Synthesis of N-nitrosoamines of the adamantane series

Full text of DOI:10.1134/S1070428010050283

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2010, Vol. 46, No. 5, pp. 760−761. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © K.A. Ovchinnikov, I.K. Moiseev, 2010, published in Zhurnal Organicheskoi Khimii, 2010, Vol. 46, No. 5, pp. 764−765.
SHORT
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Synthesis of N-Nitrosoamines of the Adamantane Series
K. A. Ovchinnikov and I. K. Moiseev
Samara State Technical University, Samara, 443100 Russia
e-mail: ikmoiseev@mail.ru
Received December 7, 2009
DOI: 10.1134/S1070428010050283
amine hydrochloride, 30 ml of 10% HCl and 60 ml of
toluene was added, the mixture was cooled to 5–10°C ,
and at vigorous stirring was added dropwise within 3 h
the sodium nitrite water solution. The reaction mixture
was maintained for 2 h at room temperature, the toluene
layer was separated, washed with water (2 × 50 ml), and
dried with sodium sulfate. The solution was evaporated
in a vacuum to obtain yellow crystalline sibstances stable
at storage.
N-Nitrosoamines hold an important place among the
nitrogen compounds. They are widely employed in the
synthesis of diazo derivatives, dialkylhydrazines,
nitramines, and exhibut a high biological activity. The
synthesis and chemical properties of N-nitrosoamines of
the aliphatic series are compiled in the review [1].
However there are virtually no published information on
the synthesis and properties of the adamantyl-containing
N-nitrosoamines [2]. We report here on the synthesis
and physicochemical properties of the N-nitrosoamines
of the adamantane series.
N-Benzyl-N-nitrosoadamantan-1-amine (IIa).
Yield 2.1 g (80%), yellow crystals, mp 80–82°C. IR
spectrum, ν, cm–1: 2908, 2854 (Ad), 1384 (NNO), 717
(C–Harom).1H NMR spectrum, δ, ppm: 1.65–2.23 m (15H,
Ad), 4.80 s (2H, CH2), 6.95 d (2H, CHarom, J 5.1 Hz),
7.22 d (2H, CHarom, J 5.1 Hz), 7.25 s (1H, CHarom). Mass
spectrum, m/z (Irel, %): 270 (5) [M]+, 135 (100) [Ad]+.
Found, %: C 75.44; H 8.12; N 10.25. C17H22N2O.
Calculated, %: C 75.52; H 8.20; N 10.36. M 270.37.
R2
R1
NHCH2R3
Iа_If
R2
N-Nitroso-N-(2-thienylmethyl)adamantan-1-
amine (IIb). Yield 2.6 g (90%), yellow crystals, mp 98–
100°C. IR spectrum, ν, cm–1: 2916, 2850 (Ad), 1647 (C–
N), 1396 (NNO), 1562, 702 (C–S). 1H NMR spectrum,
δ, ppm: 1.43–1.98 m (15H,Ad), 4.89 s (2H, CH2), 6.85 d
(1H, CHthiophene, J 3 Hz), 6.97 d (1H, CHthiophene, J 3 Hz),
7.31 d (1H, CHthiophene, J 3 Hz). Mass spectrum, m/z (Irel,
%): 276 (20) [M]+, 149 (100) [AdN]+. Found, %: C 65.09;
H 7.17; N 10.12. C15H20N2OS. Calculated, %: C 65.18;
H 7.29; N 10.14. M 276.39.
_
NaNO2 HCl
R1
_
_
o
AcOH PhMe, 5 10 C
N N O
СH2R3
IIа_IIf
R1 = H (a–d), OH (e), Me (f); R2 = H (a–e), Me (f); R3 = Ph
(a), 2-thienyl (b, e, f), 4–MeOC6H4 (c), 4–NO2C6H4 (d).
We selected for initial compounds secondary amines
Ia–If prepared by the reduction of the appropriate
azomethines with NaBH4 [3]. The nitroso group was
introduced by the nitrosation in acid medium [1, 4–7].
N-(4-Methoxybenzyl)-N-nitrosoadamantan-1-
amine (IIc). Yield 2.8 g (85%), yellow crystals, mp 206–
208°C. IR spectrum, ν, cm–1: 2920, 2854 (Ad), 1384
(NNO), 817 (C–Harom). 1H NMR spectrum, δ, ppm: 1.45–
1.90 m (15H, Ad), 3.74 s (3H, OCH3), 4.72 s (2H, CH2),
N-Nitrosoamines IIa–IIf. In a minimum volume
of the glacial acetic acid was dissolved 0.01 mol of
760

SYNTHESIS OF N-NITROSOAMINES OF THE ADAMANTANE SERIES
761
6.95 d (2H, CHarom, J 7 Hz), 7.43 d (2H, CHarom, J 7 Hz).
Mass spectrum, m/z (Irel, %): 300 (10) [M]+, 135 (100)
[Ad]+. Found, %: C 71.85; H 7.98; N 9.24. C18H24N2O2.
Calculated, %: C 71.97; H 8.05; N 9.33. M 300.39.
CHthiophene, J 3 Hz), 7.34 d (1H, CHthiophene, J 3 Hz),
7.58 d (1H, CHthiophene, J 3 Hz). Mass spectrum, m/z (Irel,
%): 304 (5) [M]+, 163 (30) [Me2Ad]+, 135 (100) [Ad]+.
Found, %: C 66.80; H 7.80; N 9.15. C17H24N2OS.
Calculated, %: C 67.07; H 7.95; N 9.20. M 304.45.
N-(4-Nitrobenzyl)-N-nitrosoadamantan-1-amine
(IId). Yield 1.7 g (55%), yellow crystals, mp 140–142°C.
IR spectrum, ν, cm–1: 2912, 2885 (Ad), 1512 (NO2), 1442
(NNO), 729 (C–Harom). 1H NMR spectrum, δ, ppm: 1.6–
IR spectra of compounds synthesized were recorded
on a spectrophotometer Shimadzu FTIR-8400S from
1
pellets with KBr. H NMR spectra were registered on
spectrometers Bruker AM300 and Varian Mercury 300
(300 MHz), internal reference TMS, solvent DMSO-d6.
Mass spectra were measured on an instrument Finnigan
Trace DCQ, ionizing electrons energy 70 eV. Elemental
analysis was performed on an analyzer Termo Finnigan
Flash 1112 NCH. The purity of compounds was checked
by TLC on Silufol plates (eluent chloroform–petroleum
ether, 1:1, development in iodine vapor).
1.9 m (15H, Ad), 4.73 s (2H, CH2), 8.00 d (2H, CHarom
,
J 7.5 Hz), 8.29 d (2H, CHarom, J 7.5 Hz). Mass spectrum,
m/z (Irel, %): 315 (5) [M]+, 135 (100) [Ad]+. Found, %:
C 64.65; H 6.51; N 13.24. C17H21N3O3. Calculated, %:
C 64.74; H 6.71; N 13.32. M 315.36.
3-[Nitroso(2-thienylmethyl)amino]adamantan-1-
ol (IIe). Yield 1.7 g (55%), yellow crystals, mp 160°C
(decomp.). IR spectrum, ν, cm–1: 3413 (OH), 2923, 2850
1
(Ad), 1635 (C–N), 1384 (NNO), 833 (C–S). H NMR
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spectrum, δ, ppm: 1.40–1.91 m (14H, Ad), 4.37 s (1H,
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6.96 d (1H, CHthiophene, J 3 Hz), 7.32 d (1H, CHthiophene
,
J 3 Hz). Mass spectrum, m/z (Irel, %): 292 (15) [M]+, 135
(100) [Ad]+. Found, %: C 61.42; H 6.74; N 9.42.
C15H20N2O2S. Calculated, %: C 61.62; H 6.89; N 9.58.
M 292.39.
3,5-Dimethyl-N-nitroso-N-(2-thienylmethyl)-
adamantan-1-amine (IIf). Yield 0.84 g (25%), yellow
crystals, mp 20–22°C. IR spectrum, ν, cm–1: 2939, 2904,
2846 (Ad), 1631 (C–N), 1438 (NNO), 702 (C–S).
1H NMR spectrum, δ, ppm: 0.81 s (6H, CH3), 1.41–
1.95 m (13H, Ad), 4.72 s (2H, CH2), 7.05 d (1H,
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