Electric dipole moments and molecular structure of aliphatic nitro compounds and oximes

Using the treatment of Smith et al. charge distributions in and consequently the dipole moments of some aliphatic nitro compounds and oximes have been evaluated. The mesomeric moment derived as a difference between the calculated and the observed values gives a clear picture as to how the positive (+M) and the negative (-M) mesomeric effects operate in such systems.

Nature, stability and bonding of the peroxy group in peroxy titanium compounds

Some physicochemical properties of peroxy titanium compounds are explained by assigning a strained triangular ring structure to the peroxy titanyl group, with a bent and reduced overlap of the O---O bonding orbitals. The stability of the peroxy group is found to depend on the stability of the other ligands. The decreasing order of stability of the peroxy group in the compounds is as: oxalato > meleato > malonato > sulphato > peroxide of titanium.

The Raman spectra of organic compounds -Part I. Methyl, ethyl, n-propyl and n-butyl alcohols

The Raman spectra of methyl alcohol, ethyl alcohol, n-propyl alcohol and n-butyl alcohol have been recorded using λ 2537 excitation. 35, 49, 45 and 51 Raman lines respectively have been identified in the spectra of these alcohols, in addition to the rotational 'wings'. In each case, a large number of additional lines have been recorded. The existence of Raman lines with frequency shifts greater than 3800 cm.-1, first reported by Bolla in the spectrum of ethyl alcohol, has been confirmed. Similar high-frequency shift Raman lines have also been recorded in the spectrum of methyl alcohol. They have been assigned as combinations. Proper assignments have been given for the prominent Raman lines appearing in the spectra of these alcohols.

Raman spectra of addition compounds of glycine (diglycine hydrochloride, diglycine hydrobromide and diglycine nitrate)

Raman spectra of single crystals of diglycine hydrochloride, diglycine hydrobromide and diglycine nitrate have been recorded for the first time. λ 2536·5 resonance radiation of mercury has been used as exciter. The spectrum of diglycine hydrochloride exhibits 10 low frequency lines and 41 lines due to internal oscillations, while that of diglycine hydrobromide exhibits 11 lines and 41 lines respectively. In the case of diglycine nitrate 46 lines have been recorded, of which 10 belong to the lattice spectrum. These spectra are compared with the Raman spectra of triglycine sulphate and α-glycine and proper assignments have been given to the internal oscillations.

Dipole moments and structure of organophosphine and organoarsine compounds

The formal charge distributions in and the dipole moments of some organophosphines and arsines have been calculated, and the dipole moments of (p-chlorophenyl)dichlorophosphine (2.28 D) and (p-bromophenyl)dichlorophosphine (2.04 D) have been determined in benzene at 35° C. The differences between the observed and the calculated moments are explained in terms of dπ---pπ back-bonding and hyperconjugative effects in alkylhaloarsines. The mesomeric effects operating in the aromatic systems are evaluated by comparing the moments with those for the corresponding aliphatic systems. In unsaturated compounds the differences are attributed to mesomeric effects involving the expansion of arsenic valence shell.

Mechanism of hydroxylation of aromatic compounds: II. Evidence for the involvement of superoxide anions in enzymatic hydroxylations

The mechanism of hydroxylation reactions catalyzed by m-hydroxybenzoate-4-hydroxylase and anthranilate hydroxylase from Aspergillus niger was investigated using superoxide dismutase from ovine erythrocytes. Inclusion of superoxide dismutase in the assay mixtures of the two enzymes resulted in complete inhibition of the hydroxylation reaction, indicating the possible involvement of superoxide anions (O2−) in these reactions.

Separation Of Beta-Apocarotenals And Related Compounds By Reversed-Phase Paper And Thin-Layer Chromatography

Tlie sclxuntion and clraractcrization of vitamins Al and An nnd related compoundsby reversed-pllasc paper cliromatogrnpl~y as well as ly thin-lqxr chromategraphy have hen rcportccl carlicrl * $. Thin-lnycr chromatography has also been used for the separatinn and charncterizatio11 of carotenoids from natural sourccs3~ ‘1. I-Iowcver, 130tr.rc,1~1~ofib scrvccl that carotenoid misturcs cannot be separated on a sin& aclsorhnt with ;1 sin& solvent. The scparntion and clctermi1wtion of carotenoid alclclydes from plants, microorganisms and animnl tissues have lxxn carriecl out by nicans of thin-layer clirf.~li~ato~apI~~U. Apocarotcnals awl apocarotcnoic acid have been detected in ornnges by the same technique’*

Synthesis, structure, transformation studies and catalytic properties of open-framework cadmium thiosulfate compounds

Five new thiosulfate based inorganic-organic hybrid open-framework compounds have been synthesized employing mild reaction conditions. Of the five compounds, [Na-2(H2O)(8)][Cd(C10H8N2)( S2O3)(2)]center dot 2H(2)O, I and [Cd-2(C10H8N2)(2)(HS2O3)(2)(S2O3)(2)][(C10H9N2)(2)(C10H8N2)(2)]center dot 8H(2)O, II have one-dimensional (1D) structures and [Cd(C10H8N2)(H2O)(2)(S2O3)]center dot 2H(2)O, III, [Cd-2(C10H8N2)(3)(S2O3)(2)], IV and [Cd-2(C10H8N2)(2.5)(S2O3)(2)], V have three- dimensional (3D) structures. The 1D structures are somewhat related, formed by the bonding between tetrahedral Cd centers (CdN2S2) and 4,4'-bipyridine (bpy) units. The inter-chain spaces are occupied by the hanging thiosulfate units in both the cases along with Na(H2O)(6) chains in I and free bpy units in II. The three 3D structures have one-dimensional cadmium thiosulfate chains linked by bpy units. Interpenetration has been observed in all the 3D structures. The 3D structures appear to be related and can be derived from fgs net. Transformation studies on the 1D compound, [Na-2(H2O)(8)][Cd(C10H8N2)(S2O3)(2)]center dot 2H(2)O, I, indicated a facile formation of [Cd(C10H8N2)(H2O)(2)(S2O3)]center dot 2H(2)O, III. Prolonged heating of I gave rise to a 3D cadmium sulfate phase, [Cd-2(C10H8N2)(2)(H2O)(3)(SO4)(2)]center dot 2H(2)O, VI. Compound VI has one-dimensional cadmium sulfate chains formed by six-membered rings connected by bpy units to form a 3D structure, which appears to resemble the topological arrangement of III. Transformation studies of III indicates the formation of IV and V, and at a higher temperature a new 3D cadmium sulfate, [Cd(C10H8N2)(SO4)], VII. Compound VII has a 4 x 4 grid cadmium sulfate layers pillared by bpy units. All the compounds were characterized by PXRD, TGA, IR and UV-visible studies. Preliminary studies on the possible use of the 3D compounds (III-VII) in heterogeneous cyanosilylation of imines appear to be promising.

Dipole moments and structure of organophosphine and organoarsine compounds

The formal charge distributions in and the dipole moments of some organophosphines and arsines have been calculated, and the dipole moments of (p-chlorophenyl)dichlorophosphine (2.28 D) and (p-bromophenyl)dichlorophosphine (2.04 D) have been determined in benzene at 35° C. The differences between the observed and the calculated moments are explained in terms of dπ---pπ back-bonding and hyperconjugative effects in alkylhaloarsines. The mesomeric effects operating in the aromatic systems are evaluated by comparing the moments with those for the corresponding aliphatic systems. In unsaturated compounds the differences are attributed to mesomeric effects involving the expansion of arsenic valence shell.

Mechanism of hydroxylation of aromatic compounds: Evidence for the involvement of superoxide anion in a model system

Hydroxylation of aromatic compounds was observed in NADH-phenazine methosulfate-O2 model system known to generate superoxide anions (Image ). Addition of superoxide dismutase prepared from ovine erythrocytes to this hydroxylating system resulted in complete inhibition, suggesting an involvement of Image in aromatic hydroxylations.

Ab initio studies on proton transfer involving Schiff base and related nitrogen compounds

Proton transfer across cationic hydrogen bonds involving Schiff base, ammonia and related compounds has been studied at the 4-31G level. Proton transfer characteristics are correlated to the proton affinities of the species involved. Hydrogen bond strengths of these hydrogen bonds are correlated to the differences in the proton affinity of the donor and the acceptor. Influence of a neighbouring hydrogen bond on the proton transfer from Schiff base to ammonia and Schiff base to water is also discussed.