Studies in spiroheterocycles. Part V. Synthesis of new fluorinated spiro[3H-indole-3,2′-oxiran]-2(1H)-ones

Reinvestigation of the reaction of 3-aroylmethyleneindol-2-ones with hydrogen peroxide has revealed that a 1:1 isomeric mixture of spiro[3H-indole-3,2′-oxiran]-2(1H)-ones is formed. The structures of the two isomers have been confirmed by their ir, pmr and mass spectral studies. Mass fragmentation patterns of these compounds are discussed.     

Kinetics and mechanism of oxidation of methanol by acid bromate

The kinetics of oxidation of methanol by bromate ion in hydrochloric acid medium has been investigated. A mechanism consistent with the experimental observations is suggested.

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Synthesis and characterization of copolymers of limonene with styrene initiated by azobisisobutyronitrile

The radical copolymerization of limonene with styrene by azobisisobutyronitrile in xylene at 80 ± 0.1 °C for 2 h, under inert atmosphere of N₂, yields alternating copolymers. The kinetic expression is R_p∝[I]^0.5[Sty]^1.0[Lim]^−1.0. The overall activation energy is calculated as 41 kJ/mol. The FTIR and ¹H-NMR spectra of copolymers show bands at 3000 and 1715 cm⁻¹ and peaks at 6.8 δ and 5.3 δ due to phenyl protons of styrene and trisubstituted olefinic protons of limonene, respectively. The values of reactivity ratios r₁(Sty)=0.0625 and r₂(Lim)=0.014, calculated by Kelen-Tüdos method. The Alfrey-Price Q-e parameters for limonene are 0.438 and −0.748, respectively. The penultimate unit effect is favoured in the present system and the value of φ is 38.49.     

SH-waves in viscoelastic heterogeneous layer over half-space with self-weight

The effect of gravity, heterogeneity and internal friction on propagation of SH-waves (horizontally polarised shear waves) in viscoelastic layer over a half-space has been studied. Using the method of separation of variables, dispersion equation has been obtained and used to recover the damped velocity of SH-waves. Both the real and imaginary parts of dispersion equation are in well agreement with the classical Love wave equation. It has been observed that heterogeneity of the medium affects the velocity profile of SH-wave significantly. Some other peculiarities have been observed and discussed in our study.     

Organotin(IV) Complexes of 2-[(2′,4′,6′- Trichlorophenylamido)]benzoic Acid: Synthesis,Coordination Chemistry,and Semi-Empirical Study

A new series of organotin(IV) complexes of aniline derivatives, R₂SnL₂ and R₃SnL [where R = Me, n-Bu, n-Oct, and Ph], have been synthesized by the reaction of ligand acid with respective organotin halides in the presence of triethylamine as base or dioctyltin oxide using a Dean–Stark trap for the removal of water under reflux conditions. Experimental details for the preparation and characterization, including elemental analysis, IR, semi-empirical study, multinuclear NMR (¹H, ¹³C, and ¹¹⁹Sn spectra and EI mass spectral studies) of all reported complexes are provided. The IR data indicate that in both di- and triorganotin(IV) carboxylates, the ligand moiety ?COO acts as a bidentate group in the solid state. Multinuclear NMR data show that triorganotin complexes exhibits a four-coordinated geometry, while diorganotin(IV) complexes show a coordination number greater than four, probably five or six, in solution state.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

Synthesis,Characterization, and Semi-Empirical Study of Organotin(IV) Complexes with 4-(Hydroxymethyl)piperidine-1-carbodithioic Acid: X-Ray Structure of Chlorodimethyl-(4-hydroxymethyl piperidine-1-carbodithioato-S,S′)tin(IV)

Abstract

Organotin complexes with the general formulae R₂SnL₂, R₂Sn(Cl)L, and R₃SnL have been synthesized where R = CH₃, n-C₄H₆, C₆H₅, C₆H₁₁, and L = 4-(hydroxy methyl)piperidine-1-carbodithioic acid. The newly synthesized complexes have been characterized by elemental analysis, IR, NMR (¹H, ¹³C and ¹¹⁹Sn), and, for one example, a single crystal x-ray structure. The FT-IR data shows the bidentate nature of the ligand. This coordination behavior is also confirmed by semi-empirical study. In the solid state, diorganotin complexes exhibit the penta/hexacoordinated geometry, whereas the triorganotin(IV) complexes show the five coordinated geometry. ¹¹⁹Sn NMR data reveal that triorganotin(IV) complexes exhibit the four coordinated geometry in solution, whereas the diorganotin(IV) compounds show the higher coordination, probably five or six. X-ray diffraction analysis of complex (2) shows a square pyramidal geometry around the tin atom on the basis of τ value.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.

GRAPHICAL ABSTRACT      

Prebiotically Plausible Autocatalytic Peptide Amyloids

The prebiotic emergence of molecules capable both of self-replication and of storing information was a defining event at the dawn of life. Still, no plausible prebiotic self-replication of biologically relevant molecules has been demonstrated. Building upon the known templating nature of amyloids, we present two systems in which the products of a peptide-bond-forming reaction act as self-replicators to enhance the yield and stereoselectivity of their formation. This first report of an amino acid condensation that can undergo autocatalysis further supports the potential role of amyloids in prebiotic molecular evolution as an environment-responsive and information-coding system capable of self-replication.     

Polarography: A classical method with a new lease of life

Classical DC polarography was introduced by Heyrovsky in 1922. Since then substantial advances have been made in the technique, its instrumentation and methodology. These, coupled with the brilliant and innovative thinking of several workers, especially Barker, have transformed polarographic analysis into a powerful analytical tool.     

Rapid identification and quantification of chlorpheniramine maleate or pheniramine maleate in pharmaceutical preparations by thin-layer chromatography-densitometry

Thin-layer chromatography (TLC)-densitometry was used to separate, identify, and quantitate chlorpheniramine maleate (CPM) and pheniramine maleate (PM) when present in combination with other drugs in pharmaceutical preparations of tablets, syrups, eye and ear drops, etc. CPM or PM was extracted (tablets, capsules, etc.) or diluted (liquid preparations, if needed) with 80% ethanol and isolated from other ingredients by TLC on silica gel G using cyclohexane-chloroform-methanol-diethylamine (4.5 + 4.0 + 0.5 + 1.0, v/v) as the mobile phase. Separated CPM and PM were detected under shortwave ultraviolet light and quantitated by scanning densitometry at 260 nm. Recoveries of CPM and PM were 100.09+/-0.77% and 100.09+/-0.87%, respectively.