Total synthesis of (-)- and (+)-lentiginosine

Total synthesis of (-)-lentiginosine was achieved from D-mannitol using highly stereoselective reactions. Similarly, (+)-lentiginosine was synthesized from L-tartaric acid.     

2-(2-Selenocyanic acid ethyl ester)-1H-benz[de] isoquinoline-1,3-(2H)-dione, synthesis photophysics and interaction with bovine serum albumin: a spectroscopic approach

The compound 2-(2-selenocyanic acid ethyl ester)-1H-benz[de] isoquinoline-1,3-(2H)-dione (SEBID), a ubiquitous, bioactive naphthalimide derivative is expected to possess an anticancer, anti-tumor and other important therapeutic activities of significant potency with low systematic toxicity. In this paper, the synthesis of the compound, photophysics of the newly prepared naphthalimide derivative and its interaction with model transport protein Bovine serum albumin (BSA) have been reported using the absorption and steady state fluorescence spectroscopic techniques exploiting the intrinsic fluorescence emission properties of BSA as a probe. Interaction of this organoselenium compound in different dioxane-water mixtures with increase in the polarity of the medium has been studied spectroscopically. Interaction of SEBID with BSA leads to a dramatic decrease in the fluorescence intensity of BSA, which suggests the binding of SEBID with the tryptophan residue of BSA. Furthermore, different thermodynamic parameters for SEBID-BSA interaction have been calculated. Rationalization of the data has been attempted, particularly in relation to prospective applications in the biomedical research.     

Radical promoted Wagner-Meerwein-type rearrangement of epoxides in camphoric systems using a Ti(III) radical source

[Chemical reaction: see text] A radical based Wagner-Meerwein-type rearrangement has been observed in camphoric systems. The radical was generated from the epoxide using Cp2TiCl as the radical source. The radical initiator Cp2TiCl was prepared in situ from commercially available Cp2TiCl2 and Zn dust in THF under argon.     

Antistatic applications of conducting polyaniline

A method is described to impart flexibility and mechanical strength to conducting polyaniline by polymerizing aniline on fabrics and on cellulose papers. The study indicates that these conducting fabrics offer 16–18 dB of shielding effectiveness for the control of electromagnetic interference (EMI) up to a frequency of 10³ MHz.     

Spectroscopic and biological studies on newly synthesized nickel(II) complexes of semicarbazones and thiosemicarbazones

Nickel(II) complexes, having the general composition Ni(L)2X2, have been synthesized [where L: isopropyl methyl ketone semicarbazone (LLA), isopropyl methyl ketone thiosemicarbazone (LLB), 4-aminoacetophenone semicarbazone (LLC) and 4-aminoacetophenone thiosemicarbazone (LLD) and X=Cl-, 1/2SO(4)2-]. All the Ni(II) complexes reported here have been characterized by elemental analyses, magnetic moments, IR, electronic and mass spectral studies. All the complexes were found to have magnetic moments corresponding to two unpaired electrons. The possible geometries of the complexes were assigned on the basis of electronic and infrared spectral studies. Newly synthesized ligand and its nickel(II) complexes have been screened against different bacterial and fungal growth.     

Synthesis and antispasmodic activity evaluation of bis-(papaverine) analogues

A new series of N-substituted bis-(tetrahydropapaverine) ring systems have been synthesised in expectation of better antispasmodic activity in comparison with papaverine. The synthesis of the targeted heterocycles is described along with a discussion of their structure activity relationship. The general synthetic methods of bis-(tetrahydropapaverine) analogues involve tetrahydropapaverine, various piperazines, diisocyanates and diisothiocyanates as starting materials. Pharmacological evaluation involves the in vitro antispasmodic activity on a freshly removed guinea pig ileum using a force displacement transducer amplifier connected to a physiograph. Among the analogues synthesized in the present study, N,N'-bis-[2-carbamoyl-1-(3,4-dimethoxybenzyl)-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinolinyl]piperazine (22), was found to be the most potent muscle relaxant (IC(50): 0.31 microM).     

4-t-Butylphenoxo complexes of oxovanadium(V)

Summary Complexes of composition [VOCl₂(OC₆H₄Bu-t-4)] (1) and [VOCl(OC₆H₄Bu-t-4)₂] (2) have been synthesized by the reaction of VOCl₃ with equimolar and bimolar amounts, respectively, of 4-t-BuC₆H₄OSiMe₃ in CCl₄ and characterized by physio-chemical techniques. The complexes react with -hydroxyaldehydes and ketones such as 2-hydroxybenzaldehyde (salicylaldehyde, salH), and 2-hydroxy-2-phenylacetophenone (benzoin, benzH), 2-hydroxyacetophenone (hapH) and also with the potassium salt of p-chlorobenzohydroxamic acid (KBHACl) in 11 and 12 molar ratios, to yield five- and six-coordinate complexes.     

Electrochemical study of triphenyltin piperidyl dithiocarbamate

The reduction of triphenyltin piperidyl dithiocarbamate in acetone has been investigated using d.c. polarography and cyclic voltammetry. Polarographic reduction yielded four well-defined waves, two of which were diffusion-controlled and two of which appear to represent adsorption processes. The cyclic voltammetric study yielded results in close agreement with the polarographic data. Results appear to indicate the release of the dithiocarbamate moiety, followed by reduction to form the triphenyltin radical, which undergoes dimerization, as well as reduction to the triphenyltin anion. For comparison, the polarographic reduction of triphenyltinchloride was investigated. A mechanism similar to that proposed by earlier authors for the polarographic behaviour of tributyltin oxide was found. For convenience, the more commonly used terminology of piperidyl dithiocarbamate is used throughout the paper, in place of (piperidine-1-carbodithioato) triphenyltin (IV).     

Differential scanning calorimetry studies on aged iron(III)-chromium(III)-hydroxide coprecipitates

DSC measurements in air from 20 to 800° are reported on aged iron(III)-chromium(III) coprecipitated hydroxides (with Fe³⁺Cr³⁺ wt% ratios of 91, 73, 11, 37 and 19). A comparison of the DSC profiles of aged coprecipitates with the thermal behaviour of freshly precipitated and well characterized samples provided information on the modification occurring in the structure and reactivity of the coprecipitates on prolonged aging.

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Zusammenfassung Es werden DSC-Messungen an gealterten kogefällten Eisen(III)Chrom(III)-hydroxiden (mit Fe³⁺Cr³⁺ Gewichtsanteilen von 91, 73, 11, 37 und 19) im Temperaturbereich von 20 bis 800° beschrieben. Ein Vergleich der DSC-Profile von gealterten Kofällungen mit dem thermischen Verhalten frisch gefällter und gut definierbarer Proben lieferte Informationen über die Veränderungen in Struktur und Reaktivität der Koniederschläge bei längerem Altern.

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Dedicated to Professor Wahid U. Malik, Founder-President, Indian Council of Chemists, India, with profound regards and fond memories of his youthful enthusiasm and ceaseless and pioneering efforts towards the development of chemical education and research activities at the University of Roorkee, Roorkee, India, on the occasion of his 70th birthday.

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Paper presented at the World Conference on Thermal Analysis, Capri (Italy), 1989.

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We thank Professor J. Pescia, Dr.G. Ablart and N. Favillier of Laboratoire de Magnétisme et d'Electronique Quantique for their interest in this work. A. C. Vajpei expresses his gratefulness to C.N.R.S. and C.N.O.U.S., Paris, for financial support of this work.     

Isomeric pyrazolo­[3,4-d]­pyrimidine-based mol­ecules: disappearance of dimerization due to interchanged substitutions

In 5-benzyl-1,7-di­methyl-4,5,6,7-tetra­hydro-1H-pyrazolo­[3,4-d]­pyrimidine-4,6-dione, C₁₄H₁₄N₄O₂, which crystallizes in space group P, weak intermolecular C—H⋯O hydrogen bonds generate dimers. The isomeric compound 1-benzyl-5,7-di­methyl-4,5,6,7-tetra­hydro-1H-pyrazolo­[3,4-d]­pyrimidine-4,6-dione, C₁₄H₁₄N₄O₂, crystallizes in space group P2₁/n, and shows no such dimerization. Instead, it exhibits C—H⋯π interactions with the phenyl ring. In both structures, the mol­ecules are linked by aromatic π–π-stacking interactions.