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room temperature for 3 h. The reaction mixture was ltered to
remove sodium chloride. Water (20 mL) was added to the
ltrate, which was extracted with CHCl3 (30 mL ꢁ 3). The
organic layer was washed with brine, dried over MgSO4 and
concentrated in vacuo. The residue was puried by ash column
chromatography (silica gel, hexanes/EtOAc) to give the benzoyl
dimethyl phosphate 9a as a colorless oil (1.3 g, 87%).
2-Fluorobenzoyl methyl phosphate 2g. White solid, dp
1
112–116 ꢀC; IR (KBr) (cmꢂ1) 2952, 1715, 1614, 1585; H NMR
(400 MHz, DMSO-d6); d 7.85 (dt, J ¼ 7.6, 1.6 Hz, 1H), 7.68–7.62
(m, 1H), 7.32 (dt, J ¼ 7.6, 1.6 Hz, 2H), 3.48 (d, J ¼ 11.3 Hz, 3H);
13C NMR (100 MHz, DMSO-d6); d 161.1 (d, J ¼ 257 Hz), 160.4 (dd,
J ¼ 7.6, 3.8 Hz), 134.9 (d, J ¼ 8.6 Hz), 132.0, 124.5 (d, J ¼ 3.8 Hz),
119.7 (dd, J ¼ 9.5, 6.7 Hz), 117.0 (d, J ¼ 22 Hz), 52.4 (d, J ¼ 6.7
Hz); MS (ESI); m/z 233 [M ꢂ H]ꢂ; anal. calcd for C8H7FNaO5P; C,
37.52; H, 2.76; N, 0. Found; C, 37.48; H, 2.91; N, 0%.
The mixture of benzoyl dimethyl phosphate 9a (1.3 g, 5.5 mmol)
and NaI (0.83 g, 5.5 mmol) in acetone (30 mL) was stirred at room
temperature for 3 days, leading to crystallization of the product,
the sodium salt of benzoyl methyl phosphate 2a (1.2 g, 93%).
Benzoyl methyl phosphate 2a.2f White solid, dp 189–191 ꢀC;
2-Chlorobenzoyl methyl phosphate 2h. Pale yellow solid, dp
95–98 ꢀC; IR (KBr) (cmꢂ1) 3394, 1717; 1H NMR (400 MHz,
DMSO-d6); d 7.78–7.72 (m, 1H), 7.56–7.38 (m, 3H), 3.47 (d,
J ¼ 11.2 Hz, 3H); 13C NMR (100 MHz, DMSO-d6); d 167.2, 132.8,
132.0, 131.2, 130.8, 130.5, 130.4, 127.3, 127.1, 52.5 (d, J ¼ 7.6
1
IR (KBr) (cmꢂ1) 2953, 1711, 1271; H NMR (400 MHz, D2O); d
7.98 (d, J ¼ 9.6 Hz, 2H), 7.61 (t, J ¼ 8.3 Hz, 1H), 7.45 (t, J ¼ 7.7 Hz,
2H), 3.63 (d, J ¼ 11.4 Hz, 3H); 13C NMR (100 MHz, DMSO-d6);
d 151.2, 143.8, 135.0, 130.1, 129.8, 128.9, 126.4, 122.5, 121.7,
118.8, 111.3; MS (FAB); m/z 239 [M + H]+; anal. calcd for
C8H8NaO5P; C, 40.35; H, 3.39; N, 0. Found; C, 40.27; H, 3.39;
N, 0%.
4-Methoxybenzoyl methyl phosphate 2b. Yellow solid, dp
190–192 ꢀC; IR (KBr) (cmꢂ1) 3444, 1697, 1251; 1H NMR
(400 MHz, DMSO-d6); d 7.90 (d, J ¼ 8.9 Hz, 2H), 7.04 (d, J ¼ 8.9
Hz, 2H), 3.84 (s, 3H), 3.50 (d, J ¼ 11.0 Hz, 3H); 13C NMR
(100 MHz, DMSO-d6); d 163.6, 163.4 (d, J ¼ 6.7 Hz), 132.2, 123.8,
114.5, 56.0, 53.0 (d, J ¼ 6.7 Hz); MS (ESI); m/z 245 [M ꢂ H]ꢂ; anal.
calcd for C9H10NaO6P$H2O; C, 37.78; H, 4.23; N, 0. Found;
C, 37.74; H, 3.86; N, 0%.
Hz); MS (ESI); 249 [M
C8H7ClNaO5P$0.6H2O; C, 33.91; H, 2.92; N, 0. Found; C, 33.96;
H, 2.89; N, 0%.
ꢂ
H]ꢂ; anal. calcd for
2-Iodobenzoyl methyl phosphate 2i. White solid, dp 108–111
ꢀC; IR (KBr) (cmꢂ1) 3599, 1716; 1H NMR (400 MHz, DMSO-d6); d
8.01 (dd, J ¼ 7.8, 1.1 Hz, 1H), 7.75 (dd, J ¼ 7.8, 1.6 Hz, 1H), 7.51
(ddd, J ¼ 7.8, 7.8, 1.1 Hz, 1H), 7.25 (ddd, J ¼ 7.8, 7.8, 1.6 Hz, 1H),
3.51 (d, J ¼ 11.2 Hz, 3H); 13C NMR (100 MHz, DMSO-d6); d 163.5
(d, J ¼ 8.6 Hz), 141.5, 136.8 (d, J ¼ 6.7 Hz), 133.3, 131.2, 128.7,
95.1, 53.1 (d, J ¼ 6.7 Hz); MS (ESI); m/z 341 [M ꢂ H]ꢂ; anal. calcd
for C8H7INaO5P$0.5H2O; C, 25.76; H, 2.16; N, 0. Found; C,
25.74; H, 2.43; N, 0%.
4-Methylbenzoyl methyl phosphate 2c. White solid, dp 173–
1
Typical procedure for the synthesis of 2-
phenylbenzimidazoles 3
175 C; IR (KBr) (cmꢂ1) 3521, 1714, 1281; H NMR (400 MHz,
ꢀ
DMSO-d6); d 7.83 (d, J ¼ 8.0 Hz, 2H), 7.32 (d, J ¼ 8.0 Hz, 2H), 3.48
(d, J ¼ 10.8 Hz, 3H), 2.38 (s, 3H); 13C NMR (100 MHz, DMSO-d6); A mixture of 1,2-phenylenediamine 1a (54 mg, 0.5 mmol) and
d 163.2 (d, J ¼ 7.7 Hz), 143.4, 129.5, 129.0, 128.5 (d, J ¼ 5.7 Hz), benzoyl methyl phosphate 2a (143 mg, 0.6 mmol) in H2O (2 mL)
52.5 (d, J ¼ 6.7 Hz), 21.1; MS (ESI); m/z 229 [M ꢂ H]ꢂ; anal. calcd was heated at 120 ꢀC for 16 h in a sealed tube. Aer cooling, the
for C9H10NaO5P$0.3H2O; C, 41.97; H, 4.15; N, 0. Found; C, reaction mixture was poured into K2CO3 aq., then extracted with
41.92; H, 4.06; N, 0%.
EtOAc. The organic layer was washed with brine, dried over
4-Chlorobenzoyl methyl phosphate 2d. White solid, dp 277– MgSO4 and concentrated in vacuo. The residue was puried by
1
280 C; IR (KBr) (cmꢂ1) 2950, 1716, 1251; H NMR (400 MHz, ash column chromatography (silica gel, hexanes/EtOAc) to
ꢀ
DMSO-d6); d 7.94 (d, J ¼ 8.8 Hz, 2H), 7.59 (d, J ¼ 8.8 Hz, 2H), 3.49 give the 2-phenyl-1H-benzo[d]imidazole 3a.
(d, J ¼ 11.2 Hz, 3H); 13C NMR (100 MHz, DMSO-d6); d 166.5,
2-Phenyl-1H-benzo[d]imidazole 3a.12 White solid, mp 260–
138.0, 131.1, 130.0, 128.9, 52.6; MS (ESI); m/z 249 [M ꢂ H]ꢂ; 262 ꢀC; IR (KBr) (cmꢂ1) 1463, 1410; 1H NMR (400 MHz, DMSO-
anal. calcd for C8H7ClNaO5P$0.6H2O; C, 33.91; H, 2.92; N, 0. d6); d 8.18 (d, J ¼ 7.2 Hz, 2H), 7.67 (d, J ¼ 7.2 Hz, 1H), 7.60–7.48
Found; C, 33.96; H, 2.89; N, 0%.
(m, 4H), 7.24–7.17 (m, 2H); 13C NMR (100 MHz, DMSO-d6); d
4-Cyanobenzoyl methyl phosphate 2e. White solid, dp 285– 151.2, 144.0, 136.0, 130.2, 129.8, 128.9, 126.4, 122.5, 121.6,
1
289 C; IR (KBr) (cmꢂ1) 3463, 2236, 1733, 1706, 1286; H NMR 118.9, 111.3; MS (ESI); m/z 195 [M + H]+.
ꢀ
(400 MHz, DMSO-d6); d 8.08 (d, J ¼ 8.4 Hz, 2H), 8.01–7.94 (m,
2-(4-Methoxyphenyl)-1H-benzo[d]imidazole 3b.15 White
2H), 3.51 (d, J ¼ 11.2 Hz, 3H); 13C NMR (100 MHz, DMSO-d6); d solid, mp 230–232 C; IR (KBr) (cmꢂ1) 3059, 2924, 1607, 1442;
135.0, 132.7, 132.5, 130.0, 129.8, 118.0, 115.2, 52.6, 52.9; MS 1H NMR (400 MHz, DMSO-d6); d 8.12 (d, J ¼ 8.9 Hz, 2H), 7.62 (d,
(ESI); m/z 240 [M ꢂ H]ꢂ; anal. calcd for C9H7NNaO5P$0.7H2O; C, J ¼ 6.9 Hz, 1H), 7.49 (d, J ¼ 6.9 Hz, 1H), 7.22–7.15 (m, 2H), 7.12
ꢀ
39.20; H, 3.07; N, 5.32. Found; C, 39.11; H, 2.93; N, 5.04%.
(d, J ¼ 8.9 Hz, 2H), 3.84 (s, 3H); 13C NMR (100 MHz, DMSO-d6); d
2-Methoxybenzoyl methyl phosphate 2f. Yellow solid, dp 161.1, 151.9, 144.4, 135.5, 128.5, 123.2, 122.6, 122.0, 119.0,
178–180 ꢀC; IR (KBr) (cmꢂ1) 3464, 2951, 2847, 2367, 2349, 2328, 114.9, 111.6, 55.9; MS (EI); m/z (%) 224 (M+, 100).
1716, 1602; 1H NMR (400 MHz, DMSO-d6); d 7.65–7.59 (m, 1H),
2-(4-Tolyl)-1H-benzo[d]imidazole 3c.12 Off-white solid, mp
7.55–7.45 (m, 1H), 7.16–7.09 (m, 1H), 7.02–6.98 (m, 1H), 3.81 (d, 237–239 ꢀC; IR (KBr) (cmꢂ1) 3030, 1651, 1503, 1432; H NMR
J ¼ 7.3 Hz, 3H), 3.48 (d, J ¼ 7.3 Hz, 2H); 13C NMR (100 MHz, (400 MHz, DMSO-d6); d 8.07 (d, J ¼ 8.0 Hz, 2H), 7.58 (brs, 2H),
DMSO-d6); d 167.5, 158.0, 132.9, 130.9, 121.6, 120.0, 112.4, 55.7; 7.36 (d, J ¼ 8.0 Hz, 2H), 7.19 (dd, J ¼ 6.0, 2.8 Hz, 2H), 2.39 (s,
MS (ESI); m/z 245 [M ꢂ H]ꢂ; anal. calcd for C9H10NaO6P$2.1H2O; 3H); 13C NMR (100 MHz, DMSO-d6); d 151.9, 140.0, 130.0, 128.0,
1
C, 35.33; H, 4.68; N, 0. Found; C, 35.12; H, 4.30; N, 0%.
126.9, 21.5; MS (EI); m/z (%) 208 (M+, 100).
This journal is © The Royal Society of Chemistry 2014
RSC Adv., 2014, 4, 3768–3773 | 3771