1
92 JOURNAL OF CHEMICAL RESEARCH 2007
1
10°C (bath temperature) for 7 h. The reaction mixture was cooled
pyrrole] (13b): Orange-yellow crystalline solid (170 mg, 35%),
-1
and poured in ice-water (50 g). The deposited solid was filtered, dried
and chromatographed over silica gel (100–200). From the reaction
mixture of 1, compounds 9 and 10 were isolated using 10% benzene
in light petrol and benzene as eluent, respectively. From the reaction
mixture of 12, compound 13 was obtained using benzene as eluent.
m.p. 168–170°C. IR: νmax/cm 3323, 3122, 2953, 1591, 1527. NMR:
1
4
δH 1.96 (4 H, s, 2 × CH ), 3.71 (6 H, s, 2 × N-CH ), 4.00 (4 H, s,
2
3
1
4
2 × OCH ) , 6.64 [4 H, brs, 2 × (4-H and 5-H)], 6.94 (2 H, d, J = 9.0 Hz,
2
2 × 3"-H), 7.07 (2 H, dd, J = 9.0, 2.2 Hz, 2 × 4"-H), 7.27 (2 H, brs, 2 × 2-
H), 7.43 (2 H, d, J = 2.2 Hz, 2 × 6"-H), 11.68 (2 H, s, exchangeable,
+
4
H-Chromen-4-one (9a): White crystalline solid (60 mg, 41%);
2 × OH). MS (positive ion electrospray); m/z 511 (M + Na ). Anal.
15
m.p. 58°C (lit. m.p. 56°C).
-Methyl-4H-chromen-4-one (9b): White crystalline solid (60 mg,
3
Calcd. for C H N O : C, 68.84; H, 5.78; N, 5.73. Found: C, 68.70;
2
8
28
2
6
6
H, 5.60; N, 5.60%.
5",5"'-(Pentamethylenedioxy)di-[3-(2-hydroxybenzoyl)-1-methyl-
1
5
7%); m.p. 92°C (lit. m.p. 93°C).
-Chloro-4H-chromen-4-one (9c): White crystalline solid (75 mg,
6
pyrrole] (13c): Orange-yellow crystalline solid (180 mg, 36%),
1
5
-1
4
2%); m.p. 138°C (lit. m.p. 140°C).
m.p. 106–108°C. IR: ν /cm 3320, 3130, 2960, 1580, 1520.
max
Compounds 9a–c are identical in all respects to those of authentic
1H NMR: δ 1.66–1.72 (2 H, m, CH ), 1.82–1.91 (4 H, m, 2 × CH ), 3.75
2
2
samples.
(6 H, s, 2 × N-CH ), 3.97 (4 H, t, J = 6.3 Hz, 2 × OCH ), 6.67–6.69
3
2
3
-[3-(2-Hydroxybenzoyl)-1-methyl-2,5-dihydropyrrol-2-yl]-
[
(
4 H, m, 2 × (4-H and 5-H)], 6.97 (2 H, d, J = 8.9 Hz, 2 × 3"-H), 7.09
2 H, dd, J = 8.9, 2.9 Hz, 2 × 4"-H), 7.31 (2 H, brs, 2 × 2-H), 7.47
4
H-chromen-4-one (10a): Yellow crystalline solid (50 mg, 29%),
-1
1
m.p. 190°C. IR: νmax/cm 3450, 3010, 2860, 1640, 1630, 1450. H
NMR: δ 3.41 (3 H, s, 1'-CH ), 3.81 (1 H, dd, J = 13.0, 6.0 Hz, 5'-H), 4.09
(2 H, d, J = 2.9 Hz, 2 × 6"-H), 11.68 (2 H, s, exchangeable, 2 × OH).
3
Anal. Calcd. for C H N O : C, 69.31; H, 6.02; N, 5.57. Found: C,
2
9
30
2
6
(
1 H, m, 5'-H), 5.17–5.20 (1 H, m, 2'-H), 6.87–6.95 (2 H, m, 3"-H
6
9.21; H, 5.93; N, 5.43%.
and 8-H), 7.02–7.09 (2 H, m, 5"-H and 6-H), 7.42–7.49 (2 H, m, 4"-
H and 7-H), 7.55 (1 H, dd, J = 7.9, 1.6 Hz, 6"-H), 7.69 (1 H, brs,
We gratefully acknowledge the U. G. C., New Delhi, for
financial assistance; Prof. C. K. Ghosh, University of Calcutta,
for helpful discussion; IICB and IACS, Jadavpur, Kolkata
for instrumental help and finally the College authority for
providing research facilities.
2
-H), 7.96 (1 H, dd, J = 7.8, 1.6 Hz, 5-H), 8.05–8.06 (1 H, m, 4'-H),
11.51 (1 H, s, exchangeable, OH). Anal. calcd. for C H NO : C,
7
2
1
17
4
2.61; H, 4.93; N, 4.03. Found: C, 72.42; H, 4.80; N, 3.98%.
-[3-(2-Hydroxy-5-methylbenzoyl)-1-methyl-2,5-dihydropyrrol-
-yl]-6-methyl-4H-chromen-4-one (10b): Yellow crystalline solid
3
2
-1
(60 mg, 32%), m.p. 208–210°C. IR: νmax/cm 3420, 2980, 2900,
1
6
4
6
7
635, 1615, 1460. NMR: δH 2.27 (3 H, s, 5"-CH ), 2.30 (3 H, s,
3
Received 1 January 2007; accepted 1 April 2007
Paper 07/4381 doi: 10.3184/030823407X203323
-CH ), 3.38 (3 H, s, 1'-CH ), 3.77 (1 H, dd, J = 12.3, 6.8 Hz, 5'-H),
3
3
.05 (1 H, dd, J = 12.3, 1.3 Hz, 5'-H), 5.11 (1 H, d, J = 6.8 Hz, 2'-H),
.81 (1 H, d, J = 8.3 Hz, 3"-H), 6.90 (1 H, d, J = 8.3 Hz, 8-H), 7.21–
.28 (3 H, m, 4"-H, 7-H and 6"-H), 7.64 (1 H, s, 2-H), 7.72 (1 H, d,
References
J = 1.0 Hz, 5-H), 8.00 (1 H, brs, 4'-H), 11.27 (1 H, s, exchangeable,
OH); δC 20.42 (ArCH ), 20.56 (ArCH ), 47.30 (N–CH ), 58.22
1
A.K. Baruah, D. Prajapati and J.S. Sandhu, J. Chem. Soc., Perkin Trans.
1, 1987, 1995.
3
3
3
(
1
(
1
2'-C), 74.54 (5'-C), 107.54 (3-C), 116.82 (3"-C), 117.74 (8-H),
19.71 (1"-C), 121.14 (4a-C), 124.50 (5"-C), 127.21 (5-C), 127.45
6-C), 131.29 (3'-C), 131.64 (6"-C), 132.24 (4'-C), 135.58 (4"-C),
35.78 (7-C), 155.63 (2-C), 157.00 (8a-C), 159.53 (2"-C), 179.07
pyran CO), 197.60 (benzoyl CO). MS (positive ion electrospray):
2
(a) A.K. Baruah, D. Prajapati and J.S. Sandhu, Tetrahedron, 1988, 44,
1241; (b) L. Tsao, V. Van, G. Sun and L. Yu, Russian J. Gen. Chem., 2001,
7
1, 767.
Z. Xie, F. Liu, Y. Hui, C. Liu and Y.Sun, J. Heterocycl. Chem., 2005, 42,
95.
3
4
6
(
(a) A.K. Kalita, A.K. Baruah, D. Prajapati and J.S. Sandhu, Indian
J. Chem., 1998, 37B, 101; (b) M.P.S. Ishar, G. Singh, K. Kumar and
R. Singh, Tetrahedron, 2000, 56, 7817; (c) M.P.S. Ishar and K. Kumar,
Tetrahedron Lett., 1999, 40, 175.
A.R. Mahajan, R.C. Baruah and J.S. Sandhu, Chem. Ind., 1990, 261.
M.P.S. Ishar, K. Kumar and R. Singh, Tetrahedron Lett., 1998, 39, 6547.
(a) C. Bandyopadhyay, K.R. Sur, R. Patra and S. Banerjee, J. Chem.
Research (S), 2003, 459; J. Chem. Res. (M), 2003, 847; (b) T. Ghosh,
R. Patra and C. Bandyopadhyay, J. Chem. Res., 2004, 47; (c) T. Ghosh
and C. Bandyopadhyay, Tetrahedron Lett., 2004, 45, 6169.
P.D. Clarke, A.O. Fitton, M. Kosmirak, H. Suschitzky and J.L. Suschitzky,
J. Chem. Soc., Perkin Trans. 1, 1985, 1747.
+
m/z 398 (M + Na ). Anal. Calcd. for C H NO : C, 73.58; H, 5.64;
2
3
21
4
N, 3.73. Found: C, 73.39; H, 5.48; N, 3.56%.
-Chloro-3-[3-(5-chloro-2-hydroxybenzoyl)-1-methyl-2,5-dihy-
dropyrrol-2-yl]-4H-chromen-4-one (10c): Yellow crystalline solid
6
5
6
7
-1
(75 mg, 36%), m.p. 202–204°C. IR: νmax/cm 3470, 3080, 2927,
1
1
647, 1629, 1467. H NMR: δ 3.42 (3 H, s, 1'-CH ), 3.79 (1 H, dd,
3
J = 12.7, 7.0 Hz, 5'-H), 4.10 (1 H, dd, J = 12.7, 1.0 Hz, 5'-H), 5.14
1 H, d, J = 7.0 Hz, 2'-H), 6.88 (1 H, d, J = 8.6 Hz, 3"-H), 6.97 (1 H,
d, J = 8.8 Hz, 8-H), 7.36–7.39 (3 H, m, 4"-H, 7-H and 6"-H), 7.66
1 H, s, 2-H), 7.90 (1 H, d, J = 1.4 Hz, 5-H), 8.00 (1 H, brs, 4'-H),
(
8
9
(
1
1.28 (1 H, s, exchangeable, OH). Anal. Calcd. for C H Cl NO : C,
21 15 2 4
A.G.P.R. Figueiredo, A.C. Tome, A.M.S. Silva and J.A.S. Cavaleiro,
Tetrahedron, 2007, 63, 910.
6
0.59; H, 3.63; N, 3.36. Found: C, 60.41; H, 3.70; N, 3.25%.
",5"'-(Trimethylenedioxy)di-[3-(2-hydroxybenzoyl)-1-methyl-
pyrrole] (13a): Orange-yellow crystalline solid (180 mg, 38%), m.p.
5
10 M.D.L. De la Torre, A.G.P. Rodrigues, A.C. Tome, A.M.S. Silva and
J.A.S. Cavaleiro, Tetrahedron, 2004, 60, 3581.
11 C.K. Ghosh, C. Bandyopadhyay and N. Tewari, J. Org. Chem., 1984, 49,
-1
1
1
06–108°C. IR: νmax/cm 3300, 3110, 2940, 1580, 1525. H NMR:
2
812.
T. Ghosh, P. Debnath and C. Bandyopadhyay, J. Indian Chem. Soc., 2006,
3, 822.
δ 2.25 (2 H, quintet, J = 6.0 Hz, CH ), 3.73 (6 H, s, 2 × N-CH ),
2
3
1
1
1
2
3
4
4
.15 (4 H, t, J = 6.0 Hz, 2 × OCH ), 6.64–6.68 [4 H, m, 2 × (4-H
2
8
and 5-H)], 6.97 (2 H, d, J = 9.0 Hz, 2 × 3"-H), 7.09 (2 H, dd, J = 9.0,
.0 Hz, 2 × 4"-H), 7.29 (2 H, d, J = 1.8 Hz, 2 × 2-H), 7.47 (2 H, d,
J = 3 Hz, 2 × 6"-H), 11.69 (2 H, brs, exchangeable, 2 × OH) Anal.
calcd. for C H N O : C, 68.34; H, 5.52; N, 5.90. Found: C, 68.50;
A.M.G. Silva, M.A.F. Faustino, A.C. Tome, M.G.P.M.S. Neves,
A.M.S. Silva and J.A.S. Cavaleiro, J. Chem. Soc., Perkin Trans. 1, 2001, 2752.
(a) T. Ghosh, S. Saha and C. Bandyopadhyay, Synthesis, 2005, 1845;
(b) T. Ghosh, K.R. Sur and C. Bandyopadhyay, J. Chem. Res., 2006,
651; (c) T. Ghosh and C. Bandyopadhyay, J. Heterocycl. Chem., 2006,
43, 1431.
3
27
26
2
6
H, 5.43; N, 5.78%.
",5"'-(Tetramethylenedioxy)di-[3-(2-hydroxybenzoyl)-1-methyl-
5
PAPER: 07/4381