November 2011
A Facile and Efficient Addition Reaction of Nitrogen-Containing Heterocyclic
Compounds with DMAD Under Neat Conditions
1443
1
1268; H-NMR (CDCl
7
C
C
9.5, 53.8, 53.1, 52.1, 50.4; HRMS (EI): m/z calcd for
3
): d ¼ 8.61 (s, 1H), 7.19–7.32 (m, 4H),
13
21
H
H
19NO
19NO
8
:
413.11, found: 413.10; Anal. Calcd for
: C, 61.02; H, 4.63; N, 3.39%. Found: C, 61.04; H,
3.90 (s, 3H), 3.81 (s, 3H), 3.76 (s, 3H), 3.66 (s, 3H); C-
NMR (CDCl
125.02, 118.7, 116.4, 115.9, 110.1, 103.3, 101.0, 99.0, 81.3,
21
8
3
): d ¼ 162.0, 160.1, 159.7, 158.2, 126.4, 127.1,
4
.61; N, 3.38%.
Tetramethyl-9-bromo-9aH-quinolizine-1,2,3,4-tetracarboxy-
55.4, 53.4, 53.1, 50.3; HRMS (EI): m/z calcd for C H NO :
19
17
9
late (4: one of diastereomers). Cream-colored solid; yield
ꢁ1
9
403.34, found: 403.30; Anal. Calcd for C19H17NO : C, 56.58;
H, 4.25; N, 3.47%. Found: C, 57.01; H, 4.31; N, 3.46%.
Tetramethyl-benzo[b]benzimidazole-2,3,4,5-tetracarboxylate
ꢀ
(
45%); mp: 150–152 C; IR (KBr) (mmax/cm ): 1740, 1711,
1
and 1710 (C ¼¼ O), 1611, 1510, 1268; H-NMR (CDCl
3
): d ¼
ꢀ
6
3
.40–6.45 (m, 2H), 5.85–5.88 (m, 1H), 5.83 (s, 1H), 3.92 (s,
(8). White solid; yield (82%); mp: 83–85 C; IR (KBr) (mmax/
13
ꢁ1
H), 3.906 (s, 3H), 3.76 (s, 3H), 3.70 (s, 3H); C-NMR
): d ¼ 162.4, 161.5, 161.0, 160.1, 105.6, 104.4, 102.6,
01.1, 101.4, 101.6, 99.2, 98.3, 76.7, 56.0, 54.8, 52.9, 51.4;
cm ): 3418 (NH), 1725, 1710, and 1700 (C ¼¼ O), 1615, 1532,
1
1245; H-NMR (CDCl
(
CDCl
3
3
): d ¼ 7.28–7.20 (m, 4H), 6.35 (s, 1H),
13
1
3.89 (s, 3H), 3.81 (s, 3H), 3.73 (s, 3H), 3.68 (s, 3H); C-
NMR (CDCl ): d ¼ 162.1, 161.4, 160.1, 159.1, 127.4, 124.6,
HRMS (EI): m/z calcd for C H BrNO : 441.01, found:
1
7
16
8
3
4
41.01; Anal. Calcd for C H BrNO : C, 46.17; H, 3.65; N,
1
121.9, 121.0, 120.7, 118.7, 107.2, 104.1, 100.8, 97.2, 74.5,
57.2, 55.0, 53.2, 50.8; HRMS (EI): m/z calcd for C H N O :
7
16
8
3
.17%. Found: C, 46.21; H, 3.61; N, 3.16%.
Tetramethyl-9-bromo-9aH-quinolizine-1,2,3,4-tetracarboxy-
19 18 2 8
18 2 8
402.35, found: 402.21; Anal. Calcd for C19H N O : C, 56.72;
late (4: the other diastereomer). Cream-colored solid; yield
ꢁ1
H, 4.51; N, 6.96%. Found: C, 57.01; H, 4.53; N, 6.94%.
Methylpyrazolo[1,2-b]benzotriazole-3-carboxylate-1-onium
ꢀ
(
45%); mp: 148–149 C; IR (KBr) (mmax/cm ): 1736, 1710,
1
ꢀ
and 1702 (C ¼¼ O), 1611, 1507, 1264; H-NMR (CDCl ): d ¼
methoxide (9). White solid; yield (90%); mp: 151–153 C; IR
ꢁ
3
1
6
3
.39–6.43 (m, 2H), 5.81–5.86 (m, 1H), 5.71 (s, 1H), 3.930 (s,
(KBr) (mmax/cm ): 1761 and 1728 (C ¼¼ O), 1614, 1497, 1454,
13
1
1435; H-NMR (CDCl
H), 3.911 (s, 3H), 3.774 (s, 3H), 3.710 (s, 3H); C-NMR
): d ¼ 162.1, 161.5, 161.7, 160.0, 105.9, 104.6, 102.7,
01.4, 101.5, 101.4, 99.6, 98.2, 76.0, 56.8, 54.7, 52.1, 51.9;
3
): d ¼ 7.81–7.78 (m, 1H), 7.46–7.38
13
(
CDCl
3
(m, 2H), 7.25–7.20 (m, 1H), 6.65 (s, 1H), 3.71 (s, 3H); C-
NMR (CDCl ): d ¼ 166.4, 162.7, 127.6, 125.4, 124.6, 123.5,
1
3
HRMS (EI): m/z calcd for C H BrNO : 441.01, found:
117.0, 116.3, 106.3, 102.3, 52.1; HRMS (EI): m/z calcd for
1
7
16
8
4
3
41.02; Anal. Calcd for C17
H
16BrNO
.17%. Found: C, 46.16; H, 3.67; N, 3.18%.
8
: C, 46.17; H, 3.65; N,
C
C
12
H
H
11
11
N
N
3
O
O
4
4
: 261.23, found: 230.01; Anal. Calcd for
: C, 55.17; H, 4.24; N, 16.09%. Found: C, 55.19;
12
3
Tetramethyl-9aH-quinolizine-1,2,3,4-tetracarboxylate
one of diastereomers). Cream-colored solid; yield (33%); mp:
(5:
H, 4.23; N, 16.08%.
ꢀ
ꢁ1
8
1
5
3
6 C; IR (KBr) (mmax/cm ): 1737, 1713, and 1691 (C ¼¼ O),
Acknowledgment. The partial financial assistance from the
Research Vice Chancellor of Azarbaijan University of Tarbiat
Moallem is gratefully acknowledged.
1
629, 1571, 1480; H-NMR (CDCl
3
): d ¼ 6.33–6.37 (m, 2H),
.80–5.83 (m, 2H), 5.22 (dd, J ¼ 1.4 and 8.4 Hz, 1H), 3.92 (s,
13
H), 3.84 (s, 3H), 3.74 (s, 3H), 3.69 (s, 3H); C-NMR
): d ¼ 165.3, 163.5, 162.8, 160.9, 107.0, 106.1, 103.4,
02.1, 102.3, 101.7, 100.0, 96.9, 78.9, 55.8, 55.5, 53.01, 51.6;
(
CDCl
3
REFERENCES AND NOTES
1
HRMS (EI): m/z calcd for C H NO S: 419.41, found:
1
9
17
8
[1] Tanaka, K.; Toda, F. Chem Rev 2000, 100, 1025.
[2] Li, C. J.; Chan, T. H. Organic Reactions in Aqueous Media;
Wiley: New York, 1997.
4
3
19.40; Anal. Calcd for C H NO : C, 56.20; H, 4.72; N,
17 17 8
.86%. Found: C, 56.24; H, 4.75; N, 3.85%.
Tetramethyl-9aH-quinolizine-1,2,3,4-tetracarboxylate
(5:
the other diastereomer). Cream-colored solid; yield (32%);
mp: 89 C; IR (KBr) (m /cm ): 1731, 1712, and 1694
[
3] Anastas, P. T.; Warner, J. C. Green Chemistry: Theory and
Practice; Oxford University Press: Oxford, 1998.
[4] Rao, M. L. N.; Awasthi, D. K.; Banerjee, D. Tetrahedron
Lett 2007, 48, 431.
ꢀ
ꢁ1
max
1
(
(
C ¼¼ O), 1633, 1568, 1479; H-NMR (CDCl ): d ¼ 6.35–6.42
3
m, 2H), 5.83–5.88 (m, 2H), 5.65 (dd, J ¼ 1.4 and 8.6 Hz,
[5] Adib, M.; Tahermansouri, H.; Aali, K. S.; Mohammadi, B.;
Bijanzadeh, H. R. Tetrahedron Lett 2006, 47, 5957.
[6] Carrera, I.; Brovetto, M. C.; Ramos, J. C.; Seoane, G. A.
Tetrahedron Lett 2009, 50, 5399.
1
3
1
5
4
H), 3.92 (s, 3H), 3.85 (s, 3H), 3.75 and 3.7 (s, 3H), 3.69 (s,
1
3
H); C-NMR (CDCl ): d ¼ 165.0, 163.1, 162.2, 159.1,
3
08.0, 106.1, 103.2, 102.7, 101.5, 101.2, 99.5, 98.1, 78.3, 55.9,
[
7] Shook, B. C.; Chakravarty, D.; Jackson, P. F. Tetrahedron
5.8, 52.0, 51.9; HRMS (EI): m/z calcd for C19
8
H17NO S:
Lett 2009, 50, 1013.
19.41, found: 419.41; Anal. Calcd for C17 : C, 56.20;
H
17NO
8
[
8] Rothenberg, G.; Downie, A. P.; Raston, C. L.; Scott, J. L.
H, 4.72; N, 3.86%. Found: C, 56.25; H, 4.75; N, 3.86%.
Tetramethyl-7,8-dimethylbenzo[b]benzimidazole-2,3,4,5-tetra-
J Am Chem Soc 2001, 123, 8701.
ꢀ
[9] Tanaka, K.; Kishigami, S.; Toda, F. J Org Chem 1991, 56, 4333.
[10] Toda, F.; Tanaka, K.; Hamai, K. J Chem Soc Perkin Trans
1 1990, 3207.
carboxylate (6). White solid; yield (85%); mp: 95–96 C; IR
ꢁ
1
(
KBr) (mmax/cm ): 3420 (NH), 1727, 1711, and 1703 (C ¼¼ O),
3
1
611, 1523, 1251; H-NMR (CDCl
s, 1H), 6.31 (s, 1H), 3.91 (s, 3H), 3.83 (s, 3H), 3.74 (s, 3H),
1
): d ¼ 7.31 (s, 1H), 7.22
[
11] Toda, F.; Suzuki, T.; Higa, S. J Chem Soc Perkin Trans 1
(
3
1
3
998, 3521.
1
3
.69 (s, 3H), 2.61 (s, 3H), 2.58 (s, 3H); C-NMR (CDCl ): d
3
[
12] Ren, Z.-J.; Cao, W.-G.; Tong, W.-Q. Synth Commun 2002,
¼
165.0, 163.7, 161.6, 160.8, 127.4, 125.3, 122.1, 121.8,
20.1, 119.8, 101.2, 100.2, 99.8, 98.9, 74.5, 56.5, 54.2, 52.3,
1.6, 31.2, 30.2; HRMS (EI): m/z calcd for C21
30.14, found: 430.10; Anal. Calcd for C H N O : C, 58.60;
2, 3475.
1
5
4
[
13] Toda, F.; Kiyoshige, K.; Yagi, M. Angew Chem Int Ed
22 2 8
H N O :
Engl 1989, 28, 320.
2
1
22
2
8
[14] Ren, Z.; Cao, W.; Tong, W.; Jin, Z. Synth Commun 2005,
H, 5.15; N, 6.51%. Found: C, 58.61; H, 5.13; N, 6.50%.
Tetramethyl-5aH-dibenzo[bd]oxazole-6,7,8,9-tetracarboxylate
3
5, 2509.
[15] Schmeyers, T.; Toda, F.; Boy, J.; Kaupp, G. J Chem Soc
ꢀ
ꢀ
(
7). White solid; yield (86%); mp: 229 C (lit. [35], 230 C); IR
ꢁ
Perkin Trans 2 1998, 989.
1
(
KBr) (mmax/cm ): 1731, 1719, and 1708 (C ¼¼ O), 1590, 1511,
[16] Acheson, R. M.; Plunkett, A. O. J Chem Soc 1964, 2676.
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet