Stereoselective synthesis of 3,4-trans-disubstituted pyrrolidines and cyclopentanes via intramolecular radical cyclizations mediated by CAN

The stereoselective intramolecular cyclizations of bis(cinnamyl)tosylamides and dimethyl bis(cinnamyl)malonates mediated by cerium(IV) ammonium nitrate leading to the synthesis of 3,4-trans-disubstituted pyrrolidines and cyclopentanes are described.     

Dislocation unpinning model of acoustic emission from alkali halide crystals

The present paper reports the dislocation unpinning model of acoustic emission (AE) from alkali halide crystals. Equations are derived for the strain dependence of the transient AE pulse rate, peak value of the AE pulse rate and the total number of AE pulse emitted. It is found that the AE pulse rate should be maximum for a particular strain of the crystals. The peak value of the AE pulse rate should depend on the volume and strain rate of the crystals, and also on the pinning time of dislocations. Since the pinning time of dislocations decreases with increasing strain rate, the AE pulse rate should be weakly dependent on the strain rate of the crystals. The total number of AE should increase linearly with deformation and then it should attain a saturation value for the large deformation. By measuring the strain dependence of the AE pulse rate at a fixed strain rate, the time constantτ _s for surface annihilation of dislocations and the pinning timeτ _p of the dislocations can be determined. A good agreement is found between the theoretical and experimental results related to the AE from alkali halide crystals.     

Interactions of Some Amino Acids with Aqueous Tetraethylammonium Bromide at 298.15 K: A Volumetric Approach

The apparent molar volumes, V_,2, of glycine, L-alanine, DL--amino-n-butyric acid, L-valine, and L-leucine have been determined in aqueous 0.25, 0.75, 1.0, and 1.5 mol-dm^–3 tetraethylammonium bromide (TEAB) solutions by density measurements at 298.15 K. These data have been used to calculate the infinite dilution apparent molar volumes, V_2,m, for the amino acids in aqueous tetraethylammonium bromide and the standard partial molar volumes of transfer (_tr V_2,m) of the amino acids from water to the aqueous salt solutions. The linear correlation of V_2,m for a homologous series of amino acids has been utilized to calculate the contribution of the charged end groups (NH₃⁺, COO^–), CH₂ group, and other alkyl chains of the amino acids to V_2,m. The results of the standard partial molar volumes of transfer from water to aqueous tetraethylammonium bromide have been interpreted in terms of ion–ion, ion–polar, and hydrophobic–hydrophobic group interactions. The volume of transfer data suggest that ion–ion or ion–hydrophilic interactions are predominant in the case of glycine and alanine, and hydrophobic–hydrophobic group interactions are predominant in the case of DL--amino butyric acid, L-valine, and L-leucine.     

Angular heterocycles. Utilization of arylaminonaphthoquinones in the synthesis of benzophenothiazines

Substituted 6-ethoxyanilino-5H-benzo[a]phenothiazin-5-ones (3a-f) were synthesized by the cyclocondensation of 2-chloro-3-ethoxyanilino-1,4-naphthoquinones with zinc mercaptides of 2-aminothiophenol in pyridine. The nmr, ir and mass spectral data are presented and discussed.     

Volumetric Properties of Aqueous 2-Chloroethanol Solutions and Volumes of Transfer of Some Amino Acids and Peptides from Water to Aqueous 2-Chloroethanol Solutions

Densities and apparent molar volumes of aqueous 2-chloroethanol were determined at temperatures from 15.0 to 34.4°C using digital densimetry. The results of the volumetric measurements have been used to calculate the following thermodynamic quantites at 25°C: V ₂ ^o = 55.05 ± 0.02 cm³-mol^–1, (V ₂ ^o/T)_p = 0.01486 ± 0.00318 cm³-K^–1-mol^–1, and (² V ₂ ^o/T ²)_p = 0.02972 ± 0.00318 cm³-K^–2-mol^–1. Partial molar volumes of transfer from water to 1 mol-dm^–3 2-chloroethanol have also been determined for L-glycine, L-alanine, L-serine, L-glutamic acid, and L-aspartic acid at 35.0°C. The transfer results have been explained in terms of the nature of the interactions of the groups in the solute and solvent. Hydration numbers of L-glycine and L-alanine have also been calculated in aqueous 2-chloroethanol.     

Carbon-13 and nitrogen-15 nuclear magnetic resonance of physostigmine (eserine)

The ¹⁵N and ¹³C nmr spectra of physostigmine are discussed along with complete assignment of the signals. This alkaloid ¹⁵ N nmr spectrum is notable because it contains nitrogens in three different environments.     

1-Phenyl-6,7-disubstituted-aminopropyl)-1,2,3,4-tetrahydroisoquinolines as possible antituberculer agents

The Condensation of 3,4-disubstituted phenylethylamine and benzaldehyde furnished l-phenyl-6,7-disubstituted-1,2,3,4-tetrahydroisoquinolines l. which on reaction with 1,3-dibromopropane gave l-phenyl-6,7-disubstituted-2-(3-bromoprophyl)-1,2,3,4-tetrahydroisoquinolines 2. The reaction of 2 with different secondary amines resulted in the synthesis of 3. The compounds 3 were screened for their in vitro antituberculer activity against Mycobacterium smegmatis, and some of them have been found to be total inhibitors of M. Smegmatis     

Iron(III) complexes of a tetradentate tripodal ligand N,N′,N″-tris (2-benzimidazolyl-methyl)amine

Summary Fe^III complexes of a tetradentate ligand with pendant benzimidazolyl groups have been synthesized and characterized. Room temperature Mössbauer spectra depict a quadruple split doublet in the case of NO _inf3 ^p– as co-ligand, while a nearly symmetrical one line spectrum is obtained for complexes with Cl^–as co-ligand. The isomer shift values are towards the lower end of the range found for other high spin Fe^III complexes. ¹H-n.m.r. spectra of the complexes reveal relatively broad linewidths with large isotropic shifts. Paramagnetically shifted resonances are observed in the range of –10.0–+70.0 p.p.m.Author to whom all correspondence should be directed.     

Direct organocatalytic in situ generation of novel push-pull dienamines: application in tandem Claisen-Schmidt/iso-aromatization reactions

A new, green, regioselective, one-step, tandem reaction of an aldehyde possessing a non-enolizable carbonyl function with a highly substituted cyclohex-2-enone, under amine catalysis afforded highly substituted phenols or 2-arylidenecyclohexanones, respectively. The yields and regioselectivities were good. Evidence for a pathway involving formation of novel push-pull dienamines is presented along with examples demonstrating the amenability of the process to combinatorial chemistry.