Download PDF
Synthesis 2003(6): 0871-0878
DOI: 10.1055/s-2003-38694
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Grignard Reagent Addition to 5-Alkylamino-4H-Imidazole 3-Oxides: Synthesis of New pH-Sensitive Spin Probes

Igor A. Kirilyuk*a, Tikhon G. Sheveleva, Denis A. Morozovb, Ekaterina L. Khromovskihb, Nikita G. Skuridinc, Valery V. Khramtsovd, Igor A. Grigor’eva
a N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, pr. Acad. Lavrentieva 9, Novosibirsk 630090, Russia
Fax: +7(3832)344752; e-Mail: kirilyuk@nioch.nsc.ru;
b Novosibirsk State University, Novosibirsk 630090, Russia
c Institute of Chemical Kinetics & Combustion, Novosibirsk 630090, Russia
d Dorothy M. Davis Heart & Lung Research Institute, The Ohio State University, Ohio, USA
Further Information

Publication History

Received 6 February 2003
Publication Date:
16 April 2003 (online)

    Permissions and Reprints All articles of this category

Abstract

4,4-Dimethyl-4H-imidazole-5-carbaldehyde oxime 3-oxides 4 were prepared by oxidation and nitrosation of 4,5,5-trimethyl-2,5-dihydro-1H-imidazol-1-ols. The oximes 4 were converted to 5-cyano derivatives; the latter react with primary or secondary amines to form 5-(di)alkylamino-4H-imidazole 3-oxides 6. Treatment of 6 with AlkMgX and subsequent oxidation yielded stable nitroxides 4-(di)alkylamino-2,5-dihydroimidazole-1-oxyls 7, the pH-sensitive spin probes.

Key words

Grignard reactions - amines - nitriles - imidazoles - free radicals - spin probes

    References

  • 1a Khramtsov VV. Weiner LM. Grigor’ev IA. Volodarsky LB. Chem. Phys. Lett.  1982,  91:  69 
    Search in Google Scholar
  • 1b Keana JFW. Acarregui MJ. Boyle SLM. J. Am. Chem. Soc.  1982,  104:  926 
    Search in Google Scholar
  • 2 Khramtsov VV. Volodarsky LB. In Biological Magnetic Resonance   Vol. 14:  Berliner LJ. Plenum Press; New York: 1998.  p.109 
    Search in Google Scholar
  • 3 Khramtsov VV. Grigor’ev IA. Foster MA. Lurie DJ. Nicholson I. Cell. Mol. Biol.  2000,  46:  1361 
    Search in Google Scholar
  • 4 Voinov MA. Martin VV. Volodarskii LB. Bull. Russ. Akad. Sci., Div. Chem. Sci. (Engl.Transl.)  1992,  41:  2091 
    Search in Google Scholar
  • 5 Volodarsky LB. Reznikov VA. Grigor’ev IA. In Imidazoline Nitroxides   Volodarsky LB. CRC Press; Boca Raton: 1988.  p.29 
  • 6 Balakirev M. Khramtsov V. Berezina T. Martin V. Volodarsky L. Synthesis  1992,  12:  1223 
    Thieme ConnectSearch in Google Scholar
  • 7 Kirilyuk IA. Grigor’ev IA. Volodarsky LB. Izv. Sib. Otd. Akad. Nauk SSSR, Ser. Khim. Nauk  1989,  2:  99 ; Chem. Abstr. 1990, 111, 232670
    Search in Google Scholar
  • 8 Grigor"ev IA. Kirilyuk IA. Volodarskii LB. Chem. Heterocycl. Compd. (Engl.Transl.)  1988,  24:  1355 
    CrossrefSearch in Google Scholar
  • 9 Schukin GI. Grigor’ev IA. Volodarsky LB. Izv. Sib. Otd. AN SSSR, Ser. Khim. Nauk.  1984,  4:  81 ; Chem. Abstr. 1985, 102, 11368
    Search in Google Scholar
  • 10 Volodarsky LB. Fust LA. Kobrin VS. Khim Heterocycl. Soedin.  1972,  9:  1246 ; Chem. Abstr. 1973, 78, 4189
    Search in Google Scholar
  • 11 Sammez MP. Katritzky AR. In Advances in Heterocyclic Chemistry   Vol. 35:  Katritzky AR. Academic Press; New York: 1984.  p.413 
    Search in Google Scholar
  • 12 Grigor"ev IA. Shchukin GI. Khramtsov VV. Vainer LM. Starichenko VF. Volodarskii LB. Bull. Acad. Sci. USSR, Div. Chem. Sci. (Engl.Transl.)  1985,  34:  2169 
    Search in Google Scholar
  • 13 Reznikov VA. Burchak ON. Vishnivetskaya LA. Volodarskii LB. Rybalova TV. Gatilov YuV. Russ. J. Org. Chem.  1997,  33:  1302 
    Search in Google Scholar
  • 14 Keana JFW. In Spin Labelling in Pharmacology   Holtzman JL. Academic Press; Orlando, Fla.: 1984.  p.1 
  • 15 Reznikov VA. Volodarsky LB. Tetrahedron  1993,  49:  10669 
    CrossrefSearch in Google Scholar
  • 16 Grigor’ev IA. Shchukin GI. Martin VV. Mamatyuk VI. Chem. Heterocycl. Compd. (Engl.Transl.)  1985,  21:  205 
    Search in Google Scholar
  • 17 Volodarskii LB. Sevastyanova TK. Zh. Org. Khim.  1971,  8:  1971 ; Chem. Abstr. 1971, 75, 140425
    Search in Google Scholar
  • 18 Khramtsov VV. Weiner LM. Eremenko S. Belchenko OI. Schastnev PV. Grigor’ev IA. Reznikov VA. J. Magn. Res.  1985,  61:  397 
    Search in Google Scholar