Kinetics of oxidation of some disaccharides in ammoniacal medium

Kinetics of oxidation of lactose, maltose, cellobiose and melibiose has been studied by hexacyanoferrate(III) in the presence of ammonia. A general mechanism involving the formation of intermediate enodiol anion has been suggested. The effects of dielectric constant and salts have been studied in detail. The oxidation products have been characterised by descending paper chromatography. Compensation effects have been observed.     

pH-metric studies on some ternary complexes of lanthanones

Stepwise mixed ligand complex formation has been cited for the formation of 111,Ln(III)—NTA—catechol ternary complexes potentiometrically [whereLn(III)=La(III), Pr(III) or Nd(III)]. The results of titration curves indicate the formation of 11,Ln(III)—NTA complexes in beginning and the addition of catechol, takes place later on in the higher buffer region. The relative stability of these ternary complexes in terms of metal ion has been reported as La(III)< 相似文献   

On the long-lived transient absorption observed in nanosecond laser photolysis studies of two polymethine cyanine dyes

It is shown that the long-lived transient absorption which is observed when solutions of cryptocyanine and DDI (1, 1′-diethyl-2, 2′-dicarbocyanine iodide) in methanol and other alcohols are exposed to nanosecond ruby laser pulses arises from a photoproduct whose formation requires consecutive absorption of two photons.     

Spin density distributions in radical anions of heterocyclic amine N-oxides

The unrestricted Hartree-Fock (UHF) method of Snyder and Amos is used to calculate, in the -electron approximation, the spin density distributions in radical anions of heterocyclic amine N-oxides. The computed spin densities are observed to be in good agreement with the experimental values. The computed spin density distribution of the radical anion of pyridine N-oxide is consistent with the greater susceptibility of pyridine N-oxide relative to pyridine to electrophilic nitration. Also, the calculations are consistent with the lower basicity of the N-oxides relative to the parent bases.     

Knoevenagel condensation of 2-carbethoxycyclohexanone and malononitrile: Synthesis of 4-cyano-3-ethoxy-1-hydroxy-5,6,7,8-tetrahydroisoquinoline,an isomer of the abnormal product

The structure of the abnormal product 1a formed in the Knoevenagel condensation of 2-carbethoxycyclohexanone and malononitrile has been further confirmed. Oxidation of the tetrahydroisoquinoline 3b using Na₂Cr₂O-AcOH-H₂SO₄ gave the keto isoquinoline 3d and the isoquinoline-1-carboxylic acid 5a. The acid chloride of 5a was condensed with diethyl ethoxymagnesiomalonate to afford after decarbethoxylation the methyl ketone 5d which on Baeyer-Villiger oxidation gave a mixture of the acetate 1g and the title compound 1b. The unambiguous synthesis of 1b confirms the structure assigned earlier to the title compound also formed during the partial hydrolysis of the diethoxy compound 1c. Condensation of 2-acetylcyclohexane-1,3-dione with malononitrile gave the quinoline derivative 4c which on ethylation yielded the ketoquinoline 4d. The present studies have confirmed that the quinoline compound 4a is also formed in the condensation of 2-acetylcyclohexanone and cyanoacetamide.     

Pressure dependence of the compressibility of alkali halides

The parameterC ₁=[(1/K _T )/P] _T , which describes the pressure variation of the compressibility, has been examined correlating the thermodynamical and interatomic potential approaches employing fewer approximations than has been usual heretofore. General expressions have been derived forC ₁ by including the thermal correction terms, which have generally been ignored in previous studies concerning thermal properties of ionic crystals. The parameterC ₁ has also been related to the Grüneisen parameter, , using a relation given earlier. The applicability of the derived equations is investigated and discussed for alkali halides employing few realistic potential forms. A good general accord is found with the available experimental data, which exhibits an essential improvement over other theoretical determinations.     

Cerate oxidimetry : Oxidation of formic,glycolic, malic,malonic and tartaric acids

1. Contrary to the observations of earlier workers, it has been shown that formic acid can be quantitatively oxidixed by ceric sulphate in the presence of concentrated sulphuric acid. 2. Tartaric, malonic, malic and glycolic acids can also be oxidized completely to carbon dioxide and water by the following general procedure : to a known amount of the organic acid is added ceric sulphate (excess) solution in dilute sulphuric acid and the mixed solution refluxed for ten to fifteen minutes. Concentrated sulphuric acid (double the volume of the reaction mixture) is then added taking care that formic acid is not lost during the addition, and the mixture again refluxed for 45 to 50 minutes. The excess ceric sulphate is determined by titrating against ferrous ammonium sulphate. 3. The complete oxidation of the above acids provides satisfactory methods for their quantitative estimation.     

Thermodynamics of molecular interactions in binary mixtures of non-electrolytes. Molar excess volumes

Molar excess volumes, V^E, for pyridine (A) + α-picoline (B), + β-picoline (B) and + γ-picoline (B) and benzene (A) + toluene (B), + o-xylene (B) and + p-xylene (B) and carbon tetrachloride (A) + n-heptane (B) have been measured dilatometrically as a function of temperature and composition and have been utilized to study B—B and B—B—B interactions in the presence of A via the Mayer—McMillan approach. A model has also been presented to account for these B—B and B—B—B interactions. The V^E data at 308.15 K have also been analysed in terms of the “graph theoretical” approach which describes the V^E data well for all these mixtures at 308.15 K. The “graph theoretical” approach has further been extended to successfully evaluate V^E data for a mixture at any temperature, T₂, when the V^E data at T₁ are known.