Oxazoline‐Based Organocatalyst for Enantioselective Strecker Reactions: A Protocol for the Synthesis of Levamisole

A chiral oxazoline‐based organocatalyst has been found to efficiently catalyze asymmetric Strecker reactions of various aromatic and aliphatic N‐benzhydrylimines with trimethylsilyl cyanide (TMSCN) as a cyanide source at ?20 °C to give α‐aminonitriles in high yield (96 %) with excellent chiral induction (up to 98 % ee). DFT calculations have been performed to rationalize the enantioselective formation of the product with the organocatalyst in these reactions. The organocatalyst has been characterized by single‐crystal X‐ray diffraction analysis, as well as by other analytical methods. This protocol has been extended to the synthesis of the pharmaceutically important drug molecule levamisole in high yield and with high enantioselectivity.     

Oxidation of triethylamine by molecular oxygen catalyzed by Ru(III)-ion

The kinetics of Ru(III) catalyzed oxidation of triethylamine by molecular oxygen has been investigated in the pH range 1.5 to 2.5 at 35°C and I=0.1 M KCl. The reaction is first order with respect to substrate, catalyst and molecular oxygen concentrations. The rate of the reaction increases with the increase of pH from 1.5 to 2.5 and then there is a slight decrease in the rate above pH 2.5. Based on the kinetic data, a mechanism for the catalytic oxidation of triethylamine is proposed. The major products in the oxidation of triethylamine are the N-oxide, diethylamine and acetaldehyde.

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, Ru(III), pH=1,5+2,5 35°C I=0,1M KCl. , . pH 1,5 2,5, pH 2,5. , . N-, .

     

Proton/Metal–Ligand Stability Constants of Complexes of Sr(II), Cr(II), and Al(III) with N-Phthaloyl Aminoacid and Benzimidazole Derivatives in Dioxane–Water Mixture

Russian Journal of Physical Chemistry A - Formation of complexes Sr(II), Cr(II), and Al(III) with ligands (1,3-dioxo-1,3-dihydro-2H-isoindol-2-yl)acetic acid (L1),...     

Geometric optimization andD P -completeness

In this paper we show a number of natural geometric optimization problems in the plane to becomplete for a classD ^P . The classD ^p contains both NP and Co-NP and is contained in ₂ ^P =P ^NP. Completeness inD ^p is exhibited under many-one and positive reductions. Further anOptP(O(logn)) result is also obtained for some of these optimization problems.Work on this paper by the first author was supported in part by NSF Grant No. MIP 85-21356 and ARO Contract No. DAAG29-85-C-0018 under Cornell/MSI. Work by the second author was supported in part by NSF Grant No. DCR 86-06366 at Ohio State and ONR Grant No. N00014-k-0045 at Harvard.On leave from Ohio State University.     

A sensitive colorimetric determination of 2,2′-dihydroxybiphenyl

Summary A colorimetric method for the determination of 2,2-dihydroxy-biphenyl in rat urine is described. The ether extract is subjected to thin-layer chromatography on silica gel-G plates in the solvent system benzene-methanol (8020) and spots corresponding to 2,2-dihydroxybiphenyl and its glucuronide derivative are eluted with ethanol. The glucuronide is hydrolysed with HCl and the 2,2-di-hydroxybiphenyl content is determined after colour development with sodium cobaltinitrite, the absorbance being read at 410 nm. The method is sensitive and reproducible. It obeys the Lambert-Beer law in the concentration range 0.7–8.9g/ml.

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Eine empfindliche kolorimetrische Methode zur Bestimmung von 2,2 -Dihydroxybiphenyl

Zusammenfassung Eine kolorimetrische Methode zur Bestimmung von 2,2-Dihydroxy-biphenyl in Rattenharn wurde beschrieben. Der ätherische Extrakt wird auf Silikagel-G-Platten dünnschicht-chromatographisch mit dem Lösungsmittelsystem Benzol-Methanol (8020) getrennt. Die dem genannten Stoff und seinem Glucuronid entsprechenden Flecken werden mit äthanol eluiert. Das Glucuronid wird mit Salzsäure hydrolysiert und der Gehalt an 2,2-Di-hydroxybiphenyl nach Ausführung der Farbreaktion mit Natriumkobalti-nitrit und Messung bei 410 nm bestimmt. Das Verfahren ist empfindlich und gut reproduzierbar. Es entspricht dem Lambert-Beerschen Gesetz zwischen 0,7 und 8,9g/ml.

     

Some constrained shortest-route problems

Summary This paper treats five constrained shortest-route problems: 1) determining the shortest route when it is constrained to pass through a given set of specified nodes; 2) determining the shortest route when it is constrained to pass through a given set of specified nodes and the specified nodes are to be visited in a fixed order; 3) finding an optimal route for the travelling-salesman problem; 4) determining the shortest route throughK sets of specified nodes when at least one node of every set of specified nodes is to occur on the shortest route; and 5) finding the shortest route through the sets of specified nodes when at least one node of every set of specified nodes is to occur on the shortest route and the sets of specified nodes are to be visited in a fixed order. The functional equation technique of dynamic programming is employed to solve problems 1), 3), and 4), while problems 2) and 5) are solved through simpler algorithms. The methods are illustrated by examples.

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Zusammenfassung Es werden fünf Kürzeste-Wege-Probleme mit besonderen Bedingungen behandelt: 1) Bestimmung des kürzesten Weges unter der Bedingung, daß die in einer gegebenen Menge spezifizierten Knoten passiert werden müssen, 2) Bestimmung des kürzesten Weges, wobei die in einer gegebenen Menge spezifizierten Knoten in einer bestimmten Reihenfolge passiert werden müssen, 3) Ermittlung der optimalen Rundreise im Travelling-Salesman Problem, 4) Bestimmung des kürzesten Weges durchK Mengen von spezifizierten Knoten, wobei aus jeder Menge wenigstens ein Knoten passiert werden muß, und 5) Bestimmung des kürzesten Weges durch Mengen von spezifizierten Knoten, wobei aus jeder Menge wenigstens ein Knoten passiert und die Mengen in einer vorgegebenen Reihenfolge aufgesucht werden müssen. Zur Lösung der Probleme 1), 3) und 4) wird die Technik der dynamischen Optimierung angewandt, während die Probleme 2) und 5) mit einfacheren Algorithmen behandelt werden. Die Methoden werden an Beispielen erläutert.

     

Effect of electron-phonon interaction on the binding energy of a wannier exciton in a polarizable medium

A new phenomenological effective interaction potential between an electron and a hole of a Wannier exciton in a polarizable medium is proposed. Binding energies of Wannier excitons are calculated variationally using this potential in several polar crystals. A close agreement between the theoretical values thus calculated and the experimental values is found in all polar crystals including thallium halides.     

Confinement and controlled release of quinine on chitosan–montmorillonite bionanocomposites

To accomplish the controlled‐release systems based on layered clay minerals, one of the best ways is to intercalate organic molecules into the interlayer gallery of clay minerals. Into a series of chitosan (CS) intercalated montmorillonite (MMT) nanocomposites, prepared via ion‐exchange route, antimalarial drug [quinine (QUI)] was loaded to act as effective drug delivery systems. Among the CS–MMT nanocomposites, higher drug adsorption with decreasing CS concentration was observed. CS–MMT and CS–MMT/QUI intercalated compounds were characterized by powder X‐ray diffraction, Fourier transform infrared spectroscopy, and thermal analysis. The synthesized nanocomposites, filled in the gelatin capsules followed by coating of Eudragit® L 100, were tested for in vitro drug release performance in the sequential buffer environments at 37 ± 0.5 °C. As no drug release (0%) was observed in the gastric fluid, the coating of Eudragit® L 100 to the capsules is highly adequate. However, the drug release rate was comparatively faster from the CS intercalated clay with compare with pure clay. The drug release kinetic data revealed that the release of QUI from the nanocomposites can be explained by modified Freundlich model. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Immobilized dimeric chiral Mn(III) salen complex on short channel ordered mesoporous silica as an effective catalyst for the epoxidation of non-functionalized alkenes

Chiral dimeric Mn(III) salen complex with 1R, 2R-(?)-diaminocyclohexane collar was immobilized on short channel large pore sized silica through a long linker of {(CH₂)₃–NH–melamine–piperazine} to investigate its performance in enantioselective epoxidation of chromenes, indene, styrene and cis β-methyl styrene in the presence of pyridine N-oxide (PyNO) as an axial base using aqueous NaOCl as an oxidant at 0 °C. The immobilized catalyst system showed high turnover frequency (TOF) and enantioselectivity for the smaller and bulkier alkenes like styrene, indene, 2,2-dimethylchromene and 6-cyano-2,2-dimethylchromene (ee up to 98%). These results are the best reported for heterogeneous catalyst under biphasic reaction conditions and were comparable to the dimeric Mn(III) salen system under homogeneous condition. The performance of the immobilized catalyst was retained for six reuse experiments. This protocol was extended to the synthesis of an antihypertensive drug (S)-Levchromakalim (ee 98%) at 1 g level.