A New Neighbouring-Group Reaction to Form Pyridopyrrolobenzoxazinediones
FULL PAPER
Table 3. IR data of 3 and 4
Entry
R
ν˜ (cmϪ1) 3
C(ϭO)N
ν˜ (cmϪ1) 4
C(ϭO)N
C(ϭO)O
CϭO
C(ϭO)O
CϭO
a
b
c
d
e
f
g
h
i
CH3
C2H5
n-C3H7
i-C3H7
tert-C4H9
CH2ϭCHϪCH2
HCϵCϪCH2
CH3OCH2CH2
ClCH2CH2
1754
Ϫ
Ϫ
Ϫ
Ϫ
1760
Ϫ
1759
Ϫ
1730
Ϫ
Ϫ
Ϫ
Ϫ
1743
Ϫ
1733
Ϫ
Ϫ
1739
Ϫ
1742
Ϫ
Ϫ
Ϫ
Ϫ
1742
1758
Ϫ
Ϫ
Ϫ
Ϫ
1759
Ϫ
Ϫ
1742
Ϫ
Ϫ
Ϫ
Ϫ
1740
Ϫ
Ϫ
Ϫ
1744
Ϫ
1746
Ϫ
Ϫ
Ϫ
1746
Ϫ
Ϫ
Ϫ
(500.13 MHz, [D6]DMSO): δ ϭ 8.32 (d, J ϭ 7.9 Hz, H-10), 8.04
(dd, J ϭ 8.2 and 1.0 Hz, H-1), 7.87 (t, J ϭ 8.2 Hz, H-2), 7.71 (d,
J ϭ 8.1 Hz, H-9), 7.59 (dd, J ϭ 8.1 and 1.0 Hz, H-3), 3.18 (s, H-
1Ј), 2.73 (s, Me) ppm. 13C NMR (125.77 MHz, [D6]DMSO): δ ϭ
165.38 (C-8), 161.44 (C-11), 156.63 (C-5), 156.53 (C-6b), 136.61 (C-
12a), 136.06 (C-2), 135.44 (C-4), 133.17 (C-10), 128.60 (C-3),
126.56 (C-9), 122.27 (C-10a), 119.94 (C-1), 112.41 (C-4a), 105.93
(C-6a), 52.37 (C-1Ј), 24.49 (Me) ppm.
7.45 (dd, J ϭ 8.0 and 0.5 Hz, H-3), 5.59 (m, H-2Ј), 5.05 (m, H-3Ј),
3.81 (m, H-1Ј), 2.79 (s, Me) ppm.
4-Chloro-6a-propargyloxy-9-methyl-5H-pyrido[3Ј,2Ј:3,4]pyrrolo[1,2-
a][3,1]benzoxazine-5,11(6aH)-dione (4g) (Table 1, entry g): 1H
NMR (500.13 MHz, CDCl3): δ ϭ 8.17 (d, J ϭ 8.2 Hz, H-7), 8.09
(d, J ϭ 8.2 Hz, H-1), 7.67 (t, J ϭ 8.3 Hz, H-2), 7.54 (d, J ϭ 7.9
Hz, H-8), 7.46 (d, J ϭ 8.2 Hz, H-3), 4.06 (dd, J ϭ 16.1 and 2.4
Hz, H-1Јa), 3.97 (dd, J ϭ 16.1 and 2.4 Hz, H-1Јb), 2.80 (s, Me),
2.31 (t, J ϭ 2.5 Hz, H-3Ј) ppm.
4-Chloro-6a-isopropoxy-8-methyl-5H-pyrido[2Ј,3Ј:3,4]pyrrolo[1,2-a]-
1
[3,1]benzoxazine-5,11(6aH)-dione (3d) (Table 1, entry d): H NMR
(500.13 MHz, [D6]DMSO): δ ϭ 8.30 (d, J ϭ 7.5 Hz, H-10), 8.02
(dd, J ϭ 8.0 and 0.5 Hz, H-1), 7.86 (t, J ϭ 8.0 Hz, H-2), 7.71 (d,
J ϭ 8.0 Hz, H-9), 7.58 (dd, J ϭ 8.0 and 0.5 Hz, H-3), 4.12 (quint,
J ϭ 6.0 Hz, H-1Ј), 2.72 (s, Me), 0.99 (d, J ϭ 6.0 Hz, H-2Јa), 0.80
(d, J ϭ 6.0 Hz, H-2Јb) ppm.
Acknowledgments
We thank Dr. Christian Lennartz for helpful discussions and Ralf
Kopecek and Thomas Schwalb for their help with experiments.
6a-Allyloxy-4-chloro-8-methyl-5H-pyrido[2Ј,3Ј:3,4]pyrrolo[1,2-a]-
[3,1]benzoxazine-5,11(6aH)-dione (3f) (Table 1, entry f): 1H NMR
(599.92 MHz, CDCl3): δ ϭ 8.12 (d, J ϭ 8.0 Hz, H-10), 8.06 (d, J ϭ
8.0 Hz, H-1), 7.64 (t, J ϭ 8.2 Hz, H-2), 7.48 (d, J ϭ 8.2 Hz, H-
9), 7.43 (d, J ϭ 8.2 Hz, H-3), 5.72 (m, H-2Ј), 5.09 (m, H-3Ј), 4.42
(m, H-1Ј), 2.78 (s, Me) ppm.
[1] [1a]
M. Tonishi, T. Katsuhira, T. Ohtsuka, Y. Miura (Nihon
Nohyaku Co., Ltd., Japan), EP 0799825, 1997 [Chem. Abstr.
1997, 127, 331402].
[1b]
G. Hamprecht, M. Menges, O. Menke,
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[Chem. Abstr. 2000, 133, 266737]. [1c] H. Takaishi, T. Katsuhira,
H. Yamaguchi, Y. Kawabata, H. Harayama, Y. Oda, M. Murai
4-Chloro-6a-propargyloxy-8-methyl-5H-pyrido[2Ј,3Ј:3,4]pyrrolo[1,2-
a][3,1]benzoxazine-5,11(6aH)-dione (3g) (Table 1, entry g): 1H-
NMR (500.13 MHz, CDCl3): δ ϭ 8.14 (d, J ϭ 7.9 Hz, H-10), 8.06
(d, J ϭ 8.2 Hz, H-1), 7.66 (t, J ϭ 8.2 Hz, H-2), 7.52 (d, J ϭ 8.0
Hz, H-9), 7.44 (d, J ϭ 8.1 Hz, H-3), 4.76 (dd, J ϭ 16.0 and 2.1
Hz, H-1Јa), 4.57 (dd, J ϭ 16.0 and 2.1 Hz, H-1Јb), 2.78 (s, Me),
2.46 (s, H-3Ј) ppm.
(Nihon Nohyaku Co., Ltd., Japan), WO 0006549, 2000 [Chem.
[1d]
Abstr. 2000, 132, 151835].
M. Adachi, T. Mizukoshi,
K. Maeda, H. Kita, S. Akiyama, K. Nakahira, T. Ohki,
N. Hamada, S. Watanabe (Nissan Chemical Industries, Ltd.
Japan), WO 0116129, 2001 [Chem. Abstr. 2001, 134, 207824].
4-Chloro-6a-methoxy-9-methyl-5H-pyrido[3Ј,2Ј:3,4]pyrrolo[1,2-a]-
[1e]
M. Tohnishi, H. Nakao, E. Kohno, T. Nishida, T. Furuya,
1
[3,1]benzoxazine-5,11(6aH)-dione (4a) (Table 1, entry a): H NMR
T. Shimizu, A. Seo, K.Sakata, S. Fujioka, H. Kanno (Nihon
Nohyaku Co., Ltd.Japan), WO 0121576, 2001 [Chem. Abstr.
2001, 134, 252360].
(500.13 MHz, [D6]DMSO): δ ϭ 8.35 (d, J ϭ 8.0 Hz, H-7), 8.10 (d,
J ϭ 8.0 Hz, H-1), 7.88 (t, J ϭ 8.5 Hz, H-2), 7.77 (d, J ϭ 8.0 Hz,
H-8), 7.59 (d, J ϭ 8.0 Hz, H-3), 3.09 (s, H-1Ј), 2.71 (s, Me) ppm.
[2]
R. Brückner, Reaktionsmechanismen, 2. Aufl., Spektrum Akad-
emischer Verlag, Heidelberg, Berlin, 2003, pp. 86Ϫ92,
590Ϫ591.
4-Chloro-6a-isopropoxy-9-methyl-5H-pyrido[3Ј,2Ј:3,4]pyrrolo[1,2-
a][3,1]benzoxazine-5,11(6aH)-dione (4d) (Table 1, entry d): 1H
NMR (500.13 MHz, [D6]DMSO): δ ϭ 8.38 (d, J ϭ 8.0 Hz, H-7),
8.06 (dd, J ϭ 8.0 and 1.0 Hz, H-1), 7.88 (t, J ϭ 8.5 Hz, H-2), 7.75
(d, J ϭ 8.0 Hz, H-8), 7.59 (dd, J ϭ 8.5 and 1.0 Hz, H-3), 3.70 (m,
H-1Ј), 2.70 (s, Me), 0.95 (d, J ϭ 6.5 Hz, H-2Јa), 0.73 (d, J ϭ 6.0
Hz, H-2Јb) ppm.
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[3b]
T. Kauffmann, Synthesis 1995, 745Ϫ755.
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[3,1]benzoxazine-5,11(6aH)-dione (4f) (Table 1, entry f): 1H NMR
(499.96 MHz, CDCl3): δ ϭ 8.16 (d, J ϭ 8.5 Hz, H-7), 8.05 (d, J ϭ
8.0 Hz, H-1), 7.66 (t, J ϭ 8.5 Hz, H-2), 7.53 (d, J ϭ 8.0 Hz, H-8),
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2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3555