with dihaloalkanes in basic reductive media. Synthesis of bis(organylthio)alkanes
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A convenient preparative synthesis of bis(organylthio)alkanes was developed. It is based on alkylation with dihaloalkanes of solutions of diorganyl disulfides in the basic reductive system hydrazine hydrate-alkali. The generation of organylthiolate anions
- Alekminskaya,Russavskaya,Korchevin,Deryagina
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- Reactivity of Rieke manganese: Synthesis of pyrrolidine and piperidine derivatives
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Low-valent manganese generated by the reduction of manganese(II) chloride using lithium naphthalenide (Rieke manganese) promotes reactions of alkyl halides with electrophiles such as acyl chloride, aldehyde, and ketone to afford alkylation products. N-Haloalkyl-N-allyltosylamides are converted to pyrrolidine and piperidine derivatives in high yields. In the reactions of aromatic aldehyde and ketone, pinacol-type coupling products are produced.
- Hojo, Makoto,Yoshizawa, Junji,Funahashi, Yoshihiro,Okada, Ryo,Nakamura, Shin-Ya,Tateiwa, Jun-Ichi,Hosomi, Akira
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- 1H- And13C-NMR and electron ionization (EI) mass spectrometric study of o- And p-substituted 1,n-diarylsulfonylalkanes, XC6H4so2(CH2)nso 2C6H4X (n = 2-5, 8, 10)+
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1,n-Diphenylsulfonylalkanes, PhSO2(CH2)nSO2Ph (n =2-5, 8, 10) and their o- or p-Cl or -OMe derivatives were prepared and their 1H- and 13C-NMR and EI mass spectra recorded and analyzed. The chemical shifts of the aliphatic α- and β-carbons showed a clear dependence on the o-aryl substitution, the o-Cl being the most shielding for both. Clear low-field effects were found also for the aliphatic α-protons in o-Cl and o-OMe derivatives. In case of p-OMe derivatives a palpable shielding of the aliphatic α-protons was also found similarly to the β-protons of the o-OMe derivatives. Characteristic mass spectrometric fragmentations which reflected both the influence of the aryl substitution and the length of the alkyl chain were observed and sometimes also exhibited the sulphinic acid rearrangement.
- Pihlaja, Kalevi,Kabilan, Senthamaraikannan,Ganapathi, Athiappan,Sankar, Punnaivanam
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p. 601 - 612
(2007/10/03)
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- INNOVATIVE APPROACH TO THE SYNTHESIS OF SULPHIDES AND THEIR CORRESPONDING SULPHONES
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A general and efficient synthetic approach to aryl-aryl bis-sulphides with aliphatic or aromatic bridges via the nucleophilic aromatic substitution (SNAr) of cyclopentadienyliron arene complexes with a number of dithiols followed by photolytic demetallation is presented in this work.The oxidation of the bis(cyclopentadienyliron) arene complexes containing bis-sulphide linkages with 3-chlorobenzoic acid gave their corresponding sulphones in very good yield (70-95percent).Mixed ether/sulphide and ether/sulphone complexes were also prepared following the same synthetic strategy.Reactions of sulphide and sulphone diiron complexes with terminal chloro groups with a number of oxygen, sulphur and carbon nucleophiles allowed for the functionalization of these complexes.The use of photolytic demetallation as a means of liberating the modified arene ligands proved to be very successful.The mild conditions, high yields and low cost of the starting iron complexes make this method one of the most general and practical routes to sulphide and sulphone compounds.
- Abd-El-Aziz, Alaa S.,Epp, Karen M.,Lei, Yun,Kotowich, Steven
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p. 1252 - 1286
(2007/10/02)
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- Dipole Moments and UV Spectra of some Long-chain Molecules
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About one hundred compounds with long-chain molecular structure have been prepared (most of them are new).The dipole moments of four α,ω-bis(p-methoxyphenylthio)alkanes and five α,ω-bis(p-methoxyphenylsulphonyl)alkanes have been determined to find the effect of chain-length.In the case of sulphones, the observed values are compared with the values calculated for free rotation around all bonds intervening the end dipoles.The uv spectra of some 1,2-(distyrylsulphonyl)ethanes, and a number of α,ω-bis(arylsulphonyl)- and α,ω-bis(aryloxy)alkanes have been recorded to examine the applicability of the principle of chromophore additivity.
- Baliah, V.,Aparajithan, K.
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p. 255 - 259
(2007/10/02)
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- Reaction Mechanism of Cathodic Crossed Coupling of Acetone with Unsaturated Compounds in Acidic Solution
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It was confirmed that the cathodic crossed coupling of acetone with unsaturated compounds in aqueous sulfuric acid could proceed smoothly, when the compounds which had radical-acceptable double bonds and were adsorbed on a mercury cathode were used.From this fact, it was concluded that the coupling occurs via the addition of a radical intermediate formed by the one-electron reduction of acetone to the double bonds on the cathode surface.Possibility of the addition of an anionic intermediate derived from acetone was excluded by no occurrence of the coupling of acetone with a polar acetylenic triple bond compound adsorbed on the cathode.
- Koizumi, Toshio,Fuchigami, Toshio,Kandeel, Zaghloul El-Shahat,Sato, Norio,Nonaka, Tsutomu
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p. 757 - 762
(2007/10/02)
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- Zur Koordination Mehrfunktioneller Thioether in Cyclopentadienyleisen-Komplexen
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+ reacts with the ligands L-L and L-L-L to give the cations + (L-L= RS(CH2)nSR, 1,4-dithiane) and + (L-L-L= 1,3,5-trithiane, tris(methylmercapto)methane) containing monodentate coordinated sulfur ligands.In a similar way, sulfur ligand bridged dinuclear dications 2+ and 2+ and trinuclear trications 3+ are formed.Irradiation of the mononuclear cations gives the chelate complexes 2-L-L)>+.
- Kuhn, Norbert,Schumann, Hans
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- Novel Alumina-catalysed Reactions of Arylthioalkyl Halides and Related Compounds
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Arylthioalkyl halides of the type ArS(CH2)nCl (Ar = phenyl or substituted phenyl, n = 1-4) undergo rearrangement on heating with neutral alumina to 1,n-bis(arylthio)alkanes of type ArS(CH2)nSAr in high yield.Similar rearrangements occur with some closely related structural types.The bis(arylthio)alkanes undergo further reaction with alumina at higher temperatures in air giving diaryl disulphides.Bis(o-iodophenylthio)methane eliminates iodine on heating with alumina, producing dibenzodithiepin.Some observations concerning the mechanism are presented.
- Jigajinni, Veerappa B.,Wightman, Richard H.
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p. 1801 - 1812
(2007/10/02)
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- REACTIONS OF SULFINYL CARBANIONS WITH ORGANOMETALLIC COMPOUNDS: PREPARATION OF
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Sulfinyl carbanions, -Li+ (R = Ph, Me; R' = H, Ph) have been observed to have often low reactivity towards neutral transition metal organometallic systems.When reactions do occur they usually involve salt eliminations and
- Lucas, C.R.
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p. 281 - 292
(2007/10/02)
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- REAKTION VON 2-ARYLMERCAPTOETHYLHALOGENIDEN MIT MAGNESIUM BZW. ALKALICYANIDEN
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By reaction of 2-arylmercaptoethylhalogenides with magnesium the main reaction products are 1,2-bisarylmercapto-ethanes.The same products are obtained in nearly quantitative yield by reaction of 2-arylmercaptoethylhalogenides with alkalicyanides. 2-arylmercaptopropionitrils can not be synthesized according to the procedure described.
- Salbeck, Gerhard
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p. 165 - 168
(2007/10/02)
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- Novel Alumina-catalysed Reactions of Arylthioalkyl Halides
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ω-Chloroalkyl aryl sulphides rearrange to αω-bisaryl thioalkanes on treatment with alumina, and an alumina-catalysed equivalent of the Ullmann biphenyl synthesis is reported.
- Jigajinni, Veerappa B.,Wightman, Richard H.,Campbell, Malcolm M.
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