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71.
Attempts to cyclise o-chlorophenyl benzyl ether, sulphide, sulphoxide and sulphone by treatment with KNH2/NH3 were unsuccessful. Similar reaction of 1-(o-chlorophenyl)-2,2-diphenylethane led to amination whereas α-(o-chlorobenzyl)phenylacetic acid gave a dihydrocoumarin. Reaction of 4- and 2-(o-chlorophenethyl)-pyridines, however, afforded products comprising benzisoquinolines and 1-pyridylbenzocyclobutenes. 相似文献
72.
73.
P. B. Ruikar M. S. Nagar M. S. Subramanian K. K. Gupta N. Varadarajan R. K. Singh 《Journal of Radioanalytical and Nuclear Chemistry》1995,201(2):125-134
The extraction of plutonium(IV), uranium(VI), zirconium(IV), europium(III) and ruthenium(III) with -pre-irradiated n-dodecane solutions of methylbutyl substituted hexanamide (MBHA), octanamide (MBOA) and decanamide (MBDA) from 3.5M HNO3 has been studied as a function of absorbed dose up to 184×104 Gray. The distribution ratios (Kd) of uranium(VI) decreased gradually up to a dose of 50×104 Gray and became almost constant thereafter, while ruthenium(III) and europium(III) were not extracted in the entire dose range studied. The Kd values of Pu(IV) decreased gradually up to 10×104 Gray, for MBOA, and 30×104 Gray for MBHA and MBDA and then increased up to a dose of 72×104 Gray, indicating the synergistic effect of radiolytic products at higher doses. The extraction of zirconium(IV) was found to increase gradually up to 72×104 Gray. However, the steep fall in Kd values of plutonium(IV), zirconium(IV) beyond a dose of 72×104 Gray was atrributed to third phase formation. The radiolytic degradation of amides was monitored by quantitative IR spectroscopy and was found to follow the order MBOA>MBDA>MBHA at 184×104 Gray having the amines and carboxylic acids as the main radiolytic products. 相似文献
74.
Magnesium formate dihydrate has been synthesized by the action of formic acid on anhydrous magnesium oxide. This product analysed as Mg(COOH)2 · 2H2O. Its mode of thermal decomposition has been studied by thermal methods of analysis including simultaneous DTA/mass spectrometry. Nitrogen adsorption surface area of the solid products at various stages of its decomposition have been obtained. X-Ray diffraction and scanning electron micrographs have also been used to interpret the results. The decomposition of magnesium formate took place in three stages, which includes a phase change, at 265°C. The endotherm at 430°C changed to an exotherm in the presence of air; it corresponded to the decomposition of a new anhydrous phase of magnesium formate. The effect of the sample holder and changing atmospheres on the DSC analysis has been investigated. A scheme is presented for the thermal decomposition. 相似文献
75.
Gupta D Roitzsch M Lippert B 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(22):6643-6652
Isocytosine (ICH; 1) exists in solution in an equilibrium of tautomers 1a and 1b with the N1 and N3 positions carrying the acidic proton, respectively. In the solid state, both tautomers coexist in a 1:1 ratio. As we show, the N3H tautomer 1b can selectively be crystallized in the presence of the model nucleobase 1-methylcytosine (1-MeC). The complex 1b x (1-MeC)2 x H2O (2) forms pairs through three hydrogen bonds between the components; hydrogen bonds between identical molecules are also formed, leading to an infinite tape structure. On the other hand, the N1H tautomer 1a co-crystallizes with protonated ICH to give [1a x ICH2]NO3 (3), again with three hydrogen bonds between the partners, yet the acidic proton is disordered over the two entities. With M(II)(dien) (M=Pt, Pd; dien=diethylenetriamine) preferential coordination of tautomer 1a through the N3 position is observed. DFT calculations, which were also extended to Pt(II)(tmeda) linkage isomers (tmeda=N,N,N',N'-tetramethylethylenediamine), suggest that intramolecular hydrogen bonding between the ICH tautomers and the co-ligands at M, while adding to the preference for N3 coordination, is not the major determining factor. Rather it is the inherently stronger Pt-N3 bond which favors complexation of 1a. With an excess of M(II)(dien), dinuclear species [M2(dien)2(IC-N1,N3)]3+ (M=Pd(II), 4 and Pt(II), 5) also form and were isolated as their ClO4(-) salts and structurally characterized. In strongly acidic medium 5 is converted to [Pt(dien)(ICH-N1)]2+ (6), that is, to the Pt(II) complex of tautomer 1b. 相似文献
76.
The various thermodynamic parameters for the periodate oxidation of six anilines, viz. aniline, p-chloroaniline, p-ethoxyaniline, o- and p-methoxyanilines and p-methylaniline have been reported and discussed. The validity of the isokinetic relationship and various linear free energy relationships (LFERs) have been tested and discussed. An attempt has been made to correlate these findings with the mechanism operative in these reactions. 相似文献
77.
MgAl2O4:Mn phosphors have been prepared at 500 °C by combustion route. Powder X-ray diffraction (XRD) indicated the presence of mono-MgAl2O4 phase. Scanning electron microscopy showed that the powder particle crystallites are mostly angular. Fourier transform infrared spectroscopy confirmed the presence of AlO6 group which makes up the MgAl2O4 spinel. Photoluminescence studies showed green/red emission indicating that two independent luminescence channels in this phosphor. The green emission at 518 nm is due to 4T1 → 6A1 transition of Mn2+ ions. The emission at 650 nm is due to the charge-transfer deexcitation associated with the Mn ion. EPR spectrum exhibits allowed and forbidden hyperfine structure at g=2.003. The g≈2.00 is due to Mn2+ ion in an environment close to tetrahedral symmetry. It is observed that N and χ increase with decrease of temperature obeying the Boltzmann law. The variation of zero-field splitting parameter (D) with temperature is evaluated and discussed. 相似文献
78.
79.
Chandra S Gupta LK 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,62(4-5):1089-1094
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. 相似文献
80.
R. S. Saxena Reshma D. Parikh K. C. Gupta 《Monatshefte für Chemie / Chemical Monthly》1984,115(2):141-146
Potentiometric and conductometric studies on the zinc, cadmium, lead—methylene bis thio acetic acid system in aqueous media reveal the formation of 1:1 and 1:2 (M:L) complexes in thepH range 3.4–5.1. Their stability constants have been determined at 20°, 30° and 40 °C by applyingCalvin andMelchior's extension ofBjerrum's method. The overall changes in thermodynamic function H, G and S accompanying complexation have been evaluated at 30 °C.
Elektrochemische Untersuchungen über Zusammensetzung, Stabilität und Thermodynamik von Zn(II)-, Cd(II)- und Pb(II)-Komplexen mit Methylen-bisthioessigsäure
Zusammenfassung Potentiometrische und konduktometrische Untersuchungen an Zink-, Cadmium- und Blei-Methylen-bis-thioessigsäure-Systemen in wäßrigem Medium zeigten die Bildung von 1:1 und 1:2 (M:L)-Komplexen impH-Bereich 3,4–5,1. Die Stabilitätskonstanten wurden bei 20°, 30° und 40 °C mittels derCalvin-Melchior-Methode (erweiterteBjerrum-Methode) bestimmt. Die thermodynamischen Parameter H, G und S der Komplexierung wurden für 30 °C ermittelt.相似文献