Search results for "Isomerization"
showing 10 items of 281 documents
Regio- and stereoselective synthesis of the enantiomers of monoterpene-based β-amino acid derivatives
2007
Abstract The regio- and stereospecific addition of chlorosulfonyl isocyanate to cis-δ-pinene enantiomers has furnished monoterpene-fused β-lactams. The observed regioselectivity can be explained by ab initio DFT modeling of transition state structures. In contrast with the less reactive α-pinane-fused β-lactam 4, the resulting β-lactams 5 and 13 containing an amino group connected to a secondary carbon possess similar reactivity to the cycloalkane-fused analogues and can be easily converted to the β-amino acid and its protected derivatives. The base-catalyzed isomerization of the cis-amino ester afforded the corresponding trans-amino ester in moderate yield.
Microscale synthesis of phosphatidyl-[3H]choline from 1,2-diacylglycerol. Assessment of isomerization by reversed-phase high-performance liquid chrom…
1995
The synthesis of rac-1-palmitoyl-2-oleoylglycero-3-phospho-[3H]choline of high specific activity was carried out on a microscale by making 7 mumol of rac-1-palmitoyl-2-oleoylglycerol react first with an equimolar amount of POCl3 and then of [3H]choline. After purification by thin-layer chromatography and normal-phase high-performance liquid chromatography and normal-phase high-performance liquid chromatography (HPLC), the yield of the synthesis of [3H]phosphatidylcholine (120 microCi/mumol) was 22%. rac-1-Palmitoyl-2-oleoylglycerol was purified before use by reversed-phase HPLC under conditions which were nonisomerizing and allowed the separation of 1,2- and 1,3-isomers of diacylglycerol. E…
Analysis of eicosapentaenoic and docosahexaenoic acid geometrical isomers formed during fish oil deodorization.
2006
International audience; Addition of long-chain polyunsaturated fatty acids (LC-PUFAs) from marine oil into food products implies preliminary refining procedures of the oil which thermal process affects the integrity of LC-PUFAs. Deodorization, the major step involving high temperatures, is a common process used for the refining of edible fats and oils. The present study evaluates the effect of deodorization temperature on the formation of LC-PUFA geometrical isomers. Chemically isomerized eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA) were used as reference samples. Fish oil samples have been deodorized at 180, 220 and 250 °C for 3 h and pure EPA and DHA fatty acid methyl esters…
Thermally Induced Isomerisation Kinetics of the 9c11t and 10t12c Conjugated Linoleic Acids in Triacylglycerols as Studied by FT-IR Spectrometry Aided…
2014
Published version of an article from the journal:The Open Spectroscopy Journa. Also available from the publisher:http://dx.doi.org/10.2174/1874383801004010041. Open Access Isomerisation kinetics of the 9c11t and 10t12c Conjugated Linoleic Acids (CLA) in triaclglycerols at isothermal conditions (250, 280 and 325oC) has been studied by infrared spectroscopy. Fifteen micro liter portions of the glycerides were placed in micro glass ampoules and sealed under nitrogen. Several glass tubes containing the same triacylglycerols were then subjected to thermal treatment. The glass tubes were removed at regular time intervals, cut open, and a part of the contents in each glass tube analysed by infrare…
Interplay of Chiral Side Chains and Helical Main Chains in Polyisocyanates
1996
Here we describe the synthesis of seven new copolymer series prepared by copolymerization of hexyl isocyanate with seven new chiral azo chromophores with an isocyano functionality. The resulting copolyisocyanates (Nylon 1) possess a helical polymer conformation. In the cases in which the chiral group and polymer chain are linked to the same phenyl ring (copolymer series VI-IX) a transfer of chirality to the polymer chain is possible. I.e. one helical twist sense is preferred in this case. By variation of the chiral center, polymers with preferable right- or left-handed helical conformation are accessible. The photochemical isomerization of the azo chromophore (trans → cis) is possible in hi…
MINDO/3 Study of the Rearrangement of 1-Methylcyclohexyl Cation to 1,2-Dimethylcyclopentyl Cation
1986
The rearrangement of the 1-methylcyclohexyl cation to the 1,2-dimethylcyclopentyl cation has been studied by MINDO/3 calculations, as an application of the branching mechanism model for cycloalkanes. Possible intermediates and transition states have been characterized by diagonalization of their Hessian matrixes. Two nonequivalent pathways, α and β scissions, are relatively close in energy. The calculated transition states are almost equivalent in energy to those found for cyclohexyl cation. Hence, the energy barriers are higher for the rearrangement of the 1-methyl than for cyclohexyl cation, because the former is less stable than the latter.
Mesomorphic Donor-Acceptor-substituted 1,4-Distyrylbenzenes
2009
Conjugated oligomers with terminal donor-acceptor substitution attract increasing attention in organic chemistry because of their outstanding and not seldom unexpected properties in materials science [1 – 4]. Although a variety of oligo(1,4-phenylene-vinylene)s with terminal donor-acceptor substitution (DAOPVs 1, Scheme 1) are known [5 – 22], the number of thermotropic liquid crystals among them is very low and is confined to monomers (n = 1), that means to certain push-pull substituted (E)-stilbenes [23 – 31]. The behavior of conjugatedmolecules, which are highly polar and form mesophases by self-organization, is very interesting for various applications of liquid crystals [3]. A big disad…
Influence of Pore-Volume Topology of Zeolite ITQ-7 in Alkylation and Isomerization of Aromatic Compounds
2002
The void structure of zeolite ITQ-7 (ISV structure) is discussed on the basis of catalytic reaction tests. The isomerization and disproportionation of meta-xylene, and the alkylation of benzene or toluene with either ethanol or isopropanol, on the acidic zeolite have been used as model reactions. The dimensions of its three-dimensional system of channels, with pores between 6.1 and 6.3 A and with lower tortuosity than those of beta zeolite, favor higher ratios of isomerization to disproportionation of meta-xylene, and of mono- to dialkylated products and iso- to n-propylbenzene during alkylation of benzene. These effects are enhanced with a partially coked ITQ-7.
Xylene isomerization and aromatic alkylation in zeolites NU-87, SSZ-33, β, and ZSM-5: molecular dynamics and catalytic studies
2004
The unique pore topology of zeolite NU-87, with 10-membered ring (MR) channels intersected by perpendicular 12-MR cavities, can offer new opportunities for alkylaromatics isomerization, as well as for aromatics alkylation. The catalytic performance has been studied for meta-xylene isomerization and disproportionation, as well as toluene alkylation with methanol, ethanol, propanol, and isopropanol. Product distribution was interpreted on the basis of pore topology and compared to zeolites with 12-MR (β), 10- and 12-MR (SSZ-33), and 10-MR (ZSM-5) zeolites. The presence of cavities allows more space for the location of bulky intermediates and/or products, and also traps the molecules, allowing…
Light-controlled reversible modulation of frontier molecular orbital energy levels in trifluoromethylated diarylethenes
2017
Among bistable photochromic molecules, diarylethenes (DAEs) possess the distinct feature that upon photoisomerization they undergo a large modulation of their π-electronic system, accompanied by a marked shift of the HOMO/LUMO energies and hence oxidation/reduction potentials. The electronic modulation can be utilized to remote-control charge- as well as energy-transfer processes and it can be transduced to functional entities adjacent to the DAE core, thereby regulating their properties. In order to exploit such photoswitchable systems it is important to precisely adjust the absolute position of their HOMO and LUMO levels and to maximize the extent of the photoinduced shifts of these energ…