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Russ.Chem.Bull., Int.Ed., Vol. 58, No. 7, July, 2009
Lipson et al.
6.88, 6.77 (both dd, 1 H each, CH, J = 9.4 Hz, J = 16.0 Hz).
MS, m/z (Irel (%)): 198 [M]+ (82), 171 (15), 155 (18), 129 (25),
121 (100), 84 (58), 77 (33).
(method A), 37% (method B), m.p. 212—214 °C (from PriOH).
Found (%): C, 54.93; H, 5.30; N, 21.40; S, 12.19. C12H14N4OS.
Calculated (%): C, 54.96; H, 5.34; N, 21.37; S, 12.21. IR, ν/cm–1
:
5ꢀ[Nꢀ(E)ꢀ3ꢀ(4ꢀNitrophenyl)propꢀ2ꢀenꢀ1ꢀylideneamino]ꢀ1Hꢀ
1,2,4ꢀtriazole (4b). Orange crystals, the yield was 57%, m.p.
269—272 °C (decomp.) (from MeOH). Found (%): C, 54.51;
H, 3.28; N, 28.89. C11H9N5O2. Calculated (%): C, 54.32;
H, 3.70; N, 28.81. IR, ν/cm–1: 3140, 3108, 3024, 2904, 1600,
1524, 1340. 1H NMR, δ: 14.07 (br.s, 1 H, NH); 9.01 (d, 1 H,
CH, J = 9.3 Hz); 8.29—7.97 (dd, 4 H, Harom, J = 8.7 Hz); 8.26
(s, 1 H, C(3)H); 7.68 (d, 1 H, CH, J = 15.6 Hz); 7.40, 7.35
(both dd, 1 H each, CH, J = 9.3 Hz, J = 15.6 Hz).
3ꢀMethylthioꢀ5ꢀ[Nꢀ(E)ꢀ3ꢀphenylpropꢀ2ꢀenꢀ1ꢀylideneamiꢀ
no]ꢀ1Hꢀ1,2,4ꢀtriazole (5a). Yellow crystals, the yield was 32%,
m.p. 173—175 °C (decomp.) (from MeOH). Found (%): C, 59.26;
H, 4.50; N, 23.00; S, 13.20. C12H12N4S. Calculated (%): C, 59.01;
H, 4.92; N, 22.95; S, 13.11. IR, ν/cm–1: 3384, 3280, 2928, 1584,
1560, 1496. 1H NMR, δ: 13.79 (br.s, 1 H, NH); 8.92 (d, 1 H,
CH, J = 9.4 Hz); 7.71—7.26 (m, 5 H, Harom); 7.20 (d, 1 H, CH,
J = 16.0 Hz); 6.77, 6.68 (both dd, 1 H each, CH, J = 9.4 Hz,
J = 16.0 Hz); 2.34 (s, 3 H, SMe).
3ꢀMethylthioꢀ5ꢀ[Nꢀ(E)ꢀ3ꢀ(4ꢀnitrophenyl)propꢀ2ꢀenꢀ1ꢀylideꢀ
neamino]ꢀ1Hꢀ1,2,4ꢀtriazole (5b). Orange crystals, the yield was
18%, m.p. 195—198 °C (decomp.) (from MeOH). Found (%):
C, 50.05; H, 3.50; N, 24.30; S, 11.08. C12H11N5O2S. Calculatꢀ
ed (%): C, 49.83; H, 3.81; N, 24.22; S, 11.07. IR, ν/cm–1: 3200,
3076, 1600, 1520, 1348. 1H NMR, δ: 14.10 (br.s, 1 H, NH); 8.98
(d, 1 H, CH, J = 9.2 Hz); 8.30—7.99 (dd, 4 H, Harom, J = 8.8 Hz);
7.68 (d, 1 H, CH, J = 15.8 Hz); 7.40, 7.35 (dd, 1 H, CH, J = 9.2 Hz,
J = 15.8 Hz); 2.45 (s, 3 H, SMe).
3264, 3128—2928, 1612. 1H NMR, δ: 7.64 (br.s, 1 H, NH);
7.30—7.38 (m, 5 H, Harom); 6.99 (d, 1 H, OH, J = 5.8 Hz); 5.86
(m, 1 H, C(7)H); 4.63 (m, 1 H, C(5)H); 2.43 (s, 3 H, SMe); 1.99
(m, 2 H, CH2). 13C NMR, δ: 39.6 (C(6)); 50.5 (C(5)); 74.5
(C(7)); 94.9 (SMe); 127.4, 128.4, 129.3, 142.4 (Carom); 155.2
(C(2)); 158.2 (C(3a)). MS, m/z (Irel (%)): 262 [M]+ (100), 233
(24), 217 (84), 130 (36), 117 (22), 105 (20).
Xꢀray diffraction study of compound 7a. Crystals of comꢀ
pound 7a are monoclinic, C12H14N4OS, at 20 °C a = 21.281(2) Å,
b = 9.240(1) Å, c = 13.921(1) Å, β = 108.09(1)°, V = 2602.0(4) Å3,
Mr = 262.33, Z = 8, the space group is P21/c, dcalc = 1.339 g cm–3
,
μ(MoꢀKα) = 0.243 mm–1, F(000) = 1104. Parameters of the unit
cell and intensities of 16758 reflections (7542 were independent,
Rint = 0.067) were measured on a Xcaliburꢀ3 diffractometer
(MoꢀKα irradiation, a CCD detector, a graphite monochromaꢀ
tor, ωꢀscanning, 2θ
= 60°). The structure was decoded by
max
direct method using the SHELXTL program package.12 Posiꢀ
tions of hydrogen atoms were found from the differential syntheꢀ
sis of electron density and refined isotropically. The structure
was refined on F2 by fullꢀmatrix leastꢀsquares method in anisoꢀ
tropic approximation for nonhydrogen atoms to wR2 = 0.183 on
7482 reflections (R1 = 0.058 on 4343 reflections with F > 4σ(F),
S = 0.977). The atom coordinates and full tables of bond disꢀ
tances and bond angles were deposited with the Cambridge Strucꢀ
tural Database (CCDC 685602).
References
5ꢀPhenylꢀ4,5,6,7ꢀtetrahydro[1,2,4]triazolo[1,5ꢀa]pyrimidinꢀ
7ꢀol (6a). A. A mixture of aminotriazole 1 (0.42 g, 5 mmol) with
aldehyde 3a (0.66 g, 5 mmol), piperidine (0.15 mL) in PriOH
(3 mL) was refluxed for 5 min, a yellow precipitate of azomeꢀ
thine 4a (0.34 g, 34%) was filtered off. Triazolo[1,5ꢀa]pyrimidinꢀ
7ꢀol 6a was isolated from a cooled filtrate as colorless precipitate,
which was recrystallized from PriOH. The yield of compound 6a
was 0.27 g (27%), m.p. 237—238 °C. Full evaporation of PriOH
from the reaction mixture left after isolation of products 4a and
6a gave an oil, from which the starting aminotriazole 1 was
isolated (0.15 g, 36%) using MeOH. Compounds 5a (the yield
was 30%) and 7a were synthesized similarly from aminopyrazole 2.
B. A mixture of aminotriazole 1 (0.42 g, 5 mmol) with aldeꢀ
hyde 3a (0.66 g, 5 mmol), piperidine (0.15 mL) in Me2CO (5 mL)
was refluxed for 5 min, cooled, compound 6a was filtered off
(0.43 g, 43%) as colorless crystals. The amorphous residue
obtained after full evaporation of Me2CO from the filtrate
was treated with MeOH to yield the starting aminotriazole 1
(0.22 g, 52%). Compound 7a was synthesized similarly from
aminotriazole 2.
For compound 6a found (%): C, 61.07; H, 5.54; N, 25.89.
C11H12N4O. Calculated (%): C, 61.11; H, 5.56; N, 25.93. IR,
ν/cm–1: 3256, 3140—2932, 1612. 1H NMR, δ: 7.43—7.33 (m, 6 H,
1 H, C(2)H, 5 H, Harom); 6.84 (br.s, 1 H, NH); 6.75 (d, 1 H,
OH, J = 5.6 Hz); 5.54 (m, 1 H, C(7)H); 4.68 (m, 1 H, C(5)H);
2.03 (m, 2H, CH2). 13C NMR, δ: 38.7 (C(6)); 50.1 (C(5)); 73.9
(C(7)); 126.7, 127.6, 128.5, 141.8 (Carom); 148.9 C(2); 153.6
(C(3a)). MS, m/z (Irel (%)): 216 [M]+ (100), 198 (30), 171 (15),
132 (45), 105 (80), 84 (30), 77 (50).
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2ꢀMethylthioꢀ5ꢀphenylꢀ4,5,6,7ꢀtetrahydro[1,2,4]triazoloꢀ
[1,5ꢀa]pyrimidinꢀ7ꢀol (7a). Colorless crystals, the yield was 23%
Received May 7, 2008;
in revised form March 3, 2009