ACCEPTED MANUSCRIPT
(s, 1H, HPy), 7.53 (d, J = 6.6 Hz, 1H, HAr), 7.49 (s, 1H, HAr), 7.34 (d, J = 8.5 Hz, 1H, HAr),
1
3
6
3
1
.89 (s, 1H, HPyrazole), 2.36 (s, 3H, PyrazoleCH ), 2.33 (s, 3H, ArCH ). C NMR (DMSO-d ,
3 3 6
00 K, ppm): δ 159.7, 148.0, 145.4, 144.1, 143.5, 141.7, 141.5, 135.0, 133.9, 132.7, 128.4,
25.4, 121.4, 117.5, 21.5, 13.5. Anal.Calcd for C16 : C, 62.33; H, 3.92; N 18.17.
12 4 3
H N O
Found: C, 52.15; H, 3.93; N, 18.26.
4
.6.9 5-Chloro-2-methylbenzo[f]pyrazolo[1,5-d]pyrido[3,2-b][1,4]oxazepine (3j). Off-white
1
solid, m.p. 133-135 °C (i-PrOH). H NMR (DMSO-d
6
, 300 K, ppm): δ 8.39 (d, J = 4.3 Hz,
1
H, HPy), 8.00 (d, J = 7.9 Hz, 1H, HPy), 7.77 (s, 1H, HAr), 7.44-7.59 (m, 3H, HAr+HPy), 6.87
13
(
s, 1H, HPyrazole), 2.34 (s, 3H, CH
3
). C NMR (DMSO-d
6
, 300 K, ppm): δ 160.1, 147.4,
1
1
3
46.3, 145.1, 144.0, 142.3, 141.7, 136.3, 133.7, 132.1, 129.2, 127.4, 125.4, 121.5, 120.0,
08.3, 14.2. Anal. Calcd for C17
.56; N, 14.88.
3
H10ClN O: C, 63.50; H, 3.55; N 14.81.Found: C, 63.31; H,
4
.6.10 Methyl 5-chloro-2-methylbenzo[f]pyrazolo[1,5-d]pyrido[3,2-b][1,4]oxazepine-10-
1
carboxylate (3k). Beige solid, m.p. 152-154 °C (i-PrOH). H NMR (DMSO-d
6
, 300 K, ppm):
δ 8.87 (s, 1H, HPy), 8.45 (s, 1H, HPy), 7.80 (s, 1H, HAr), 7.67 (d, J = 8.9 Hz, 1H, HAr), 7.58 (d,
13
J = 8.8 Hz, 1H, H ), 6.94 (s, 1H, H
), 3.94 (s, 3H, COOCH ), 2.31 (s, 3H, CH ). C
3 3
Ar
Pyrazole
NMR (DMSO-d
6
, 300 K, ppm): δ 154.8, 150.4, 148.2, 144.2, 143.1, 140.9, 139.2, 132.0,
1
1
5
31.4, 127.9, 126.5, 124.8, 122.7, 110.8, 107.6, 14.1. IR (NaCl) ν1716 (C=O), 1596 (Py),
581 (Py), 1307 (C-O-C), 1240 (Ar-O-Ar), 770 (C-Cl). Anal. Calcd for C17
9.75; H, 3.54; N 12.30.Found: C, 59.57; H, 3.54; N, 12.36.
3 3
H12ClN O : C,
4
.6.11 5-Chloro-2-methyl-10-nitrobenzo[f]pyrazolo[1,5-d]pyrido[3,2-b][1,4]oxazepine (3l).
1
Grey solid, m.p. 184-186 °C (i-PrOH). H NMR (DMSO-d
6
, 300 K, ppm): δ 9.21 (s, 1H,
H
Py), 8.90 (s, 1H, HPy), 7.83 (s, 1H, HAr), 7.68 (d, J = 8.9 Hz, 1H, HAr), 7.61 (d, J = 9.2 Hz,
1
3
1
1
1
2
H, HAr), 7.04 (s, 1H, HPyrazole), 2.36 (s, 3H, CH
3 6
). C NMR (DMSO-d , 300 K, ppm): δ
53.1, 152.6, 147.4, 143.8, 143.1, 141.3, 139.7, 131.1, 130.7, 128.4, 126.9, 123.2, 122.6,
09.5, 13.4.Anal. Calcd for C15
.76; N, 17.13.
9 4 3
H ClN O : C, 54.81; H, 2.76; N 17.04. Found: C, 54.67; H,
4
.6.12 2-(Trifluoromethyl)benzo[f]pyrazolo[1,5-d]pyrido[3,2-b][1,4]oxazepine (3m). White
1
solid, m.p. 118-120 °C (i-PrOH). H NMR (DMSO-d
6
, 300 K, ppm): δ 8.48 (d, J = 3.8 Hz,
1
H, HPy), 8.11 (d, J = 7.5 Hz, 1H, HPy), 7.82 (d, 1H, J = 7.5, HAr), 7.53-7.68 (m, 3H,
1
3
H +H ), 7.52 (s, 1H, H
), 7.41 (t, 1H, J = 7.0 Hz, H ). C NMR (DMSO-d , 300 K,
Ar 6
Py
Ar
Pyrazole
ppm): δ 156.0, 147.0, 146.0 (q, J = 99.8 Hz), 142.9, 132.4, 131.7, 129.8, 126.8, 126.3, 121.5
1
4