Enantiomer differentiation in intramolecular carbon—hydrogen insertion reactions of racemic secondary alkyl diazoacetates catalyzed by chiral dirhodium(ii) carboxamidates

Highly efficient kinetic resolution of racemic secondary alkyl diazoacetates in intramolecular carbon-hydrogen insertion reactions has been achieved using chiral dirhodium(ii) carboxamidates. Products formed from catalytic diazo decomposition of racemic 2-octyl diazoacetate and, separately, its (2R)- and (2S)-enantiomeric forms, as well as bothcis- andtrans-2-methylcyclohexyl diazoacetates, have been systematically evaluated. Enantioselectivities up to 99 %ee have been obtained for -lactone formation. -Lactone production has been observed and, although minor with cyclohexyl diazoacetates, is the major insertion pathway for diazo decomposition of 2-octyl diazoacetate.Dedicated to Academician of the RAS N. S. Zefirov (on his 60th birthday).Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1798–1803, September, 1995.Financial support for this research from the National Institutes of Health (GM 46503) and the National Science Foundation of the United States is gratefully acknowledged. We thank D. A. Pierson for her preparation of 2-methylcyclohexyl diazoacetates and preliminary studies of their diazo decomposition and A. Melekhov from the Higher College of Chemistry for his preparation and catalytic studies of rac-2-octyl diazoacetate.     

Real-time onboard wind and windshear determination,part 2: Detection

This paper is concerned with windshear detection in connection with real-time wind identification (Ref. 1). It presents a comparative evaluation of two techniques, one based on the shear/downdraft factor and one based on the wind difference index. The comparison is done with reference to a particular microburst, that which caused the 1985 crash of Flight Delta 191 at Dallas-Fort Worth International Airport.The shear/downdraft factor has the merit of combining the effects of the shear and the downdraft into a single entity. However, its effectiveness is hampered by the fact that, in a real situation, the windshear is accompanied by free-stream turbulence, which tends to blur the resulting signal. In turn, this results in undesirable nuisance warnings if the magnitude of the shear factor due to free-stream turbulence is temporarily larger than that due to true windshear. Therefore, proper filtering is necessary prior to using the shear/downdraft factor in detection and guidance. One effective way for achieving this goal is to average the shear/downdraft factor over a specified time interval . The effect of on the average shear/downdraft factor is studied.     

The influence of cyclodextrin complexation on proton transfer in piperidinomethyl-2-naphthol

Summary Piperidinomethyl-2-naphthol forms inclusion complexes with -cyclodextrin with an equilibrium constant of 265M ^–1 in aqueous solution. The proton transfer equilibrium between the neutral and the zwitterionic form is strongly influenced by the association.

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Der Einfluß der Komplexierung mit -Cyclodextrin auf das Protontransfer-Gleichgewicht in Piperidino-2-naphthol (Kurze Mitt.)

Zusammenfassung Piperidinomethyl-2-naphthol bildet Einschlußkomplexe mit -Cyclodextrin mit einer Gleichgewichtskonstante von 265M ^–1. Das Protontransfer-Gleichgewicht zwischen neutraler Form und zwitterionischer Struktur wird durch diese Assoziation stark beeinflußt.

     

Base-catalyzed cyclization of β-(2-arylaminoethoxy)styrenes

-(2-Arylaminoethoxy)styrenes undergo cyclization in the presence of KOH to giveN-aryl-2-benzyloxazolidines inca. 90 % yield. The structures of the products were confirmed by IR and NMR spectroscopy.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 340–341, February, 1994.     

Alkylation of cyclododecanone with α,ω-dibromoalkanes under conditions of phase-transfer catalysis

Alkylation of cyclododecanone with ,-dibromoalkanes Br(CH) _n Br (n=3, 4, 5) under conditions of phase-transfer catalysis in the presence of KOH results in the formation of either bicyclic ketones forn=3 and 5 or a mixture of bicyclic and spirocyclic ketones forn=4.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1436–1438, August, 1994.     

On invexity-type nonlinear programming problems

In this paper, we propose a new class of nonlinear programing, called SFJ-invex programming. The optimality characterization shows that a problem is SFJ-invex if and only if a Fritz John point together with its multiplier, is a Fritz John saddle point of the problem. Under any constraint qualification assumption, a problem is SFJ-invex if and only if a Kuhn-Tucker point together with its multiplier is a Kuhn-Tucker saddle point of the problem. Furthermore, a generalization of the SFJ-invex, class is developed; the applications to (h, )-convex programming, particularly geometric programming, and to generalized fractional programming provide a relaxation in constraint qualification for differentiable problems to get saddle-point type optimality criteria.The author wishes to thank the referee for helpful comments.     

Preparation and characterization of a viscosity index improver for naphthenic and paraffinic base oils

Copolymers of -methyl styrene and 2-ethylhexyl acrylate were prepared in a benzene solution. The presence of the copolymers were confirmed by solubility, IR and NMR tests. The molecular weight and the polydispersity of the polymers were estimated by GPC. The copolymers obtained were blended with paraffinic and naphthenic base oils. The viscosity, the viscosity index (VI) the Q value as well as the stability to shear and oxidation were obtained for these blends. The results are compared with the results obtained with an oil blend containing a commonly used high temperature additive. Two of the copolymers obtained have shown to be good alternatives for specific applications.Presented at the Symposium, 76^th CSC Congress, Sherbrooke, Quebec, May 30–June 3, 1993, honoring Professor Donald Patterson on the occasion of his 65^th birthday.     

Interactions between octyl-β-D-glucoside and α-amino acids or small peptides

The interactions between octyl--D-glucoside and glycine in water have been investigated by surface tension, viscosity, and density measurements. The results show that the -amino acid causes an unexpected lowering of the critical micellar concentration of octyl--D-glucoside. Such a finding has been interpreted in temss of dipole-dipole interactions between the hydrophilic site of the surfactant and the peptidic cosluttes. From three to seven amino acid molecules have been estimated to be coordinated with each glucoside unity in the micellar state. The research has been extended to glycine oligopeptides and L-lysine. The latter compound has effects similar to those observed with glycine whereas diglycine and triglycine show weaker effects on the micellization process.     

Study of chemical bonds in a-B/C:H films by electron probe microanalysis

This paper describes the study of chemical bonds in amorphous hydrogen rich boron/carbon (a-B/C:H) films by electron probe microanalysis. The films were deposited on Si single crystals by plasma chemical vapour deposition with a precursor-carborane (C₂B₁₀H₁₂) in a laboratory setup. A film thickness and B/C ratio up to a value of 8000 Å and 4, respectively, have been obtained. The analysis of boron and carbon X-ray emission spectra has shown that the nearest order in the films is characterized by the coexistence of C-C, B-C and B-B bonds for B/C 1 and of B-B and B-C bonds for B/C 4. After two years exposure in air the oxygen content in the films increases from 2–5 to 15–20 at.%.     

Polynitro-substitutedN-alkylalkaneimidoyl chlorides

The reaction of -fluorosubstituted polynitroalkylaldimines with HCl results in replacement of the fluorine atom by a chlorine atom. The hitherto unknown -chlorosubstituted polynitroalkylaldimines have been obtained, and their X-ray structural investigation has been performed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 440–443, March, 1994.