- Investigation of the reaction of dithiocarbamic acid salts with trimethyl orthoformate and styrene epoxide
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The reaction of dithiocarbamic acid salts with trimethyl orthoformate in the presence of BF3·OEt2 was investigated to give 4-(N,N-dialkyldithiocarbamato)-2-dialkyliminio-1,3-dithietane tetrafluoroborates in good yields. Additionally, a one-pot procedure for the synthesis of 2-iminium-1,3-dithiolanes from the BF3·OEt2 catalyzed reaction of dithiocarbamic acid salts with styrene epoxide is described.
- Ziyaei Halimehjani, Azim,Hajilou Shayegan, Mojtaba,Poshteh, Shiva Shakori,Amani, Vahid,Notash, Behrouz,Hashemi, Mohammad M.
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- A catalyst-free 1,4-Michael-type reaction of in situ generated ortho-quinone methides (o-QMs) with dithiocarbamic acid salts in water
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Abstract: A catalyst-free conjugate addition of dithiocarbamic acid salts to in situ generated ortho-quinone methides (o-QMs) was investigated for the first time. Several dithiocarbamate derivatives of 4-hydroxycoumarine, 4-hydroxypyrone and 2-naphthol were synthesized in moderate-to-good yields in water at room temperature. Graphical abstract: [Figure not available: see fulltext.] Catalyst-free addition of dithiocarbamic acid salts to in situ generated o-QMs in water at room temperature.
- Aryanasab, Fezzeh,Shabanian, Meisam
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- Cu-mediated one-pot three-component synthesis of 3-N-substituted 1,4,2-benzodithiazine 1,1-dioxide derivatives
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A novel and efficient copper-catalyzed one-pot procedure for the synthesis of 3-N-substituted 1,4,2-benzodithiazine 1,1-dioxide derivatives from 2-halobenzenesulfonamides, amines and CS2 is described. The reaction proceeds through Ullmann-type S-arylation, intramolecular addition of NH2 with C[dbnd]S and dehydrosulfide, which provides a new and useful strategy for construction of cyclic aromatic sulfonamides.
- Dong, Wei,Ge, Zemei,Wang, Xin,Li, Ridong,Li, Runtao
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- DFT calculations in the assignment of solid-state NMR and crystal structure elucidation of a lanthanum(III) complex with dithiocarbamate and phenanthroline
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The molecular, crystal, and electronic structures as well as spectroscopic properties of a mononuclear heteroleptic lanthanum(iii) complex with diethyldithiocarbamate and 1,10-phenanthroline ligands (3 : 1) were studied by solid-state 13C and 15N cross-polarisation (CP) magic-angle-spinning (MAS) NMR, X-ray diffraction (XRD), and first principles density functional theory (DFT) calculations. A substantially different powder XRD pattern and 13C and 15N CP-MAS NMR spectra indicated that the title compound is not isostructural to the previously reported analogous rare earth complexes with the space group P21/n. Both 13C and 15N CP-MAS NMR revealed the presence of six structurally different dithiocarbamate groups in the asymmetric unit cell, implying a non-centrosymmetric packing arrangement of molecules. This was supported by single-crystal X-ray crystallography showing that the title compound crystallised in the triclinic space group P1. In addition, the crystal structure also revealed that one of the dithiocarbamate ligands has a conformational disorder. NMR chemical shift calculations employing the periodic gauge including projector augmented wave (GIPAW) approach supported the assignment of the experimental 13C and 15N NMR spectra. However, the best correspondences were obtained with the structure where the atomic positions in the X-ray unit cell were optimised at the DFT level. The roles of the scalar and spin-orbit relativistic effects on NMR shielding were investigated using the zeroth-order regular approximation (ZORA) method with the outcome that already the scalar relativistic level qualitatively reproduces the experimental chemical shifts. The electronic properties of the complex were evaluated based on the results of the natural bond orbital (NBO) and topology of the electron density analyses. Overall, we apply a multidisciplinary approach acquiring comprehensive information about the solid-state structure and the metal-ligand bonding of the heteroleptic lanthanum complex.
- Gowda, Vasantha,Laitinen, Risto S.,Telkki, Ville-Veikko,Larsson, Anna-Carin,Antzutkin, Oleg N.,Lantto, Perttu
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- Enthalpies of formation of crystalline dialkylammoniumdialkyldithiocarbamates: alkyl = ethyl, n-propyl, i-propyl, n-butyl, and i-butyl
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The standard (p0 = 101.325 kPa) molar enthalpies of formation of some crystalline dialkylammoniumdialkyldithiocarbamates were determined at 298.15 K by both solution-reaction calorimetry and by rotating-bomb calorimetry.The values from the two methods agreed to within the limits of experimental error, giving the weighted mean values: R = Ethyl, ΔfH0m(R2NH2S2CNR2, cr): -249.2+/-2.2 kJ*mol-1; R = n-Propyl: -353.2+/-1.3 kJ*mol-1; R = i-Proyl: -349.6+/-1.3 kJ*mol-1; R = n-Butyl: -461.3+/-1.6 kJ*mol-1; R = i-Butyl: -463.8+/-1.4 kJ*mol-1.
- Silva, Manuel A. V. Ribeiro Da,Reis, Ana M. V.,Pilcher, Geoffrey
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- Glycosyl dithiocarbamates: β-selective couplings without auxiliary groups
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In this article, we evaluate glycosyl dithiocarbamates (DTCs) with unprotected C2 hydroxyls as donors in β-linked oligosaccharide synthesis. We report a mild, one-pot conversion of glycals into β-glycosyl DTCs via DMDO oxidation with subsequent ring opening by DTC salts, which can be generated in situ from secondary amines and CS2. Glycosyl DTCs are readily activated with Cu(I) or Cu(II) triflate at low temperatures and are amenable to reiterative synthesis strategies, as demonstrated by the efficient construction of a tri-β-1,6-linked tetrasaccharide. Glycosyl DTC couplings are highly β-selective despite the absence of a preexisting C2 auxiliary group. We provide evidence that the directing effect is mediated by the C2 hydroxyl itself via the putative formation of a cis-fused bicyclic intermediate.
- Padungros, Panuwat,Alberch, Laura,Wei, Alexander
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p. 2611 - 2624
(2014/04/17)
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- Utilization of carbon disulfide as a powerful building block for the synthesis of 2-aminobenzoxazoles
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This protocol describes a novel, mild and convenient route to afford 2-aminobenzoxazoles in high yields, and represents a significant advance towards an environmentally friendly strategy. Aliphatic amines are made to react with carbon disulfide to provide intermediate dithiocarbamates (DTC), which in the presence of 2-aminophenol, subsequently undergo successive intermolecular nucleophilic attack and desulfurization to produce 2-aminobenzoxazoles within 3 h.
- Guntreddi, Tirumaleswararao,Allam, Bharat Kumar,Singh, Krishna Nand
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p. 9875 - 9880
(2013/09/02)
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- Glycal assembly by the in situ generation of glycosyl dithiocarbamates
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Glycal assembly offers an expedient entry into β-linked oligosaccharides, but epoxyglycal donors can be capricious in their reactivities. Treatment with Et2NH and CS2 enables their in situ conversion into glycosyl dithiocarbamates, which can be activated by copper triflate for coupling with complex or sterically congested acceptors. The coupling efficiency can be further enhanced by in situ benzoylation, as illustrated in an 11-step synthesis of a branched hexasaccharide from glucals in 28% isolated yield and just four chromatographic purifications.
- Padungros, Panuwat,Alberch, Laura,Wei, Alexander
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supporting information; experimental part
p. 3380 - 3383
(2012/09/22)
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- Investigation of the reaction of dithiocarbamic acid salts with aromatic aldehydes
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A reaction of dithiocarbamic acid salts with carbonyl compounds was investigated for the first time in the presence of BF3?OEt 2. The reaction is temperature dependent and gives gem-bis(dithiocarbamates) at 35-45 °C as a molecule with high equivalents of dithiocarbamate groups. At lower temperatures (15-20 °C), the 2-iminium-1,3-dithietane is obtained as the only product. The structure of a 2-iminium-1,3-dithietane was accomplished by X-ray crystallographic analysis.
- Ziyaei Halimehjani, Azim,Hajiloo Shayegan, Mojtaba,Hashemi, Mohammad Mahmoodi,Notash, Behrooz
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supporting information; experimental part
p. 3838 - 3841
(2012/10/08)
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- Synthesis, light harvesting, and energy transfer properties of a Zinc porphyrin linked poly(phenyleneethynylene)
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The synthesis of a zinc porphyrin linked conjugated homopolymer is presented. The synthetic strategy employed a directional polymerization of 1-iodo-2,5-dioctyl-4'-ethynyltolane in the presence of [10,20-bis(3,5-bis-tert- butylphenyl]-5,15-diethynylporphinato]zinc(II) (12) or [10,20-bis(3,5-bis-tert- butylphenyl]-5,15-dibromoporphinato]zinc(II) (10). In the case of 12 the reaction was found to give a polymer product with a constant ratio of zinc porphyrin to incorporated monomer units regardless of the molecular weight. In the case of 10, however, the ratio of zinc porphyrin to incorporated monomer units decreased with increasing molecular weight of the polymer product. The polymer products were separated into fractions using preparative SEC. Studies of the energy transfer properties from the polymer to the zinc porphyrin revealed that there was little energy transfer in solution but quantitative energy transfer in the solid state. The polymer products proved difficult to handle in terms of device construction where a thin polymer film is sandwiched between two electrodes. We found this to be a consequence of the palladium catalysis employed during the polymerization. We finally discuss the issues concerning the problems with remnants from the Pd catalyst in the polymer samples and their removal.
- Nielsen, Kim T.,Spanggaard, Holger,Krebs, Frederik C.
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p. 1180 - 1189
(2007/10/03)
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- NEW DERIVATIVES OF DITHIOCARBAMIC ACID. I. REACTION OF ORGANIC DITHIOCARBAMIC ACIDS WITH ALKYL VINYL ETHERS AND SULFIDES
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1-Alkoxy- and 1-alkylthio-1-(organodithiocarbamoyl)ethanes, which are new types of dithiocarbamic esters, were obtained with high yields by the reaction of organic dithiocarbamic acids, produced in situ from secondary amines and carbon bisulfide, with alkyl vinyl ethers and sulfides.
- Trofimov, B. A.,Amosova, S. V.,Ivanova, N. I.,Tarasova, O. A.,Al'pert, M. L.,et al.
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p. 1925 - 1928
(2007/10/02)
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- THERMAL DECOMPOSITION OF TRIS(N,N-DISUBSTITUTED DITHIOCARBAMATE) COMPLEXES OF As(III), Sb(III) AND Bi(III).
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Thermal studies on tris(N,N-disubstituted dithiocarbamates) of arsenic(III), antimony(III) and bismuth(III) of the type M left bracket S//2CX right bracket //3 (M equals As, Sb, Bi; X equals NEt//2, N(CH//2)//4O) by simultaneous TG, DTG and DTA were carried out in air and nitrogen atmospheres. The apparent activation energies were determined by the graphical method of Freeman-Carroll, modified for n equals 1, and Piloyan's two methods from the TG and DTG curves. The TTN temperatures were calculated from the TG profiles. A possible mechanism of the decomposition reaction is suggested on the basis of the results of their pyrolysis and their mass spectral data. The intermediates obtained at the ends of various decomposition stages were identified via elemental analysis and i. r. and mass spectral data, whereas the residues were identified by X-ray powder diffraction analysis.
- Lalia-Kantouri,Manoussakis
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p. 1151 - 1169
(2008/10/08)
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- INVESTIGATION IN THE FIELD OF BIACETYLENE DERIVATIVES. XLII. ADDITION OF AMMONIUM DITHIOCARBAMATES TO BIACETYLENE
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A simple method was developed for the production of cis-1-buten-ynyl dialkyldithiocarbamates and 1,4-bis(dialkylthiocarbamoylthio)-1,3-butadienes by the reaction of biacetylene and carbon bisulfide in the presence of secondary amines without a catalyst in protic and aprotic solvents.
- Sokolyanskaya, L. V.,Vavilova, A. N.,Volkov, A. N.,Trofimov, B. A.
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p. 2025 - 2028
(2007/10/02)
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