Determination of copper impurities in nickel and cobalt salts by atomic absorption spectroscopy

Summary A method is described for the rapid determination of traces of copper in the ppm range in cobalt and nickel salts. The % standard deviation for the analysis is reported as 3.4 to 3.7 for aequous solutions and 4.8 to 5.0 for carbon tetrachloride sprayed directly into the flame after extraction.

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Zusammenfassung Ein Verfahren zur raschen Bestimmung von Kupferspuren im ppm-Bereich in Kobalt- und Nickelsalzen wurde beschrieben. Die Standardabweichung in wäßrigen Lösungen beträgt 3,4 bis 3,7%, bei unmittelbarem Versprühen der Tetrachlorkohlenstoffextrakte in die Flamme 4,8 bis 5,0%.

     

Nitration of pentaerythritol by HNO3-H2SO4-H2O system

Conclusions It was shown experimentally that the nitrating agent in the O-nitration of pentaerythritol by HNO₃-H₂SO₄-H₂O nitrating mixtures is not the nitronium cation but evidently the free unionized nitric acid molecule.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 134–140, January, 1970.     

Sterically controlled reductive oligomerisations of CO by activated magnesium(i) compounds: deltate vs. ethenediolate formation

An extremely bulky, symmetrical three-coordinate magnesium(i) complex, [{(^TCHPNacnac)Mg}₂] (^TCHPNacnac = [{(TCHP)NCMe}₂CH]⁻, TCHP = 2,4,6-tricyclohexylphenyl) has been prepared and shown to have an extremely long Mg–Mg bond (3.021(1) Å) for such a complex. It was shown not to react with either DMAP (4-dimethylaminopyridine) or CO. Three unsymmetrical 1 : 1 DMAP adducts of less bulky Mg–Mg bonded species have been prepared, viz. [(^ArNacnac)Mg–Mg(DMAP)(^ArNacnac)] (^ArNacnac = [(ArNCMe)₂CH]⁻ Ar = 2,6-xylyl (Xyl), mesityl (Mes) or 2,6-diethylphenyl (Dep)), and their reactivity toward CO explored. Like the previously reported bulkier complex, [(^DipNacnac)Mg–Mg(DMAP)(^DipNacnac)] (Dip = 2,6-diisopropylphenyl), [(^DepNacnac)Mg–Mg(DMAP)(^DepNacnac)] reductively trimerises CO to give a rare example of a deltate complex, [{(^DepNacnac)Mg(μ-C₃O₃)Mg(DMAP)(^DepNacnac)}₂]. In contrast, the two smaller adduct complexes react with only two CO molecules, ultimately giving unusual ethenediolate complexes [{(^ArNacnac)Mg{μ-OC(H) C(DMAP^−H)O}Mg(^ArNacnac)}₂] (Ar = Xyl or Mes). DFT calculations show the latter reactions to proceed via reductive dimerizations of CO, and subsequent intramolecular C–H activation of Mg-ligated DMAP by “zig–zag” [C₂O₂]²⁻ fragments of reaction intermediates. Calculations also suggest that magnesium deltate complexes are kinetic products in these reactions, while the magnesium ethenediolates are thermodynamic products. This study shows that subtle changes to the bulk of the reacting 1 : 1 DMAP–magnesium(i) adduct complexes can lead to fine steric control over the products arising from their CO reductive oligomerisations. Furthermore, it is found that the more activated nature of the adduct complexes, relative to their symmetrical, three-coordinate counterparts, [{(^ArNacnac)Mg}₂], likely derives more from the polarisation of the Mg–Mg bonds of the former, than the elongated nature of those bonds.

Subtle changes to the bulk of 1 : 1 adducts of DMAP with magnesium(i) complexes leads to steric control over the products arising from their reductive oligomerisations of carbon monoxide.      

High-throughput cytochrome P450 inhibition screening via cassette probe-dosing strategy. IV. Validation of a direct injection on-line guard cartridge extraction/tandem mass spectrometry method for simultaneous CYP3A4, 2D6 and 2E1 inhibition assessment

A highly efficient direct injection on-line guard cartridge extraction/tandem mass spectrometry (DI-GCE/MS/MS) method has been validated for high-throughput evaluation of cytochrome P450 (CYP) 3A4, 2D6 and 2E1 inhibition potential via cassette dosing of midazolam, dextromethorphan and chlorzoxazone using human hepatic microsomes and 96-well microtiter plates. Microsomal incubations were terminated with formic acid, centrifuged, and the resulting supernatants were injected for analysis by DI-GCE/MS/MS. Due to the novel use of an extremely short C(18) guard cartridge (4 mm in length), this method exhibits several advantages such as no sample preparation, excellent on-line extraction, short run time (2.5 min), and minimized source contamination and performance deterioration. The DI-GCE/MS/MS method demonstrates acceptable accuracy and precision for the simultaneous quantification of 1'-hydroxymidazolam, dextrorphan and 6-hydroxychlorzoxazone in microsomal incubations. The inhibition potential of CYP3A4, 2D6 and 2E1 has been evaluated using their known selective inhibitors. The IC(50) values measured by the cassette dosing approach (high-throughput) are consistent with those observed by an individual dosing regimen (conventional) and are all in good agreement with the literature values. The results suggest that the cassette probe-dosing strategy may provide an in vitro approach to minimize cost while maximizing throughput of CYP inhibition evaluation of new chemical entities in support of drug discovery and development.     

Applications of benzotriazole methodology in heterocycle ring synthesis and substituent introduction and modification

Applications of benzotriazole methodology for the preparation of heterocyclic compounds are reviewed. The characteristic advantages of benzotriazole as a synthetic auxiliary are first briefly considered. This is followed by a summary of its use in ring synthesis in which the construction of small; five-membered; six-membered; and larger heterocyclic rings using benzotriazole methodology are each examined separately. Finally, consideration of the use of benzotriazole in the ring annulation - particularly benzannulation - of heterocycles. Subsequent sections deal with the introduction of substituents into aromatic heterocycles; the ring substitution of saturated heterocycles; and benzotriazole assisted modification of heterocyclic substituents. The present review supplements a recent comprehensive review of benzotriazole chemistry [1] which covers the literature through 1996.     

Isothermal degradation of poly-2,2′-(m-phenylene)-5,5′-bibenzimidazole

The isothermal degradation of poly-2,2′-(m-phenylene)-5,5′-bibenzimidazole in vacuo has been studied. Measurement of the increase in pressure with time, coupled with infrared analysis, was used to determine the distribution of the degradation products. Processes A and B with different second-order rate laws were determined to be significant in the temperature range of 550–700°C. Process A leads to the formation of equimolar quantities of hydrogen and ammonia and has an activation energy of 68 kcal/mole. Process B leads to the production of HCN, NH₃, and H₂ in the ratio of 1:1:2.5 and has an activation energy of 77 kcal/mole. The activation energies and the rate laws are consistent with a mechanism in which the initial degradation step is the bimolecular reaction of two aromatic rings.     

Synthesis, tautomeric states and crystal structure of (Z)-ethyl 2-cyano-2-(3H-quinazoline-4-ylidene) acetate and (Z)-ethyl 2-cyano-2-(2-methyl-3H-quinazoline-4-ylidene) acetate

The new compounds (Z)-ethyl 2-cyano-2-(3H- and 2-methyl-3H-quinazoline-4-ylidene) acetate (1 and 2, respectively) were synthesized by multi-step reactions. The structures in a solution have been determined by (1)H-NMR spectroscopy and in the crystal form by X-ray analysis. Molecule 1 crystallized in a primitive monoclinic cell, space group capital ER, P2(1/c). The cell dimensions are a=7.970(6) A, b=7.061(2) A, c=20.537(7) A, beta=97.69(5) degrees , V=1145.3(10) A(3). Molecule 2 crystallized in a triclinic cell, space group P-1, the cell dimensions are a=8.196(5) A, b=8.997(6) A, c=9.435(4) A, alpha=74.22(4) degrees, beta=89.75(4) degrees , gamma=74.07(5) degrees , V=641.9(6) A(3). In both compounds the presence of intra-molecular NH---O=C hydrogen bonding between the nitrogen atom in position 3 of the quinazoline ring and a carbonyl group of the ethyl cyanoacetate residue was proven by quantum-chemical, (1)H-NMR and X-ray methods.     

Enthalpimetric and thermometric determination of some nitrogen containing bases and some physiologically active alkaloids

Summary The enthalpimetric determination of a series of bases by using the reaction of the bases and sodium tetraphenylboron is described. The accuracy of the method is analytically acceptable, over the range 3×10^–5 moles to 7.5×10^–4 moles. The upper limit is determined by the bulk of the precipitate.Dosage forms of some physiologically active alkaloids contain more than the upper limit of analyte. Yet, preliminary investigations using silicotungstic acid indicate that this is suitable for thermometric titrations.

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Enthalpimetrische und thermometrische Bestimmung stickstoffhaltiger Basen und physiologisch aktiver Alkaloide

Zusammenfassung Die enthalpimetrische Bestimmung einiger N-haltiger Basen erfolgte aufgrund der Reaktion mit Natriumtetraphenyloborat. Die Genauigkeit ist im Bereich von 3 · 10^–5-7,5 · 10^–4 Mol befriedigend. Eine obere Grenze der Anwendbarkeit ergibt sich aus der Menge des anfallenden Niederschlags. Diese wird bei der Bestimmung von Formulierungen einiger physiologisch aktiver Alkaloide überschritten. Jedoch ist in diesem Fall eine thermometrische Titration mit Hilfe von Silicowolframsäure möglich.

Lecture presented at Euroanalysis I Conference, 28. 8.–1. 9. 1972 in Heidelberg, Germany.