Chiral synthons from carvone, Part 40. A simple, enantiospecific approach to both enantiomers of 1 alpha,25-dihydroxyvitamin D-3 A-ring precursors from R-carvone

A simple and direct approach to both enantiomeric series of A-ring derivatives of 1 alpha,25-dihydroxyvitamin D-3 and the corresponding 1 alpha,3 alpha-derivatives, starting from the abundantly available R-carvone, is described. (C) 2000 Elsevier Science Ltd. All rights reserved.

Dielectric properties of glasses prepared by quenching melts of superconducting Bi‐Ca‐Sr‐Cu‐O cuprates

Glasses obtained from quenching melts of superconducting bismuth cuprates of the formula Bi2(Ca,Sr)n+1CunO2n+4 with n=1 and 3 exhibit novel dielectric properties. They possess relatively high dielectric constants as well as high electrical conductivity. The novel dielectric properties of these cuprate glasses are likely to be of electronic origin. They exhibit a weak microwave absorption due to the presence of microcrystallites.

Electrical and Dielectric Behaviour at the Critical Point of Binary Liquids: Acetonitrile + Cyclohexane

The electrical capacitance and resistance of the binary liquid mixture cyclohexane + acetonitrile are measured in the one phase and two phase regions at spot frequencies between 5 kHz and 100 kHz. This sample has a very low gravity affected (∼0.6 mK) region. In one phase region the capacitance data show a sharp, ∼0.7% increase above background within 0.5 degrees of Tc whereas the resistance has a smooth increase of ∼1.5% above background in a (T−Tc) range of 4 degrees. Two phase values of capacitance and resistance from the coexisting phases are used to determine the critical parameters Tc (critical temperature), Rc (resistance at Tc) and Cc (capacitance at Tc). A precise knowledge of these parameters reduces the uncertainty on the critical exponent 0 for C and R. The one phase capacitance data fit to an (1 - α) exponent in a limited temperature range of 0.2 degrees. Resistance data strongly support an (1 - α) exponent over the entire 5 degree range.

An enantiospecific approach to pinguisanes from (R)-carvone. Total synthesis of (+)-pinguisenol

Enantiospecific total synthesis of (+)-pinguisenol 1, a sesquiterpene containing a cis-1,2,6,7-tetramethylbicyclo[4.3.0]nonane carbon framework incorporating two vicinal quaternary carbon atoms and four cis-oriented methyl groups on four contiguous carbon atoms, isolated from a liverwort, is described. The orthoester Claisen rearrangement of the allyl alcohol 9, obtained from (R)-carvone, generates the ester 12. Intramolecular cyclopropanation of the diazo ketone 13, derived from the ester 12, furnishes the tricyclic ketone 7. Degradation of the isopropenyl group followed by regioselective reductive cyclopropane ring cleavage transforms compound 7 into the hydroxy ketone 21. Wolff–Kishner reduction of the hydroxy ketone 21 followed by oxidation and Grignard reaction furnishes pinguisenol (+)- 1.

Metabolism of a monoterpene ketone, R-(+)-pulegone—a hepatotoxin in rat

R-(+)-Pulegone was administered orally to rats and the urinary metabolites were investigated. Six metabolites were isolated and purified using column and thin layer chromatographic techniques. Metabolites were identified by i.r., n.m.r. and mass spectral analyses.The neutral metabolites isolated from urine of rats treated with pulegone (I) were: pulegol (II), 2-hydroxy-2(1'-hydroxy-1'-methylethyl)-5-methylcyclohexanone (III), 3,6-dimethyl-7a-hydroxy-5,6,7,7a-tetrahydro-2(4H)-benzofuranone (V) and menthofuran (VII). Metabolites II and III were also excreted in conjugated form.Acidic metabolites isolated from urine of rats treated with pulegone (I) were: 5-methyl-2(1'-methyl-1'-carboxyethylidene)cyclohexanone (IV) and 5-methyl-5-hydroxy-2(1'hydroxy-'-carboxyethyl)cyclohexanone (VI).

Crystal structure and conformation study of N-methyl-t-3-methyl-r-2, c-6-diphenylpiperidin-4-one thiosemicarbazone

Thiosemicarbazones are having the ability to bind with metal and inhibit the enzyme ribonucleoside diphosphate reductase(RDR),an enzyme which is involved in the synthesis of DNA precursors in the mammalian cells.The title compound N-methyl-t-3-methyl-r-2, c-6-diphenylpiperidin-4-one thiosemicarbazone (NMMDPT), CCDC 218052, was prepared using Mannich reaction and characterized by X-ray diffraction methods.The crystal data are:C20H24N4S; M.W= 352.49, triclinic,space group P (1) over bar, a = 8.467(2)angstrom, b = 10.228(2)angstrom, c = 12.249(2)angstrom; lpha=92.595(3)degrees, beta=104.173(3)degrees, gamma=13.628(3)degrees; V=930.0(3)angstrom(3), Z=2, D-cal=1.259Mgm(-3),mu=0.184mm(-1),lambda (MoKalpha)=0.71073 angstrom, final R1 and wR2 are 0.0470 and 0.1052, respectively. The piperidine rings adopt chair conformation. The planar phenyl rings are oriented equatorially at 2,6-positions of the piperidine ring. The molecular packing can be viewed as dimers held together by two N-H...S types of intermolecular hydrogen bonds. Weak C-H...pi interactions also support the stability of the molecules in the crystal in addition to van der Waals forces. (c) 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

13C-N.M.R. studies of discotics

13C-N.M.R. spectra of benzene-hexa-n-octanoate (a discotic liquid-crystalline material) show significant differences in the isotropic, mesomorphic and solid states. The presence of four molecules per asymmetric unit is required to explain the results in the solid state.

Trends in the stability of ternary oxides: Systems M-Pb-O (M = Ca, Sr, Ba)

Recent experimental investigations of phase equilibria and thermodynamic properties of the systems M-Pb-O, where M = Ca, Sr or Ba, indicate a regular increase in thermodynamic stability of ternary oxides, MPbO3 and M2PbO4, with increasing basicity of the oxide of the alkaline-earth metal. Number of stable interoxide compounds at 1100 K in the systems M-Pb-O (M = Mg, Ca, Sr, Ba) increases in unit increments from Mg to Ba. In this paper, experimentally determined standard Gibbs energies of formation of M2PbO4 (M = Ca, Sr, Ba) and MPbO3 (M = Sr, Ba) from their component binary monoxides and oxygen gas are combined with an estimated value for CaPbO3 to delineate systematic trends in thermodynamic stability of the ternary oxides. The trends are interpreted using concepts of tolerance factor and acid-base interactions. All the ternary oxides in these systems contain lead in the tetravalent state. The small Pb4+ ions polarize the surrounding oxygen ions and cause the formation of oxyanions which are acidic in character. Hence, the higher oxidation state of lead is stabilized in the presence of basic oxides of alkaline-earth group. A schematic subsolidus temperature-composition phase diagram is presented for the system BaO-PbO-O-2 to illustrate the change in oxidation states in binary and ternary oxides with temperature.

Microstructure related influence on the electrical properties of pulsed laser ablated (Ba, Sr)TiO3 thin films

The microstructural dependence of electrical properties of (Ba, Sr)TiO3(BST) thin films were studied from the viewpoint of dc and ac electrical properties. The films were grown using a pulsed laser deposition technique in a temperature range of 300 to 600 degrees C, inducing changes in grain size, structure, and morphology. Consequently, two different types of films were realized, of which type I, was polycrystalline, multigrained, while type II was [100] oriented possessing a densely packed fibrous microstructure. Leakage current measurements were done at elevated temperatures to provide evidence of the conduction mechanism present in these films. The results revealed a contribution from both electronic and ionic conduction. In the case of type I films, two trapping levels were identified with energies around 0.5 and 2.73 eV, which possibly originate from oxygen vacancies V-O and Ti3+ centers, respectively. These levels act as shallow and deep traps and are reflected in the current-voltage characteristics of the BST thin films. The activation energy associated with oxygen vacancy motion in this case was obtained as 1.28 eV. On the contrary, type II films showed no evidence of deep trap energy levels, while the identified activation energy associated with shallow traps was obtained as 0.38 eV. The activation energy obtained for oxygen vacancy motion in type II films was around 1.02 eV. The dc measurement results were further elucidated through ac impedance analysis, which revealed a grain boundary dominated response in type I in comparison to type II films where grain response is highlighted. A comparison of the mean relaxation time of the two films revealed three orders of magnitude higher relaxation time in the case of type I films. Due to smaller grain size in type I films the grains were considered to be completely depleted giving rise to only grain boundary response for the bulk of the film. The activation energy obtained from conductivity plots agree very well with that of dc measurements giving values 1.3 and 1.07 eV for type I and type II films, respectively. Since oxygen vacancy transport have been identified as the origin of resistance degradation in BST thin films, type I films with their higher value of activation energy for oxygen ion mobility explains the improvement in breakdown characteristics under constant high dc field stress. The role of microstructure in controlling the rate of degradation is found useful in this instance to enhance the film properties under high electric field stresses. (C) 2000 American Institute of Physics. [S0021-8979(00)00418-7].

Support theorems on R-n and non-compact symmetric spaces

We consider convolution equations of the type f * T = g, where f, g is an element of L-P (R-n) and T is a compactly supported distribution. Under natural assumptions on the zero set of the Fourier transform of T, we show that f is compactly supported, provided g is. Similar results are proved for non-compact symmetric spaces as well. (C) 2010 Elsevier Inc. All rights reserved.