Vol. 25, No. 17 (2013)
Synthesis of Novel Diarylpyrrole-2-carbaldehydes by Ring Transformations 9597
-
1
+
(Irel %): m/z 317 [M +2], 315 [M ] (100), 204 [M -PhCl] (12),
+
+
1
361.51 (-NO
2
), 2365.43 (aromatic ring), 1037.49 cm (C-Br
bond) H NMR spectrum (CDCl , 300MHz), δ ppm(J, Hz):
.636 (s, 1H, CHO), 8.360-7.618 (m, 8H, Ar-H), 7.019 (d,
H, pyrrole-H, J = 3.15 Hz ), 6.655 (d, 1H, pyrrole-H, J =
1
+
111 [PhCl] (45) 75 [ Ph] (27), 139 [PhCl] (69), 280 [M -Cl]
3
9
1
3
(11) found (%) C 64.31; H 3.18; N 4.32), C17
calcd. (%) C 64.55; H 3.48; N 4.43
5-(4’-Chlorophenyl)-1-(4"-bromophenyl) -1H-pyrrole-
2
H11Cl NO (315)
13
.15 Hz) C NMR spectrum (CDCl , 75 MHz) δ ppm: 177.45
3
(
C=O aldehyde), 142.66, 132.34, 132.23, 131.83, 131.60,
31.11, 130.93, 126.71, 125.23, 113.91, 108.06 (Ar-C) mass
2-carbaldehyde (16): Brown crystals, m.p. 98 ºC (EtOH) FTIR
-1
1
(KBr, νmax, cm ): 1677.94 (C=O aldehyde), 2322.89 (aromatic
1
ring), 1094.65 (C-Cl bond) , 1040.37 (C-Br bond), H NMR
+
+
spectrum (EI, 70 eV, (Irel %): m/z 372 [M +2] (100), 370 [M ]
91) found (%) C 54.98; H 2.76; N 7.44 C17 (370)
calcd. (%) C 55.13; H 2.97; N 7.56.
-(5’-Formyl-1-(4"-nitrophenyl)-1H-pyrrol-1-yl)benzoic
acid (12): Brown crystals, m.p. 150 ºC (EtOH) FTIR (KBr,
(
H11BrN O
2 3
3
spectrum (CDCl , 300 MHz), δ ppm (J, Hz): 9.636 (s, 1H,
CHO), 7.750-7.292 (m, 8H, Ar-H), 6.818 (d, 1H, pyrrole-H,
13
4
J = 7.50 Hz), 6.204 (d, 1H, pyrrole-H, J = 2.80 Hz) C NMR
spectrum (CDCl , 75 MHz) δ ppm: 177.18 (C=O aldehydes)
158.19, 152.20, 135.67, 129.26, 128.94, 127.49, 126.50,
3
-1
ν
max, cm ): H 2363.72 (aromatic ring), 1715.12 (C=O acid),
1
686.17 (C=O aldehyde), 1599.94 and 1341.94 (Asym and
1
), 3114.28 (-OH acid) H NMR spectrum (CDCl
124.94, 123.27, 107.95 (Ar-C) mass spectrum (EI, 70 eV, (Irel
+
%): m/z 361 [M +2] (100), 359 [M ] (72), 111 [PhCl] (43)
+
sym -NO
2
3
,
3
00 MHz), δ ppm (J, Hz): 9.721 (s, 1H, CHO), 8.317-7.342
m, 8H, Ar-H), 7.029 (d, 1H, pyrrole-H, J = 2.85 Hz), 7.017
found (%) C 56.91; H 3.10; N 3.56 C17
(%) C 56.82; H 3.06; N 3.89.
H11BrClNO (359) calcd.
(
(
13
d, 1H, pyrrole-H, J = 2.85 Hz), C NMR spectrum (CDCl
3
,
4-(2"-Formyl-5-(4’-chlorophenyl)-1H-pyrrol-1-yl)
benzoic acid (17): Light yellow crystals, m.p. 212 ºC (EtOH)
7
1
1
5 MHz) δ ppm: 178.89 (C=O aldehyde),140.36, 131.58,
30.87, 130.21, 128.90, 127.60, 125.03, 113.83, 109.31,
-1
FTIR (KBr, νmax, cm ): 2341.29 (aromatic ring) 1717.11 (C=O
acid), 1659.90 (C=O aldehyde) 3115.21 (-OH acid), 1094.88
+
06.55 (Ar-C) Mass spectrum (EI, 70 eV, (Irel %): m/z 336 [M ]
+
78), 306 [M -CHO] (66) , 289 [M -NO2] ( 32) found (%) C
+
1
(C-Cl bond), H NMR spectrum (CDCl
(
3
, 300MHz), δ ppm(J,
6
3
4.21; H 3.46; N 8.21 C18
.57; N 8.33.
H
12
N
2
O
5
(336) calcd. (%)C 64.28; H
Hz): 9.639 (s, 1H, CHO), 7.755-7.293 (m, 8H, Ar-H), 7.221
(d,1H, pyrrole-H, J = 3.20 Hz), 6.808 (d, 1H, pyrrole-H, J =
1
3
5
-(4’-Chlorophenyl)-1-phenyl-1H-pyrrole-2-carbal-
3
3.20 Hz), 11.559 (COOH). C NMR spectrum (CDCl , 75
dehyde (13):Yellow crystals, m.p. 82 ºC (EtOH) FTIR (KBr,
νmax, cm ): 1614.87 (C=O aldehyde), 1092.01 (C-Br bond)),
MHz) δ ppm: 177.45 (C=O aldehyde), 147.59, 134.92, 133.56,
130.24, 129.63, 129.22, 125.05, 124.44, 123.12, 121.28,
110.72, 108.01 (Ar-C) mass spectrum (EI, 70 eV, (Irel %): m/z
-1
1
3
H NMR spectrum (CDCl , 300MHz), δ ppm(J, Hz): 9.610 (s,
+
+
+
+
1
H, CHO), 7.707-7.189 (m, 8H, Ar-H), 7.033 (d, 1H, pyrrole-
327 [M +2], 325 [M ] (53), 279 [M - COOH] (33), 217 [M -
13
H, J = 3.50 Hz), 6.514 (d, 1H, pyrrole-H, J = 3.50 Hz) C
NMR spectrum (CDCl , 75 MHz) δ ppm: 178.90 (C=O alde-
hyde), 144.87, 132.43, 129.74, 129.61, 128.70, 125.95, 125.64,
25.39, 124.73,123.13, 121.04, 110.08, 106.04(Ar-C) mass
PhCOOH] (33) Found 5 C 66.08; H 3.59; N 3.98 C18
(325) calcd. (%) C 66.46; H 3.69; N 4.30.
H12ClNO
3
3
5-(4’-Bromophenyl)-1-phenyl-1H-pyrrole-2-
carbaldehyde (18): Red crystals, m.p. 122 ºC (EtOH) FTIR
-1
(KBr, νmax, cm ): 2341.84 (aromatic ring) 1661.86 (C=O
1
+
+
spectrum (EI, 70 eV, (Irel %): m/z 284 [M +2], 282 [M ] (40),
+
1
aldehyde) H NMR spectrum (CDCl
2
54 [M -CHO] (5) found (%) C 72.25; H 4.52; N 4.76
12ClNO (281) calcd. (%) C 72.59; H 4.27; N 4.98.
-(4’-Chlorophenyl)-1-(4"-nitrophenyl)-1H-pyrrole-2-
carbaldehyde (14): Light brown crystals m.p. 165 ºC (EtOH)
3
, 300 MHz), δ ppm(J,
Hz): 9.635 (s, 1H, CHO), 8.282 (d, 2H, Ar-H), 7.680 (d, 2H,
C
17
H
5
Ar-H, J = 4.50 Hz )7.572 (d, 1H,Ar-H, J = 4.50 Hz), 7.441 (d,
1H, Ar-H), 7.299 (d, 1H, 7.220 (d, pyrrole-H, J = 2.75 Hz),
13
6.827 (d, pyrrole-H, J = 2.75 Hz) C NMR spectrum (CDCl ,
3
-1
FTIR (KBr, νmax, cm ): 1628.38 (C=O aldehyde), 1584.86 and
1
1
328.36 (asym and sym -NO
spectrum (CDCl , 300 MHz), δ ppm (J, Hz): 9.638 (s, 1H,
CHO), 8.072-7.295 (m, 8H, Ar-H), 7.322 (d, 1H, pyrrole-H,
2
), 1094.51 (C-Cl bond), H NMR
75 MHz) δ ppm: 177.23 (C=O aldehyde), 166.39 (COOH),
165.91 (C=O ester), 158.22, 152.18, 132.21, 131.97, 131.72,
129.60, 127.89, 126.18, 125.09, 123.94, 123.34, 121.18,
108.04 (Ar-C) mass spectrum (EI, 70 eV, (Irel (%)): m/z 327
3
1
3
J = 3.20 Hz), 6.821 (d, 1H, pyrrole-H, J = 3.20 Hz) C NMR
spectrum (CDCl , 75 MHz) δ ppm: 177.22 (C=O aldehyde),
52.37, 149.29, 129.27, 128.95, 126.52, 126.33, 125.11,
24.90, 121.45, 113.37, 108.50, 107.97 (Ar-C) mass spec-
+
+
+
3
[M +2], 325 [M ] (12), 250 [M - Ph] (100) found (%) vC
1
1
62.98; H 3.43; N 4.61 C17
H 3.69; N 4.30.
5-(4’-Bromophenyl)-1-(4"-nitrophenyl)-1H-pyrrole-2-
H12BrNO (325) calcd. (%) C 62.76;
+
+
trum (EI, 70 eV, (Irel %): m/z 328 [M +2], 326 [M ] (72), 205
+
[
M -PhNO
2
] (100) found (%) C 62.13; H 3.11; N 8.64
(326) calcd. (%) C 62.57; H 3.37; N 8.58.
-(4’-Chlorophenyl)-1-(4"-chlorophenyl) -1H-pyrrole-
-carbaldehyde (15): Dark red crystals, m.p. 196 ºC (EtOH);
carbaldehyde (19): Brown crystals, m.p. 128 ºC (EtOH) FTIR
-
1
C
17
H
11ClN
2
O
3
(KBr, νmax, cm ): 2363.80 (aromatic ring) 1628.71 (C=O
aldehyde), 1586.45 and 1298.23 (asym and sym -NO ), 1033.65
, 300 MHz), δ ppm
5
2
1
2
(C-Br bond), H NMR spectrum (CDCl
3
-1
FTIR (KBr, νmax, cm ): 1658.80 (C=O aldehyde), 2563.01
(J, Hz) : 9.642 (s, 1H, CHO), 7.564 (d, 2H, Ar-H), 7.521 (d,
2H, Ar-H),7.492 (d, 1H, Ar-H), 7.304 (d, 1H, Ar-H,) 6.721 (d,
1
(
aromatic ring), 1092.17(C-Cl bond) H NMR spectrum
CDCl , 300 MHz), δ ppm(J, Hz): 9.639 (s, 1H, CHO), 7.754-
.293 (m, 8H, Ar-H), 7.220 (d, 1H, pyrrole-H, J = 3.50 Hz),
1
3
(
3
pyrrole-H, J = 3.50 Hz), 6.622 (d, pyrrole-H, J = 3.50 Hz) C
NMR spectrum (CDCl , 75 MHz) δ ppm: 177.47 (C=O alde-
7
6
3
1
3
.808 (d, 1H, pyrrole-H, J = 3.50 Hz). C NMR spectrum
, 75 MHz) δ ppm: 177.21 (C=O aldehyde), 135.70,
hyde), 149.38, 130.24, 126.33, 125.12, 125.06, 124.70, 123.06,
121.47, 109.36 (Ar-C) mass spectrum (EI, 70 eV, (Irel (%)):
(CDCl
3
+
m/z 372 [M +2], 370 [M ] (100), 342 [M -CHO] (50), 325
+
+
1
1
29.29, 129.15, 128.78, 127.51, 126.53, 125.65, 123.16,
18.45, 108.61, 107.97 (Ar-C) mass spectrum (EI, 70 eV,
+
+
+
2 2
[M -NO ] (25), 245 [M -PhNO ] (22), 217 [M -PhBr] (11)