Complexing tendencies of UO 22+ and Th4+ in their mixed ligand complexes with aminopolycarboxylates and resorcinol or its derivatives

Formation contants (log K _MAL ^MA ) of mixed ligand complexes MAL, where M = UO ₂ ²⁺ or Th⁴⁺, A = IMDA, NTA, HEDTA, EDTA, CDTA or DTPA, and L = resorcinol (res), 2-methyl resorcinol (2-Me-res), 5-methyl resorcinol (5-Me-res) or 4-chloro resorcinol (4-Cl-res), have been determined pH-metrically by the Irving-Rossotti approach at 25°C and at an ionic strength,I = 0.2(moldm⁻³KNO₃). The observed stability sequences are IMDA > NTA > HEDTA > EDTA > CDTA > DTPA, and 4-Cl-res > 5-Me-res > 2-Me-res > res with respect to primary and secondary ligands, respectively. Th⁴⁺ forms more stable mixed complexes than UO ₂ ²⁺ . The A ΔlogK values are negative due mainly to the charge repulsion involved in the complexation MA + L⇋MAL.     

Identification of inhibitors of DNA topoisomerase II from a synthetic library of glycoconjugates

A library of 24 glycoconjugates related to glycosylated beta-amino acid derivative (I) was been prepared and screened against DNA topoisomerase-II of the filarial parasite S. cervi. Among these, compound 6 was found to be a potent inhibitor of DNA topoisomerase-II with 95% inhibition at 1.09 microM. Furthermore, compound 6 was at least three times more potent than the lead compound, glycosylated beta-amino acid derivative I.     

Some remarks on the use of rational functions as variational functions

When a Padé-type function is used as a trial function, it is necessary to investigate the location of singularities and the zeros of the optimized function. It is shown that an unacceptable wave function can sometimes yield numerically acceptable values because of the nature of the integration procedure. It is also shown that it is possible to remove the undesirable features of a lower order form by invoking the next approximation.     

One-Pot Synthesis and Fungicidal Activity of Pyrimidinylidenamido- and Thiazolinylidenamidomonothiophosphoric Esters

A novel one-pot synthesis of four new classes of amidothiophosphoric esters and trisamidothiophosphoric esters is developed. (1-Alkyl-2-pyrimidinylidenamido)bis(diethylamido)thiophosphates, (1-alkyl-2-pyrimidinylidenamido)bis (O-2/4-methylphenyl)thiophosphates, (3-alkyl-2-thiazolinylidenamido)bis (diethylamido)thiophosphate and (3-alkyl-2-thiazolinylidenamido)bis(O-2/4-methylphenyl)thiophosphates are obtained from the nucleophilic substitution and oxidation of N-alkyl-2-cycloiminylidenaminodichlorophosphines generated in situ from the reaction of the corresponding N-alkyl-2-aminocycloiminium halide with phosphorus trichloride and triethylamine. The synthesized thiophosphoric esters have been investigated for fungicidal properties.     

MASS SPECTROMETRIC FRAGMENTATION OF UNSYMMETRICALLY SUBSTITUTED METHYLPHOSPHONATE DIESTERS

Abstract

A series of structurally related unsymmetrically substituted methylphosphonate diesters have been synthesised and subjected to electron impact (El) mass spectral studies. These studies though aimed at total identification of the compounds, resulted in certain interesting observations and hence are being reported. In order to confirm the observations under electron impact and to support the mechanism of fragmentation we have also performed MSNS experiments in both daughter ion and parent ion modes.     

First Example of Intramolecular C-H Insertion Reaction in an Amino Acid Derived α-Diazoketone

Rh-Catalyzed intramolecular C-H insertion reaction of L-leucine derived α-diazoketone is described.     

A Convenient Method of Benzylic Oxidation with Pyridinium Chlorochromate

Oxidation of indans and tetralin derivatives to their corresponding indanones and tetralones is of considerable value i n organic synthesis and many methods have been reported for accomplishing this conversion. Traditionally these oxidations are performed with chromic acid in acetic acid and the yields in general are moderate. Recently Eisenbraun4 has studied indetail the benzylic oxidation with the Jones reagent and compared the selectivity and yield of oxidation with other chromium(V1) reagents like bipyridinim chlorochrmate, (BiPCC). It was found that there was no improvement in yield and in the case of BiPCC a molar ratio 16% 1 (oxidant: substrate) was employed to get     

Measurements of atmospheric electrical conductivities during the total solar eclipse of 22 July, 2009

The effect of total solar eclipse on atmospheric conductivities has been studied. Continuous measurements of both types of positive and negative electrical conductivities and some meteorological parameters in conjunction with the total solar eclipse of 22 July, 2009 were made from 21 to 23 July, 2009 at Roorkee (29°52′ N, 77°53′ E, 275 m above sea level). Roorkee observed 90% maximum obscurity of eclipse since it was close to the path of totality. The event started from 05:28 AM IST and ended at 07:42 AM IST with the total eclipse at 06:30 AM IST. Considerable increase of both positive and negative conductivities were recorded during the eclipse with respect to those made on any other day. Increase in relative humidity and decrease in temperature were also observed during the period of eclipse.     

The Mechanism of Thionyl Chloride Reaction with Dialkyl Alkylphosphonothionate Using 31 P NMR

Based on 31 P NMR studies of thionyl chloride reaction with dialkyl alkylphosphonothionates, a method for preparation of alkylphosphonic dichloride has been investigated. A mechanism via intermediacy of ester chloride is suggested.     

Substituted Diorganotin(IV) O,O’-Alkylene Dithiophosphates: Synthesis and Spectral Aspects

Six new substituted diphenyltin(IV) O,O′-alkylene dithiophosphates, (C₆H₅)₂Sn(X)S(S) POGO [G = —CH₂C(CH₃)₂CH₂—, X = Cl (1), SCN (3), ClO₄ (5); G = —CH₂C (C₄H₉)(C₂H₅)CH₂—, X = Cl (2), SCN (4), ClO₄ (6)], were synthesized by the reaction of the corresponding ammonium salts of the O,O’-alkylene dithiophosphates with an appropriate organotin(IV) chloride. The compounds were characterized on the basis of elemental and spectral analyses (ESI mass spectrometry, IR, ¹H, ¹³C, ³¹P, and ¹¹⁹Sn NMR). The presence of a four-coordinated Sn atom and monodentate O,O’-alkylene dithiophosphate moiety in compounds 1–4 as well as bidentate O,O’-alkylene dithiophosphate unit in compounds 5,6 is established.