Studies on intramolecular Diels-Alder reactions of furo[3,4-c]pyridines in the synthesis of conformationally restricted analogues of nicotine and anabasine

En route to conformationally restricted analogues of nicotine and anabasine, a novel synthetic route to bridged anabasines is described that hinges on a domino intramolecular [4 + 2]-cycloaddition/ring opening-elimination sequence of 3-amino-substituted furo[3,4-c]pyridines. Extension of this route to bridged nicotines, however, proved abortive, even when the dienophile tether is activated by a p-tolylsulfonyl group or when the diene moiety is activated by an electron-releasing methoxy substituent. A detailed density functional theoretical study (B3LYP/6-31+G) was undertaken to provide insight into the factors that facilitate an intramolecular Diels-Alder reaction in the former case.     

A new natural product and insecticidal amides from seeds of Piper nigrum Linn

Studies on the petroleum ether soluble and insoluble fraction of ethanol extract of dried ground seeds of Piper nigrum resulted in the isolation and structure elucidation of 1 new and 11 known compounds which include 3 hitherto unreported constituents, namely, cinnamylideneacetone, 3,4-methylenedioxyphenylpropiophenone and 2-hydroxy-4,5-methylenedioxypropiophenone from this plant.     

Insecticidal amides from fruits of Piper nigrum Linn

The petroleum ether and ethyl acetate fractions of dried ground seeds of Piper nigrum Linn. afforded sixteen compounds (1-16) including one new insecticidal amide, pipwaqarine (1) and six constituents (3,4,6,7,11,15) previously unreported from this plant. The structure of (1) has been elucidated through extensive 1D-, 2D-NMR spectral studies as, 1-[13-(3',4'-methylenedioxyphenyl)-2E,4E,12E-tridecatrienoyl]-N-isopentylamide, while those of known constituents through comparison of spectral data. 1 exhibited toxicity of 30ppm against fourth instar larvae of Aedes aegypti Liston determined by WHO method. A portion of petroleum ether fraction was also subjected to GC and GC-MS analysis resulting in the identification of three compounds (17-19) using the NIST Mass spectral search program 1998 and Kovat's retention indices. Two of these compounds, 17 and 18, are reported for the first time from this plant.     

Organic Dyes Containing a 1,3‐indandione Moiety as Light Harvesting Materials

Organic dipolar compounds containing a 1,3‐indandione‐5,6‐dicarboxylic acid moiety as an electron acceptor group were examined for the feasibility of using as the light harvesting material in dye‐sensitized solar cells. Two compounds with triphenylamine donor moieties were synthesized by attaching it to 1,3‐indandione‐5,6‐dicarboxylic acid. The device made with these simple dyes achieved a quantum yield up to 2.5 %, which is comparable to the widely used dye made with cyanoacrylic acid. The spectroscopic properties of these compounds were analysed with the aid of theoretical models according to the time‐dependent density functional theory.     

Synthesis and Reactions of 1,4,4a,5,8,8a-Hexahydro-1,4-Methano-5,8-Ethenonaphthalene

The preparation of the titled compound 1 is described. Its photochemical reaction and its formation of a molybdenum carbonyl complex are also reported.     

Wave shaping through finite electromagnetic bandgap structure

Transmission mechanisms and wave steering under localized feeding conditions through a finite electromagnetic bandgap structure are investigated both experimentally and theoretically. The artificial propagating medium consists of a two-dimensional metallic wire structure dimensioned for millimetre wave operation. By analogy with electron propagation in semiconductor heterostructures, the signatures of ‘modal‘ and ‘fluid‘ propagation regimes are experimentally demonstrated. Data are then analysed through electric field patterns calculated by means of a three-dimensional solver of Maxwell‘s equations.     

Fluorescence Quenching Effects of Donor-Acceptor Pairs Through A Rigid Spacer

Heptacyclo [6.6.0.02,6.03,13.04,11.05,9,010,14] tetradecane is a cage-shaped molecule of both high symmetry (D2d) and high rigidity. In our previous reports, it has been used as an unique spacer group for electron transfer processes between a donor (D) and an acceptor (A) substituent. The D and A chromophores can be aligned along a straight line, either coplanar (0° dihedral angle) or perpendicular (90° dihedral angle) with respect to each other. Knowledge collected in this work may be useful for the design of photo-electronic devices, such as electrochemical sensors, photovoltaic cells, molecular rectifiers and switches, etc.     

Preparation of Hydroquinone‐Containing Polymers by ROMP

Polymers containing ortho‐ and para‐hydroquinone moieties 5a,b and 6a are prepared in good yields by ROMP from hydroquinone‐fused norbornadiene derivatives 1a,b and 2a . Oxidation of 5b yielded a quinone derivative 7 , which is evidenced by a strong absorption at 1656 cm^?1 in infrared spectrum.     

Reaction‐Based Colorimetric and Ratiometric Fluorescence Sensor for Detection of Cyanide in Aqueous Media

A stilbene‐based compound ( 1 ) has been prepared and was highly selective for the detection of cyanide anion in aqueous media even in the presence of other anions, such as F^?, Cl^?, Br^?, I^?, ClO₄^?, H₂PO₄^?, HSO₄^?, NO₃^?, and CH₃CO₂^?. A noticeable change in the color of the solution, along with a prominent fluorescence enhancement, was observed upon the addition of cyanide. The color change was observed upon the nucleophilic addition of the cyanide anion to the electron‐deficient cyanoacrylate group of 1 . The spectral changes induced by the reaction were analyzed by comparison with two model compounds, such as compound 2 with dimethyl substituents and compound 3 without a cyanoacrylate group. An intramolecular charge‐transfer (ICT) mechanism played a key role in the sensing properties, and the mechanism was supported by DFT/TDDFT calculations.