CARBENIUM IONS IN SUBSTITUTION REACTIONS
1021
b. A solution of 0.09 g (0.65 mmol) of imidazole in
7 mL of THF was cooled to 0°C, 0.37 g (1.31 mmol)
of salt 5a was added, and 0.12 g (0.65 mmol) of amine
1 was then added with stirring. The subsequent proce-
dure was the same as in a. Yield 0.21 g (87%).
1H NMR spectrum, δ, ppm: 2.57 t (1H, 7-H, J =
5.4 Hz), 5.23–5.31 m (2H, 1-H, 6-H), 6.18–6.23 m
(2H, 2-H, 5-H), 6.69–6.71 m (2H, 3-H, 4-H), 6.97–
7.36 m (12H, Harom). Found: m/z 362.1542 [M + H]+.
C26H19NO. Calculated: M + H 362.4110.
4′-H, 5′-H, J = 5.5 Hz), 8.31 d (2H, 4-H, 6-H, J =
3.0 Hz). Found: m/z 276.1129 [M + H]+. C17H13N3O.
Calculated: M + H 276.1131.
Triclinic crystal system, space group P-1,
C17H13N3O; unit cell parameters [295(2) K]: a =
8.5519(17), b = 9.0036(17), c = 10.2897(19) Å; α =
110.501(17), β = 108.397(17), γ = 95.156(16)°; V =
686.05(85) Å3; Z = 2; dcalc = 1.33 g/cm3; F(000) =
287.9; μ = 0.086 mm–1. Total of 5151 reflection
intensities were measured, including 3151 independent
reflections (Rint = 0.0379) and 1948 reflections with
I > 2σ(I)]. Final divergence factors: R1 = 0.0581,
wR2 = 0.1459 [reflections with I > 2σ(I)]; R1 = 0.0905,
wR2 = 0.1764 (all independent reflections); goodness
of fit S = 1.020.
N-(Cyclohepta-2,4,6-trien-1-yl)pyrimidin-2-
amine (10). Amine 3, 0.19 g (2 mmol), was added in
one portion to a solution of 0.18 g (1 mmol) of salt 4 in
2 mL of water and 4 mL of ethanol. The transparent
solution was kept for 1.5 h at room temperature and
neutralized to pH 8 with 10% aqueous ammonia. Yield
0.17 g (92%), white crystals, mp 100–102°C (from
N-Tritylpyrimidin-2-amine (12). Salt 6, 0.83 g
(2.5 mmol), was added in one portion to a solution of
0.24 g (2.5 mmol) of amine 3 in 10 mL of methylene
chloride. The resulting solution was refluxed for 0.5 h
and cooled, the solvent was completely removed, and
the residue was treated with 10% aqueous ammonia to
pH 8. The precipitate was filtered off and recrystal-
lized. Yield 0.54 g (63%), white crystals, mp 168–
169°C (from benzene). 1H NMR spectrum spectrum, δ,
ppm: 3.10 s (1H, NH), 6.41 t (1H, 5-H, J = 4.8 Hz),
7.18–7.34 m (15H, Harom), 8.03 d (2H, 4-H, 6-H, J =
6.0 Hz). Found: m/z 338.1647 [M + H]+. C23H19N3.
Calculated: M + H 338.1652.
1
hexane). H NMR spectrum, δ, ppm: 3.89 br.s (1H,
NH), 4.37–4.41 d.t (1H, 1-H, J = 4.54, 4.47 Hz), 5.56–
5.60 m (2H, 2-H, 7-H), 6.30–6.34 m (2H, 3-H, 6-H),
6.61 t (1H, 5′-H, J = 7.32 Hz), 6.75–6.77 m (2H, 4-H,
5-H), 8.32 d (2H, 4′-H, 6′-H, J = 3.6 Hz). Found:
m/z 186.1028 [M + H]+. C11H12N3. Calculated:
M + H 186.1026.
Monoclinic crystal system, space group P21/c,
C11H11N3; unit cell parameters [295(2) K]: a =
9.701(3), b = 7.280(3), c = 14.350(4) Å; β = 92.83(3)°;
V = 1012.2(6) Å3; Z = 4. The structure was solved by
the full-matrix least-squares method in anisotropic
approximation for all non-hydrogen atoms. The NH
hydrogen was localized from the difference electron
density maps and was refined independently in iso-
tropic approximation; the other hydrogen atoms were
refined according to the riding model in isotropic
approximation with dependent thermal parameters.
Final divergence factors: R1 = 0.0579, wR2 = 0.1547
[1384 reflections with I > σ(I)]; R1 = 0.0978, wR2 =
0.1897 (2406 independent reflections); goodness of
fit S = 1.033.
Monoclinic crystals, space group I2/a, C23H19N3;
unit cell parameters [295.0(2) K]: a = 28.9764(46), b =
9.1914(14), c = 15.1479(25) Å; β = 95.983(15)°; V =
4012.42(64) Å3; Z = 8; dcalc = 1.25 g/cm3; F(000) =
1592; μ = 0.074 mm–1. Total of 18 937 reflection
intensities were measured, including 4910 independent
reflections (Rint = 0.0421) and 3409 reflections with
I > 2σ(I)]. Final divergence factors: R1 = 0.0716, wR2 =
0.1999 [reflections with I > 2σ(I)]; R1 = 0.1005, wR2 =
0.2156 (all independent reflections); S = 1.072.
The CIF files containing complete sets of crystallo-
graphic data for compounds 10–12 were deposited to
the Cambridge Crystallographic Data Centre (CCDC
entry nos. 1 832 665, 1 832 664, and 1 832 663,
data_request/cif.
N-(9H-Xanthen-9-yl)pyrimidin-2-amine (11).
Salt 5b, 0.13 g (0.5 mmol), was added in one portion
to a solution of 0.09 g (1 mmol) of amine 3 in 5 mL of
ethanol. After stirring, the mixture became homogene-
ous, and a solid precipitated in 10 min. After 1.5 h, the
mixture was neutralized to pH 8 with 10% aqueous
ammonia. Yield 0.09 g (66%), white crystals, mp 179–
180°C (from EtOH). 1H NMR spectrum, δ, ppm: 2.20 t
(1H, NH, J = 4.6 Hz), 5.97 d (1H, 9′-H, J = 6.9 Hz),
6.62 t (1H, 5-H, J = 3.6 Hz), 7.07–7.16 m (4H, 2′-H,
3′-H, 6′-H, 7′-H), 7.34 m (2H, 1′-H, 8′-H), 7.53 d (2H,
REFERENCES
1. Sanechika, K., Kajigaeshi, S., and Kanemasa, S.,
Synthesis, 1977, no. 3, p. 202.
2. Yunnikova, L.P., Akentieva, T.A., and Makhova, T.V., Int.
J. Org. Chem., 2013, vol. 3, no. 2, p. 148.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 54 No. 7 2018