470
Russ.Chem.Bull., Int.Ed., Vol. 52, No. 2, February, 2003
Glushkov et al.
2a—c (3.5 mmol) in 50% aqueous MeOH (8 mL) at 0—5 °C.
The reaction mixture was stirred at this temperature for 10 min
and then gemꢀdinitroethane (0.36 g, 3 mmol) was added. The
reaction mixture was stirred at ∼20 °C for 15 min and then at
50—55 °C for 1 h, after which the mixture was cooled to –5 °C.
The precipitate that formed was filtered off and recrystallized
from EtOH.
Potassium salts of 4ꢀnitraminoꢀ1,2,4ꢀtriazolium 1ꢀnitroimides
8a—c (general procedure). Compound 2a—c (3 mmol) and
AcOK (0.64 g, 6.5 mmol) were added to a suspension of NO2BF4
(0.43 g, 3.2 mmol) in MeCN (15 mL) at –25 °C. The reaction
mixture was stirred at the temperature from –25 to –20 °C for
40 min, was warmed to ∼20 °C during 30 min, and then stirred
for 2 h. The precipitate that formed was filtered off and exꢀ
tracted with hot MeOH (5×15 mL). The extract was concenꢀ
trated on a rotary evaporator. The filtrate was concentrated to
1/4 of the initial volume. The precipitate was filtered off, comꢀ
bined with the residue obtained after concentration of the filꢀ
trate (see above), and recrystallized from aqueous EtOH.
Experimental
The melting points were measured on a Boetius stage. The
1H NMR spectra were recorded on a Bruker WMꢀ250 instruꢀ
ment (250 MHz) in DMSOꢀd6. The IR spectra were measured
on a URꢀ20 instrument in KBr pellets.
The physicochemical and spectroscopic characteristics of
the resulting compounds are given in Tables 1 and 2, respecꢀ
tively.
Triethylammonium salts of 4ꢀnitraminoꢀ1,2,4ꢀtriazoles 1´a—c
(general procedure). Triethylamine (1.3 mL, 1.0 g, 10.0 mmol)
was added to a suspension of compound 1a—c (9.0 mmol) in
EtOH (10—15 mL). The reaction mixture was heated until the
precipitate was completely dissolved and then concentrated on a
rotary evaporator to dryness. The oily products thus obtained
were used in subsequent reactions without additional purifiꢀ
cation.
1ꢀAminoꢀ1,2,4ꢀtriazolium 4ꢀnitroimides 2a—c (general proꢀ
cedure). OꢀPicrylhydroxylamine (6.0 mmol) was gradually added
to a solution of the corresponding triethylammonium salt of
4ꢀnitraminoꢀ1,2,4ꢀtriazole 1a—c (5.0 mmol) in anhydrous
CHCl3 (30 mL). The reaction mixture was stirred at ∼20 °C for
3 h. The precipitate that formed was filtered off, washed with
CHCl3 and cold EtOH, and recrystallized from aqueous EtOH.
1ꢀArylideneaminoꢀ1,2,4ꢀtriazolium 4ꢀnitroimides 3a—g (genꢀ
eral procedure). The corresponding aromatic aldehyde
(3.5 mmol) and one drop of H2SO4 were added to a suspension
of compound 2a—c (3.0 mmol) in EtOH (15 mL). The reaction
mixture was stirred at 50—55 °C for 1 h, concentrated on a
rotary evaporator to 1/2 of the initial volume, and cooled. The
precipitate that formed was filtered off and recrystallized
from MeOH.
1ꢀAcylaminoꢀ1,2,4ꢀtriazolium 4ꢀnitroimides 4a—e (general
procedure). The corresponding acyl chloride (1.7 mmol) and
4ꢀdimethylaminopyridine (1.7 mmol) were added to a suspenꢀ
sion of compound 2a—c (1.5 mmol) in MeCN (4 mL). The
reaction mixture was stirred at ∼20 °C for 1 h and then at
45—50 °C for 3—5 h, after which the mixture was concentrated
on a rotary evaporator and water (5 mL) was added to the
residue. The mixture was acidified with HCl to pH 1 and cooled
to 0 °C. The precipitate that formed was filtered off and recrysꢀ
tallized from aqueous EtOH.
1ꢀ(N,NꢀDimethylaminomethyleneamino)ꢀ1,2,4ꢀtriazolium
4ꢀnitroimides 5a—c (general procedure). Acyl chloride
(3.2 mmol) was added to a solution of compound 2a—c
(3.0 mmol) in DMF (4 mL) at 0 °C. The reaction mixture was
stirred at 0—5 °C for 15 min and then at 45—50 °C for 2 h, after
which the mixture was concentrated on a rotary evaporator and
the residue was recrystallized from aqueous PriOH.
This study was financially supported by the Russian
Foundation for Basic Research (Project No. 00ꢀ15ꢀ
97455).
References
1. A. I. Glushkov, O. P. Shitov, A. V. Mezhenin, and V. A.
Tartakovsky, Izv. Akad. Nauk, Ser. Khim., 2002, 1229 [Russ.
Chem. Bull., Int. Ed., 2002, 51, 1332].
2. P. C. Wade, B. R. Vogt, T. P. Kissick, and L. M. Simpkins,
J. Med. Chem., 1982, 25, 331.
3. N. Di Mola and E. Bellasio, Farmaco Ed. Sci., 1985, 40, 517.
4. US Pat. 5889161; Chem. Abstr., 1999, 130, 239630.
5. Y. Tamura, J. Minamikawa, and M. Ikeda, Synthesis,
1977, 1, 1.
6. V. M. Vinogradov, I. L. Dalinger, and S. A. Shevelev,
Mendeleev Commun., 1993, 3, 111.
7. V. A. Vyazkov, O. P. Shitov, and V. A. Tartakovsky, Zh. Org.
Khim., 2001, 7, 1086 [Russ. J. Org. Chem., 2001, 7, 1044
(Engl. Transl.)].
8. J. Epsztajn, A. R. Katritzky, E. Lunt, J. W. Mitchell, and
G. Koch, J. Chem. Soc., Perkin Trans. 1, 1973, 2622.
9. C. L. Dickinson, W. J. Middlenton, and V. A. Elgelhardt,
J. Org. Chem., 1962, 27, 2470.
10. E. E. Glover and K. T. Rowbotton, J. Chem. Soc., Perkin
Trans. 1, 1974, 15, 1792.
11. V. V. Kuz´menko, I. M. Nanavyan, and A. F. Pozharskii,
Khim. Geterotsikl. Soedin., 1992, 190 [Chem. Heterocycl.
Compd., 1992, 28, 154 (Engl. Transl.)].
1ꢀ(3ꢀPhenylureido)ꢀ1,2,4ꢀtriazolium 4ꢀnitroimides 6a—c
(general procedure). Phenyl isocyanate (1.6 mmol) was added to
a solution of compound 2a—c (1.5 mmol) in DMF (2 mL) at
5—10 °C. The reaction mixture was stirred at this temperature
for 15 min and then at 40 °C for 1 h, after which the mixture was
concentrated on a rotary evaporator and the residue was recrysꢀ
tallized from aqueous EtOH.
12. J. de Mendoza, T. Torres, and M. D. Badia, Monatsh. Chem.,
1988, 199, 1041.
13. V. A. Myasnikov, V. A. Vyazkov, O. P. Shitov, and V. A.
Tartakovsky, Izv. Akad. Nauk SSSR, Ser. Khim., 1991, 1239
[Bull. Acad. Sci. USSR, Div. Chem. Sci., 1991, 40, 1116 (Engl.
Transl.)].
1ꢀ[(2,2ꢀDinitropropyl)amino]ꢀ1,2,4ꢀtriazolium 4ꢀnitroimides
7a—c (general procedure). A 32% formaldehyde solution
(0.47 mL, 5.0 mmol) was added to a suspension of compound
Received June 26, 2002;
in revised form September 20, 2002
Glushkov
