A high-power X-band pulsed microwave induced catalytic decomposition of methane with integral acoustic measurements

A high-power microsecond pulsed microwave system operating in the X-band region was used for the catalytic conversion of methane. Microwave microsecond pulses at repetition rates of 50 and 80 Hz were used to initiate chemical reactions. The Microwave-Induced Acoustic technique was employed in combination with gas chromatography for on-line detection of chemical products. Methane was converted to C₂ and C₃ hydrocarbons. The selectivity of ethane in hydrocarbon products can be >90 %. The contribution of hydrogen evolution and carbon deposition has been shown to be important. A comparison between previous experiments performed with millisecond pulse durations is given.     

Visible light induced photocatalytic reaction of rhodamine B dye via 12-tungstosilicic acid in water

Using 12-tungstosilicic acid (SiW124-) as the catalyst, rhodamine B (RhB) dye in an aerated aqueous solution can undergo an effective photocatalytic stepwise N-deethylation process under visible light irradiation, and dioxygen is reduced to hydrogen peroxide by the reducedSiW12 4-. This provides the potential for moving polyoxometalate-based photocatalytic processes from the near-UV into the visible region of the spectrum.     

Chiral environments for asymmetric hydrogenation of model didehydro-amino acid residues

Dedicated to Professor John C. Sheehan on the occasion of his sixty-fifth birthday Nmr and glc analysis of diastereoisomeric mixtures of dipeptides has been used to study the asymmetric hydrogenation of model benzoyldidehydro- and trifluoroacetyldidehydro-dipeptide methyl esters. Chiral enhancement of one isomeric form appears to be independent of the N-terminal acyl group, but is significantly influenced by the choice of amino-acid in the C-terminal position. C-Terminal aromatic amino-acids and their derivatives give the best chiral enhancement during hydrogenation of a neighbouring dehydroamino-acid residue.     

Imidomethylation of C-nucleophiles using O-phthalimidomethyl trichloroacetimidate and catalytic amounts of TMSOTf

The O-phthalimidomethyl trichloroacetimidate (1), as a latent aminomethylating agent, exhibits high electrophilicity towards a variety of C-nucleophiles in the presence of catalytic amounts of TMSOTf and mild reaction conditions. The nucleophiles include aromatics, alkenes and active methylene compounds 2-11 whereby a phthalimidomethyl group could be introduced to give compounds 12-22. Removal of the phthaloyl group gave the respective amines, β-amino ketones, and β-amino acids. The O-(trichloroacetamido)methyl trichloroacetimidate (35) was also found to be a good amidomethylating agent.     

Direct evidence for the gas phase thermal polymerization of styrene. Determination of the initiation mechanism and structures of the early oligomers by ion mobility

We present here direct evidence for the thermal self-initiated polymerization of styrene in the gas phase and establish that the initiation process proceeds via essentially the same mechanism (the Mayo mechanism) as in condensed phase polymerization. Furthermore, we provide structural identifications of the dimers and trimers formed in the gas phase.     

A polystyrene-supported triflating reagent for the synthesis of aryl triflates

An insoluble polystyrene-supported triflating reagent has been prepared by suspension co-polymerization of N-(4-vinylphenyl)trifluoromethanesulphonimide, styrene and the JandaJel^® cross-linker. This reagent, in the presence of triethylamine, allows for the efficient synthesis of aryl triflates from a wide range of phenols in a process that permits the desired product to be isolated from the reaction mixture in essentially pure form via several filtration and concentration operations. Adding to the utility of this reagent is its ability to be easily recovered, regenerated and reused. Both soluble and insoluble bifunctional polymers containing trialkylamine moieties in addition to triflimide groups were also prepared and examined as triflating reagents. Unfortunately these reagents afforded only modest yields of the desired products in representative reactions.     

SYNTHESIS AND THERMAL PROPERTIES OF POLYBENZOXAZOLE FROM SOLUBLE PRECURSOR WITH HYDROXY-SUBSTITUTED POLYENAMINONITRILE

Aromatic polybenzoxazole (PBO) precursor, hydroxy-substituted polyenaminonitrile, was prepared by direct polycondensation of 1,4-bis(l-chloro-2,2-dicyanovinyl)benzene (CCB) and 4,6-diaminoresorcinol dihydrochloride (DAR) using pyridine and N,N-dimethylacetamide as condensing agent and solvent. The precursor has good solubility in polar aprotic solvent which is due to the strong dipolar nature of the main chain. The soluble precursor was subjected to thermal cyclization in an inert atmosphere to convert it into the corresponding PBO, which has its 5% weight loss temperature at 540℃ The fully cyclized PBO were characterized by FT-IR and TGA. The introduction of 10% mol 1,3,5-benzenetricarboxylic chloride (BTC) into the main chain not only has little effect on the solubility of PBO precursor but also raises its 5% weight loss temperature to 552℃ and char yield at 700℃ for the cyclized PBO with BTC.     

CIDEP studies of a radical pair produced upon excitation of the molecular complex of acridine and acridan in the solid state at room temperature

The time-resolved ESR signal of a triplet radical pair was detected upon excitation of a solid mixture of acridine and acridan at room temperature. The ZFS parameters of the triplet radical pair were determined to be D=−0.0100 cm⁻¹ and E=0.00053 cm⁻¹. The structure of the radical pair is discussed on the basis of the data.