J. Banothu, S. Basavoju, and R. Bavantula
Vol 000
Scheme 3. Proposed mechanism for the formation of trans spiro-cyclopropane derivatives.
O
O
O
Br
N
N
N
Base
Base
Br-
Cl
Cl
Cl
[
B]
[
A]
O
O
O
R-CHO
R
O
[
C]
O
R
O
O
R
N
-
Pyridine
O
O
Cl
O
Cl
R = Aryl
J = 8.4 Hz, 1H), 7.38–7.43 (m, 3H), 7.56 (d, J = 8.4 Hz, 2H), 7.74
2-(4-Chlorobenzoyl)-3-(4-methylphenyl)-spiro[cyclopropane-
1,2′-inden]-1′,3′-dione (4f). Colorless solid; mp 232–234°C;
1
3
(
d, J = 7.2 Hz, 1H), 7.86–7.96 (m, 6H); C NMR (100 MHz,
À1
1
DMSO-d ): δ 194.5, 192.8, 189.9, 141.1, 140.9, 138.8, 136.2,
IR (KBr) υmax (cm ): 1741, 1705, 1689, 1592, 744; H NMR
(400 MHz, DMSO-d ): δ 2.29 (s, 3H), 3.92 (d, J = 8.8 Hz, 1H),
4.62 (d, J = 8.8 Hz, 1H), 7.12 (d, J = 8.0 Hz, 2H), 7.34 (d,
6
1
1
36.0, 134.7, 134.4, 131.4, 131.2, 129.9, 129.2, 128.8, 127.1,
22.7, 45.7, 41.2, 38.7, MS (ESI) m/z: 444 (M + Na); Anal.
6
13
Calcd for C H Cl O : C, 68.43; H, 3.35; Found: C, 68.59;
J = 8.0 Hz, 2H), 7.56 (d, J = 8.4 Hz, 2H), 7.84–7.93 (m, 6H);
C
2
4
14
2 3
H, 3.44.
-(4-Chlorobenzoyl)-3-(4-chlorophenyl)-spiro[cyclopropane-
,2′-inden]-1′,3′-dione (4c). Colorless solid; mp 222–224°C;
NMR (100 MHz, DMSO-d ): δ 194.3, 193.0, 190.4, 141.4,
6
2
141.2, 138.6, 137.1, 135.8, 134.6, 129.8, 129.4, 129.1, 128.6,
+
1
122.6, 122.5, 47.0, 41.6, 38.8, 20.7; MS (ESI) m/z: 400 (M );
À1
1
IR (KBr) υmax (cm ): 1739, 1707, 1689, 1590, 743; H NMR
3
Anal. Calcd for C25H17ClO : C, 74.91; H, 4.27; Found: C,
(
400 MHz, CDCl ): δ 4.14 (d, J = 8.8 Hz, 1H), 4.18 (d,
74.79; H, 4.36.
3
13
J = 8.8 Hz, 1H), 7.29–7.39 (m, 6H), 7.79–7.89 (m, 6H);
C
2-(4-Chlorobenzoyl)-3-(4-methoxyphenyl)-spiro[cyclopropane-
NMR (100 MHz, CDCl
3
): δ 193.9, 193.8, 189.1, 141.9, 141.8,
1,2′-inden]-1′,3′-dione (4g). Brown solid; mp 158–160°C; IR
–
1
1
1
1
40.4, 135.5, 135.4, 134.3, 134.2, 130.6, 130.4, 129.7, 129.2,
28.6, 123.1, 122.9, 47.1, 41.2, 40.3; MS (ESI) m/z: 421 (M );
(KBr) υmax (cm ): 1739, 1706, 1690, 1583, 1214, 745;
NMR (400 MHz, CDCl ): δ 3.78 (s, 3H), 4.16 (d, J = 8.8 Hz,
1H), 4.56 (d, J = 8.8 Hz, 1H), 6.83 (d, J = 8.0 Hz, 2H), 7.36 (d,
H
+
3
Anal. Calcd for C H Cl O : C, 68.43; H, 3.35; Found: C,
2
4
14
2 3
13
6
8.61; H, 3.45.
-(4-Chlorobenzoyl)-3-(4-fluorophenyl)-spiro[cyclopropane-
,2′-inden]-1′,3′-dione (4d). Colorless solid; mp 214–216°C;
J = 8.0 Hz, 2H), 7.58 (d, J = 8.4 Hz, 2H), 7.86–7.95 (m, 6H);
C
2
NMR (100 MHz, CDCl ): δ 194.3, 194.2, 190.6, 151.1, 142.1,
3
1
140.7, 136.1, 135.4, 135.3, 134.8, 133.3, 130.4, 129.5, 128.2,
À1
1
IR (KBr) υmax (cm ): 1737, 1706, 1682, 1594, 742; H NMR
400 MHz, CDCl ): δ 4.17 (d, J = 8.8 Hz, 1H), 4.24 (d,
123.2, 122.9, 114.6, 55.6, 47.7, 42.6, 41.0; MS (ESI) m/z: 416
+
(
(M ); Anal. Calcd for C H ClO : C, 72.03; H, 4.11; Found: C,
3
25 17
4
J = 8.8 Hz, 1H), 7.13 (d, J = 8.0 Hz, 2H), 7.28–7.39 (m, 4H),
72.25; H, 4.18.
1
3
7
.78–7.94 (m, 6H); C NMR (100 MHz, CDCl
3
): δ 194.1,
2-(4-Chlorobenzoyl)-3-(3,4-dimethoxyphenyl)-spiro[cyclopropane-
1
1
4
93.9, 189.2, 159.3, 141.7, 140.4, 139.4, 135.5, 135.3, 134.5,
34.2, 130.6, 129.8, 128.8, 123.4, 122.8, 115.8, 47.3, 41.4,
1,2′-inden]-1′,3′-dione (4h). Pale yellow solid; mp 203–205°C; IR
(KBr) υmax (cm ): 1739, 1707, 1689, 1582, 1225, 743; H NMR
À1
1
+
0.1; MS (ESI) m/z: 404 (M ); Anal. Calcd for C H ClFO :
(400 MHz, CDCl ): δ 3.80 (s, 3H), 3.85 (s, 3H), 4.12 (d, J=8.8Hz,
2
4
14
3
3
C, 71.21; H, 3.49; Found: C, 71.40; H, 3.38.
1H), 4.60 (d, J=8.8Hz, 1H), 6.84–6.98 (m, 3H), 7.52 (d, J=8.4Hz,
2H), 7.78–7.96 (m, 6H); C NMR (100 MHz, CDCl ): δ 194.1,
3
13
2
-(4-Chlorobenzoyl)-3-(3-nitrophenyl)-spiro[cyclopropane-
1
,2′-inden]-1′,3′-dione (4e). Colorless solid; mp 239–241°C;
194.0, 188.7, 150.1, 146.2, 141.8, 140.2, 137.1, 135.6, 135.2, 134.1,
À1
1
IR (KBr) υmax (cm ): 1738, 1704, 1685, 1589, 1528, 742; H
NMR (400 MHz, DMSO-d ): δ 4.10 (d, J = 8.8 Hz, 1H), 4.80 (d,
133.7, 130.0, 128.8, 124.5, 122.9, 120.6, 115.6, 112.2, 55.9, 55.6,
+
47.1, 41.4, 40.6; MS (ESI) m/z: 446 (M ); Anal. Calcd for
6
J = 8.8 Hz, 1H), 7.55–7.65 (m, 3H), 7.85–7.95 (m, 6H), 7.99 (d,
C
26
H
19ClO
2-(4-Chlorobenzoyl)-3-(2-hydroxyphenyl)-spiro[cyclopropane-
1,2′-inden]-1′,3′-dione (4i). Yellow solid; mp 197–198°C; IR
5
: C, 69.88; H, 4.29; Found: C, 69.97; H, 4.35.
13
J = 7.6 Hz, 1H), 8.16 (d, J = 8.0 Hz, 1H), 8.49 (s, 1H); C NMR
100 MHz, DMSO-d ): δ 193.8, 193.4, 189.9, 147.5, 141.5,
41.4, 138.7, 136.5, 135.9, 135.8, 135.1, 134.5, 129.9, 129.4,
29.1, 124.5, 122.7, 46.3, 41.1, 38.2; MS (ESI) m/z: 454
14ClNO : C, 66.75; H, 3.27; N,
.24; Found: C, 66.63; H, 3.42; N, 3.37.
(
6
À1
1
1
1
(KBr) υmax (cm ): 3342, 1738, 1708, 1689, 1585, 742; H NMR
(400 MHz, CDCl ): δ 4.12 (d, J = 8.8 Hz, 1H), 4.58 (d, J = 8.8 Hz,
1H), 6.84 (d, J = 7.6 Hz, 1H), 7.19–7.44 (m, 3H), 7.57 (d,
J = 8.4Hz, 2H), 7.82–7.94 (m, 6H), 9.17 (s, 1H, OH); C NMR
3
(
M + Na); Anal. Calcd for C24
H
5
13
3
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet