326
R. Ghorbani-Vaghei et al. / C. R. Chimie 17 (2014) 324–330
1611, 1579, 1540;
d
H (500 MHz, DMSO) 2.39 (3H, s) 7.37
2.2.12. Spectra data of 4-(4-(pyridin-3-yl)pyrimidine)
colorless powder (65%); mp 85–86 8C; Rf (17%
acetone/n-hexane) 0.20; IR (KBr) 1579,
cmÀ1
1546, 1521; dH (500 MHz, CDCl3) 7.53 (1H, dd, J = 7.89,
3.89 Hz), 7.81 (1H, dd, J = 5.28, 1.26 Hz), 8.50 (1H, d,
J = 7.89), 8.80 (1H, d, J = 3.81 Hz) 8.89 (1H, d, J = 5.28 Hz),
(2H, d, J = 7.8 Hz), 8.06 (1H, d, J = 5.4 Hz), 8.12 (2H, d,
J = 7.76 Hz), 8.82 (1H, d, J = 5.36 Hz), 9.2 (1H, s); dC
(125 MHz, DMSO); 21.8, 117.6, 127.7, 130.5, 134.0, 142.1,
158.7, 159.5, 163.3. [Found: C, 77.70; H, 5.91; N, 16.29.
A
(
vmax
,
)
C
13H14N2 requires C, 77.62; H, 5.92; N, 16.46%]; MS, m/z
(%): 170 (M+, 100), 115 (55), 91 (30), 79 (25), 39 (40)
(Table 2, entry 6).
9.34 (1H, s), 9.36 (1H, d, J = 0.78 Hz); dC (125 MHz, CDCl3);
117.4, 124.3, 135.3, 148.6, 151.9, 158.3, 159.8, 161.8.
(Found: C, 68.14; H, 4.92; N, 26.36. C10H7N3 requires C,
68.78; H, 4.49; N, 26.74%); MS, m/z (%): 157 (M+, 100), 130
(25), 103 (30), 76 (25) (Table 2, entry 12).
2.2.7. Spectra data of 4-(4-methoxyphenyl)pyrimidine
A pale yellow powder (52%); mp 77–79 8C (79.7–
80.3 8C) [12]; Rf (17% acetone/n-hexane) 0.19; IR (KBr)
(v
max, cmÀ1) 1607, 1579, 1540; dH (500 MHz, CDCl3) 3.91
2.2.13. Spectra data of 4-(2-methoxybenzyl)pyrimidine
(3H, s), 7.05 (2H, d, J = 8.7 Hz), 7.67 (1H, d, J = 5.08 Hz), 8.10
(2H, d, J = 8.7 Hz), 8.73 (1H, d, J = 5.11 Hz), 9.24 (1H, s); dC
(125 MHz, CDCl3); 55.8, 114.8, 116.5, 129.1, 129.2, 157.5,
159.4, 162.6, 163.8 (Table 2, entry 7).
A yellow oil (58%); Rf (17% acetone/n-hexane) 0.31; IR
(KBr) (v dH (300 MHz,
max, cmÀ1) 2962, 1598, 1579, 1540;
CDCl3) 2.40 (2H, s), 3.78 (3H, s), 6.98–7.26 (4H, m), 7.43
(1H, s), 8.50 (1H, s), 9.08 (1H, s); dC (125 MHz, CDCl3);
22.5, 55.6, 110.8, 120.7, 130.6, 130.7, 131.8, 132.7, 156.7,
157.0, 170.2. (Found: C, 71.83; H, 5.95; N, 13.98.
2.2.8. Spectra data of 4-(4-isopropylphenyl)pyrimidine
A pale yellow powder (49%); mp 45–49 8C; Rf (17%
C12H12N2O requires C, 71.98; H, 6.04; N, 13.99%); MS,
m/z (%): 200 (M+, 20), 103 (10), 84 (35), 49 (65), 35 (85)
acetone/n-hexane) 0.27; IR (KBr) (
v
max, cmÀ1) 2962, 1609,
1578, 1540; dH (500 MHz, CDCl3) 1.33 (6H, d, J = 6.9 Hz)
3.02 (1H, m, J = 6.9 Hz) 7.41 (2H, d, J = 8.19 Hz), 7.72 (1H, d,
J = 5.0 Hz), 8.07 (2H, d, J = 8.19 Hz), 8.77 (1H, d, J = 5.0 Hz),
(Table 2, entry 13).
2.2.14. Spectra data of 4-benzyl-5-methylpyrimidine
9.28 (1H, s);
d
C (125 MHz, CDCl3); 24.2, 34.5, 117.1, 127.6,
A yellow oil (56%); Rf (17% acetone/n-hexane) 0.28; IR
127.7, 134.4, 152.8, 157.6, 159.4, 164.3. (Found: C, 78.52;
H, 7.28; N, 14.02. C13H14N2 requires C, 78.75; H, 7.12; N,
14.13%); MS, m/z (%): 198 (M+, 50), 183 (100), 168 (50), 103
(10), 79 (6) (Table 2, entry 8).
(KBr) (v dH (300 MHz, CDCl3)
max, cmÀ1) 2921, 1578, 1552;
2.42 (3H, s), 3.78 (3H, s), 6.98–7.26 (4H, m), 7.43 (1H, s),
8.50 (1H, s), 9.08 (1H, s); dC (125 MHz, CDCl3); 22.1, 35.9,
126.2, 126.7, 128.3, 128.5, 128.8, 132.0, 137.6, 156.7, 166.0.
(Found: C, 77.53; H, 6.65; N, 14.80. C12H12N2 requires C,
78.23; H, 6.57; N, 15.21%); MS, m/z (%): 184 (M+, 25), 115
(100), 91 (30), 43 (70), 28 (75) (Table 2, entry 14).
2.2.9. Spectra data of 5-methyl-4-phenylpyrimidine
A pale yellow powder (64%); mp 29–30 8C (30.2–
30.4 8C)[12]; Rf (17% acetone/n-hexane) 0.26; IR (KBr)
(v dH (300 MHz, CDCl3)
max, cmÀ1) 2960, 1602, 1572, 1539;
3. Results and discussion
2.39 (3H, s), 7.47–7.60 (5H, m), 8.62 (1H, s), 9.11 (1H, s); dC
(75 MHz, CDCl3); 17.1, 128.2, 128.4, 128.8, 129.4, 137.7,
156.4, 158.5, 165.1 (Table 2, entry 9).
In a continuation of our interest in the application of
N,N,N’,N’-tetrabromobenzene-1,3-disulfonamide (TBBDA)
[23] in organic synthesis, [23–32], we wish to report here a
facile and improved protocol for the preparation of
aliphatic, heterocyclic and aromatic pyrimidines from
triethoxymethane, ammonium acetate and various ketone
derivatives in the presence of TBBDA as a catalyst under
solvent-free conditions (Scheme 1).
2.2.10. Spectra data of 4-(3, 4-dimethoxyphenyl)pyrimidine
A grey powder (55%); mp 84–86 8C; Rf (17% acetone/n-
hexane) 0.22; IR (KBr) (
1542; H (500 MHz, CDCl3) 3.96 (3H, s), 4.02 (3H, s), 7.01
v
max, cmÀ1) 2937, 1601, 1576,
d
(1H, d, J = 8.4 Hz), 7.67 (1H, dd, J = 8.4, 1.74 Hz), 7.70 (1H, d,
J = 5.32 Hz) 7.80 (1H, d, J = 8.4, 1.64 Hz), 8.74 (1H, d,
The advantages of TBBDA are as follows:
J = 5.26 Hz), 9.25 (1H, s); dC (125 MHz, CDCl3); 56.4, 110.2,
ꢀ
ꢀ
the preparation of TBBDA is easy;
tBBDA is stable under atmospheric conditions for 2
months;
after completion of the reaction, the catalyst is recovered
and can be reused several times without decreasing the
yield.
111.5, 116.6, 120.6 129.5, 149.9, 152.2, 157.5, 159.4,
163.7. (Found: C, 66.25; H, 5.24; N, 13.12. C12H12N2O2
requires C, 66.65; H, 5.59; N, 12.96%); MS, m/z (%): 216
(M+, 100), 173 (25), 130 (25), 103 (18), 79 (16) (Table 2,
entry 10).
ꢀ
2.2.11. Spectra data of 4-(pyridin-4-yl)pyrimidine
Initially, we decided to explore the role of our catalyst in
A
colorless powder (70%); mp 79–81 8C; Rf (17%
acetone/n-hexane) 0.24; IR (KBr) 1577,
(vmax
,
cmÀ1
)
ethanol, acetonitrile and toluene as a solvent system for
the synthesis of 4-phenylpyrimidine (Table 2, entry 1) used
as a model compound. In the absence of a catalyst, no
pyrimidine was observed, even after a prolonged reaction
time. Since the synthesis of pyrimidine failed in the
absence of catalyst, the effect of the catalyst was also
investigated in various conditions, and the results are
presented in Table 1.
1536; dH (500 MHz, DMSO) 8.14 (2H, d, J = 5.85 Hz), 8.23
(1H, d, J = 5.26 Hz), 8.79 (2H, d, J = 5.85 Hz), 8.99 (1H, d,
J = 5.27 Hz), 9.35 (1H, s); dC (125 MHz, DMSO); 118.8,
121.7, 144.0, 151.1, 159.6, 159.8, 161.3. (Found: C, 68.36;
H, 5.01; N, 26.44. C10H7N3 requires C, 68.78; H, 4.49; N,
26.74%); MS, m/z (%): 157 (M+, 100), 130 (20), 103 (40), 76
(25), 53 (20) (Table 2, entry 11).