- Sequential Interaction of Enamine with O, O-Dialkyldithiophosphoric Acid and Electrophilic Reagent
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The adduct of O, O-dialkyldithiophosphoric acid and enamine reacts exothermically with an electrophilic reagent. In the case of sulfenyl bromide, the iminium salt reduced at the C-Br bond and bis(dialkoxythiophosphorylthio)-disulfide have been formed, experimentally evidencing the reaction of 2-halogenated ald- and ketimines with dithioic acid via the intermediate formation of enamine.
- Gazizov, M. B.,Ivanova, S. Yu.,Khairullin, R. A.,Kirillina, Yu. S.,Shamsutdinova, L. P.
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- Three component reactions of enamines, O,O-dialkyldithiophosphoric acids, and electrophiles
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The product of addition of O, O-dialkyldithiophosphoric acid to enamine reacted with the third reaction component of electrophilic nature, for instance, acetyl chloride, α-bromo ether, or sulfenyl bromide. The reaction involving sulfenyl bromide gave the
- Gazizov, M. B.,Gazizova, K. S.,Ivanova, S. Yu.,Khairullin, R. A.,Khayarov, Kh. R.,Kirillina, Yu. S.
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- Reaction of P(IV) Dithio Acids with N-Alkyl-α-chloroketimines
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Effect of the substituent on the imine carbon atom on the result of the reaction of P(IV) dithio acids with N-Alkyl-α-chloroketimines has been studied. New types of ketones containing (O,O-diisopropyl phosphorothioyl)sulfanyl and (diphenylphosphinothioyl)
- Khairullin,Gazizov,Kirillina, Yu. S.,Khayarov, Kh. R.,Ivanova, S. Yu.
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- Bis(O,O-diisopropoxy phosphinothioyl) disulfide - A highly efficient sulfurizing reagent for cost-effective synthesis of oligo (nucleoside phosphorothioate)s
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A new sulfurizing reagent is reported for the automated synthesis of phosphothioate analogues of oligonucloetides via the phosphoramidite method. Bis(O,diisopropoxy phosphinothioyl) disulfide (S-Tetra, 1) is relatively inexpensive to prepare, easy to handle, and efficiently sulfurizes internucleotide phosphites, thus allowing the practical synthesis of oligo(nucleoside phosphorothioate)s with exceptionally high sulfur content.
- Stec, Wojciech J.,Uznanski, Bogdan,Wilk, Andrzej,Hirschbein, Bernard L.,Fearon, Karen L.,Bergot, B. John
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- Triphenylbismuth(v) di[(iso)nicotinates]-transmetallation agents or divergent organometalloligands? First organobismuth(v)-based silver(i) coordination polymers
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The reaction of Ph3BiCl2 with alkali salts of isonicotinic and nicotinic acids afforded Ph3Bi[O(O)CC5H4N-4]2 (1) and Ph3Bi[O(O)CC5H4N-3]2 (2), respectively, which were characterized by multinuclear NMR spectroscopy in solution, mass spectrometry and IR spectroscopy in the solid state. Their molecular structures were established by single-crystal X-ray diffraction. For both 1 and 2 the molecules contain a trigonal bipyramidal C3BiO2 core, with the phenyl groups in equatorial positions. The potential use of 1 and 2 as ditopic organometalloligands was investigated. The reaction of 1 or 2 with Me3SnCl (1:2 molar ratio) resulted in carboxylato ligand exchange and the formation of Me3Sn[O(O)CC5H4N-4] (3) and Me3Sn[O(O)CC5H4N-3] (4) besides Ph3BiCl2. The crystals of both 3 and 4 contain 1-D coordination polymers built through intermolecular N → Sn interactions. The treatment of Ni[S2P(OiPr)2]2 with 1 and 2, respectively, resulted, in addition to di(carboxylato)nickel(ii) derivatives, in isolation of Ph3Bi and the disulphane [(iPrO)2P(S)S]2. New coordination polymers were obtained by reacting 1 and 2 with various silver(i) salts: [Ag{Ph3Bi[O(O)CC5H4N-4]2}(OTf)] (5), [Ag{Ph3Bi[O(O)CC5H4N-3]2}(OTf)]·CH2Cl2 (6·CH2Cl2), [Ag{Ph3Bi[O(O)CC5H4N-4]2}](SbF6)·2THF (7·2THF), [Ag{Ph3Bi[O(O)CC5H4N-3]2}](SbF6)·CH2Cl2 (8·CH2Cl2) and [Ag{Ph3Bi[O(O)CC5H4N-3]2}(NO3)]·CH2Cl2 (9·CH2Cl2). The crystal structures of 5 and 6 can be described as 1-D chains linked by triflate bridges in pairs of chains and 2-D networks, respectively. Compound 7 features a 2-D grid-like topology of the network, with tecton 1 acting as a tridentate ligand through both nitrogen and one oxygen atoms. The linker 2 molecules adopt either cis (compound 6) or trans (compounds 8 and 9) conformation. Complexes 8 and 9 are 1-D chain polymers exhibiting zig-zag and wavy motifs, respectively. The dimensionality of the structures is extended by the presence of supramolecular interactions (π?π, Ag?Ag, Ag?O).
- Ben Kiran, Ahmad,Mocanu, Teodora,P?llnitz, Alpár,Shova, Sergiu,Andruh, Marius,Silvestru, Cristian
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- Reactions of the N-isopropyl-α-chloroketimines with PIV dithioacids
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A primary iminium salt formed in the reaction of PIV dithioacids with N-isopropyl-α-chloroketimines is transformed into products of nucleophilic substitution of the chlorine atom by dithiophosphorus group (SN pathway), if the imine carbon atom is bonded to the donor and small-volume methyl group, or undergoes reduction of the CCl bond (C-Cl→C-H) (Red pathway), when it is bonded with the bulky acceptor phenyl group. The same effect of substituents was discovered, when replacing methyl group with phenyl one in the position 2 of N-tert-butyl-2-chloraldimines: SN: Red ratio is 1: 0 in the case of Me and 1: 9 in the case of Ph. The iminium salts were transformed into new type ketones containing a phosphor functionality.
- Gazizov,Khairullin,Kirillina, Yu. S.,Ivanova, S. Yu.,Khayarov, Kh. R.,Khairullina
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p. 2241 - 2245
(2019/02/07)
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- Reactions of N-tert-butyl-2,2-dichloro(dibromo)propanimines and O,O-dialkyldithiophosphoric acids
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The reactions of O,O-dialkyldithiophosphoric acids and N-tert-butyl-2,2-dichloro(dibromo)propanimines initially gave primary iminium salts. These salts subsequently reacted with another two acid molecules resulting firstly in reduction of the C-Hal bond and then nucleophilic substitution of the halogen by the (dialkoxythiophosphorylthio) group. The reactions studied resulted in formation of the reduction-substitution product of the primary iminium salt and bis(dialkoxythiophosphoryl)disulfide.
- Gazizov, Mukattis B.,Khairullin, Rafail A.,Aksenov, Nikita G.
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p. 272 - 274
(2016/01/12)
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- Reaction of O,O-dialkyldithiophosphoric acid with N-tert-butyl-2,2-dihalopropanimines
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O,O-Dialkyldithiophosphoric acid reacted with N-tert-butyl-2,2-dihalopropanimines to give iminium salt as a primary product, which further sequentially undergoes reaction with two equivalents of dithiophosphoric acid to initially reduce the C—X (X = Cl, Br) bond in the iminium salt and then nucleophilic replacement of the halogen atom with dialkoxydithiophosphate group. The final reaction products are the reduction—substitution product of the primary salt and bis(dialkoxythiophosphoryl) disulfide.
- Gazizov,Khairullin,Aksenov,Kirillina, Yu. S.,Bandikova, A. Yu.
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p. 1119 - 1121
(2017/01/13)
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- Reactions of O,O-dialkyldithiophosphoric acids with N-tert-butyl-2-bromo-2-methylpropanimine and its salts
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Abstract The reactions of O,O-dialkyldithiophosphoric acids with N-tert-butyl-2-bromo-2-methylpropanimine and its salts resulted in reduction of the carbon-bromine bond in the iminium salt giving bis(dialkoxythiophosphoryl)disulfide and N-tert-butyl-2-methylpropaniminium bromide. This represents the first example of C-Br bond reduction by O,O-dialkyldithiophosphoric acids.
- Gazizov, Mukattis B.,Khairullin, Rafail A.,Aksenov, Nikita G.,Sinyashin, Oleg G.
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p. 4993 - 4996
(2015/08/04)
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- Reaction of O,O-dialkyldithiophosphoric acids with N-alkyl-2-haloaldimines
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Synthetic results of reactions of O,O-dialkyldithiophosphoric acids with N-alkyl-2-haloaldimines fundamentally depend on the nature of the halogen: in the case of Cl-substituted imines the reaction afforded 2-(dialkoxythiophosphorylthio)iminium chlorides, with bromoimines bis(dialkoxythiophosphoryl) disulfide and unsubstituted iminium bromide were obtained. According to dynamic 31P NMR spectroscopy data the reason for this difference is the presence or absence of a free acid in the reaction medium.
- Khairullin,Gazizov,Aksenov,Khayarov, Kh. R.
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p. 2099 - 2105
(2015/10/29)
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- On the reaction of bis(phosphothioyl)disulfanes with hydroxamic acids, part I: Ionic versus radical reaction pathways
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Among sodium N-alkyl-4-chlorobenzohydroxamates treated with bis(phosphothioyl)disulfanes >P(S)SSP(S)P(S) is phosphorothioyl, phosphonothioyl, and phosphinothioyl), only the N-methyl one yields quantitatively the respective O-phosphothioyl derivatives exhibiting complete inversion of configuration at phosphorus in a reaction whose products are inert toward dithiophosphate arising in the reaction. For branched N-alkyl benzohydroxamates, products of a SET process predominated. The mechanism of the title reaction is discussed.
- Przychodzen, Witold,Chojnacki, Jaroslaw
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p. 271 - 282
(2008/09/19)
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- Effect of solute-co-ordinating solvent interactions and temperature on the EPR and electronic spectra of bis(dithiophosphato)copper(II)
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The self-redox reaction proceeding between two molecules of the complex bis(disubstituted-dithiophosphato)copper(II), CuII(R2-dtp)2, is studied by EPR and UV-VIS spectroscopy in DMFA, DMSO and pyridine. The effect of temperature and disulphide concentration in the solutions is also evaluated. The EPR spectra show that the g-values of CuII(R2-dtp)2 increase when it is dissolved in co-ordinating solvents, whereas the copper hyperfine splitting decreases compared to the corresponding values in non-co-ordinating solvents. Under the same conditions, a hypsochromic shift is observed in the maximal absorption at 420 nm of the electronic spectra which corresponds to the ligand-to-metal charge-transfer (LMCT) transition of the complex. The results are explained with the formation of axial or equatorial adducts between CuII(R2-dtp)2 and the co-ordinating solvents used. On the other hand, the molar absorptivity of the LMCT band and the intensity of the EPR spectrum increase strongly with the nature of the used co-ordinating solvent, the time after dissolution and the quantity of added disulphide. Both also depend on the size and shape of remote ligand substituents and they increase in the order Me2P(S)S-S(S)P(RO)2] to the CuII(R2-dtp)2 solution. As a result, the molar absorptivity value at the maximum of the LMCT band of Cu[(i-PrO)2-dtp]2 increases from 7.9×103 m-1dm3cm-1 immediately after dissolution to 2.9×104 m-1dm3cm-1. In DMSO and pyridine, the intensity of both the EPR signal and LMCT band of CuII(R2-dtp)2 continuously decrease after the preparation of the solutions. A small increase is only observed immediately after the addition of the corresponding disulphide of dithiophosphate. While DMFA forms stable adducts with Cu[(i-PrO)2-dtp]2, adduct formation with DMSO and pyridine destroys the initial complex.
- Yordanov, Nicola D.,Ranguelova, Kalina
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p. 1171 - 1180
(2007/10/03)
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- REACTIVITE DE L'ACIDE O,O'-DIISOPROPYLDITHIOPHOSPHORIQUE SUR DES ALCYNES VRAIS SULFURES
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Reactivity of O,O'-diisopropyldithiophosphoric acid towards sulfurated monosubstituted alkynes.The reactivity of sulfurated monosubstituted alkynes with O,O'-diisopropyldithiophosphoric acid has been investigated, by three different methods (MeCN, Triton B, AIBN).Two types of alkenes were isolated.The selectivity of this reaction was studied. 13C and 31P NMR of these new sulfurated alkenes were reported. - Key words: O,O'-diisopropyldithiophosphoric acid, alkynes, sulfurated alkenes, 13C NMR, 31P NMR.
- Dodin-Carnot, V.,Curci, M.,Wilhelm, J. C.,Mieloszynski, J. L.,Paquer, D.
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p. 219 - 226
(2007/10/03)
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- Method of synethesizing sulfurized oligonucleotide analogs
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A method for synthesizing sulfurized oligonucleotide analogs, such as phosphorothioate and phosphorodithioate analogs, is provided that employs a thiophosphorus compound, such as a thiophosphoric, dithiophosphoric, thiophosphinic, or dithiophosphinic acid disulfide or polysulfide, as a sulfurizing agent. The method of the invention may be used to sulfurize any phosphorous(III)-containing intermediate. Preferably, the method is practiced on a commercial DNA synthesizer using phosphoramidite and/or phosphorthioamidite intermediates.
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- 13C and 31P Solid-State NMR Studies of Bis(dialkoxythiophosphoryl) Disulfides
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The principal elements of the chemical shift tensors for the phosphorus atoms in three bis(dialkoxythiophosphoryl) disulfides were determined from both static and magic angle spinning NMR spectra, using the intensities of the peak in the spinning sidebands relative to those of the central band in the latter method.These studies show that it is possible to deduce a mode of molecular motion in the solid state by analysis of the shielding parameters.Variable-temperature 13C and 31P CP MAS NMR of these samples from 190 to 320 K revealed a peculiar motion of the methoxy group and a rigid P-S-S-P backbone for bis(dimethoxythiophosphoryl) disulf ide.In addition, these studies confirmed that it is possible to distinguish the different x-ray crystal structures from the solid-state NMR experiments.
- Chu, Po-Jen,Potrzebowski, Marek J.
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p. 477 - 485
(2007/10/02)
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- 31P CIDNP IN THE REACTION OF ZINC DIISOPROPYLDITHIOPHOSPHATE WITH METHYL ETHYL KETONE PEROXIDE AND CUMENE HYDROPEROXIDE IN BENZENE
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The free-radical nature of the reactions of a series of dithiophosphate complexes of zinc with peroxides was established by 31P chemically induced dynamic nuclear polarization (CIDNP).The polarization coefficient, the reaction rate constant, and the nucle
- Gainullin, R. M.,Ismaev, I. E.,Il'yasov, A. V.
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p. 2029 - 2032
(2007/10/02)
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- Reactions of Copper(II) with - (R = Et or Pri) and Single-crystal X-Ray Studies of Cu*bipy and Cu*2PPh3
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The position of the equilibrium (i) (R = Et or Pri) has been shown to be solvent dependent.The 2Cu2 2Cu + 2 (i) addition of nitrogen bases or triphenylphosphine affects the position of the equilibrium; for instance aromatic bases and PPh3 favour the formation of copper(I) adducts.The structures of two such adducts, Cu*bipy (1) (bipy = 2,2'-bipyridyl) and Cu*2PPh3 (2), have been determined by X-ray methods.Complex (1) is triclinic, space group P, with a = 9.388(6), b = 10.208(7), c = 10.704(7) Angstroem, α = 95.88(5), β = 68.44(5), γ = 115.94(6) deg, and Z = 2. 2190 Independent reflections above background were measured and the structure refined to R 0.080.Complex (2) is monoclinic, space group P21/n, with a = 11.88(1), b = 14.70(1), c = 22.09(1) Angstroem, β = 91.0(1) deg, and Z = 4. 4 087 Independent reflexions above background were measured and the structure refined to R = 0.056.Complex (1) exists as a centrosymmetric dimer with a Cu-S-P-S-Cu-S-P-S chair-shaped ring in which two S2P(OEt)2 groups bridge two four-coordinate metal atoms.The co-ordination spheres of the metal atoms consist of two sulphur atoms and two nitrogen atoms from chelating bipy groups , making up a distorted tetrahedral environment.Complex (2) is monomeric, with the metal atom bound to two PPh3 molecules and a - ion to give an approximately tetrahedral co-ordination sphere.
- Drew, Michael G. B.,Forsyth, George A.,Hasan, Masihul,Hobson, Richard J.,Rice, David A.
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p. 1027 - 1034
(2007/10/02)
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- ELECTRON SPIN RESONANCE STUDIES OF THE PHOTOLYSIS AND RADIOLYSIS OF O,O'-DIALKYL HYDROGEN PHOSPHORODITHIOATES , THEIR SALTS, CORRESPONDING DISULPHIDES, AND RELATED COMPOUNDS : FORMATION OF THIO AND DITHIO RADICALS, RADICAL IONS, AND PHOSPHORUS-CENTRED RADICALS
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Isotropic and anisotropic e.s.r. parameters are reported for some dialkoxy(thiophosphoryl)thio radicals .> generated by photolysis of some O,O'-dialkyl hydrogen phosphorodithioates, their salts, and corresponding disulphides .The unpaired electron in these radicals is evidently shared equally between the two sulphur atoms in an in-plane orbital; the variation of the linewidth with viscosity and temperature is interpreted in terms of spin-rotation interaction.The radicals are very short-lived (with 2kt ca.E9 dm3 mol-1 s-1); though they are apparently unreactive towards either aliphatic alkenes or oxygen, they react rapidly to give peroxyl radicals in the presence of both.The analogous oxygen-substituted radicals (RO)2P(O)S. posses the unpaired electron localized on sulphur: though they prove undetectable in fluid solution (presumably on account of marked linebroadening) their rapid reaction with the corresponding anion to give the ?*-species 2-. could be monitored.Solid-state spectra from photochemically generated dithio radicals (RO)2P(X)S2.(X=O or S) are also reported.Finally, radiolysis of solid samples of these compounds leads to the characterization of anisotropic spectra from the appropriate thio and dithio radicals as well as those from electron-loss species (RSSR+.) and electron-gain radicals .-type (RSSR)-. and phosphoranyl-type structure -.P(OR)2(X)SSP(X)(OR)2>; structural aspects, matrix effects, and further reactions .PL3 and alkyl radicals> are discussed.
- Gilbert, Bruce C.,Kelsall, Paul A.,Sexton, Michael D.,McConnachie, Glen D. G.,Symons, Martyn C. R.
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p. 629 - 640
(2007/10/02)
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- REDOX REACTIONS OF ANTIMONY(III) O,O-DISUBSTITUTED PHOSPHORODITHIOATES WITH FERRIC CHLORIDE
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The reaction of antimony(III) tris-(O,O-diethylphosphorodithioate) with three equivalents of ferric chloride in ether solution has been found to give ferrous chloride, bis-(O,O-diethylthiophosphoryl) disulfide and dichloroantimony O,O-diethyl phosphorodithioate as the major products.However, a relatively low yield of bis-(O,O-diethylthiophosphoryl) trisulfide was also obtained.The structures of these products were established by independent syntheses.Several additional antimony(III) tris-(O,O-disubstituted phosphorodithioates) were prepared, and the major organic product obtained by reaction of each of these compounds with three equiva lents of ferric chloride was the corresponding bis-(O,O-disubstituted thiophosphoryl) disulfide.A mechanism for this reaction has been suggested, and evidence in support of the mechanism has been presented.The various antimony(III) tris-(O,O-dialkyl phosphorodithioates) are passivating agents in petroleum refining.The results reported in this and in our previous papers indicate that such compounds undergo a variety of reactions with components of crude petroleum prior to the ultimate pyrolysis reactions which occur in the fluid catalytic cracking process.
- Woo, Edward J.,Kalbacher, Barbara J.,McEwen, William E.
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p. 269 - 278
(2007/10/02)
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