PAPER
Synthesis of 1,4-Oxazepin-7-ones Using Baylis–Hillman Products as Key Intermediates
2235
Table 4 NMR and Mass Spectral Data of 9 (continued)
Product
1H NMR (250 MHz, CDCl3) , J (Hz)
13C NMR (62.9 MHz, CDCl3)
MS, m/z
9ac
E-isomer: 0.87 (d, 3 H J = 6.8), 2.02 (s, 3 E-isomer: 9.4 (+, CH3), 38.3 (+, CH3), 50.4 (–, 340.4
H), 2.73–2.89 (m, 1 H), 3.48–3.60 (m, 2 CH2), 52.2 (+, CH3), 63.8 (+, CH), 74.2 (+,
[MH+],
CH), 126.2, 127.9, (+, 2 2 CH), 128.4, 129.6 308.2
(+, 2 2 CH), 126.8, 128.6 (+, 2 1 CH), 131.4 232.2,
H), 3.83 (s, 3 H), 4.83–4.87 (m, 1 H),
7.13–7.36 (m, 10 H), 7.80 (s, 1 H)
N
OMe
Z-isomer: 70.93 (d, 3 H, J = 6.9), 2.26 (s, (Cquat), 135.2 (Cquat), 142.0 (+, CH), 142.6
3 H), 2.73–2.89 (m, 1 H), 3.48–3.60 (m, 2 (Cquat), 169.1 (Cquat
H), 3.65 (s, 3 H), 4.83–4.87 (m, 1 H), 6.66 Z-isomer: 9.6 (+, CH3), 38.6 (+, CH3), 51.8 (+,
194.1,
166.1
)
O
OH
(s, 1 H), 7.13–7.36 (m, 10 H)
CH3), 60.4 (–, CH2), 64.0 (+, CH), 73.2 (+,
CH), 126.2, 128.0, 128.3, 128.3 (+, 4 2 CH),
126.9, 128.2 (+, 2 1 CH), 133.1 (Cquat), 134.1
(+, CH), 135.5 (Cquat), 169.9 (Cquat
)
9ad
E-isomer: 2.70–2.74 (m, 2 H), 2.83 (br s, E-isomer: 45.2 (–, CH2), 50.6 (–, CH2), 52.2
236.2
[MH+],
204.1
[M+ –
OMe],
194.1
2 H), 3.55–3.61 (m, 4 H), 3.80 (s, 3 H),
7.23–7.43 (m, 5 H), 7.80 (s, 1 H)
(+, CH3), 60.7 (–, CH2), 128.6, 129.37 (+, 2
CH), 129.0 ( +, CH), 130.4 (Cquat), 135.0
Z-isomer: 2.70–2.74 (m, 2 H), 2.83 (br s, (Cquat), 142.1 (+, CH), 168.5 (Cquat), 169.5
N
OMe
2 H), 3.55–3.61 (m, 4 H), 3.71 (s, 3 H),
6.79 (s, 1 H), 7.23–7.43 (m, 5 H, C6H5)
(Cquat)
Z-isomer: 50.1 (–, CH2), 51.7
O
OH
(–, CH2), 53.3 (+, CH3), 60.8 (–, CH2), 128.2,
128.7 (+, 2 CH), 128.4 (+, CH), 132.2 (Cquat),
135.3 (+, CH), 135.5 (Cquat
)
9ba
E-isomer: 1.17–1.70 (m, 6 H), 1.79–1.89 E-isomer: 23.6, 24.3, 27.4 (–, 3CH2), 48.1 (–, 335.3
(m, 1 H), 2.18–2.26 (m, 1 H), 2.35–2.38 CH2), 51.2 (–, CH2, ), 52.6 (+, CH3), 62.2 (+, [MH+],
(m, 1 H), 2.73–2.81 (m, 1 H), 3.15 (d, 1 H, CH), 62.6 (–, CH2), 123.7 (+, 2 CH), 130.1 (+, 305.3,
NO2
J = 13.0), 3.40 (dd, 1 H, J = 3.5, 11.8),
3.68–3.74, 3.87–4.06 (2 m, 1 H + 1 H),
2 CH), 134.6 (Cquat), 138.5 (+, CH), 141.9,
147.5, 168.3 (Cquat
303.3
N
OMe
)
[M+ –
3.85 (s, 3 H), 7.49–7.54 (m, 2 H), 7.76 (s, Z-isomer: 23.6, 24.3 (–, 2 CH2), 51.6 (–, CH2), OMe],
O
1 H), 8.22–8.27 (m, 2 H)
52.1 (+, CH3), 57.5 (–, CH2), 61.5 (+, CH),
273.2,
116.1
OH
Z-isomer: 1.17–1.70 (m, 6 H), 1.97–2.04 123.5 (+, 2 CH), 129.0 (+, 2 CH), 131.8 (+,
(m, 1 H), 2.83–2.95 (m, 1 H), 3.03 (d, 1 H, CH), 137.1, 142.2, 147.2, 169.0 (Cquat
)
J = 13.3), 3.50 (dd, 1 H, J = 3.9, 13.5),
3.67 (s, 3 H), 3.68–3.74, 3.87–4.06 (2 m,
1 H + 1 H), 6.80 (s, 1 H), 7.37–7.40 (m, 2
H), 8.14–8.21 (m, 2 H)
9bd
E-isomer: 2.11 (s, 3 H), 2.49–2.53 (m, 2 E-isomer: 41.7 (+, CH3), 52.3 (–, CH2), 52.5
H), 2.61 (br m, 1 H), 3.40 (s, 2 H), 3.56– (+,CH3), 58.7 (–, CH2), 58.9 (–, CH2), 123.7,
294.2
[M+],
NO2
3.60 (m, 2 H), 3.82 (s, 3 H), 7.56–7.60,
8.19–8.24 (2 m, 2 H + 2 H), 7.78 (s, 1 H) CH), 141.7, 147.6, 168.1 (Cquat
Z-isomer: 2.29 (s, 3 H), 2.49–2.53 (m, 2 Z-isomer: 42.0 (+, CH3), 52.1 (+, CH3), 60.4
130.4 (+, 2 CH + 2 CH), 134.0 (Cquat), 139.4 (+, 263.2
Me
N
)
[M+ –
OMe
OMe],
H), 2.61 (br m, 1 H), 3.56–3.60 (m, 2 H), (–, CH2), 61.8 (–, CH2), 123.5, 129.0 (+, 2 CH 174.2,
O
3.66 (s, 3 H), 6.78 (s, 1 H), 7.37–7.42,
8.11–8.17 (2 m, 2 H 2 H)
+ 2 CH), 132.2 (+, CH), 136.3 (Cquat
)
149.2,
115.2
OH
9ca
E-isomer: 1.17–1.73 (m, 6 H), 1.84–1.94 E-isomer: 21.3 (+, CH3), 23.8, 24.2, 27.4 (–, 3 304.2
(m, 1 H), 2.21–2.29 (m, 1 H), 2.37 (s, 3 CH2), 47.7 (–, CH2), 51.0 (–, CH2), 52.2 (+,
[MH+],
NO2
H), 2.79–2.87 (m, 1 H), 3.28 (d, 1 H, J = CH3), 62.0 (+, CH), 62.6 (–, CH), 129.2 (+, 2 272.1,
12.9), 3.40 (dd, 1 H, J = 3.5, 11.7), 3.83 (s, CH), 129.4 (+, 2 CH), 130.5, 132.3, 138.7
3 H), 3.84–4.10 (m, 1 H + 1 H), 7.09–7.29 (Cquat), 141.9 (+, CH), 169.2 (Cquat
(m, 4 H), 7.77 (s, 1 H)
Z-isomer: 1.17–1.73 (m, 6 H), 1.84–1.94 CH2), 51.3 (–, CH2), 51.7 (+, CH3), 57.8 (–,
(m, 1 H), 2.21–2.29 (m, 1 H), 2.33 (s, 3 CH2), 61.4 (+, CH), 62.5 (–, CH2), 128.3 (+, 2
H), 2.96 (d, 1 H, J = 13.9), 3.04–3.11 (m, CH), 129.0 (+, 2 CH), 132.0, 132.5, 138.2
[M+ –
OMe],
N
OMe
)
Z-isomer: 14.2 (+, CH3), 21.3, 23.7, 24.3 (–, 3 208.1,
O
116.0
OH
1 H), 3.40 (dd, 1 H, J = 3.5, 11.7), 3.68 (s, (Cquat), 134.4 (+, CH), 170.3 (Cquat
)
3 H), 3.84–4.10 (m, 1 H + 1 H), 6.70 (s, 1
H), 7.09–7.29 (m, 4 H)
9cb
E-isomer: 2.13 (s, 3 H), 2.33 (s, 3 H),
2.49–2.53 (m, CH2), 2.96 (br s, 1 H), 3.46 (+, CH3), 52.2 (–, CH2), 58.7 (–, CH2), 58.7
E-isomer: 21.3 (+, CH3), 41.6 (+, CH3), 52.1
264.2
Me
[MH+],
(s, 2 H), 3.56–3.60 (m, 2 H), 3.79 (s, 3 H), (–, CH2), 129.2 (+, 2 CH), 129.6 (Cquat), 129.8 232.1
Me
N
7.15–7.18, 7.31–7.35 (2 m, 2 H + 2 H),
7.77 (s, 1 H)
(+, 2 CH), 132.2, 139.0 (Cquat), 142.5 (+, CH), [M+ –
OMe
169.0 (Cquat
)
OMe],
208.2
O
OH
Synthesis 2002, No. 15, 2232–2242 ISSN 0039-7881 © Thieme Stuttgart · New York