Enantioselective syntheses of diquinane and (cis, anti, cis)-linear triquinanes

The enantioselective syntheses of diquinane and cis, anti, cis-linear triquinanes, starting from the readily available (S)-campholenaldehyde, employing an intramolecular rhodium carbenoid CH insertion reaction, are described. (C) 2010 Elsevier Ltd. All rights reserved.

Hydrothermal synthesis and characterization of CaSO4 pseudomicrorods

Calcium sulphate (CaSO4) pseudomicrorods have been synthesized by alow-temperature hydrothermal method using CaSO4 powder as a precursor and hexadecylamine as a surfactant at 180 degrees C for at different intervals of time. The powder X-ray diffraction pattern indicates that the as-formed pseudomicrorods are of orthorhombic phase with lattice parameters a = 7.0023(4) angstrom, b = 6.9939(5) angstrom and c = 6.2434(4) angstrom. Scanning electron microscopy images show that the pseudomicrorods have diameters of about 0.2-2.5 mm and lengths of about 2-10 mm. Fourier transform infrared spectroscopy shows a strong doublet near 609 and 681 cm(-1) arising from nu(4) (SO42) bending vibrations. The strongest band observed at 1132 cm(-1) is associated with nu(3) (SO42-) stretching vibrations. The band near 420-450 cm(-1) is attributed to nu(2) (SO42-) bending vibrations. The Raman spectrum exhibits an intense peak at 1008 cm(-1) associated with the SO42- mode. The photoluminescence spectrum exhibits UV bands (330, 350 nm), strong green bands (402, 436 nm) and weak blue bands (503 nm). A widening of the optical band gap was observed as the particle size decreased.

The syntheses, characterizations, X-ray crystal structures and properties of Cu(I) complexes of a bis-bidentate schiff base ligand

Bis-bidentate Schiff base ligand L and its two mononuclear complexes [CuL(CH3CN)(2)]ClO4 (1)and [CuL(PPh3)(2)]ClO4 (2)have been prepared and thoroughly characterized by elemental analyses, IR, UV-Vis, NMR spectroscopy and X-ray diffraction analysis. In both the complexes the metal ion auxiliaries adopt tetrahedral coordination environment. Their reactivity, electrochemical and photophysical behavior have been studied. Complex 1 shows reversible Cu-II/I couple with potential 0.74 V versus Ag/AgCl in CH2Cl2. At room temperature L is weakly fluorescent in CH2Cl2, however in Cu(I)complexes 1 and 2 the emission in quenched. (C) 2009 Elsevier B. V. All rights reserved.

Syntheses of the trans,meso- and racemic C11 acids, degradation products of diterpene acids

Syntheses of the isomers of the C11 acid, 1(a),3(a)- dimethylcyclohexane-1 (e),2(e),3(e)-tricarboxylic acid (A) and 1(a),3(e)-dimethylcyclohexane-1(e),2(e),3(a)-tricarboxylic acid (B), the latter by two different routes, are reported. Two of the four possible isomers of the precursor triester, trimethyl 1-methylcyclohexane-1,2,3-tricarboxylate, on individual methylation followed by hydrolysis, gave the trans,meso-acid (A), identified by comparison with an authentic sample, and the cis,trans-form (B) whose structure and configuration were proved by comparison with a specimen obtained by the unambiguous and highly stereoselective second synthesis. This demonstrated that methylation of the triester isomers occurs stereospecifically and exclusively at C-3. In the second sequence, it has been possible to assign definite conformations to four key intermediates and the final product, directly from n.m.r. spectra, from changes in these spectra accompanying specific steps, and from chemical evidence. Comparison of the n.m.r. spectra of the isomeric triesters (A) and (B) has provided unequivocal proof of the accepted trans,meso configuration for the abietic acid degradation product (A).

Enantioselective formal total syntheses of Clavukerin A and isoclavukerin A via a ring-closing metathesis reaction

Enantioselective formal total syntheses of the marine trisnorsesquiterpenes clavukerin A and isoclavukerin A, starting from (R)-limonene employing an RCM reaction as the key step, are described.

Syntheses based on cyclohexadienes. Part 2. Convenient synthesis of 6-alkylsalicylates, 6-alkyl 2,4-dihydroxybenzoate, and 2,5-dialkylresorcinols

A one pot synthesis of 6-alkylsalicylates and 6-alkyl-2,4- dihydroxybenzoates is described. Cycloaddition of 1-methoxycyclohexa-1,4- or 1,3-dienes with alkylpropiolic esters results in the regio-specific formation of 2-alkyl-6-methoxybenzoates. Thus, methyl 2-methoxy-6-methyl benzoate, methyl 2,4-dimethoxy-6-methylbenzoate, methyl 2,5-dimethoxy-6-methylbenzoate, methyl 2-methoxy-4,6-dimethylbenzoate, and ethyl 2-butyl-4,6-dimethoxybenzoate, have been prepared. By making use of this method, the synthesis of two dihydroisocoumarins namely (±)-mellein (12) and (±)-6-methoxy- mellein (14) is described. Employing a similar strategy, a novel route to 2,5-dialkylresorcinols has been developed. Stemphol (24b) and the antibiotic DB2073 (24d) have been synthesized.

Synthesis based on cyclohexadienes: Part 30 - Syntheses of 2-nor-cedrene and some analogues of funebrene

A novel method for the construction of tricyclo[5.3.1.0(1,5)]undecane and tricyclo[6.3.1.0(1,6)]dodecane frame work has been developed. Thus the alcohols 6, 18, 21 and 29 undergo Lewis acid-catalysed rearrangement to the tricyclic ketones 5, 19, 22 and 30. Dehydrogenation of 22 to the enone 23 proves the synchronous anti-migration of the methanobridge during the skeletal rearrangement. Finally, one carbon homologation of the ketones 5 and 19 leads to the syntheses of 2-norcedrene 4 and some analogues of funebrene 20 and 30.

Characterization of barium titanate fine powders formed from hydrothermal crystallization

A detailed evaluation of size, shape and microstrains of BaTiO3 crystallites produced by hydrothermal crystallization at 90 – 180 °C and 0.1 – 1.2 MPa, from amorphous TiO2· xH2O (3 < × < 8) gel and aqueous Ba(OH)2 is presented, using X-ray line-broadening and TEM studies. Whereas the concentration of Ba(OH)2 and the acceptor impurities affect the crystallite shape, the stoichimetry with respect to Ba/Ti, donor as well as acceptor impurities, and the temperature of crystallization influence the microstrains. It is shown that strains in the crystallites are related to the point defects in the lattice. Compensation of the residually present hydroxyl ions in the oxygen sublattice by cation vacancies results in strains leading to metastable presence of the cubic phase at room temperature. Studies on the diffuse phase transition behaviour of these submicron powders show that the stable tetragonal phase is produced only on annealing at high temperatures where the mobility of cations vacancies are larger. Heat-treatment reduces anisotropy and strain in undoped samples, whereas annealing is less effective in doped materials. Comparison of the crystillite size by TEM showed better agreement with the Warren—Averbach method.

In situ surface modification of molybdenum-doped organic-inorganic hybrid TiO2 nanoparticles under hydrothermal conditions and treatment of pharmaceutical effluent

Molybdenum-doped TiO2 organic-inorganic hybrid nanoparticles were synthesized under mild hydrothermal conditions by in situ surface modification using n-butylamine. This was carried out at 150 degrees C at autogeneous pressure over 18 h. n-Butylamine was selected as a surfactant since it produced nanoparticles of the desired size and shape. The products were characterized using powder X-ray diffraction, Fourier transform infrared spectrometry, dynamic light-scattering spectroscopy, UV-Vis spectroscopy and transmission electron microscopy. Chemical oxygen demand was estimated in order to determine the photodegradation efficiency of the molybdenum-doped TiO2 hybrid nanoparticles in the treatment of pharmaceutical effluents. It was found that molybdenum-doped TiO2 hybrid nanoparticles showed higher photocatalytic efficiency than untreated TiO2 nanoparticles.

Rearrangement of homobrendane derivatives. Total syntheses of racemic copacamphor, ylangocamphor, and their homologs

Rearrangement of a homobrendane derivative 8a to perhydro-1,4-methanoindenesy stem 9a could be brought about either by p-toluenesulfonic acid or boron trifluoride etherate. Similarly, rearrangement of 8b-d led to the formation of perhydro-1,4-methanoindened erivatives 9b-d. On the basis of the location of substituents in the starting material and the product, a probable mechanistic pathway has been suggested. The appropriate modification of the peripheral functionalities in 9 led to efficient total syntheses of (f)-copacamphor (15a),(f)-ylangocamphor (16a), and their homologues 15b and 16b.

Syntheses and structural studies of new bicyclic 1,3-diphenyl-1,3,2.lambda.3,4.lambda.3-diazadiphosphetidines

Reactions of cis-[(C6H5N)PC1]z(1 ) with the difunctional reagents HO(CH2)20H,H (CH3)N(CHz)zN(CH3)HH, (CH3)N(CH& OH, and HO(CHz)30Hi n the presence of triethylamine yield the new bicyclic 1,3,2X3,4h3-diazadiphosphetidines[( C6H5- N)PIZ[-O(CHZ)Zo-l (2), [(C6H5N)PlZ[-(CH3)N(CHZ)ZN(CH3)-l (319 [(C6H~N)PlZ~-(CH3)N(cHZ)20 (4), and [(C6H5 N)P],[-Q(CH2),0-] (5), respectively. The products have been characterized by elemental analyses and IR and NMR spectroscopic data. The structures of 4 and 5 have been determined by single-crystal X-ray analysis. Crystal data for 4: monoclinic, P2,/c, a = 9.823 (2) A, b = 8.608 (1) A, c = 18.423 (3) A, i3 = 90.55 (1)O, Z = 4. Crystal data for 5 monoclinic, P2,/c, a = 9.727 (2) A, b = 8.064 (2) A, c = 19.702 (4) A, @ =I 91.31 (l)', 2 = 4. The structures have been solved by direct methods and refined to R = 0.028 for 4 and R = 0.050 for 5. Compound 4 is the first example of an aminoalkoxy-l,3,2X3,4X3-diazadiphosphetidine. The PzNz ring is slightly puckered in both 4 and 5 and the puckering occurs in a manner opposite to that observed for cis-[(RN)PX],structures.