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Isomer Formation (isomer + formation)
Selected AbstractsEffects of hydrogenation parameters on trans isomer formation, selectivity and melting properties of fatEUROPEAN JOURNAL OF LIPID SCIENCE AND TECHNOLOGY, Issue 3 2008Anar Musavi Abstract Effects of hydrogenation conditions (temperature, hydrogen pressure, stirring rate) on trans fatty acid formation, selectivity and melting behavior of fat were investigated. To this aim, soybean oil was hydrogenated under various conditions and fatty acid composition, trans isomer formation, slip melting point (SMP), solid fat content (SFC) and iodine number (IV) of the samples withdrawn at certain intervals of the reactions were monitored. A constant ratio (0.03%) of Nysosel 222 was used in the various combinations of temperature (150, 165 and 180,°C), stirring speed (500, 750 and 1000,rpm) and hydrogen pressure (1, 2 and 3,bar). Raising the temperature increased the formation of fatty acid isomers, whereas higher stirring rates decreased this formation, while changes in hydrogen pressure had no effect or slightly reduced it, depending on other parameters. Results also indicated that the trans fatty acid ratio increased with IV reduction, reached the highest value when the IV was about 70 and decreased at IV < 70 due to saturation. Selectivity values (S21) at that point ranged between 5.78 and 11.59. Lower temperatures and higher stirring rates decreased not only the trans isomer content but also the S21 values at significant levels. However, same effects were not observed with the changes in hydrogen pressure. It was determined that a high SMP does not necessarily mean a high SFC. Selective conditions produced samples with higher SFC but lower SMP, which is possibly because of higher trans isomer formation as well as lower saturation. [source] Cyclization of Trichloroacetimidates by Olefin Aminopalladation ,-Heteroatom EliminationEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 36 2009Ansis Maleckis Abstract The cyclization of ,-acetoxy- O -allyl- and ,-acetoxy- O -homoallyl-trichloroacetimidates to 4-vinyloxazolines and a 4-vinyldihydrooxazine has been efficiently achieved by olefin aminopalladation,,-heteroatom elimination. (Z)-Allylic imidates bearing a secondary ,-acetoxy group underwent PdII -catalysed cyclization to give the E isomers of 4-vinyloxazolines selectively and gave no Overman rearrangement products. Using a chiral substrate, it has been demonstrated that cyclization to 4-vinyloxazolines occurs with high chirality transfer. Stereoselective E isomer formation and chirality transfer provided a basis from which to discuss the possible reaction mechanism. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Stereoselective Construction of a Highly Functionalized Taxoid ABC-Ring System: the C2,C9 Oxa-Bridge ApproachEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 19 2005Sylvain Hamon Abstract The goal of this investigation is to assemble the 20-carbon unit 1 of the taxoid diterpene skeleton with a high level of stereocontrol by means of a three-reaction sequence developed in this laboratory. The strategy involves seven C,C bond-forming operations together with eighteen functional group transformations, circumventing the stereoselectivity issue altogether. Furthermore, there is no isomer formation and hence no need for chromatographic separation. A temporary oxa-bridge (C2/C9) was used as a problem-solving approach. The key step in the planned sequence was based on achieving the last C,C bonding between C11 and C12, following a successful C11 functionalization. X-ray analyses of 8b, 17, 18, 19, 20, and 21, together with extensive use of 800 MHz 1H (200 MHz 13C) NMR spectra, support the suggested structures. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] Escherichia coli cyclophilin B binds a highly distorted form of trans -prolyl peptide isomerFEBS JOURNAL, Issue 18 2004Michiko Konno Cyclophilins facilitate the peptidyl-prolyl isomerization of a trans -isomer to a cis -isomer in the refolding process of unfolded proteins to recover the natural folding state with cis -proline conformation. To date, only short peptides with a cis -form proline have been observed in complexes of human and Escherichia coli proteins of cyclophilin A, which is present in cytoplasm. The crystal structures analyzed in this study show two complexes in which peptides having a trans -form proline, i.e. succinyl-Ala- trans -Pro-Ala- p -nitroanilide and acetyl-Ala-Ala- trans -Pro-Ala-amidomethylcoumarin, are bound on a K163T mutant of Escherichia coli cyclophilin B, the preprotein of which has a signal sequence. Comparison with cis -form peptides bound to cyclophilin A reveals that in any case the proline ring is inserted into the hydrophobic pocket and a hydrogen bond between CO of Pro and N,2 of Arg is formed to fix the peptide. On the other hand, in the cis -isomer, the formation of two hydrogen bonds of NH and CO of Ala preceding Pro with the protein fixes the peptide, whereas in the trans -isomer formation of a hydrogen bond between CO preceding Ala-Pro and His47 N,2 via a mediating water molecule allows the large distortion in the orientation of Ala of Ala-Pro. Although loss of double bond character of the amide bond of Ala-Pro is essential to the isomerization pathway occurring by rotating around its bond, these peptides have forms impossible to undergo proton transfer from the guanidyl group of Arg to the prolyl N atom, which induces loss of double bond character. [source] Multiple-Well, multiple-path unimolecular reaction systems.INTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 4 2001Vibrationally excited 2-methylhexyl radicals formed by shock wave activation or by chemical activation can isomerize by multiple pathways to form any of six stable isomers, can fragment by multiple CH and CC bond fission pathways, and can be collisionally stabilized. Master equation simulations of chemical activation and of shock wave activation are used to explore the generic behavior of this complicated coupled system. Selecting the argon pressure in chemical activation systems that produce the 2-methyl-1-hexyl radical isomer (1) can control the yield of specific isomers. Shock heating of 1 also shows a highly regular sequence of isomer formation. This regular behavior is because the first isomerization steps are faster than subsequent steps. Other radical isomers, such as 2-methyl-3-hexyl (3), do not show such regular behavior, because the first isomerization step is slower than subsequent steps. Incubation and unimolecular rate-constant fall-off are observed in the shock wave simulations. The unimolecular rate-constant fall-off for the coupled system produces low-pressure limiting rate constants proportional to [M]n, where n can be greater than unity. The fact that n can be greater than unity is a natural feature of multichannel coupled unimolecular reaction systems, but detection of the effect in experiments may be very demanding. © 2001 John Wiley & Sons, Inc. Int J Chem Kinet 33: 246,261, 2001 [source] | ||||||||||