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(6H, СМе2), 0.96 s (1H, NH), 1.50 m (2H, МеСН2·
CH2N=), 2.46 s (2Н, СН2NСН2Ме), 2.50 q (2Н,
NСН2Ме, 3JHН 7.5 Hz), 3.21 t (2H, МеСН2CH2N, 3JHН
3.35 Hz), 7.37 s (1H, N=СН).
(CDCl3), δ, ppm: 1.10–1.60 m (12Н, Ме2СНО, 6Н,
Ме2С, 3Н, the signals of MeСН2N are partially
overlapped), 2.64–3.08 m (4Н, СН2NНСН2Me), 3.44
d.d (1Н, РСН, 2JPH 13.7, 3JHН 4.0 Hz), 4.89 heptet (2Н,
3
3
3
РОСН3Me1Me2, JPH
3
= JН 3H
1
3
= JН H = 6.3 Hz), 6.97
2
3
Dimethyl [2-methyl-1-(1,2,4-triazol-4-ylamino)-
propyl]phosphonate (Va). To 3.15 g (0.0228 mol) of
N-(1,2,4-triazol-4-yl)-2-methylpropanimine IIIa was
added dropwise under argon 2.63 g (0.0239 mol) of
dimethylphosphorous acid IVa. To this mixture 3–
4 times was added 5–6 drops of sodium alcoholate.
The reaction mixture slightly warmed. The mixture
was kept at room temperature for 3 days. Then the
solvent was removed, and the residue was precipitated
from an ethyl acetate–toluene mixture. Yield 2.5 g
(44%), mp 103–104°C. 1H NMR spectrum (CDCl3), δ,
3
d.d (1Н, NHN, JPH 17.0, JHH 4.0 Hz), 8.47 s (2H,
C2N3H2). 31Р NMR spectrum (CDCl3): δP 22.1 ppm.
Dimethyl [2-methyl-1-(1,2,4-triazol-4-ylamino)
propyl]phosphonate picrate (VIa). To a solution of
0.65 g (0.0026 mol) of dimethyl [2-methyl-1-(1,2,4-
triazol-4-ylamino)propyl]phosphonate Va in 5.5 ml of
ethanol was added in small portions a solution of 0.6 g
(0.0026 mol) of picric acid in 5.13 ml of ethanol. The
mixture was kept at room temperature for 24 h. The
precipitated crystals were filtered off and dried in a
vacuum. Yield 0.86 g (70%), mp 140–142°C. 1H NMR
spectrum (acetone-d6), δ, ppm: 1.23 d and 1.28 d (6Н,
3
ppm: 1.25 d and 1.30 d (6Н, СМе2, JНН 7.0 Hz), 2.24
m (1Н, СНМе2), 3.29 d.d (1Н, РСН, 2JРН 15.0, 2JНН 4 Hz),
3
3
3.91 d [6Н, Р(ОМе)2, JРН 10.8 Hz], 6.00 br.s (1Н,
СМе2, JНН 7.0 Hz), 2.34 m (1Н, СНМе2), 3.83 d and
NH), 8.47 s (2Н, С2Н2N3). 31Р NMR spectrum
(CDCl3): δP 27.0 ppm. Found, %: C 38.85; H 6.65; N
22.54; P 12.25. C8H17PO3N4. Calculated, %: C 38.71;
H 6.9; N 22.57; P 12.48.
3.85 d [6Н, Р(ОМе)2, 3JРН 10.7 Hz], 3.86 d [1Н, РСН,
2JРН 13.6 Hz, the signal is partially overlapped with the
signals of Р(ОМе)2], 7.41 br.s (2Н, +NH2), 8.87 s (2Н,
С2Н2N3), 9.56 s (2Н, С6Н2). 31Р NMR spectrum
(acetone-d6): δP 25.3 ppm. Found, %: С 35.77; Н 4.11;
N 20.83; Р 6.75. С14Н20РO10N7. Calculated, %: С
35.38; Н 4.02; N 20.59; Р 6.5.
Dimethyl [2,2-dimethyl-1-(propylamino)-3-(ethyl-
amino)propyl]phosphonate (Vb). To 3.68 g (0.0216 mol)
of N-propyl-2,2-dimethyl-3-(ethylamino)propanimine
IIIc was added dropwise under argon 2.38 g (0.0216 mol)
of dimethylphosphorous acid IVa. The reaction
mixture slightly warmed. The mixture was kept at
room temperature for 5 days and distilled in a vacuum.
Yield 3.23 g (55%), bp 84–85°C (0.05 mm Hg), nD20
Dimethyl [2,2-dimethyl-1-(propylamino)-3-(ethyl-
amino)propyl]phosphonate dipicrate (VIb). To a
solution of 2.62 g (0.0114 mol) of picric acid in 15 ml
of ethyl acetate was added in small portions 1.42 g
(0.0057 mol) dimethyl [2,2-dimethyl-1-(propylamino)-
3-(ethylamino)propyl]phosphonate Vb in 8 ml of ethyl
acetate. The reaction mixture slightly warmed. The
mixture was kept at room temperature for 24 h. The
precipitated crystals were filtered off, recrystallized
from ethanol, and dried in a vacuum. Yield 3.65 g
1
1.4582. H NMR spectrum (CDCl3 + CCl4), δ, ppm:
1.20–1.70 m (6H, СМе2, 3Н, NСН2Ме, 3Н, СН2СН2Ме
and NНЕt), 1.75–2.10 m (2Н, NСН2СН2Me and 1Н,
NHРr), 2.60–3.30 m. (1Н, РСН, 2H, NHСН2Et, 2Н,
ССН2NН, 2Н, NHСН2Me), 3.75 m (6Н, МеОР). 31Р
NMR spectrum (CCl4): δP 30.9 ppm.
1
(87%), mp 125°C. H NMR spectrum (acetone-d6), δ,
+
3
Diisopropyl [2,2-dimethyl-1-(1,2,4-triazol-4-yl-
amino)-3-(ethylamino)propyl]phosphonate (Vc). To
a solution of 6.98 g (0.0421 mol) of isopropylphos-
phorous acid IVb in 40 ml of benzene was added
under argon with stirring 8.21 g (0.0421 mol) of N-
(1,2,4-triazol-4-yl)-2,2-dimethyl-3-(ethylamino)propan-
imine IIIb. To this mixture were added few small
pieces of metallic sodium. The reaction mixture slightly
warmed. The mixture was kept at room temperature
for 2–3 days. The reaction mixture was treated with
ether and filtered from the small amount of crystalline
product. After the removal of the solvent in a high
vacuum the residue was recrystallized from ether.
ppm: 0.94 t (3Н, NСН2СН2Me, JHН 7.0 Hz), 1.35 t
+
3
(3Н, NСН2Me, JHН 7.0 Hz), 1.37 s and 1.40 s (6Н,
Me2), 1.69 m (2Н, NСН2СН2Me), 3.03 sextet and
+
+
+
3.23 м (2Н, NСН2СН2Me), 3.30 q (2Н, NСН2Me,
3JHН 7.0 Hz), 3.40 d and 3.54 d (2Н, СН2N+Et, JHН
2
13.2 Hz), 3.62 d (1Н, РСН, 2JРН 17.7 Hz), 3.90 d (6Н,
2МеОР, 3JРН 11 Hz), 4.70–6.10 br.s (4Н, 2+NН2), 8.80
s (4Н, 2АrO). 31Р NMR spectrum (С4Н8О2): δP 29.2 ppm.
Found, %: С 38.70; Н 4.72; N 15.09; Р 4.45. С24Н35·
РO17N8. Calculated, %: С 39.03; Н 4.77; N 15.17; Р 4.19.
Diisopropyl [2,2-dimethyl-1-(1,2,4-triazol-4-yl-
amino)-3-(ethylamino)propyl]phosphonate picrate
(VIc). To a solution of 1.34 g (0.0037 mol) diisopropyl
1
Yield 9.12 g (60%), mp 88°C. H NMR spectrum
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 6 2012