Search results for "Aromatization"
showing 10 items of 14 documents
A Dehydrogenase Dual Hydrogen Abstraction Mechanism Promotes Estrogen Biosynthesis: Can We Expand the Functional Annotation of the Aromatase Enzyme?
2018
Cytochrome P450 (CYP450) enzymes are involved in the metabolism of exogenous compounds and in the synthesis of signaling molecules. Among the latter, human aromatase (HA) promotes estrogen biosynthesis, which is a key pharmacological target against breast cancers. After decades of debate, interest in gaining a comprehensive picture of HA catalysis has been renewed by the recent discovery that compound I (Cpd I) is the reactive species of the peculiar aromatization step. Herein, for the first time, a complete atomic-level picture of all controversial steps of estrogen biosynthesis is presented. By performing cumulative quantum-classical molecular dynamics and metadynamics simulations of abou…
Mechanism of triplet photosensitized Diels-Alder Reaction between indoles and cyclohexadienes: theoretical support for an adiabatic pathway.
2006
Diels-Alder reactions between indoles (InHs) and 1,3-cyclohexadienes (CHDs) were achieved by using aromatic ketones as photosensitizers. For instance, irradiation of deaerated dichloromethane solutions containing benzoylthiophene (BT, 1 mM), indole (20 mM), and phellandrene (40 mM), in the presence of an acylating agent, led to the N-acetylated Diels-Alder cycloadduct in 46% yield (endo:exo ratio of 1.8:1). Energy transfer from the BT triplet to the CHD gave rise to diene dimers as byproducts. Several combinations of CHDs, InHs, and aromatic ketones were tested; the Diels-Alder reaction was found to be a general process, except when the indole nucleus was substituted at position 2 or 7 and …
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…
Non-oxidative dehydroaromatization of methane:an effective reaction regeneration cyclic operation for catalyst life extension
2015
[EN] Non-oxidative methane aromatization is an attractive direct route for producing higher hydrocarbons. It is highly selective to benzene despite the low conversion due to thermodynamic limitations, and Mo/H-ZSM-5, the first catalyst proposed for this reaction, is still considered as one of the most adequate. The major problem of this process is the severe catalyst deactivation due to the rapid build-up of carbonaceous deposits on the catalysts. Here we present an effective regeneration procedure that extends the life of Mo/zeolite based catalysts by combining reaction periods of 1.5 h with 0.5 h regeneration steps in a continuous cyclic mode and methane activation after each regeneration…
Visible-light photoredox catalyzed synthesis of pyrroloisoquinolines via organocatalytic oxidation/[3 + 2] cycloaddition/oxidative aromatization reac…
2014
Beilstein journal of organic chemistry 10, 1233-1238 (2014). doi:10.3762/bjoc.10.122
2,9-Dimethylpicene: Synthesis, Mutagenic Activity, and Identification in Natural Samples
1990
Abstract 2,9-Dimethylpicene (2,9-DMPic) has been conveniently synthesized via a new route involving oxidative photocyclization of suitable substituted diarylethylenes and has been characterized by high-resolution 400-MHz 1H-NMR spectroscopy. Furthermore, 2,9-DMPic exhibits a typical line narrowed emission spectrum in n-decane matrix frozen at 15 K (Shpol'skii effect). Its unambiguous identification in a natural sample has been performed by this technique, providing strong evidence for the formation of this compound through aromatization of triterpenoid natural precursors. The mutagenicity of this naturally occurring methylated polycyclic aromatic hydrocarbon (PAH) has been examined in six h…
Aroma behaviour during steam cooking within a potato starch-based model matrix.
2012
To help understand the organoleptic qualities of steam cooked foods, the kinetics of aroma release during cooking in a potato starch based model matrix was studied. Behaviour of components having a major impact in potato flavour were studied using solid phase micro extraction-gas chromatography (SPME-GC). Evolution of microstructure of potato starch model-matrix during steam cooking process was analyzed using environmental scanning electron microscopy (ESEM). Both aroma compounds that are naturally present in starch matrix and those that were added were analyzed. Both the aroma compounds naturally presented and those added had different behaviour depending on their physico-chemical properti…
Step growth polymerization via tandem ene and diels-alder reactions
1997
In contrast to other electron deficient enophiles or dienophiles which react with 1,4-cyclohexadiene (1,4-CHD) under aromatization, 1,2,4-triazoline-3,5-diones react in a defined reaction sequence. In a first step the 1,4-cyclohexadiene reacts via an ene-reaction. The intermediately formed substituted 1,3-cyclohexadiene immediately reacts in a Diels-Alder reaction. The regiochemistry of the Diels-Alder reaction is controlled by the solvent polarity. This reaction sequence can be used to synthesize polymers. Low-molar-mass model compounds were synthesized to elucidate the stereochemistry of the polymers. By varying the bistriazolinedione, polymers with backbones of different rigidity are ava…
Influence of preparation conditions on the catalytic performance of mo/h-zsm-5 for methane dehydroaromatization
2021
[EN] Methane, the main component of natural gas, is an interesting source of chemicals and clean liquid fuels, and a promising alternative raw material to oil. Among the possible direct routes for methane conversion, its aromatization under non-oxidative conditions has received increasing attention, despite the low conversions obtained due to thermodynamic limitations, because of its high selectivity to benzene. Mo/H-ZSM-5, the first bifunctional zeolite-catalyst proposed for this reaction, is still considered as one of the most adequate and has been widely studied. Although the mono- or bifunctional nature of the MDA mechanism is still under debate, it is generally accepted that the Mo spe…
Reactivity of cellulose during hydrothermal carbonization of lignocellulosic biomass
2020
Abstract Hydrothermal carbonization (HTC) of pure cellulose (CE) and birchwood (BW) samples was carried out at temperatures between 160 and 280 °C, 0.5 h residence time and biomass-to-water ratio 1:5, to investigate the reactivity of cellulose in lignocellulosic biomass. Thermogravimetric analysis (TGA) and Fourier transform infrared spectroscopy (FTIR) showed that the CE samples remained unaltered at temperatures up to 220 °C, but were significantly decomposed at 230 °C producing a thermal recalcitrant aromatic and high energy-dense material. FTIR showed that dehydration and aromatization reactions occurred at temperature equal or higher than 230 °C for the CE samples while a similar incre…