Photochemical Reaction between Tertiary Allylic Amines and Chromium Carbene Complexes: Synthesis of Lactams via a Zwitterion Aza Cope Rearrangement

Photolysis of chromium carbene complexes in the presence of tertiary allylic amines resulted in a zwitterionic aza Cope rearrangement to produce unsaturated lactams in fair yield.     

Synthesis and properties of cobalt(III) complexes of 4-substituted pyridine-capped dioxocyclams

Cobalt(III) acetate and cyanide complexes of a series of 5,12-dioxocyclams capped across the 1,8-position by 4-substituted pyridines or pyrazine were synthesized and fully characterized. Both the spectroscopic and structural parameters for these complexes were remarkably insensitive to the electronic nature of the capping group, which ranged from the pi-accepting pyrazine group to the sigma-donating 4-[(dimethylamino)phenyl]pyridyl group. All of the complexes underwent an irreversible, one-electron reduction [Co(III)-->Co(II)] at potentials ranging from -0.95 V vs saturated calomel electrode (SCE) for the pyrazine-capped cobalt acetate complex to -1.36 V vs SCE for the pyridine-capped cobalt cyanide complexes. Pyridine-capped cobalt(III) cyanide complex underwent reaction with Rh2(OAc)4 and ruthenium(II) phthalocyanine[bis(benzonitrile)] to form tetrametallic and trimetallic complexes through coordination bridging by the cyanide nitrogen lone pair. These complexes represent two quite different structural types for cyanide-bridged polymetallics. Complex has a relatively long (2.192 A) cyanide N-to-Rh bond, and the CN-Rh bond angle (157.6 degrees) is strongly distorted from linear. In contrast, complex has a substantially shortened cyanide N-to-Ru bond (2.017 A) and an almost linear arrangement along the entire bridging axis of the molecule.     

Reaction of optically active alpha-aminoallenylstannanes with aldehydes formed in situ from the Lewis-acid-catalyzed rearrangement of epoxides

Reaction of optically active alpha-oxazolidinonylallenylstannanes with oxiranes in the presence of BF3.OEt2 produced beta-hydroxypropargylamines with high syn diastereoselectivity and high enantioselectivity through an initial Lewis-acid-catalyzed rearrangement of the oxirane to the corresponding aldehyde via an alkyl, aryl, or hydride shift. This permits the use of readily available oxiranes as alternatives to aldehydes that are difficult to prepare and/or unstable.     

Performance of slotted pores in particle manufacture using rotating membrane emulsification

This paper addresses the use of different slotted pores in rotating membrane emulsification technology.Pores of square and rectangular shapes were studied to understand the effect of aspect ratio (1-3.5) and their orientation on oil droplet formation.Increasing the membrane rotation speed decreased the droplet size,and the oil droplets produced were more uniform using slotted pores as compared to circular geometry.At a given rotation speed,the droplet size was mainly determined by the pore size and the fluid velocity of oil through the pore (pore fluid velocity).The ratio of droplet diameter to the equivalent diameter of the slotted pore increased with the pore fluid velocity.At a given pore fluid velocity and rotation speed,pore orientation significantly influences the droplet formation rate: horizontally disposed pores (with their longer side perpendicular to the membrane axis) generate droplets at double the rate of vertically disposed pores.This work indicates practical benefits in the use of slotted membranes over conventional methods.     

Telechelic sulfate ionomers. I. Preparation and solution and thermal properties

New telechelic ionomers with zinc and sodium sulfate salt terminal groups on hydrogenated polybutadiene (HPB) backbones ( I ) were prepared from hydroxyl-terminated hydrogenated polybutadiene (HTHPB) of three different molecular weights (1350, 2100, and 3200 g/mol). Quantitative acid-base titration, elemental analysis, and NMR spectroscopy were used to verify the structure, and further characterization included differential scanning calorimetry (DSC) and solution viscometry. The DSC results indicated that the ionomers are free of impurities within the limit of the resolution of the method. Glass transition temperatures determined by DSC indicated that the elevation in glass transition temperature by ionic crosslinking was most strongly dependent on the molecular weight of the backbone of the telechelic ionomer. The solution viscometry results showed that the sulfation reaction did not cause either covalent crosslinking or chain scission. Furthermore, the solubility characteristics of the sulfate-terminated hydrogenated polybutadiene (STHPB) oligomers were shifted towards a preference for polar solvents by the presence of salt groups. The lower molecular weight ionomers of the series showed polyelectrolyte-like extension at very dilute concentrations in polar solvents. The onset of polymer gelation in hexane was observed for the ionomers which had the highest molecular weight backbones.     

Fabrication and characterization of gold/acrylic polymer nanocomposites

We report the method of incorporation of preformed gold nanoparticles (AuNPs) into the acrylic polymer (AP) matrices and optical, TEM characterization of AuNP/AP bulk and film composite. It was shown that incorporation of dodecanethiol-covered AuNP can be enhanced in the presence of SiO₂ nanoparticles, enabling at the same time a wider range of tailoring of composite properties for optical processing.     

Direct synthesis of 1,1'-[1,4-phenylenebis(methylene)]-bis- 1,4,8,11-tetraazacyclotetradecane octahydrochloride (AMD 3100) without the use of protecting groups

A four-step synthesis of the title compound starting from methyl acrylate, ethylenediamine, and dimethyl malonate is reported. The synthesis can be run on a multigram scale and is operationally simple. The use of protecting groups is avoided by utilizing the trioxocyclam as the key coupling intermediate.     

Absorption enhancement of oligothiophene dyes through the use of a cyanopyridone acceptor group in solution-processed organic solar cells

Improvements in the performance of small molecule-based organic solar cells have been reported through the use of a cyanopyridone acceptor group. This acceptor fragment enhances the absorbance of an oligothiophene-based dye and enables the addition of a solubilising alkyl chain that facilitates simple device fabrication from solution.