Molecular structure of 6-methyleneoxytetracycline hydrobromide

The structure of 4(dimethylamino)-1, 4, 4a, 5, 5a, 6, 11, 12a-octahydro-3, 5, 10, 12, 12a-pentahydroxy-6-methylene-1, 11-dioxo-2-naphthacenecarboxamide hydrobromide salt was determined by an X-ray analysis. One methacycline cation and one bromide anion were found in the asymmetric unit of an orthorhombic cell, space group P2₁2₁2₁,a 9.580(1),b 12.147(2),c 18.735(3) å,V2180.0(5) å³, Z4,D _c 1.59 g cm^–3, (MoK) 19.15 cm^–1. The structure was solved and refined toR(F) 0.062 andR _w(F) 0.064 by a full matrix least-squares procedure. The conformation of the methacycline cation is found to be similar to that reported for 6-demethyl-7-chlorotetracycline hydrochloride trihydrate.     

Chemistry of Thiobenzoates: Syntheses, Structures, and NMR Spectra of Salts of [M(SOCPh)(3)](-) (M = Zn, Cd, Hg)

The salts (Ph(4)E)[M(SOCPh)(3)] (M = Zn, Cd, or Hg; E = P or As) are produced by the reaction of Zn(NO(3))(2).6 H(2)O, Cd(NO(3))(2).4H(2)O or HgCl(2) with Et(3)NH(+)PhCOS(-) and (Ph(4)E)X (E = P, X = Br; E = As, X = Cl) in aqueous MeOH in the ratios M(II):PhCOS(-):Ph(4)E(+) = 1:>/=3:>/=1. The crystal structures of (Ph(4)P)[Zn(SOCPh)(3)] (1), (Ph(4)As)[Cd(SOCPh)(3)] (2) and (Ph(4)P)[Hg(SOCPh)(3)] (3) have been determined by single-crystal X-ray diffraction experiments. Crystal data for 1: triclinic; space group P&onemacr;; Z = 2; a = 10.819(2) ?, b = 13.219(3) ?, c = 15.951(3) ?; alpha = 101.75(2) degrees, beta = 97.92(1) degrees, gamma = 109.18(2) degrees. Crystal data for 2: triclinic; space group P&onemacr;; Z= 2; a = 10.741(2) ?, b = 13.168(2) ?, c = 15.809(2) ?; alpha = 101.00(1) degrees, beta = 97.65(1) degrees, gamma = 109.88(1) degrees. Crystal data for 3: monoclinic; space group P2(1)/n; Z = 4; a = 13.302(2) ?, b = 14.276(2) ?, c = 21.108(2) ?; beta = 90.92(1) degrees. The compounds 1 and 2 are isomorphous and isostructural. In the anions [M(SOCPh)(3)](-) the metal atoms have trigonal planar coordination by three sulfur atoms. The metal atoms are further more weakly coordinated intramolecularly to one (M = Hg) or two (M = Zn, Cd) thiobenzoate oxygen atom(s). Using the Bond Valence approach it is found that the contribution of M.O bonding to the total bonding is in the order Cd > Zn > Hg. The metal ((113)Cd, (199)Hg) NMR signals of [M(SOCPh)(3)](-) (M = Cd, Hg) are more shielded than those found for MS(3) kernels in thiolate complexes, a difference attributed to the M(.)O bonding in the thiobenzoate complexes. The (113)Cd resonance of [Cd(SOCPh)(3)](-) in dilute solution is in the region anticipated from dilution data for [Na(Cd{SOCPh}(3))(2)](-).     

The synthesis, coordination chemistry and ethylene polymerisation activity of ferrocenediyl nitrogen-substituted ligands and their metal complexes

Treatment of aminoferrocene with substituted 2-hydroxybenzaldehydes yields the air- and moisture-stable ligands 1–4, which were then reacted to form the chromium dichloride complexes 5–7 and the nickel bis-chelate species 8 and 9. The metal compounds are very air-sensitive but the chromium compounds act as pre-catalysts for the polymerisation of ethylene. Reaction of 1,1′-bis(amino)ferrocene with similarly substituted 2-hydroxybenzaldehyes or simple benzaldehyde gives the ligands 10–12 and 17, respectively. The X-ray crystal structure of 11 shows the molecule to have non-crystallographic C₂ symmetry and to be linked by C–Hπ interactions between the anthracene rings. Titanium-containing complexes 13–16 can be formed utilising ligands 10–12 and there is a change in geometry within the complexes dependent on the adjacent co-ligands, whilst ligand 17 can be reacted with PdClMe(COD) to form the chelate complex 18. Cyclic voltammetric studies have been carried out on 18 and its oxidised analogue 19, but both complexes are inactive towards ethylene polymerisation.     

Synthesis and 119mSn Mössbauer studies of cationic tributyltin complexes

A series of cationic tributyltin complexes with a tetraphenylborate counter anion, [Bu₃SnL₂]⁺BPh₄,^?, where L = DMSO, Ph₃PO, Ph₃,AsO, pyO or DMF, and L₂ = diphosO₂, has been prepared and their ^119mSn Mössbauer spectra investigated. These indicate that the triorganotin cation occupies a pentacoordinate trigonal bipyramidal geometry with equatorial organic groups when L = monodentate donor, whilst the bidentate diphosO₂ ligand produces a mer-R₃SnX₂ stereochemistry about tin.     

Kinetik und Mechanismus der Oxydation von 1,2,4,5-Tetramethylbenzol in essigsaurem Medium

The liquid phase oxidation of 1.2.4.5-tetramethylbenzene catalysed by cobaltous acetate and promoted by KBr in acetic acid was kinetically studied. In view of deriving the kinetic equation for the absorption of oxygen, a number of experiments were carried out. The values of the activation energy and of the preexponentA=10¹⁴ were determined as well. The resulting kinetic equation: $$ - \frac{{d\left[ {O_2 } \right]}}{{d\tau }} = 10^{14} \cdot \exp \left( { - \frac{{84,460 \times 10^3 }}{{RT}}} \right) \cdot C_{C_6 H_2 (CH_3 )_4 }^{0,5} \cdot C_{Co(OAc)_2 }^{0,5} \cdot C_{KBr}^{0,5} $$ is in accordance with the theoretically derived expression of this type.     

A comprehensive approach to argumentation

A reasoning model, based on the logic of argumentation, is described. The model represents argumentation as a directed graph in which nodes and arcs can be colored using an ordinal set of weightings and in which the attributes of both nodes and arcs can be modified. It is thus able to deal with the undercutting or augmenting of arguments. Weightings can be propagated through the graph to generate unique weightings for any node or arc. The model is able to deal with contradiction. It can incorporate numerical methods and is able to handle qualitative and quantitative reasoning.     

Isofuranonaphthoquinones from ventilago maderaspatana: Crystal structure of ventilone-C

From the root bark of Ventilago maderaspatana (Rhamnaceae) five isofuranonaphthoquinones have been isolated. Ventilone-A is 4,9-dihydro-5,8-dihydroxy-6,7-methylenedioxy-1-methylnaphtho[2,3-c] furan-4,9-dione and B is the 5-methyl ether. Ventilone-C has the structure 1,3,4,9-tetrahydro-8-hydroxy-5-methoxy-6, 7-methylenedioxy-1-methylnaphtho[2,3-c]furan-4,9-dione, D is the isomeric 8-methyl ether, and E is the 5,8-dimethyl ether. Structures were determined by spectroscopic methods, and X-ray crystallographic analysis of ventilone-C.     

Electrochemical reduction of uracil in dimethyl sulfoxide: Autoprotonation of the anion radical

The electrochemical reduction of uracil in dimethyl sulfoxide was investigated, using d.c.and a.c. polarography, cyclic voltammetry, and controlled potential electrolysis. Uracil is reduced in a one-electron step (E_1/2=?2.3 V); the apparent number of electrons transferred (n) decreases from one at infinite dilution to one-half at concentrations above 1mM. The concentration dependent n-value is due to proton transfer by the parent compound to the radical anion formed on reduction. Such a proton transfer, which has been observed for 2-hydroxypyrimidine, deactivates part of the uracil, which would otherwise be available for reduction, by formation of the more difficultly reducible conjugate base. The uracil anion forms insoluble mercury salts, producing two oxidation waves (E_1/2 of ?0.1 and ?0.3 V); the latter wave is due to formation of a passivating film on the electrode. Digital simulations indicate that the protonation rate exceeds 10⁵M^?1 s^?1 and that, at low uracil concentration, some of the free radical formed on protonation is further reduced. At concentrations exceeding 1 mM, all of the free radical dimerizes. The effect of added acids and base on the electrochemical behavior is described.