Search results for "Conjugated"
showing 10 items of 288 documents
Conjugate Alkynylation of Electrophilic Double Bonds. From Regioselectivity to Enantioselectivity
2018
This review surveys the historical efforts addressed toward the development of the conjugate alkynylation reaction. The regio- and enantioselective conjugate alkynylation of electron-deficient double bonds, most commonly unsaturated carbonyl compounds, has been an elusive reaction for a long time. Intensive research during the last decades has resulted in the identification of a number of effective reagents and catalysts to perform this reaction. Non-stereoselective conjugate alkynylation of unsaturated carbonyl compounds was first achieved by using preformed alkynyl organometallics and later with terminal alkynes under catalytic conditions. These methods paved the way for the development o…
Determination of the absolute configuration of (−)-abietic acidviaits (4R,5R,9R,10R)-7,13-abietadien-18-ylp-bromobenzoate derivative
2006
The absolute configuration of the title bromo derivative of abietic acid, C27H35BrO2, has been determined. The structural analysis confirms the absolute stereochemistry for (−)-abietic acid proposed by Bose & Struck [(1959). Chem. Ind. (London), pp. 1628–1630] on the basis of optical rotatory dispersion measurements. The molecule exhibits a trans anti 6/6/6 tricyclic hydrocarbon skeleton, with the cyclohexane ring in the expected chair form and the two cyclohexene rings, the double bonds of which are conjugated, in half-chair conformations.
From linear quaterthiophene to sulflower: A comparative theoretical study
2009
Abstract In this paper, we report a theoretical study of four types of thiophene-based oligomers showing the same number of C C double bonds and very different molecular structures. The comparative study has been performed on the basis of B3LYP/6-31G∗∗ calculations. The way the thiophene rings are linked together has a remarkable influence on the molecular and electronic properties. Linear quaterthiophene and heptathienoacene show similar aromatic structures but a loss of π-conjugation is detected for the latter due to the condensation of thiophene rings. A blue shift of the most intense electronic transition is predicted for fused heptathienoacene compared with non-fused quaterthiophene. C…
Experimental and theoretical studies on corals. I. Toward understanding the origin of color in precious red corals from Raman and IR spectroscopies a…
2009
An attempt to explain the origin of the vivid red color in precious pink and red corals was undertaken. Raman and IR spectroscopies were applied to characterize white, pink and red corals. The position of the Raman signal near 1500 cm −1 of some corals and pearls was associated by several authors with the presence of the mixture of all-trans-polyenic pigments, containing 6 – 16 conjugated C C bonds or β-carotenoids. This hypothesis was examined theoretically by performing extensive B3LYP-DFT calculations of vibrational spectra of the model polyenic compounds. The B3LYP/6-311++G ∗∗ predicted positions of the dominating Raman mode depend on the number of C Cu nits (Cn parameter) and can be ac…
Interaction Mechanisms between guaiacols and lignin: the conjugated double bond makes the difference.
2011
Lignin is considered to be responsible for a selective sorption of phenolic compounds on wood. In order to investigate the mechanisms involved, two similar guaiacol compounds--only differing by the nature of the para side chain--were adsorbed on oak wood extracted lignin. Vapor sorption-desorption isotherms indicated that about 3.5 wt % of 4-vinylguaiacol is adsorbed near saturation whereas it is only 0.8% for 4-ethylguaiacol. For both compounds, the isotherms displayed a hysteresis though significantly greater for 4-vinylguaiacol. Analyses of the hydroxyl stretching region of FTIR spectra of the lignin/4-ethylguaiacol and lignin/4-vinylguaiacol complexes indicated that physisorption via hy…
Asymmetric diastereodivergent Michael addition of 2-chloromalonate esters to conjugated imines enabled by catalyst metal change
2019
Despite recent progress in asymmetric diastereodivergent reactions leading to products bearing two stereogenic centers, little research has been devoted to processes were a stereogenic center and a double bond are formed. Here, we report the asymmetric diastereodivergent Michael addition of 2-chloromalonate esters to N-tosyl β,γ-unsaturated α-ketimino esters to give chiral α,β-dehydro-α-aminoesters bearing either a Z or E enamine moiety, using pyBOX-metal complexes. Diastereodivergency is achieved by simply changing the metal ion from a trivalent La(III) to a divalent Ca(II) ion, providing the Z or E enamines. Computational studies reveal the crucial role of London interactions between the …
Die Isomerisierung des Linolsäuremethylesters mit Rhodiumkomplexen
1977
Die isolierten Doppelbindungen des Linolsauremethylesters konnen mit Rhodiumkomplexen und Zinn(II)chlorid-Dihydrat als Katalysatorsystem konjugiert werden. Die Abhangigkeit der Reaktion von verschiedenen Phosphor- und Stickstoffliganden am Rhodium wurde untersucht. Tri-p-tolylphosphin als Ligand ergab den aktivsten Katalysator, der auch noch bei 25°C eine wirkungsvolle Isomerisierung bewirkt. The Isomerisation of Linoleic Acid Methyl Ester with Rhodium Complexes The isolated double bonds of the linoleic acid methyl ester were conjugated with rhodium complexes plus SnCl2 · 2H2O as catalysts. The dependence of the reaction on phosphorous and nitrogen ligands was studied. The most active catal…
Designing conjugated microporous polymers for visible light-promoted photocatalytic carbon–carbon double bond cleavage in aqueous medium
2018
The production of valuable carbonyl compounds directly from alkenes via carbon–carbon double (CC) bond cleavage is a highly important reaction. As a promising alternative to traditional metal-catalyzed thermal reaction conditions, photocatalysis offers an environmentally friendly and sustainable synthetic strategy. However, most photocatalysts used so far were homogeneous, molecular and transition metal-based catalytic systems. Here, we report a structural design strategy of conjugated microporous polymers (CMPs) as a class of metal-free, heterogeneous, stable and reusable photocatalysts for visible light-promoted CC bond cleavage reaction. Via different electron donor and acceptor combinat…
Design, synthesis and photovoltaic properties of [60]fullerene based molecular materials
2005
Abstract The possibility to use new organic semiconductor materials, in place of silicon wafers, in the fabrication of photovoltaic devices on substrates offer the prospect of lower manufacturing costs, particularly for large area applications. Thus, one of the most promising areas in fullerene research involves its potential application, mixed with conjugated polymers, in mimicking photosynthesis and in the related solar energy conversion. The tendency to phase segregation in blends of C60 derivatives and conjugated polymers has to be optimized to improve both charge photogeneration and transport in photovoltaic devices. In order to optimize device performances, a great deal of work has be…
Electronic communication through pi-conjugated wires in covalently linked porphyrin/C60 ensembles
2005
Novel photo- and electroactive triads, in which pi-conjugated p-phenylenevinylene oligomers (oPPVs) of different length are connected to a photoexcited-state electron donor (i.e., zinc tetraphenylporphyrin) and an electron acceptor (i.e., C(60)), were designed, synthesized, and tested as electron-transfer model systems. A detailed physicochemical investigation, concentrating mainly on long-range charge separation and charge recombination and kinetics, revealed small attenuation factors beta of 0.03+/-0.005 A(-1). Energy matching between the HOMO levels of C(60) and oPPVs emerged as a key parameter for supporting molecular-wire-like behavior: It favors rapid and efficient electron or hole in…