The molecular and crystal structures of two diastereomeric 3,4-dihydropyrromethenones

The molecular and crystal structures of the two racemic diastereomeric 3,4-dihydropyrromethenone derivatives1 and2 of configurations (Z) and (E) were determined at 93 K (1, 2) and at room temperature (1). From an analysis of the crystallographically observed temperature coefficients a pseudorotation flexibility of the pyrrolidinone ring in the crystal is deduced. In both compounds a nearly orthogonal arrangement between the two heterocyclic ring systems is observed, which is ascribed to the steric bulk of the substituents in positions 1 and 3 of the pyrrolidinone ring.Herrn Prof.Josef Schurz zum 60. Geburtstag gewidmet.     

Excess and partial excess molar volumes of mixing of N,N-dibutyl-2-ethylhexamide with dodecanol

Excess and excess partial molar volumes of mixing of the system N,N-dibutyl-2-ethylhexylamide (DBEHA) + dodecanol (DDA) were determined at 25, 35, 45, 55 and 65°C. The excess molar volumes exhibit a maxima at each temperature at approximatelyx _DBEHA = 0.3 and a minima close tox _DBEHA = 0.9. The values of the excess volumes in general increase with the temperature. The partial excess molar volumes are calculated from the smoothed data and the results are discussed in the light of postulated amide-alcohol interactions.     

Theoretical Study on the Structures and Electronic Spectra of the Derivatives of C_(60)-P-2,4,6-Triphenyl Borazinc

1 INTRODUCTION The electron-transfer reaction of C60 derivatives, especially light-induced electron-transfer reaction, has been an active research field for a long time. Many researches are focused on the long-live charge- separated state caused by electron-transfer[1]. And several electron-transfers between electron donor and C60 or intramolecular electron-transfer have been confirmed. As an example, TTF-C60 is proved to be a short-live charge-separated compound[2].Due to the excelle…     

New homochiralortho-palladated matrix bearing a bulky substituent at the carbon stereocenter

A new homochiral dimericortho-palladated complex bearing a bulkytert-butyl substituent at the carbon stereocenter was synthesized from optically activeN,N-dimethyl-α-tert-butylbenzylamine. Regioselective activation of only the aromatic C−H bond was shown to occur during the cyclometallation process proceeding under very mild conditions due to steric effects. Spectral characteristics of mononuclear derivatives of the new dimeric complex indicate that the five-membered palladacycle exists predominantly in one of two possible chiral conformations with the axial position of thetert-butyl substituent. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1375–1384, July, 1997.     

An investigation of the reliability of the Galerkin-Petrov method

It is shown that the Galerkin-Petrov method if applied in a controlled way yields reliable results for excited states of the same symmetry classifications as the ground state. Computations are performed for the 2¹ S and 3¹ S states of He. The problem of optimizing nonlinear parameters of the basis functions by means of the GP method is discussed. A special optimization scheme is suggested and numerically illustrated for someS states of He.     

Interaction of (1-phenylethyl)indole-2-carbonitrile with C-nucleophiles

Methods of obtaining ketones and enamino esters have been developed on the basis of reactions of 1-(1-phenylethyl)indole-2-carbonitrile with organomagnesium and organozinc compounds. Removal of a benzyl group from the indole nitrogen atom by the Grignard reagent has been discovered. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1179–1183, August, 2006.     

Recent development in HPLC enantioseparation — a selected review

Summary Recent developments in the field of separating optical isomers by HPLC are discussed in this brief review. In particular it is focussed on various techniques for direct enantioseparation, the interpretation of possible enantioselective separation mechanisms, and the advantages and limitations of the diverse methods. This goal is supported by representative and selected examples of chiral separations.     

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.