Synthesis of 2,5-bis(spirocyclohexane)-substituted nitroxides of pyrroline and pyrrolidine series, including thiol-specific spin label: an analogue of MTSSL with long relaxation time.
The nitroxides of 7-azadispiro[5.1.5.2]pentadecane and 7-azadispiro[5.1.5.2]pentadeca-14-ene series have been prepared, including thiol-specific methane thiosulfonate spin label for site-directed spin labeling. The effect of spirocyclohexane moieties on chemical and spectral properties has been studied. The obtained temperature dependencies of electron spin relaxation parameters demonstrate that new nitroxides may be suitable for PELDOR distance measurements at 80-120 K. Moreover, the new nitroxides demonstrated much higher stability toward reduction by ascorbate than spirocyclohexane-substituted nitroxides of piperidine series and showed 1.3-3.14 times lower reduction rates compared to corresponding 2,2,5,5-tetramethyl nitroxides.
N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry Sb RAS, Academician Lavrentjev Ave. 9, Novosibirsk, 630090, Russia. kirilyuk@nioch.nsc.ru
Igor A
IA
Kirilyuk
Yuliya F
YF
Polienko
Olesya A
OA
Krumkacheva
Rodion K
RK
Strizhakov
Yurii V
YV
Gatilov
Igor A
IA
Grigor'ev
Elena G
EG
Bagryanskaya
D003497:Cyclic N-Oxides / Q000138:chemical synthesis* / Q000737:chemistry*; D004578:Electron Spin Resonance Spectroscopy; D008698:Mesylates / Q000138:chemical synthesis* / Q000737:chemistry*; D015394:Molecular Structure; D009569:Nitric Oxide / Q000138:chemical synthesis* / Q000737:chemistry*; D011758:Pyrroles / Q000138:chemical synthesis* / Q000737:chemistry; D011759:Pyrrolidines / Q000138:chemical synthesis* / Q000737:chemistry*; D013113:Spin Labels; D013141:Spiro Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D013438:Sulfhydryl Compounds / Q000138:chemical synthesis* / Q000737:chemistry*
D003497:Cyclic N-Oxides; D008698:Mesylates; D011758:Pyrroles; D011759:Pyrrolidines; D013113:Spin Labels; D013141:Spiro Compounds; D013438:Sulfhydryl Compounds; C013231:pyrroline; D009569:Nitric Oxide; C034248:(1-oxyl-2,2,5,5-tetramethylpyrroline-3-methyl)methanethiosulfonate; C032519:pyrrolidine