- 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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- 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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- 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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- 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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- A PHOTO-INDUCED REACTION BY VISIBLE LIGHT VIA A CHARGE TRANSFER COMPLEX
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The reduction of tropylium cation (Tr+) with concomitant oxidation of O,O'-dialkyldithiophosphate anions (dtp-) have been achived by visible irradiation of their acetonitrile solution in presence of a bipyridium dication; the later via its charge transfer complex with dtp- acts as a light-harvest and as an electron relay.
- Deronzier, Alain
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- DITHIOPHOSPHATO-PLATINUM-COMPLEXES FOR THE TREATMENT OF CANCERS
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Complex of formulas: (I), (II) or (III): which are suitable for the treatment of tumors.
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Page/Page column 32-33
(2008/06/13)
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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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- Synthesis and properties of (diethoxyphosphinothioylthio)methyl derivatives of 5-alkyl-4,5-dihydro-1,2,4-triazin-6(1H)-ones
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(Dialkoxyphosphinothioylthio)methyl derivatives of 5-alkyl-4,5-dihydro-1,2,4-triazin-6(1H)-ones are formed when an excess of O,O-dialkyl hydrogen phosphodithioates is used.In presence of mineral acids the triazine ring is split.Under these conditions N-ethyl-5-alkyl-1,4,5,6-tetrahydro-6-oxo-1,2,4-triazine-4-carboxamides are recyclized to 5-alkyl-3-ethylhydantoins.
- Sapozhnikova, Zh.Z.,Prokof'eva, A.F.,Volkova, V.N.,Mel'nikov, N.N.
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p. 2275 - 2284
(2007/10/02)
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- A primary molybdosulfenamide
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A sulfide bridge of the Mo(V) dimer anion [Mo2(NC7H7)2(S2P(OC 2H5)2)2(μ-S) 2(μ-O2CCH3)]- reacted with hydroxylamine-O-sulfonic acid to give the primary molybdosulfenamide [Mo2(NC7H7)2(S2P(OC 2H5)2)2(μ-S)(μ-O 2CCH3)(μ-SNH2)]. This sulfenamide reacted with acetic anhydride to give the imide [Mo2(NC7H7)2(S2P(OC 2H5)2)2(μ-S)(μ-O 2CCH3)(μ-SNHCOCH3)]. Treatment of sulfenamide with (C2H5O)2PS2H or C6H5SH gave reductive S-N cleavage. The disulfide-bridged complex [Mo2(NC7H7)2(S2P(OC 2H5)2)2(μ-S)(μ-O 2CCH3)(μ-S2PS(OC2H 5)2)] was also prepared.
- Noble, Mark E.
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p. 1337 - 1342
(2008/10/08)
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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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- 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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