Molecular Design of pH-Sensitive Spin Probes in the 2,3,4,6,7,8-Hexahydro­imidazo[1,5-a]pyrimidine Series with Different Lipophilic/Hydrophilic Properties­

Abstract

New pH-sensitive spin probes - 2,3,4,6,7,8-hexahydro­imidazo[1,5-a]pyrimidines - were synthesized by the reaction of 4-amino-2,5-dihydro-2,2,5,5-tetramethyl-1H-imidazol-1-oxyl with aminomethylated α,β-unsaturated carbonyl methiodides or hydrochlorides. Introduction of hydrophilic (COOH) or lipophilic (C₁₀H₂₁) groups in the aminomethylated compounds allowed the synthesis of pH-sensitive spin probes with different solubilities.

radicals - enone - Mannich bases - spin probes - amidine

References

<A NAME="RZ06705SS-1A">1a</A> Volodarsky LB. Reznikov VA. Ovcharenko VI. Synthetic Chemistry of Stable Nitroxides   CRC Press; Boca Raton: 1994.  p.1-225  

<A NAME="RZ06705SS-1B">1b</A> Benoit D. Chaplinski V. Braslau R. Hawker CV. J. Am. Chem. Soc.  1999,  3904 

<A NAME="RZ06705SS-2">2</A> De Nooy AEL. Besemer AC. Van Bekkum H. Synthesis  1996,  1153 

<A NAME="RZ06705SS-3">3</A> Berliner LJ. Reuben J. Biological Magnetic Resonance   Vol. 8:  Plenum Press; New York, London: 1989.  p.1-650  

<A NAME="RZ06705SS-4">4</A> Khramtsov VV. Grigor’ev IA. Foster MA. Lurie DJ. Nicholson I. Cell. Mol. Biol.  2000,  46:  1361 ; and references cited therein

<A NAME="RZ06705SS-5">5</A> Khramtsov VV. Volodarsky LB. In Biological Magnetic Resonance   Vol. 14:  Plenum Press; New York: 1998.  p.109 

<A NAME="RZ06705SS-6">6</A> Reznikov VA. Skuridin NG. Khromovskikh EL. Khramtsov VV. Russ. Chem. Bull.  2003,  2052 

<A NAME="RZ06705SS-7">7</A> Kirilyuk IA. Bobko AA. Grigor’ev IA. Khramtsov VV. Org. Biomol. Chem.  2004,  1025 

<A NAME="RZ06705SS-8">8</A> Kirilyuk IA. Bobko AA. Khramtsov VV. Grigor’ev IA. Org. Biomol. Chem.  2005,  1269 

<A NAME="RZ06705SS-9">9</A> Khramtsov VV. Weiner LM. In Imidazoline Nitroxides   Vol. 2:  Volodarsky LB. CRC Press; Boca Raton: 1988.  p.37-80  

<A NAME="RZ06705SS-10">10</A> Khramtsov VV. Volodarsky LB. In Biological Magnetic Resonance   Vol. 14:  Berliner LJ. Plenum Press; New York: 1998.  p.118 

<A NAME="RZ06705SS-11">11</A> Khlestkin VK. Tikhonov AYa. Heterocycl. Commun.  2002,  245 

<A NAME="RZ06705SS-12">12</A>

Crystallographic data for the structure reported in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC- 149032. Copies of the data can be obtained free of charge on application to CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK [fax: [phone], e-mail: [e-mail]].

<A NAME="RZ06705SS-13">13</A> Volodarsky LB. Imidazoline Nitroxides   Vol. 1:  CRC Press; Boca Raton: 1988.  p.59 

<A NAME="RZ06705SS-14A">14a</A> Voinov MA. Martin VV. Volodarsky LB. Izv. Acad. Nauk Ser. Khim.  1992,  2642 

<A NAME="RZ06705SS-14B">14b</A> Berezina TA. Reznikov VA. Volodarsky LB. Tetrahedron  1993,  10693 

<A NAME="RZ06705SS-14C">14c</A> Balakirev MYu. Khramtsov VV. Berezina TA. Martin VV. Volodarsky LB. Synthesis  1992,  1223 

<A NAME="RZ06705SS-15">15</A> Girreser U. Heber D. J. Prakt. Chem.  2000,  230 

<A NAME="RZ06705SS-16">16</A> Girreser U. Heber D. Schütt M. Synthesis  1999,  1637 

<A NAME="RZ06705SS-17">17</A> Pelletier SW. Franz RJE. J. Org. Chem.  1952,  855 

<A NAME="RZ06705SS-18">18</A> Kirilyuk IA. Shevelev TG. Morozov DA. Khromovskih EL. Scuridin NG. Khramtsov VV. Grigor’ev IA. Synthesis  2003,  871 

<A NAME="RZ06705SS-19">19</A> Najer H. Chabrier P. Guidicelli R. Bull. Soc. Chim. France  1956,  613 

<A NAME="RZ06705SS-20">20</A> De Cointet P. Loppinet V. Sornay R. Morinere JL. Boucherle A. Renson FJ. Voegelin H. Dumont C. Chim. Ther.  1973,  574 

<A NAME="RZ06705SS-21">21</A> Grigor’ev IA. Dikanov SA. In Imidazoline Nitroxides   Vol. 1:  Volodarsky L. B. Ed., CRC Press; Boca Raton: 1988.  p.90