Investigation of the phosphinyl analog of α-ketoglutaric acid

It was shown by³¹P and¹³C NMR spectroscopy that methyl(3-carboxy-3-oxopropyl)phosphinic acid (4-methylhydroxyphosphinyl-2-oxobutyric acid) (1) and the amide (2) of the latter exist in keto forms in non-aqueous solutions. In aqueous solutions an equilibrium between the keto,gem-diol, and enol forms has been observed. The proportions of the diol and enol forms increase as the acidity of the media increases. Silylation of acid 1 with hexamethyldisilazane gives the tris(trimethylsilyl) derivative of enol form (3) (Z- andE-isomers).Translated fromIzyestiya Akadetnii Nauk. Seriya Khimicheskaya, No. 1, pp. 125–128, January, 1994.     

Voltammetry in Undiluted Acetic Acid. In Situ Determination of Water

Water present in undiluted acetic acid can be monitored in situ with Pt and Au microelectrodes using differential pulse and square‐wave voltammetries. Both reduction and oxidation peaks can be obtained. The best quantitative analytical results were obtained for the anodic peak, the Pt microelectrode, and differential pulse voltammetry. The anodic water peak is located at +1.55 V vs. the quasi reference Pt electrode. The voltammetric peak obtained at Pt electrode is apparently not a diffusional one, however, the calibration plot obtained by employing this peak is linear over a wide concentration range, up to 4 mol dm^?3. The detection limit has been estimated as 2.3 mM or 0.0043 v/v%. The developed method may be particularly useful, since the Karl Fischer method can not be used to determine water in glacial acetic acid due to the estrification reaction of acetic acid with methanol. A voltammetric wave of undiluted acetic acid could not be obtained in the positive and negative ranges of potential.     

HPLC of antibiotics. 1. Streptolydigin and related compounds

Two new acyltetramic acids related to streptolydigin have been isolated from fermentations of Streptomyces lydicus. The principal members of this complex were resolved by TLC on silica gel. However, the methods of detection, permanganate spray or bioautography, were not suitable for both crude fermentation broths and purified extracts. Gas chromatography is unsuitable for the detection of either underivatized or silylated streptolydigins. High performance liquid chromatography (HPLC) particularly on triethylaminoethyl cellulose is rapid and sensitive and is the method of choice for the analysis of both crude and purified samples. Using high performance liquid chromatography, two components were detected in the complex, which are not observed using any of the other chromatographic procedures.     

Reactions of 1,2,4-Triazines with Nucleophiles. 6. Use of SNH Methodology for the Direct Introduction of Cyclic Diketone Residue into the 1,2,4-Triazine Ring FORENAME = D. N.

3-R-6-Phenyl-1,2,4-triazine 4-oxides react with cyclic -diketones (dimethylbarbituric acid, dimedone, and indan) in both acidic (substrate activation) and basic conditions (nucleophile activation) with formation of ^H-adducts, intermediates in the nucleophilic substitution of hydrogen (S_N ^H) in 3-R-5-Nu-4-hydroxy-6-phenyl-4,5-dihydro-1,2,4-triazines. Oxidative aromatisation of these intermediates or auto-aromatisation of acylated (benzoyl chloride) at the NOH -adducts with elimination of benzoic acid gave the corresponding substituted 1,2,4-triazine 4-oxides or 1,2,4-triazines.     

Synthesis of new functional derivatives of pyrazolidine from 1-acetyl-3-methyl-5-nitromethyl-2-phenylpyrazolidine

3-Nitromethylpyrazolidine reacts with derivatives of unsaturated acids and reducing agents with the formation of polyfunctional compounds of the pyrazolidine nucleus. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1365–1369, September, 2006.     

新型重整催化剂的研究—Pt／BaKL型沸石中钡的作用

本文采用XRD,NH_3-TPD,IR以及TEM等方法考察了Pt/BaKL沸石中Ba~(2+)的作用。NH_3-TPD结果表明,交换Ba~(2+)后的L型沸石的酸性,由于阳离子的作用仅在弱酸范围内有些改变,但与载铂的沸石的催化活性无明显的对应关系。IR及XRD谱线表明,BaKL沸石中Ba~(2+)在最佳交换度(26.3%)时,随预培烧温度的提高,使Ba~(2+)处于沸石孔道中B、C、D位置,接近于最佳分布,此时IR谱线上1421cm~(-1)处有一新峰。当沸石负载铂后,因铂与Ba~(2+)的相互作用,新峰消失,导致铂粒在沸石上分布更加均匀;铂粒在1.5—3.0nm之间占有最大比例,使得Pt/BaKL沸石呈现芳构化活性及选择性高于Pt/KL沸石,分别为～98%和～95%。     

Reaction of η5-cyclopentadienylbis(triphenylphosphine)cobalt(I) with alkadiynes. Preparation and reactions of bicyclic cobalt metallocycles and a stable trimethylsilyl-substituted mono-complexed alkadiyne. Comments on the mechanism of cobalt-catalyzed alkyne cooligomerization

Reactions of η⁵-cyclopentadienylbis(triphenylphosphine)cobalt(I) (5) with several 2,n-alkadiynes (2) were investigated. Each of these reactions leads initially to a material in which one of the acetylene functional groups is π-coordinated to cobalt; this complex then undergoes conversion to a metallocycle. In cases where the two acetylene functions are connected by three- and four-carbon bridges (2b, 2c), metallocycles formed by intramolecular reaction of two acetylene functions in the same molecule may be isolated. In cases where the acetylene functions are joined by larger or smaller bridges, the reactions are more complex, and both inter- and intramolecular metallocycles are formed. Reactions of 5 with 1,8-bis(trimethylsilyl)-1,7-octadiyne (16) gives an isolable crystalline mono-acetylene complex (17), this material is stable in the solid state but undergoes conversion to metallocycle (18) in benzene solution. The relationship of these results to the mechanism of the CpCo(CO)₂-catalyzed benzocycloalkene synthesis is discussed; it is suggested that intramolecular metallocycles are intermediates in reactions leading to benzocyclopentanes and -cyclohexenes, but intermolecular metallocycles are probably involved in reactions leading to benzocyclobutenes.     

Substituted pyrazine-di-N-oxides as the mediators of catalytic oxidation of organic compounds

The mechanism of oxidation of 2,5-dimethyl-, 2,3,5,6-tetramethyl-, 2,3-dimethyl-5,6-cyclohexa, and 3-phenyl-5,6-cyclohexapyrazine-di-N-oxides is studied by cyclic voltammetry, quantum chemical simulations, and ESR electrolysis. The studies are carried out on electrodes of glassy carbon and Pt in 0.1 M LiClO₄ solutions in acetonitrile. ESR spectra of radical cations of substituted pyrazine-di-N-oxides are recorded. The effects of the temperature, oxygen, and the additions of water, pyridine, and acid on the shape of cyclic voltamograms and the intensity of ESR signals of pyrazine-di-N-oxides are studied. A quantum-chemical simulation of the reaction of pyrazine-di-N-oxide radical cations with acetonitrile is carried out. The oxidation of substituted pyrazine-di-N-oxides is described by the E₁C₁E₂C₂ mechanism, which includes the stage of the formation of a complex between the di-N-oxide radical cation and acetonitrile.     

Calculation of the proton affinities of polyfluorobenzenes and the activation energies for 1,2-hydrogen shifts in their carbocations

Isolated polyfluorobenzene (PFB) molecules and their protonated forms are investigated by the AM1 method with full geometry optimization. The proton affinities of PFB are estimated for different protonated positions. The proton affinity of PFB averaged over all isomers is shown to decrease monotonically as the number of fluorine atoms in the molecule increases. The relative populations of different isomers of arenonium ions (AI) formed by PFB protonation are determined. From the calculated data, the value of ⁺ for the F atom in theipso-position is estimated as 1.00. The activation energies of the 1,2-hydrogen shifts in AI are calculated. The dependences of the proton affinity and the activation energies of 1,2-hydrogen shifts on the number of halogen atoms are found to have distinct characters for PFB and polychlorobenzenes. The physical reasons for these difference are discussed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1878–1882, November, 1993.     

Chemistry of metal hydrides : XXI. Insertion of acetylenes into palladium hydrides

trans-Pd(NO₃)H(PCy₃)₂ (I) when treated with Et₄NCl forms the hydride trans-PdClH(PCy₃)₂ which in turn reacts with AgPF₆ in acetonitrile to give trans-[PdH(CH₃CN)(PCy₃)₂]PF₆ (III). Both I and III react smoothly with acetylenes containing one electron-withdrawing group to give alkenyl products. The geometry of the resulting alkenyl ligand implies that cis addition has occurred and that the hydridic hydrogen adds to the acetylenic carbon containing the electron-withdrawing group.Acetylenes containing two electron-withdrawing groups give mixtures from which both alkenyl and zerovalent acetylene compounds can sometimes be isolated. In the presence of proton sponge, monosubstituted acetylenes still give alkenyl products while those substituted with two electron-withdrawing groups give the zerovalent products in good yield. The relevance of these results to an understanding of the nature of the migratory insertion reaction is discussed.