caa a22 4500 475760468 CHVBK 20180406123549.0 cr unu---uuuuu 170329e20001001xx s 000 0 eng 10.1007/BF02496333 doi (NATIONALLICENCE)springer-10.1007/BF02496333 The reactivity of 3,5-dimethylidene-2,2,6,6-tetramethyl-4-oxopiperidin-1-oxyl and its diamagnetic N -methyl analog in nucleophilic addition of amines and diels—Alder dimerization [Elektronische Daten] [A. Shapiro, O. Borbulevich, S. Koroteev, A. Malievskii] 3,5-Dimethylidene-1,2,2,6,6-pentamethyl-4-oxopiperidine was shown by the kinetic method to be less reactive than 3,5-dimethylidene-2,2,6,6-tetramethyl-4-oxopiperidin-1-oxyl in the nucleophilic addition of secondary amines and Diels—Alder dimerization. According to the quantum-chemical AM1 calculations, this is due to the difference in the structures of the activated complexes (in the reactions with amines) and to the "press” effect created by theN-methyl group that impedes the necessary cycle flattening (in the Diels—Alder reaction). Kluwer Academic/Plenum Publishers, 2000 nitroxyl radical nationallicence diamagnetic analog nationallicence piperidine nationallicence dimerization nationallicence kinetics nationallicence rate constants nationallicence "press” effect nationallicence AM1 method nationallicence quantum-chemical calculations nationallicence Shapiro A. Institute of Biochemical Physics, Russian Academy of Sciences, 4 ul. Kosygina, 117977, Moscow, Russian Federation aut Borbulevich O. A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 ul. Vavilova, 117813, Moscow, Russian Federation aut Koroteev S. Institute of Biochemical Physics, Russian Academy of Sciences, 4 ul. Kosygina, 117977, Moscow, Russian Federation aut Malievskii A. Institute of Biochemical Physics, Russian Academy of Sciences, 4 ul. Kosygina, 117977, Moscow, Russian Federation aut Russian Chemical Bulletin Kluwer Academic Publishers-Plenum Publishers 49/10(2000-10-01), 1682-1686 1066-5285 49:10<1682 2000 49 11172 https://doi.org/10.1007/BF02496333 text/html Onlinezugriff via DOI 1 research-article jats NATIONALLICENCE 856 40 https://doi.org/10.1007/BF02496333 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Shapiro A. Institute of Biochemical Physics, Russian Academy of Sciences, 4 ul. Kosygina, 117977, Moscow, Russian Federation aut NATIONALLICENCE 700 1- Borbulevich O. A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 ul. Vavilova, 117813, Moscow, Russian Federation aut NATIONALLICENCE 700 1- Koroteev S. Institute of Biochemical Physics, Russian Academy of Sciences, 4 ul. Kosygina, 117977, Moscow, Russian Federation aut NATIONALLICENCE 700 1- Malievskii A. Institute of Biochemical Physics, Russian Academy of Sciences, 4 ul. Kosygina, 117977, Moscow, Russian Federation aut NATIONALLICENCE 773 0- Russian Chemical Bulletin Kluwer Academic Publishers-Plenum Publishers 49/10(2000-10-01), 1682-1686 1066-5285 49:10<1682 2000 49 11172 Metadata rights reserved Springer special CC-BY-NC licence nationallicence BK010053 XK010053 XK010000 NATIONALLICENCE NATIONALLICENCE NL-springer