SYNTHESIS OF 3-AMINOMETHYL-SUBSTITUTED PYRAZOLES
1203
(ССO), 156.73 (С=N), 160.81 (СО). Mass spectrum: m/z
167.1178 [M + H]+. C9H14N2O·HCl. M 166.2203.
δ, ppm: 1.70 m (4Н, 2СН2), 2.72 m (7Н, 2СН2, СН3),
8.63 br.s (1Н, NН). Found, %: C 59.77; H 6.65; N 15.48.
C9H12N2O2. Calculated, %: C 59.99; H 6.71; N 15.55.
REFERENCES
3-(N-Methylaminomethyl)-5-phenylisoxazole
hydrochloride (VIIIe). To a dispersion of 30 g (0.8 mol)
of NaBH4 in 1 liter of anhydrous THF under argon was
added dropwise 70 ml (0.26 mol) of 48% BF3·Et2O solu-
tion in anhydrous ether, and the mixture was stirred for
0.5 h at room temperature. To the prepared ВН3 solution
was gradually added 61 g (0.3 mol) of amide VIIe, the
mixture was boiled for 4 h, then it was cooled and treated
with ~100 ml of saturated NaHCO3 solution adding it by
small portions, and the resulting mixture was stirred for
1 h. After adding 0.5 l of water and 0.5 l of ethyl acetate
the organic layer was separated, and the water layer was
additionally extracted with ethyl acetate (2 × 200 ml).
The combined extracts were dried with MgSO4 and fil-
tered through a celite bed. After the neutralization of the
alkaline solution with 6 N HCl solution in dioxane till
weak acidic reaction (~100 ml) the solvents were distilled
off, the residue was crystallized from a mixture ethyl
ether–ethanol, 2:1. Yield 37 g (54%), mp 229–232°С. IR
spectrum, ν, cm–1: 2368, 1596, 1452. 1Н NMR spectrum,
δ, ppm: 2.63 s (3Н, СН3), 4.32 s (2Н, СН2NH), 7.26 s (1Н,
СН), 7.56 m (3Н, HAr), 7.85 m (2Н, HAr), 9.86 br.s (2Н,
NH·HCl). 13С NMR spectrum, δ, ppm: 32.31 (СН3), 42.51
(СН2), 100.57 (СН), 125.57, 126.28, 129.36, 130.77
(CAr), 157.57 (C=N), 169.74 (СО). Mass spectrum: m/z
189.1025 [M + H]+. C11H12N2O·HCl. M 188.2259.
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3-(N-Methylaminomethyl)-4,5,6,7-tetrahydro-
benzo[d]isoxazole hydrochloride (VIIIf) was similarly
obtained from 66.2 g (0.4mol) of amide VIIf by the ac-
tion of ВН3 formed from 39.6 g (1.05 mol) of NaBH4
and 93 ml (0.35mol) 48% BF3·Et2O in 1 liter of solution
anhydrous THF. Yield 46 g (57%), mp 147–149°С. IR
spectrum, ν, cm–1: 2952, 2712, 1644, 1580, 1452, 1412.
1Н NMR spectrum, δ, ppm: 1.68 m [4Н, СН2(СН2)2СН2],
2.52 s (3Н, СН3), 2.60 t (2Н, СН2СО, J 5.9 Hz), 2.67 t
(2Н, СН2ССN, J 5.6 Hz), 4.24 s (2Н, СН2NH), 9.78 br.s
(2Н, NH·HCl). 13С NMR spectrum, δ, ppm: 18.12
(СН2СО), 20.83 (СН2СН2СО), 21.52 (СН2СН2ССN),
21.60 (СН2ССN), 32.13 (СН3), 40.31 (СН2NH), 115.59
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 47 No. 8 2011