The Structure of 9b-Methyl- 3afl,3b~,5 a~t,9a0h9bfl, 11 afl-perhydrophenanthro-[2,l-b]furan-7-one

C17H2602, M, = 262, triclinic, PI, a = 8.513(2), b = 8.970(2), c = 11.741(3)A, a = 120.51 (5), fl = 93.30(4), y = 68.43(4) ° , V = 708.9,/k 3, Z = 2, D O = 1.213, D e = 1.227 Mg m -a, g(Mo Ka, 2 = 0.7107 ,&) = 0.084 mm -1, F(000) = 288. The structure, solved by direct methods, has been refined to an R value of 5.9% using 1361 intensity measurements. The ring junctions, in sequence from either end of the polycycle, are cis, trans and cis.

Synthetic studies towards the phloroglucin natural product hyperforin: construction of the fully prenylated bicyclic core

An approach towards the highly functionalized bicyclo[3.3.1]nonan-9-one core of the complex PPAP-based natural product hyperforin, with the full complement of prenyl substituents in required stereo-disposition, is delineated.

Self-Assembly of Bile Steroid Analogues: Molecules, Fibers, and Networks

Structural and rheological features of a series of molecular hydrogels formed by synthetic bile salt analogues have been scrutinized. Among seven gelators, two are neutral compounds, while the others are cationic systems among which one is a tripodal steroid derivative. Despite the fact that the chemical structures are closely related, the variety of physical characteristics is extremely large in the structures of the connected fibers (either plain cylinders or ribbons), in the dynamical modes for stress relaxation of the associated SAFINs, in the scaling laws of the shear elasticity (typical of either cellular solids or fractal floc-like assemblies), in the micron-scale texture and the distribution of ordered domains (spherulites, crystallites) embedded in a random mesh, in the type of nodal zones (either crystalline-like, fiber entanglements, or bundles), in the evolution of the distribution and morphology of fibers and nodes, and in the sensitivity to added salt. SANS appears to be a suitable technique to infer all geometrical parameters defining the fibers, their interaction modes, and the volume fraction of nodes in a SAFIN. The tripodal system is particularly singular in the series and exhibits viscosity overshoots at the startup of shear flows, an “umbrella-like” molecular packing mode involving three molecules per cross section of fiber, and scattering correlation peaks revealing the ordering and overlap of 1d self-assembled polyelectrolyte species.

Facile conversion of electron rich benzylic hydrocarbons to carbonyl compounds by peroxydisulphate and copper ions

A convenient method for the conversion of electron rich benzylic hydrocarbons to carbonyl compounds is reported.

Structure of 2-(2,6-dimethoxyphenyl)-2,5- dimethylbicyclo[3.2.1]octane-6,8-dione

C18H2204, orthorhombic, P212~21, a = 7.343 (4), b = 11.251 (4), c = 19.357 (4)A, Z = 4, Dr, ' = 1.20, D e = 1.254 g cm -3, F(000) = 648, p(MoKa) = 0.94 cm -~. X-ray intensity data were collected on a Nonius CAD-4 diffractometer and the structure was solved by direct methods. Full-matrix least-squares refinement gave R = 0.052 (R w = 0.045) for 1053 observed reflections. The stereochemical configuration at C(2) has been shown to be 2-exo-methyl-2-endo-(2,6-dimethoxyphenyl), i.e. (3) in contrast to the structure (2) assigned earlier based on its ~H NMR data.

Structure and Conformation of an Antidepressant Drug, Nitroxazepine Hydrochloride Monohydrate

CIsH20N3Oa+.C1-.H2 O, M r = 395, orthorhombic, Pn21a, a = 7.710 (4), b = 11.455 (3), c -- 21.199 (3)/k, Z = 4, V = 1872.4/k 3, D m = 1.38, D C = 1.403 g cm -3, F(000) = 832, g(Cu Kct) = 20.94 cm -l. Intensities for 1641 reflections were measured on a Nonius CAD-4 diffractometer; of these, 1470 were significant. The structure was solved by direct methods and refined to an R index of 0.045 using a blockdiagonal least-squares procedure. The angle between the least-squares planes through the benzene rings is 125.0 (5) ° and the side chain is folded similarly to one of the independent molecules of imipramine hydrochloride.

Microsomal 11-Alpha-hydroxylation of progesterone in Aspergillius ochraceus: Part I: Characterization of the hydroxylase system

Microsomes (105,000xg sediment) prepared from induced cells of A.ochraceus was found to hydroxylate progesterone to 11-Alpha-hydroxyprogesterone (11a-OHP) in high yields (85-�90% in 30 min.) in the presence of NADPH and O2. The pH optimum for the hydroxylase was found to be 7.7. However, for the isolation of active microsomes grinding of the mycelium should be carried out at pH 8.3. Metyrapone, carbon monoxide, SKF-525A, p-CMB and N-methyl maleimide inhibited the hydroxylase activity indicating the involvement of cytochrome P-450 system. The inhibition of the hydroxylase by cytochrome Image and the presence of high levels of NADPH-cytochrome Image reductase in induced microsomes suggest that the reductase could be one of the components in the hydroxylase system.

Photochemical oxidation of thio ketones: steric and electronic aspects

Oxidation of diaryl, aryl alkyl, and dialkyl thioketones by singlet oxygen generated via self-sensitization and other independent methods yielded the corresponding ketone and sulfine in varying amounts. A zwitterionic/ diradical intermediate arising out of the primary interaction of singlet oxygen with the thiocarbonyl chromophore is believed to be the common intermediate for the ketone and sulfine. While closure of the zwitterion/diradical to give 1,2,3-dioxathietane would lead to the ketone, competing oxygen elimination is believed to lead to the sulfine. This partitioning is governed by steric and electronic factors operating on the zwitterionic/diradical intermediate.

A study in Crystal engineering: Solid-state photodimerization of chloro- and methyl-coumarins

Use of chloro and methyl substitution in crystal engineering and their interchangeability in terms of mode of packing have been examined in a series of substituted coumarins. Photoreactivity in the solid state lists been correlated with the crystallograhic structures of these coumarins. The packing of chloro-substituted aromatic compounds has been investigated by analysing the arrangement of 132 compounds. Results substantiate the use of the chloro group as a steering agent and show that the chloro and methyl groups are not always interchangeable.

Topochemical dimerization of non-parallel double bonds: 7-methoxycoumarin

X-ray crystal structure analysis of 7-methoxycoumarin reveals that the reactive double bonds are rotated by about 65° with respect to each other, the centre-to-centre distance between the double bonds being 3.83 Å. In spite of this unfavourable arrangement, photodimerization occurs in the crystalline state yielding the syn-head-tail dimer as the only product. Lattice energy calculations on ground-state molecules in crystals throw light on the mechanism of the reaction.

Concerning hypophyllanthin

The structure (1) for hypophyllanthin was confirmed by X-ray crystallography.

Cyclononitols: a flexible synthetic approach towards nine-membered carbasugar analogues

A novel, concise, stereocontrolled approach to nine-membered carbasugar analogues (cyclononitols) from a bicyclo[4.3.1]deca-2,4-dien-10-one scaffold, harbouring a `locked' cyclononane ring and latent functionalities, is described.

Preparation and catalytic studies of palladium nanoparticles stabilized by dendritic phosphine ligand-functionalized silica

Silica is a prominently utilized heterogeneous metal catalyst support. Functionalization of the silica with poly(ether imine) based dendritic phosphine ligand was conducted, in order to assess the efficacy of the dendritic phosphine in reactions facilitated by a silica supported metal catalyst. The phosphinated poly(ether imine) (PETIM) dendritic ligand was bound covalently to the functionalized silica. For this purpose, the phosphinated dendritic ligand containing an amine at the focal point was synthesized initially. Complexation of the dendritic phosphine functionalized silica with Pd(COD)Cl-2 yielded Pd(II) complex, which was reduced subsequently to Pd(0), by conditioning with EtOH. The Pd metal nanoparticle thus formed was characterized by physical methods, and the spherical nanoparticles were found to have >85% size distribution between 2 nm and 4 nm. The metal nanoparticle was tested as a hydrogenation catalyst of olefins. The catalyst could be recovered and recycled more than 10 times, without a loss in the catalytic efficiency.