1392
POPOV et al.
IVg, a mixture of 1.5 g (0.0085 mol) of 2-hydroxy-
2-cyanoadamantane II, 3.68 (0.02 mol) of
at 110°С for 2–3 h until the amount of the released water
became equimolar. After the reaction completion, the
mixture was cooled and washed with water. Toluene
was distilled off from the organic layer, and the residue
was vacuum-distilled to obtain 9.4 g (0.0418 mol) of
VIa. Yield 83.6%, bp 181–183°С (10 mm Hg). 1Н NMR
spectrum, δ, ppm: 1.76–2.38 m (2Н, Ad), 6.43–6.54 m
(2Н, Ph), 6.83–6.93 m (2Н, Ph), 7.09–7.12 m (1Н, Рh).
Found, %: С 85.31, Н 8.47, N 6.18. C16H19N. Calculated,
%: С 85.28, Н 8.50, N 6.22.
g
2,4-dinitrophenylhydrazine IIIk, and 65 ml of technical-
grade ethanol (stirred until compound IIIk fully
dissolved) was refluxed for 8 h. The product crystallized
from the reaction mixture as yellow-orange crystals,
which were filtered off. We obtained 1.87 g (0.0054 mol)
of IVk. Yield 64%, mp 183–185°С. 1Н NMR spectrum,
δ, ppm: 1.81–2.25 m (14Н, 2,2-Ad), 3.13 s (1Н, NH),
7.89–8.99 m (3Н, С6Н3), 11.10 s (1Н, NH). Found, %:
С 59.52, Н 5.54, N 16.29. C17H19N4О4. Calculated, %:
С 59.48, Н 5.54, N 16.33.
2-Adamantylidene(p-methylphenyl)amine VIb.
Similarly to the synthesis of VIa, from 3 g (0.02 mol)
of adamantanone I, 2.68 g (0.025 mol) of Vb, and 0.1 g
of toluenesulfonic acid in 30 ml of toluene, we obtained
4.3 g (0.018 mol) of VIb. Yield 90.1%, bp 199–202°С
2-N-Piperidino-2-cyanoadamantane IVl. Similarly
to the synthesis of IVg, from 1.5 g (0.0085 mol) of
2-hydroxy-2-cyanoadamantane II and 3 g (0.035 mol)
of piperidine in 10 ml of technical-grade ethanol, after
the work-up, we obtained 1.41 g (0.00578 mol) of IVl.
Yield 68%, mp 77–78°С, bp 240–242°С (20 mm Hg).
1Н NMR spectrum, δ, ppm: 1.35–2.34 m (14Н, 2,2-
Ad, 6Н, 3СН2Pip), 2.59 br.s (4Н, 2CH2N). Found, %:
С 78.64, Н 9.82, N 11.51. C16H24N2. Calculated, %:
С 78.69, Н 9.83, N 11.48.
1
(10 mm Hg). Н NMR spectrum, δ, ppm: 1.74–1.97 m
(14Н, Ad), 2.21 s (3Н, СН3), 6.39–6.91 m (4Н, С6Н4).
IR spectrum, ν, cm–1): 1720 (C=N). Found, %: С 85.26,
Н 8.86, N 5.88. C17H21N. Calculated, %: С 85.30,
Н 8.84, N 5.85.
2-Adamantylidene(p-methoxyphenyl)amine VIс.
Similarly to the synthesis of VIa, from 7.5 g (0.05 mol)
of adamantanone I, 6.5 g (0.052 mol) of Vс, and 0.1 g
of toluenesulfonic acid in 30 ml of toluene, we obtained
11.1 g (0.0435 mol) of VIс. Yield 87%, bp 217–220°С
2-N-Morpholino-2-cyanoadamantane
IVm.
Similarly to the synthesis of IVg, from 5 g (0.0282 mol)
of 2-hydroxy-2-cyanoadamantane II and 8 g (0.092 mol)
of dried morpholine IIIm in 30 ml of technical-
grade ethanol, after the work-up, we obtained 5.27 g
(0.0214 mol) of IVm. Yield 76%, bp 249–250°С
1
(20 mm Hg). Н NMR spectrum, δ, ppm: 1.71–2.73 m
(14Н, Ad), 3.68 s (3Н, ОСН3), 6.43 m (2Н, С6Н4),
6.64 m (2Н, С6Н4). Found, %: С 79.98, Н 8.27, N 5.45.
C17H21NО. Calculated, %: С 79.96, Н 8.29, N 5.49.
1
(20 mm Hg). Н NMR spectrum, δ, ppm: 1.35–2.20 m
(14Н, 2,2-Аd), 2.58 t [4Н, (CH2)2N, J = 0.6 Hz], 3.72 t
[4Н, (CH2)2O, J = 0.8 Hz. Found, %: С 73.20, H 8.92,
N 11.42. C15H22N2О. Calculated, %: С 73.17, Н 8.94,
N 11.38.
2-Adamantylidene(4-bromophenyl)amine VId.
Similarly to the synthesis of VIa, from 7.5 g (0.05 mol)
of adamantanone I, 9 g (0.052 mol) of Vd, and 0.2 g of
toluenesulfonic acid in 30 ml of toluene, we obtained
13.3 g (0.0435 mol) of VId. Yield 88%, bp 213–216°С
2-N-Piperazino-2-cyanoadamantane IVn. Simi-
larly to the synthesis of IVg, from 1.8 g (0.0102 mol)
of 2-hydroxy-2-cyanoadamantane II and 3.5 g
(0.0407 mol) of piperazine IIIn in 10 ml of technical-
grade ethanol, after the work-up, we obtained 1.55 g
(0.0063 mol) of IVn. Yield 62%, bp 259–262°С (20 mm
Hg), mp 117–118°С. 1Н NMR spectrum, δ, ppm: 1.67–
2.35 m (15Н, 2,2-Ad, 1Н, NH), 2.80 t [4Н, (CH2)2N,
J = 1.2 Hz], 2.95 t [4Н, (CH2)2O, J = 1.4 Hz]. Found,
%: С 73.49, H 9.39, N 11.12. C15H23N3. Calculated, %:
С 73.47, H 9.39, N 17.14.
1
(8 mm Hg). Н NMR spectrum, δ, ppm: 1.68–2.62 m
(14Н, Ad), 6.42–7.27 m (4Н, С6Н4). Found, %: С 63.14,
Н 5.90, N 4.56. C16H18NBr. Calculated, %: С 63.17,
Н 5.96, N 4.60.
2-Adamantylidene(о-aminophenyl)amine
VIe.
Similarly to the synthesis of VIa, from 3 g (0.02 mol)
of adamantanone I, 2.7 g (0.025 mol) of Ve, and 0.1 g
of toluenesulfonic acid in 50 ml of toluene, we obtained
3.89 g (0.0162 mol) of VIe. Yield 81%, bp 228–230°С
1
(8 mm Hg). Н NMR spectrum, δ, ppm: 1.58–2.02 m
(14Н, Ad), 3.37 s (2Н, NH2), 6.31–6.48 m (4Н, 1,2-
С6Н4). Found, %: С 80.02, Н 8.34, N 11.59. C16H20N2.
Calculated, %: С 79.96, Н 8.39, N 11.66.
2-Adamantylidene(phenyl)amine
VIa.
To
7.5 g (0.05 mol) of adamantanone I, we added 5.5 g
(0.059 mol) of Va, 0.2 g of toluenesulfonic acid, and
50 ml of toluene. Then the reaction mixture was refluxed
2-Adamantylidene(1-naphthyl)amine
VIf.
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 85 No. 9 2012