Reaction of pentafluorobenzoylpyruvic acid with amines

Reactions of pentafluorobenzoylpyruvic acid with amines afford the respective enamines. The intramolecular cyclization of the latter results inN-substituted 4-quinolone-2-carboxylic acids. Ammonia and triethylamine favor the cyclization of pentafluorobenzoylpyruvic acid to 2-carboxychromone.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 299–302, February, 1994.     

Influence of intrachain hydrogen bonding on the cyclization of a polystyrene chain

Cyclization of a polystyrene chain (M_n = 10,600; M_w/M_n = 1.09) both ends labeled with 4-(1-pyrenyl)butanoamide groups was studied in cyclohexane between 25 and 95°C. The amide groups (peptide bonds) at both ends can form an intrachain hydrogen bond between the amide hydrogen at one chain end and the carbonyl oxygen at the other. The presence of two sets of conformers, random coils, and chains cyclized through hydrogen bonding, complicates the data analysis. The pyrene excimer kinetics of this polymer is well described by a model composed of two monomers (hydrogen bonded and nonbonded chains) and one excimer, in equilibrium. The cyclization rate constant for hydrogen-bonded chains is larger than the one for nonhydrogen-bonded chains. The pyrene excimer binding energy (ca. 1.6 kcal/mol) is lower than the published value for nonhydrogen-bonded chains (～ 9 kcal/mol), suggesting that intrachain hydrogen bonding hinders the stabilization of the excimer. © 1994 John Wiley & Sons, Inc.     

Synthesis of a new tricyclic 3-(tetrazol-5-yl)pyridine system from 2-(azidomethyl)nicotinonitriles

2-Methyl-3-cyanopyridines were converted into the corresponding 2-azidomethyl derivatives, which then underwent an intramolecular cycloaddition reaction. A novel heterocyclic system containing a 3-(tetrazol-5-yl)pyridine unit was obtained in this way.     

The intramolecular hydrogen bond in ortho-hydroxy acetophenones

The crystal structures of two ortho-hydroxy ketones (5-chloro-2-hydroxyacetophenone (I K) and 3,5-dichloro-2-hydroxyacetophenone (II K)) have been determined with X-ray diffraction at 100 K. A comparison of steric effects on properties of pseudoaromatic hydrogen bonds in ortho-hydroxy acetophenone and ortho-hydroxy ketimines have been carried out with the application of crystallographic data.

Nuclear quadrupole resonance (NQR) spectra have been measured and interpreted.     

Application of the stabilization method to interacting resonances

The stabilization method is applied to the case of interacting resonances in the photo-dissociation of van der Waals clusters composed by a rare gas atom bound to a dihalogen molecule. The study of an illustrative two-dimensional model consisting in a T-shaped NeI₂ molecule shows the adequacy of the method whenever the projection of the stabilization wave functions on the assumed prepared initial state is accounted for. The agreement of the fragmentation cross-sections with some previous results using the effective resolvent method and accurate close-coupling calculations is excellent. The method reveals its utility as a complementary tool since allows, through the analysis of the stabilization wave function in terms of zero-order levels, a precise characterization of the resonant states involved. Received 5 April 2002 / Received in final form 24 May 2002 Published online 19 July 2002     

对称双吡咯甲烷的合成与分子内氢键的研究

５－甲基吡咯－２－羧酸酯在磺酰氢，溴或四乙酸铅作用下，生成相应的在５－甲基上含取代基的产物，后者不经分离不便可自缩合得标题化合物，核磁共振氢谱研究和分子构象木匠，当３，３位的取代基为甲酸（酯）基或乙酸（酯）基时，可形成３，３位酯基与另一吡咯环上的氮氢之间的分子内氢键，而３，３位是其它取代基，如乙酰基，丙酸（酯）基，丁酸（酯）基时不能形成类似的分子内氢键。     

Mannich bases as model compounds for intramolecular hydrogen bonding I. Solid state structures and molecular calculations

Summary A survey of the structures and the properties of the hydrogen bonds inortho-aminomethylphenols and -naphthols in the solid state is presented. The results are compared with molecular structure calculations. The solid state complexes can exist in the molecular or in zwitterionic form. In the last case, only intermolecular hydrogen bonds forming cyclic dimers or linear chains were detected.

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Mannich-Basen als Modelle für Intramolekulare Wasserstoffbrücken, 1. Mitt. Festkörperstrukturen und Molekülrechnungen

Zusammenfassung Eine Übersicht über Strukturen und Eigenschaften von Wasserstoffbrücken inortho-Aminomethylphenolen und -naphtholen wird präsentiert. Die Ergebnisse werden mit Molekülrechnungen verglichen. Im Festkörper existieren diese Verbindungen in neutraler oder in zwitterionischer Form. Für den zweiten Fall können nur intermolekulare Wasserstoffbrücken nachgewiesen werden, und zwar in Dimeren oder in linearen Ketten.

     

Multinuclear magnetic resonance studies on intramolecular chalcogen-tin coordination in compounds of the type Me2Sn(X)CH2CH2P(E)Ph2 (X = Halogen, E = Chalcogen)

Multinuclear magnetic resonance data for the title compounds are presented and discussed. The intramolecular coordination observed in the solid state is shown to be retained in solution. The best probes for the presence or absence of pentacoordination at tin are provided by the various tin-element coupling constants, although chemical shifts are in some cases also informative. A selenium-proton correlated spectrum indicated that the coupling constant ¹J(Sn,Se) has a positive sign.