Amino acid derivatives of C60 fullerene were studied by solid-state NMR spectroscopy. The spectroscopic data given in this work suggest that the compounds under study are derivatives of C60 fullerene and corresponding amino acids. The fullerene core is attahced to the amino acids via the amino group.
A comparative study of the relative antioxidant activity (RAA) of fullerene С 60 and its amino acid derivatives is performed via amperometry and fluorimetry. The sizes of nanoparticles in the corresponding colloidal solutions are determined via dynamic light scattering (photon correlation spectroscopy) to study the effect the steric factors of the investigated compounds have on the magnitude of the RAA. Data are subjected to statistical correlation regression analysis using results obtained for the RAA dependence of fullerene С 60 and salt forms of its acid derivatives on the corresponding sizes of nanoparticles in colloidal aqueous solutions. A close negative (inverse) correlation is identified between the size of nanoparticles in a solution and their antioxidant properties, with a pronounced synergic effect related to the influence of both chemical structure of the studied compounds and their structural organization in colloid solution. It is found that the structure of a substituent in a molecule of amino acid derivative of fullerene С 60 also influences the size of the forming nanoparticles. At the same time, reductive properties of amino acid derivatives of fullerene С 60 are generally determined by the electron effects of substituents.
Means of synthesis are developed and a physicochemical study of ligands based on 2,3,6-О-cellulose derivatives for asymmetric hydrogenation catalysts is performed.
Esterification of 3-hydroxy-2-naphthoic acid with homologous primary and secondary alkenyl alcohols with different chain lengths in the presence of N,N'-carbonyldiimidazole (CDI) and 1,8-diazabicyclo[ 5.4.0]undec-7-ene (DBU) in N,N-dimethylformamide gave the corresponding esters.
An effect of modification conditions of powdered nickel-cobalt catalysts on enantioselectivity of hydrogenation of ethyl acetoacetate has been studied. Addition of NaBr to the modifying solution of RR-(+)-tartaric acid does not improve enantioselectivity of the catalyst. When the Ni-Co catalysts are modified with amino acids, the best results are obtained with L-β-phenylalanine (17% ee).
Electroreduction of an equilibrium menthone-isomenthone mixture at a controlled potential in a diaphragm cell on various cathodes was studied. The influence exerted by the nature of a solvent and of an electrode, electrode material, and various additives on the reduction stereoselectivity of ketones was examined. Conditions for a predominant formation of the most stable of the four isomeric alcohols being formed, menthol, were found.
The surface cobalt concentration in the powder bimetallic Ni-Co catalysts (ratio Co/Ni ≈ 0.25) was shown by X-ray photoelectron spectroscopy to be 2–4 times that of the volume content. Both Ni and Co exist in mixed valent states, viz. , M 0 and M 2+ , even after catalyst reduction. After ethyl acetoacetate hydrogenation, the cobalt content on the surface increases 16 times compared to that in the bulk. In addition, the metals are partially oxidized, and the amount of Ni 0 and Co 0 in the surface layers of the catalyst decreases 2–3 times. It was assumed that the increase in the cobalt content indicates an increase in the amount of cobalt complexes that involve the modifier, substrate, and reaction product, and which shield the nickel active sites. As a result, the enantioface differentiating ability of the catalyst decreases.
The influence of the metal content on the support, the conditions of the preparation of the catalysts, and the reaction conditions on the enantioselectivity of the liquid-phase hydrogenation reaction of ethyl acetoacetate in the presence of Ni and Ni-Co catalysts supported on Al2O3 and SiO2, and modified by RR(+)-tartaric acid, was investigated. The maximal optical yield (66–76%) was obtained for the 20% Ni/Al2O3 catalyst.
ChemInformVolume 21, Issue 9 Preparative Organic Chemistry ChemInform Abstract: Stereoselective Hydrogenation of a Menthone - Isomenthone Mixture on Heterogenous Ni, Ni-Co, and Co Catalysts. N. D. ZUBAREVA, N. D. ZUBAREVA Inst. org. khim. im. Zelinskogo AN SSSR, MoskvaSearch for more papers by this authorE. I. KLABUNOVSKII, E. I. KLABUNOVSKII Inst. org. khim. im. Zelinskogo AN SSSR, MoskvaSearch for more papers by this authorL. A. KHEIFITS, L. A. KHEIFITS Inst. org. khim. im. Zelinskogo AN SSSR, MoskvaSearch for more papers by this author N. D. ZUBAREVA, N. D. ZUBAREVA Inst. org. khim. im. Zelinskogo AN SSSR, MoskvaSearch for more papers by this authorE. I. KLABUNOVSKII, E. I. KLABUNOVSKII Inst. org. khim. im. Zelinskogo AN SSSR, MoskvaSearch for more papers by this authorL. A. KHEIFITS, L. A. KHEIFITS Inst. org. khim. im. Zelinskogo AN SSSR, MoskvaSearch for more papers by this author First published: February 27, 1990 https://doi.org/10.1002/chin.199009075AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume21, Issue9February 27, 1990 RelatedInformation
A study was carried out on the effect of the nature of the catalysts, additives, and solvents on the stereoselectivity of the liquid-phase hydrogenation of an equilibrium menthone-isomenthone mixture to give menthols. Neoisomenthol, which is the least stable of all the menthol isomers, was predominantly formed on a cobalt catalyst modified by (+)-tartaric acid in ethyl acetate at 130°C and 10 MPa.
ChemInformVolume 19, Issue 45 Preparative Organic Chemistry ChemInform Abstract: Heterogeneous Ni-Co-Catalysts in the Enantioselective Hydrogenation of Ethyl Acetoacetate. N. D. ZUBAREVA, N. D. ZUBAREVA Inst. org. khim. im. Zelinskogo AN SSSR, MoskvaSearch for more papers by this authorE. I. KLABUNOVSKII, E. I. KLABUNOVSKII Inst. org. khim. im. Zelinskogo AN SSSR, MoskvaSearch for more papers by this author N. D. ZUBAREVA, N. D. ZUBAREVA Inst. org. khim. im. Zelinskogo AN SSSR, MoskvaSearch for more papers by this authorE. I. KLABUNOVSKII, E. I. KLABUNOVSKII Inst. org. khim. im. Zelinskogo AN SSSR, MoskvaSearch for more papers by this author First published: November 8, 1988 https://doi.org/10.1002/chin.198845112AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume19, Issue45November 8, 1988 RelatedInformation
For Raney Cu-Ru and Cu-Pd catalysts non-additive changes in the strength of the catalyst-hydrogen bond and in the catalytic activity and enantioselectivity were found to occur with changing composition, indicating the presence of a ligand effect in these systems.
Thermal-desorption and isotope methods were used to investigate the state of hydrogen found on the surface of ruthenium framework catalysts. The possibility of the migration of chemisorbed hydrogen from the ruthenium was demonstrated.