Search results for "Isomerization"
showing 10 items of 281 documents
Partialsynthese neuer Ergolinderivate aus Clavinalkaloiden, 2. Mitt.1) O-Acyl-8-hydroxymethyl-6-methylergol-8-ene und -ergol-9-ene
1983
Die Titelverbindungen sind durch Acylierung von Elymoclavin (1) bzw. Lysergol (2) mit Saurechloriden, im Fall der Ester von 2 auch durch Isomerisierung von O-Acyl-1 mit aktiviertem Al2O3 darstellbar. Umgekehrt fuhrt die Acylierung von 2 in bestimmten Fallen spontan zur Bildung eines Gemisches der O-Acylderivate von 1 und 2.. Partial Synthesis of New Ergoline Derivatives from Clavine Alkaloids, II: O-Acyl-8-(hydroxymethyl)-6-methylergol-8-enes and -ergol9-enes The title compounds can be prepared by acylation of elymoclavine (1) and lysergole (2), respectively, with acid chlorides or, in the case of the esters of 2, by isomerization of O-acyl-1 with activated Al2,O3. On the other hand, in cer…
Gold(I) Complexes Nuclearity in Constrained Ferrocenyl Diphosphines: Dramatic Effect in Gold‐Catalyzed Enyne Cycloisomerization
2020
International audience; Di-tert-butylated-bis(phosphino)ferrocene ligands bearing phosphino substituents R (R=phenyl, cyclohexyl, isopropyl, mesityl, or furyl) allow tuning the selective formation of Au(I) halide complexes. Thus, dinuclear linear twocoordinate, but also rare mononuclear trigonal three-coordinate and tetrahedral four-coordinate complexes were formed upon tuning of the conditions. Both Au(I) chloride and rarer Au(I) iodide complexes were synthesized, and their X-ray diffraction analysis are reported. The significance of the control of structure and nuclearity in Au(I) complexes is further illustrated herein by its strong effect on the efficiency and selectivity of gold-cataly…
Photochemical and photocatalytic isomerization of trans -caffeic acid and cyclization of cis -caffeic acid to esculetin
2016
Abstract The photoisomerization of trans-caffeic acid to cis-caffeic acid has been studied in the presence of N2 in homogeneous aqueous solutions and in suspensions of various TiO2 catalysts. The results supported the hypothesis of an energy transfer process from TiO2 to the substrate due to the recombination of the photogenerated electron–hole pairs. The differences among the measured photostationary [cis]/[trans] ratios have been attributed to the different physico-chemical properties of the catalysts. In particular, the lowest ratio measured in the presence of Merck TiO2 was ascribed to the very low adsorption of trans-caffeic acid onto the surface of this sample. In the presence of O2 a…
A green way to gamma-lactams through a copper catalyzed ARGET-ATRC in ethanol and in the presence of ascorbic acid
2011
Abstract A ‘green’ ARGET-ATRC, for the CuCl[PMDETA] catalysed cyclo -isomerization of N -allyl-α-polychloroamides to γ-lactams is described. The process works efficiently (yields 78–96%), uses a bio-solvent, as ethanol, and exploits the reducing feature of ascorbic acid to limit, at a low level (2–4%), the amount of catalyst. To preserve the efficacy of the catalytic cycle, addition of Na 2 CO 3 is essential, which quenches the HCl released during the CuCl[PMDETA] regeneration step. Profitable features of the process are: mild reaction temperatures (25–37 °C), relatively short reaction times (usually 5 h) and low solvent volumes (2 mmol of substrate/mL of ethanol). The method, upon stoichio…
Multifunctionality in spin crossover materials
2005
Abstract One of the most important trends in the spin crossover (SCO) field is focused on the synthesis of new molecule-based functional materials in which the SCO properties may be combined with other physical or chemical properties in a synergic fashion. The current stage of investigations regarding interplay and synergic effects between SCO, magnetic coupling, liquid crystalline properties, host–guest interactions, non-linear optical properties, electrical conductivity, and ligand isomerization is highlighted and discussed.
A photoswitchable helical peptide with light-controllable interface / transmembrane topology in lipidic membranes
2021
AbstractAccording to the three-step model, the spontaneous insertion and folding of helical transmembrane (TM) polypeptides into lipid bilayers is driven by three sequential equilibria: solution-to-membrane interface (MI) partition, unstructured-to-helical folding, and MI-to-TM helix insertion. However, understanding these three steps with molecular detail has been challenged by the lack of suitable experimental approaches to rapidly and reversibly perturb membrane-bound hydrophobic polypeptides out of equilibrium. Here, we report on a 24-residues-long hydrophobic α-helical polypeptide, covalently coupled to an azobenzene photoswitch (KCALP-azo), which displays a light-controllable TM/MI eq…
Conformation resolved induced infrared activity: trans- and cis-formic acid isolated in solid molecular hydrogen
2011
We report combined experimental and theoretical studies of infrared absorptions induced in solid molecular hydrogen by different conformers of formic acid (HCOOH, FA). FTIR spectra recorded in the H(2) fundamental region (4120-4160 cm(-1)) reveal a number of relatively strong trans-FA induced Q-branch absorptions that are assigned by studying both FA-doped parahydrogen (pH(2)) and normal hydrogen (nH(2)) samples. The induced H(2) absorptions are also studied for HCOOD doped nH(2) crystals for both the trans and cis conformers that show resolvable differences. Samples containing90% of the higher energy cis-HCOOD conformer are produced by in situ IR pumping of the OD stretching overtone of tr…
Metastable ion studies. 4—mass spectral fragmentation and isomerization in the esters of chlorinated propenoic acids
1983
Metastable peaks have been used to study the fragmentation pathways of the methyl and trideuteriomethyl chloropropenoates and chloromethyl propenoate. The molecular ion peaks of the unsaturated esters are more intense than those of the saturated esters, α-Cleavage, [MOCH3]+, produces the base peak in almost all compounds, the relative abundances of the additional peaks being low for chloromethyl propenoate. The losses of H2O, CH3. and COOH. indicate the isomerization of some ionized chloro esters to the chlorinated 2-butenoic acid molecular ions. An intense loss of H2O observed for methyl 2-chloropropenoate indicates its most facile isomerization, [ester]+˙ → [acid]+˙, whereas the isomeriza…
An ab initio and DFT study of the fragmentation and isomerisation of MeP(O)(OMe)+
2004
The fragmentation behaviour of the ion MeP(O)OMe+ has been investigated using quantum mechanical calculations at the B3LYP and MP2 levels to support experiments made with an Ion Trap Mass Spectrometer. Two mechanisms for the loss of CH2O are found, one involving a 1,3-H migration to phosphorus and the other a 1,2-methyl migration to give P(OMe)2+ followed by a 1,3-H migration. In each case an ion-dipole complex is formed that rapidly dissociates to yield CH2O. The relative importance of each route has been previously determined experimentally via isotopic labelling experiments, and the theoretical results are found to be consistent with these experimental results. The mechanisms suggested i…
Preparation and reactivity of macrocyclic dienynes
2010
Abstract (1 E ,5 E )-Cyclopentadeca-1,5-dien-3-yne ( 1c ), which represents the first macrocyclic 1,5-dien-3-yne, can be obtained by thermal- or butyllithium-induced fragmentation of the corresponding 1,2,3-selenadiazole 8 . The ( E , E )-dienyne functionality causes a geometrical strain E g , which enhances the reactivity in addition ( 1c → 12 , 13 ) and cycloaddition ( 1c → 10 ) reactions and lowers the isomerization barrier to the unstrained ( E , Z )-configuration 1d ( E g = 0). A slow process 1c → 1d occurs even at ambient temperatures within several weeks.