- Substituted phenol compounds useful for anesthesia and sedation
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The invention provides substituted phenol compounds and pharmaceutical compositions containing substituted phenol compounds which are useful for inducing or maintaining anesthesia or sedation in a mammal. This invention also provides methods for inducing or maintaining anesthesia or sedation in a mammal using substituted phenol compounds.
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- Oxidation of olefins by palladium(II). 18. Effect of reaction conditions, substrate structure and chiral ligand on the bimetallic palladium(II) catalyzed asymmetric chlorohydrin synthesis
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The effect of electronic factors, solvent composition, identity of the chiral bidentate, and olefin structure on the yields and enantioselectivities of the asymmetric chlorohydrin synthesis were investigated. Electronic effects on the chlorohydrin reaction were tested by oxidation of phenyl allyl ether p-substituted by H, Cl, CH3O and CN. All species gave same similar yields and enantioselectivities indicating that electronic effects are not important. Varying the solvent composition of the THF-H2O mixtures indicated that the optimal solvent mixture contains more than 85% THF. Variation of added [Cl-] indicated that the added chloride had to be greater than 0.2 M for high yields and %ee's. Under ideal conditions the enantioselectivities of the chlorohydrins from the phenyl allyl ethers were more than 90%ee. Vinylacetic acid, methyl acrylate and trans-cinnamaldehyde were unreactive under the usual reaction conditions while 2-hydroxy-3-butene and allyl acetate give lower %ee's than did the phenyl allyl ethers. Styrene and α- methylstryrene gives comparable rates of reactions but the %ee's were lower with the latter. (2,6-Diisopropyl)phenyl allyl ether and 2- hydroxy-3-butene give high %ee's indicating that steric hindrance was not a major factor. All of the chiral bridging ligands tested gave satisfactory results except for DACH. A strange case was BZOX which did not give any induction at all. Structural studies showed the ligands are not large enough to bridge both Pd(II) in the bimetallic catalyst so one Pd(II) contained both ligand groups of the bidentate ligand and was thus unreactive. The other Pd(II) of the dimer was reactive but did not contain any chiral ligands to induce optical activity.
- El-Qisairi, Arab K,Qaseer, Hanan A,Henry, Patrick M
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p. 168 - 176
(2007/10/03)
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- Thermodynamic, spectroscopic, and density functional theory studies of allyl aryl and prop-1-enyl aryl ethers. Part 1. Thermodynamic data of isomerization
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A chemical equilibration study of the relative thermodynamic stabilities of seventy isomeric allyl aryl ethers (a) and (Z)-prop-1-enyl aryl ethers (b) in DMSO solution has been carried out. From the variation of the equilibrium constant with temperature the Gibbs energies, enthalpies, and entropies of isomerization at 298.15 K have been evaluated. Because of their low enthalpies, the (Z)-prop-1-enyl aryl ethers are strongly favored at equilibrium, the Gibbs energies of the a→b isomerization ranging from -12 to -23 kJ mol-1. The entropy contribution is negligible in most reactions, but occasionally small positive values less than +10 J K-1 mol-1 of the entropy of isomerization are found. The equilibration studies were also extended to involve two pairs of related isomeric ethers with a Me substituent on C(2) of the olefinic bond. The Me substituent was found to increase the relative thermodynamic stability of the allylic ethers by ca. 3.4 kJ mol-1.
- Taskinen, Esko
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p. 1824 - 1834
(2007/10/03)
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