Search results for "cyclic"
showing 10 items of 2439 documents
Influence of structural factors and enzyme type on the reactivity and enantioselectivity of the enzymatic esterification of bicyclic meso dialcohols
1992
The meso dialcohols 1–7, obtained from the Diels-Alder adducts furan/maleic anhydride, furan/dimethyl acetylenedi-carboxylate, and cyclopentadiene/maleic anhydride, were subjected to enzymatic esterification in organic solvents. A mixture of the corresponding chiral monoacetates and the meso diacetates was obtained. It has been found that reaction rate and enantioselectivity markedly depend on substrate structure, temperature, enzyme type, and nature of the solvent. The presence of an oxygen bridge and an exo configuration are the two structural features which lead to the highest enantioselectivity values.
Kinetische Untersuchungen zu Diels‐Alder‐Reaktionen des Cyclooctins mit anschließender Aromatisierung
1984
Aus Cyclooctin (1) und den cyclischen Dienen 2a – g entstehen die Tricyclen 3a – g, die ganz unterschiedliche Stabilitat aufweisen. 3a, b, f und g zerfallen spontan. Unter Abspaltung von CO2, SO2, CO und N2 entstehen die aromatischen Verbindungen 4a – c. 3c eliminiert beim Erhitzen C2H4. 3e wird thermisch kaum mehr gespalten, aber ganz effizient bei der Photolyse, und 3d ist schlieslich gegenuber einer Aromatisierung stabil. Die thermische Ethylenabspaltung und die doppelte Photodecarbonylierung werden kinetisch untersucht. Kinetic Investigations of Diels-Alder-Reactions of Cyclooctyne with Consecutive Aromatization The tricyclic compounds 3a – g, generated from cyclooctyne (1) and the cycl…
Novel enantiomerically pure 2-amino-1,4-diols from chiral 4-hydroxymethyl-5-iodo-1,3-oxazin-2-ones
2004
Abstract Reduction of (4 S ,5 S ,6 S )-4-hydroxymethyl-5-iodo-6-methyl-1,3-oxazin-2-one 2a and (4 S ,5 S ,6 R )-4-hydroxymethyl-5-iodo-6-phenyl-1,3-oxazin-2-one 2b with tributyltin hydride in ethanol afforded 1,3-oxazin-2-one 3a and 1,3-oxazolidin-2-one 4b , respectively. Hydrolysis of 3a and 4b under basic conditions led to enantiomerically pure aminodiols 1a and 1b . Reduction of 2b in refluxing toluene led to the unexpected bicyclic tetrahydrofuro[3 a , d ]-1,3-oxazolidin-2-one 5 as the sole product.
Carbazole-based green and blue-BODIPY dyads and triads as donors for bulk heterojunction organic solar cells.
2020
Two BODIPY derivatives with one (B2) and two (B3) carbazole moieties were synthesized and applied as electron-donor materials in organic photovoltaic cells (OPV). Their optical and electrochemical properties were systematically investigated. These BODIPY dyes exhibit excellent solubility in organic solvents and present high molar extinction coefficients (1.37–1.48 × 105 M−1 cm−1) in solutions with absorption maxima at 586 nm for mono-styryl groups and at 672 nm for di-styryl groups. The introduction of the styryl moieties results in a large bathochromic shift and a significant decrease in the HOMO–LUMO energy-gaps. The BODIPY dyes show relatively low HOMO energies ranging from −4.99 to −5.1…
Cycloadditionen von Benzothiet und aromatischen Nitroso‐Verbindungen
1993
Cycloaddition Reactions of Benzothiete and Aromatic Nitroso Compounds The new heterocyclic ring systems 4H-3,1,2-benzoxathiazines 4 and 2,3-dihydro-1,2-benzothiazol 1-oxides 6 can be synthesized by cycloaddition of benzothiete (1) and aromatic nitroso compounds 3. The regioselectivity of the primary step and the secondary thermal or acid-catalyzed rearrangements are discussed.
Bicyclo[6.1.0]nonine
1988
MNDO-Rechnungen zeigen, das fur die drei konstitutionsisomeren cis-Bicyclo[6.1.0]nonine (1–3) jeweils zwei energiearme, zueinander diastereomere Konformere a und b existieren. Zur experimentellen Uberprufung werden die mit der Selenadiazol-Methode oder durch Dehydrobromierung hergestellten, hoch gespannten Bicyclen mit Hilfe von 1H- und 13C-NMR-Messungen auf die Population der Konformeren und auf deren wechselseitige Umwandlung durch Inversion der Achtringe untersucht. Bicyclo[6.1.0]nonine MNDO calculations reveal that two diastereomeric conformations a and b of low energy exist for each of the three isomeric cis-bicyclo[6.1.0]nonynes (1–3). For the experimental proof, the highly strained b…
A polyhedral oligomeric silsesquioxane-based catalyst for the efficient synthesis of cyclic carbonates
2015
Polyhedral oligomeric silsesquioxane functionalized with imidazolium chloride peripheries (POSS-Imi) was successfully synthesized through a novel synthesis protocol. The solid was extensively characterized via1H NMR, 13C NMR and IR spectroscopy as well as combustion chemical analysis, mass spectrometry and transmission electron microscopy. Moreover, an in-depth investigation through 29Si NMR was performed. POSS-Imi was used for the first time as a catalyst for the conversion of CO2 and epoxides into cyclic carbonates with excellent results in terms of both yield and selectivity. The catalyst displayed improved catalytic performance with respect to unsupported 1-butyl-3-methylimidazolium chl…
Tetraurea calix[4]arenes with sulfur functions: synthesis, dimerization to capsules, and self-assembly on gold.
2007
Various calix[4]arene derivatives, fixed in the cone conformation by decylether groups and functionalized at their wide rim by urea residues, were synthesized. In two compounds (4f,g) sulfur functions were attached to the urea groups via different spacers in order to allow binding to metal surfaces. While they exist as single molecules in polar solvents, tetraurea calix[4]arenes of this type (4) combine to form dimeric capsules in aprotic, apolar solvents. A solvent molecule is usually included in such a capsule, if no guest with a higher affinity is present. In the presence of an equimolar amount of the tetratosylurea 5, the exclusive formation of heterodimers, consisting of one molecule o…
Solvent-dependent formation of Os(0) complexes by electrochemical reduction of [Os(CO)(2,2'-bipyridine)(L)Cl2]; L = Cl(-), PrCN.
2014
Cyclic voltammetry and ultraviolet-visible/infrared (UV-vis/IR) spectroelectrochemistry were used to study the cathodic electrochemical behavior of the osmium complexes mer-[Os(III)(CO) (bpy)Cl3] (bpy = 2,2'-bipyridine) and trans(Cl)-[Os(II)(CO) (PrCN)(bpy)Cl2] at variable temperature in different solvents (tetrahydrofuran (THF), butyronitrile (PrCN), acetonitrile (MeCN)) and electrolytes (Bu4NPF6, Bu4NCl). The precursors can be reduced to mer-[Os(II)(CO) (bpy(•-))Cl3](2-) and trans(Cl)-[Os(II)(CO)(PrCN) (bpy(•-))Cl2](-), respectively, which react rapidly at room temperature, losing the chloride ligands and forming Os(0) species. mer-[Os(III)(CO) (bpy)Cl3] is reduced in THF to give ultimate…