Regioselectivity in Reactions of Bis‐Hydrazonoyl Halides with Some Bifunctional Heterocycles

Bis‐hydrazonoyl chloride 1 reacts regioselectively with 3‐mercapto‐1,2,4‐triazole 2a , 2,3‐dihydro‐3‐thioxo‐1,2,4‐triazin‐5(4H)‐one 2b and 2‐mercaptobenzimidazole 2c to give the hitherto unknown annelated 2,3‐bis‐(phenylhydrazono)thiazoles 6a‐c , respectively. Reactions of 1 with the methylthio derivatives of such heterocycles afforded the annelated 3,3′‐bis‐(1,2,4‐triazoles) 11a‐c , respectively. Similar reaction of 1 with 2‐phenylamino‐4(3H)‐pyrimidinones 4 gave 2,3‐bis(phenylhydrazono)imidazo[1,2‐a]pyrimidin‐5(1H)‐ones 16 . Oxidation of 6c yielded the corresponding bis(phenylazo) derivative 15 . The regiochemistry of the studied reactions is discussed.     

Spectrophotometric estimation of cobalt(II) with nitrilotriacetic acid

A convenient and efficient method for the estimation of cobalt(II) ions in the presence of other metal ions is described. Interference of metal ions such as iron(II), iron(III), nickel(II), manganese(II), and copper(II) have been investigated. Only iron(III) ions seriously affect this determination. Copper(II) and nickel(II) ions do not interfere if present in a molar-ratio less than 1:2 in the cobalt(II) ion solution. Cobalt(II)-nickel(II) and cobalt(II)-copper(II) binary mixtures can be efficiently analyzed at selective wavelengths.     

Simultaneous determination of uranium and thorium in high grade thorium ores

A routine procedure has been developed for the simultaneous determination of uranium and thorium in high concentration thorium ores. INAA is used to determine the uranium and thorium concentration. However, for very low concentrations of uranium a radiochemical procedure based on the use of NPy/benzene as an extractant has to be employed. The precision and accuracy of the method has been determined by analyzing IAEA and NBL standard thorium/uranium ores.     

Proficiency test exercise on the determination of natural levels of radionuclides in mushroom reference material

The results from a proficiency test exercise for the determination of natural levels of radionuclides in mushroom reference material carried out by laboratories in six different countries are discussed. These laboratories submitted data on seven radionuclides, namely ¹³⁴Cs, ¹³⁷Cs, ⁴⁰K, ⁹⁰Sr, ²⁴¹Am, ²²⁶Ra, and ²¹⁰Po. However, only the data received for three of these radionuclides could be statistically evaluated to obtain consensus mean values and confidence intervals (at a significance level of 0.05). The contents of ¹³⁴Cs, ¹³⁷Cs and ⁴⁰K were quantified as 4.4, 2,899 and 1,136 Bq/kg, respectively.     

Dietary evaluation of toxic elements through integrated diet

Several potentially toxic trace elements, namely, Hg, Pb, Cd, As, Sb, Br and Se have been measured by INAA in combination with AAS techniques in the integrated diet representative of the inhabitants of Gujranwala, a highly industrialized city of Pakistan. The dietary intake values for these elements have been estimated from the prevailing concentration level in the summer and winter season diets, which reveals that present intake data are well within the reported WHO values and can be considered to be safe. Posslble sources of food contamination by the toxic elements and their adverse impacts on human heaith are briefly discussed.     

Isotope shift studies in the second spectrum of neodymium in UV region

Isotope shift (IS) Δσ (142–150) have been measured in 92 spectral lines of Nd⁺ in the region 3290–3955 Å, employing recording Fabry-Perot spectrometer and highly enriched isotopic samples excited in a liquid-nitrogen cooled hollow cathode. Earlier IS measurement in UV region of Nd II spectrum is available for only a few lines, New classification has been made for several of the spectral lines studied presently. We have also revised the earlier suggested classification for some of the Nd II lines on the basis of observed isotope shifts. The transitions presently studied mostly involve high lying odd parity energy levels above 30,000 cm^?1 having neither electronic configuration assignment nor term isotope shifts (ΔT) evaluated. The present study would thus enable to evaluate ΔT values of some of these high lying odd levels, which should be helpful in suggesting possible electronic configurations.     

Kinetics and Mechanism of the Epoxidation of Alkyl-Substituted Alkenes by Hydrogen Peroxide, Catalyzed by Methylrhenium Trioxide

Epoxidations of alkyl-substituted alkenes, with hydrogen peroxide as the oxygen source, are catalyzed by CH(3)ReO(3) (MTO). The kinetics of 28 such reactions were studied in 1:1 CH(3)CN-H(2)O at pH 1 and in methanol. To accommodate the different requirements of these reactions, (1)H-NMR, spectrophotometric, and thermometric techniques were used to acquire kinetic data. High concentrations of hydrogen peroxide were used, so that diperoxorhenium complex CH(3)Re(O)(eta(2)-O(2))(2)(H(2)O), B, was the only predominant and reactive form of the catalyst. The reactions between B and the alkenes are about 1 order of magnitude more rapid in the semiaqueous solvent than in methanol. The various trends in reactivity are medium-independent. The rate constants for B with the aliphatic alkenes correlate closely with the number of alkyl groups on the olefinic carbons. The reactions become markedly slower when electron-attracting groups, such as halo, hydroxy, cyano, and carbonyl, are present. The rate constants for catalytic epoxidations with B and those reported for the stoichiometric reactions of dimethyldioxirane show very similar trends in reactivity. These findings suggest a concerted mechanism in which the electron-rich double bond of the alkene attacks a peroxidic oxygen of B. These data, combined with those reported for the epoxidation of styrene (a term intended to include related molecules with ring and/or aliphatic substituents) by B and by the monoperoxo derivative of MTO, suggest that all of the rhenium-catalyzed epoxidations occur by a common mechanism. The geometry of the system at the transition state can be inferred from these data, which suggest a spiro arrangement.     

Absolute configuration of 1β,10β-epoxydesacetoxymatricarin isolated from Carthamus oxycantha by means of TDDFT CD calculations

The absolute configuration of 1β,10β-epoxydesacetoxymatricarin 1, a sesquiterpenoid isolated from Carthamus oxycantha, was established by TDDFT CD calculations in combination with single crystal X-ray analysis. Since the solid-state CD spectrum shows contributions from intermolecular interactions in the crystal, 1 represents a test case for our solid-state CD/TDDFT approach.     

Water promoted one-pot synthesis of 2′-aminobenzothiazolomethyl naphthols and 5-(2′-aminobenzothiazolomethyl)-6-hydroxyquinolines

A novel one-pot, three-component condensation reaction of an aldehyde, 2-aminobenzothiazole and 2-naphthol or 6-hydroxyquinoline in water to give 2′-aminobenzothiazolomethyl naphthols or 5-(2′-aminobenzothiazolomethyl)-6-hydroxyquinolines in high yields at 90 °C without using any catalyst, is described.     

A remark on the SLLN for random partial sums

Summary By representing the strong law of large numbers for partial sums in its equivalent form that an integer-valued random variable N is finite with probability one it is possible to obtain resutls on the rate of convergence as 0.In this note a rate of convergence is obtained when the index of the sum itself is a random variable (not necessarily independent of the observations).Research supported in part by the National Research Council of Canada while the author was with McMaster University. The author is indebted to the referees for several helpful comments and criticisms