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Organic & Biomolecular Chemistry
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7.45 (d, 1H, J = 8.5 Hz), 7.14–7.09 (m, 3H), 7.03 (d, 2H, J = 7.6 Hz), 6.40 (d, 1H, obtain unsymmetrical ((1H-pyrrol-1-yl)phenyl)-1H-pyrroles. Nitrobenzene
J = 3.4 Hz), 6.15 (d, 1H, J = 3.4 Hz), 2.01 (s, 3H), 1.94 (s, 3H); 13C NMR (100 derivative (1.0 mmol) and indium powder (460 mDg,O4I:.010m.1m03o9l)/wC5aOs pBl0a2c1e0d1iDn
MHz, CDCl3) δ 147.2, 144.7, 139.0, 134.3, 132.9, 130.7, 130.3, 128.2, 127.0, toluene (2 mL), and was added acetic acid (0.572 mL, 10 mmol) and 2,5-
126.2, 125.8, 121.7, 109.0, 108.4, 17.5, 12.7; IR (NaCl) 3074, 2923, 1600, hexanedione (or 1-phenyl-1,4-pentanedione, 1.0 mmol) in toluene (3 mL) to
1527, 1446, 1350 cm-1; GC–MS m/z (rel intensity) 292 (M+,100), 277 (16), the mixture. The reaction mixture was stirred at 80 oC for 2,5-hexanedione
246 (15), 230 (22), 115 (9), 89 (7); HRMS m/z calc. for C18H16N2O2 292.1212, (or reflux for 1-phenyl-1,4-pentanedione) under nitrogen. After the reaction
found 292.1248.
was completed, the reaction mixture was diluted with ethyl acetate (30 mL),
filtered through Celite, poured into 10% aqueous NaHCO3 solution (30 mL),
and then the aqueous layer was extracted with ethyl acetate (30 mL x 3).
The combined organic extracts were dried over MgSO4, filtered, and
concentrated. The residue was eluted with hexane for most derivatives or
ethyl acetate/hexane (v/v = 5/95) for benzonitrile derivatives through a
neutral silica gel column to give the corresponding pyrroles. As all of the
final products were unknown compounds, the structures of the pyrroles
were fully characterized by 1H NMR, 13C NMR, FTIR, GC–MS and HRMS data.
2-Methyl-1-(6-methyl-3-nitrophenyl)-5-phenyl-1H-pyrrole (16). Yield
91%. Yellow solid, mp 134–135 oC. TLC (30% ethyl acetate/hexane) Rf 0.75;
1H NMR (400 MHz, CDCl3) δ 8.21 (d, 1H, J = 2.2 Hz), 8.15 (dd, 1H, J = 8.3, 2.2
Hz), 7.36 (d, 1H, J = 8.3 Hz), 7.16–7.08 (m, 3H), 7.06–7.02 (m, 2H) 6.39 (s, 1H,
J = 3.4 Hz), 6.15 (s, 1H, J = 3.4 Hz), 2.02 (s, 3H), 1.92 (s, 3H); 13C NMR (100
MHz, CDCl3) δ 146.5, 145.2, 139.6, 134.4, 132.9, 131.5, 130.8, 128.2, 127.1,
126.2, 124.4, 123.1, 108.9, 108.3, 17.7, 12.8; IR (NaCl) 3070, 2927, 2854,
1600, 1523, 1442, 1350 cm-1; GC–MS m/z (rel intensity) 292 (M+, 100), 277
(17), 246 (11), 230 (25), 115 (11), 89 (6); HRMS m/z calc. for C18H16N2O2
292.1212 found 292.1215.
2,5-Dimethyl-1-[4-(2-methyl-5-phenyl-1H-pyrrol-1-yl)phenyl]-1H-pyrrole
(20). Yield 92% (Table 4, entry1), 79% (entry 8). White solid, mp 161–162 oC.
TLC (20% ethyl acetate/hexane) Rf 0.66; 1H NMR (400 MHz, CDCl3) δ 7.25–
7.03 (m, 9H), 6.39 (d, 1H, J = 3.4 Hz), 6.14 (d, 1H, J = 3.4 Hz), 5.92 (s, 2H),
2.23 (s, 3H), 2.04 (s, 6H); 13C NMR (100 MHz, CDCl3) δ 138.7, 137.9, 134.2,
133.2, 131.4, 129.1, 128.7, 128.6, 127.8, 127.7, 125.8, 108.8, 107.8, 105.9,
13.3, 12.8; IR (NaCl) 3105, 3058, 2977, 2920, 1600, 1512, 1442, 1392 cm-1;
GC–MS m/z (rel intensity) 326 (M+, 100), 311 (24), 230 (12), 162 (36), 115
(10); HRMS m/z calc. for C23H22N2 326.1783, found 326.1770.
1-(2-Methoxy-4-nitrophenyl)-2-methyl-5-phenyl-1H-pyrrole (17). Yield
88%. Yellow solid, mp 119–120 oC. TLC (30% ethyl acetate/hexane) Rf 0.70;
1H NMR (400 MHz, CDCl3) δ 7.85–7.81 (m, 2H), 7.24–7.06 (m, 4H), 7.02 (d,
2H, J = 6.8 Hz), 6.37 (d, 1H, J = 3.2 Hz), 6.14 (d, 1H, J = 3.2 Hz), 3.76 (s, 1H),
2.08 (s, 1H); 13C NMR (100 MHz, CDCl3) δ 155.8, 147.9, 134.7, 134.3, 133.1,
131.6, 130.6, 128.0, 127.2, 126.1, 115.9, 108.9, 108.1, 107.1, 56.1, 12.5; IR
(NaCl) 3093, 2939, 1600, 1527, 1450, 1346, 1257 cm-1; GC–MS m/z (rel
intensity) 308 (M+,100), 293 (12), 262 (16), 231 (11), 115 (7); HRMS m/z calc.
for C18H16N2O3 308.1161 found 308.1147.
2,5-Dimethyl-1-[3-(2-methyl-5-phenyl-1H-pyrrol-1-yl)phenyl]-1H-pyrrole
o
(21). Yield 92% (Table 4, entry 2), 90% (entry 9). White solid, mp 87–88 C.
TLC (30% ethyl acetate/hexane) Rf 0.83; 1H NMR (400 MHz, CDCl3) δ 7.48 (t,
1H, J = 7.9 Hz), 7.28 (dt, 1H, J = 7.9, 2.0 Hz), 7.16–7.14 (m, 3H), 7.07 (t, 3H, J
= 2.0 Hz), 6.94 (t, 1H, J = 2.0 Hz), 6.34 (d, 1H, J = 3.4 Hz), 6.10 (d, 1H, J = 3.4
Hz), 5.83 (s, 2H), 2.19 (s, 3H), 1.86 (s, 6H); 13C NMR (100 MHz, CDCl3) δ 140.1,
139.5, 134.3, 133.3, 131.4, 129.4, 128.68, 128.61, 128.0, 127.9, 127.5, 127.2,
125.8, 108.9, 107.8, 105.8, 13.3, 12.7; IR (NaCl) 3101, 3062, 2974, 2920,
1604, 1492, 1392 cm-1; GC–MS m/z (rel intensity) 326 (M+,100), 311 (11),
295 (5), 230 (5), 162 (11); HRMS m/z calc. for C23H22N2 326.1783, found
326.1759.
1-(2-Fluoro-4-nitrophenyl)-2-methyl-5-phenyl-1H-pyrrole (18). Yield 50%.
Orange solid, mp 101–102 oC. TLC (30% ethyl acetate/hexane) Rf 0.71; 1H
NMR (400 MHz, CDCl3) 1H NMR (400 MHz, CDCl3) δ 8.07 (dd, 1H, J = 9.1, 2.3
Hz), 8.02 (dd, 1H, J = 8.5, 2.3 Hz), 7.31–7.25 (m, 1H), 7.19–7.12 (m, 3H),
7.06–7.03 (m, 2H), 6.40 (d, 1H J = 3.4 Hz), 6.18 (d, 1H J = 3.4 Hz), 2.15 (s, 3H);
δ 7.99 (dd, 1H, J = 9.1, 2.3 Hz), 7.94 (dd, 1H, J = 8.7, 2.3 Hz), 7.21 (t, 1H, J =
8.0Hz), 7.12-6.95 (m, 5H), 6.32 (d, 1H J = 3.4 Hz), 6.09 (d, 1H J = 3.4 Hz), 2.06
(s, 3H); 13C NMR (100 MHz, CDCl3) δ 157.4 (d, 1H, J = 255.7 Hz), 147.4 (d, 1H,
J = 9.1 Hz), 134.9, 133.6 (d, 1H, J = 13.2 Hz), 132.5, 131.4, 128.3, 127.5, 126.6,
119.6 (d, 1H, J = 3.3 Hz), 112.6 (d, 1H J = 24.8 Hz), 110.0, 109.0, 12.5; IR
2,5-Dimethyl-1-[2-methyl-4-(2-methyl-5-phenyl-1H-pyrrol-1-yl)phenyl]-
(NaCl) 3090, 2923, 1604, 1531, 1504, 1350 cm-1 GC–MS m/z (rel intensity) 1H-pyrrole (22). Yield 85%. White solid, mp 127–129 oC. TLC (30% ethyl
296(M+, 100), 250 (46), 235 (7), 115 (6), 94 (6); HRMS m/z calc. for acetate/hexane) Rf 0.84; 1H NMR (400 MHz, CDCl3) δ 7.13–7.07 (m, 8H), 6.38
C17H13FN2O2 296.0961 found 296.0961.
(d, 1H, J = 3.4 Hz), 6.11 (d, 1H, J = 3.4 Hz), 5.92 (s, 2H), 2.22 (s, 3H), 1.93 (s,
6H), 1.87 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 139.4, 138.2, 137.3, 134.2,
1-(4-Fluoro-3-nitrophenyl)-2-methyl--5-phenyl-1H-pyrrole (19). Yield 133.4, 131.4, 130.6, 129.4, 128.0, 127.8, 127.7, 126.8, 125.7, 108.8, 107.7,
o
93%. Yellow Solid, mp 108–109 C. TLC (30% ethyl acetate/hexane) Rf 0.63;
1H NMR (400 MHz, CDCl3) δ 7.92 (dd, 1H, J = 6.3, 2.0 Hz), 7.36–7.34 (m, 1H),
7.26–7.11 (m, 6H), 7.03 (d, 2H, J = 7.3 Hz), 6.35 (d, 1H, J = 2.9 Hz), 6.13 (d, 1H,
J = 2.9 Hz), 2.18 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 154.1 (d, J = 266.5 Hz),
135.8 (d, J = 4.1 Hz), 135.3 (d, J = 9.1 Hz), 134.4, 132.5, 131.3, 128.3, 128.1,
126.4, 125.4 (d, J = 2.5 Hz), 119.0, 118.8, 109.8, 108.7, 13.3; IR (NaCl) 3093,
2943, 1600, 1531, 1450, 1346 cm-1; GC–MS m/z (rel intensity) 296 (M+, 100),
250 (48), 235 (45), 207 (7), 115 (11), 94 (11), 63 (5); HRMS m/z calc. for
C17H13FN2O2 296.0961 found 296.0949.
105.7, 17.0, 13.2, 12.3; IR (NaCl) 3101, 3058, 2977, 2920, 1604, 1513, 1442,
1419, 1388 cm-1; GC–MS m/z (rel intensity) 340 (M+,100), 325 (86), 310 (14),
230 (13), 169 (30), 154 (13), 115 (11); HRMS m/z calc. for C24H24N2 340.1939,
found 340.1918.
2,5-Dimethyl-1-[2-methyl-5-(2-methyl-5-phenyl-1H-pyrrol-1-yl)phenyl]-
1H-pyrrole (23). Yield 84%. yellow oily liquid. TLC (30% ethyl acetate/hexane)
Rf 0.83; 1H NMR (400 MHz, CDCl3) δ 7.33 (d, 1H, J = 8.0 Hz), 7.21 (dd, 1H, J =
8.0, 2.0 Hz), 7.15–7.05 (m, 5H), 6.89 (d, 1H, J = 2.0 Hz), 6.32 (d, 1H, J = 3.4
Hz), 6.09 (d, 1H, J = 3.4 Hz), 5.84 (s, 2H), 2.18 (s, 3H), 1.93 (s, 3H), 1.77 (s, 6H);
13C NMR (100 MHz, CDCl3) δ 138.5, 137.8, 136.4, 134.2, 133.4, 131.4, 130.9,
129.0, 128.2, 128.1, 128.0, 127.9, 125.7, 108.7, 107.7, 105.4, 16.7, 13.3, 12.3;
IR (NaCl) 3055, 2923, 1612, 1508, 1442, 1392 cm-1; GC–MS m/z (rel intensity)
General procedure for the indium-mediated reaction of (1H-pyrrol-1-
yl)nitroarenes with 2,5-hexanedione or 1-phenyl-1,4-pantanedione to
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