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Organic & Biomolecular Chemistry
Page 6 of 9
DOI: 10.1039/C8OB02071J
ARTICLE
Journal Name
+
(
d, J = 2.4 Hz, 1H), 5.72 – 5.63 (m, 1H), 3.96 (q, J = 7.2 Hz, 2H), 3.92 114.5, 113.1, 110.5, 55.4, 51.9. HRMS (ESI) calcd for [M+H]
13
+
(s, 3H), 3.79 (s, 3H), 1.02 (t, J = 7.2 Hz, 3H). C NMR (150 MHz, [C24
H
19
N
2
O
4
] 399.1339, found 399.1337.
Methyl 6-(3-methoxyphenyl)-12-oxo-12H-indazolo[2,1-a]cinnoline-
-carboxylate (3q). Following the general procedure, 3q was
CDCl
3
) δ 166.7, 160.9, 157.5, 155.0, 136.8, 136.4, 134.7, 131.3,
1
31.1, 130.4, 130.3, 128.7, 123.4, 121.9, 116.2, 112.8, 109.9, 103.2,
5
+
9
7.1, 93.8, 60.9, 56.1, 55.8, 13.9. HRMS (ESI) calcd for [M+H]
1
obtained as a yellow solid (62.8 mg, 79% yield): H NMR (600 MHz,
CDCl ) δ 9.05 (dd, J = 8.4, 1.2 Hz, 1H), 8.06 – 7.95 (m, 1H), 7.47 –
13-oxo-7-phenyl-13H-[1,3]dioxolo[4,5-f]indazolo[2,1- 7.41 (m, 2H), 7.37 – 7.33 (m, 1H), 7.24 – 7.16 (m, 3H), 7.12 (dd, J =
a]cinnoline-6-carboxylate (3l). Following the general procedure, 3l 8.4, 2.4 Hz, 1H), 7.01 (d, J = 7.2 Hz, 1H), 6.98 – 6.91 (m, 1H), 5.76 –
+
[C
26
H
23
N
2
O
5
] 443.1601, found 443.1598.
3
Ethyl
1
13
was obtained as a yellow solid (79.2 mg, 93% yield): H NMR (600 5.68 (m, 1H), 3.81 (s, 3H), 3.50 (s, 3H). C NMR (150 MHz, CDCl
MHz, CDCl ) δ 8.57 (d, J = 9.0 Hz, 1H), 7.96 (d, J = 7.8 Hz, 1H), 7.59 (t, 166.0, 160.1, 157.3, 138.8, 136.3, 133.9, 132.5, 131.3, 130.3, 128.5,
J = 7.8 Hz, 1H), 7.52 (t, J = 7.8 Hz, 2H), 7.45 (m, 2H), 7.16 (t, J = 7.2 125.9, 123.8, 123.5, 122.5, 122.0, 119.9, 116.6, 116.5, 116.2, 114.7,
3
) δ
3
+
+
19 2 4
Hz, 1H), 7.14 – 7.09 (m, 1H), 6.79 (d, J = 9.0 Hz, 1H), 5.99 (s, 2H), 113.1, 110.2, 55.5, 51.9. HRMS (ESI) calcd for [M+H] [C24H N O ]
5
3
1
1
.61 (d, J = 8.4 Hz, 1H), 4.00 (q, J = 7.2 Hz, 2H), 1.00 (t, J = 7.2 Hz, 399.1339, found 399.1341.
1
3
3
H). C NMR (150 MHz, CDCl ) δ 165.3, 157.0, 145.5, 141.6, 137.9,
Methyl
6-(furan-2-yl)-12-oxo-12H-indazolo[2,1-a]cinnoline-5-
36.6, 131.2, 130.7, 130.5, 130.3, 129.0, 128.1, 123.5, 122.5, 116.7,
12.8, 110.0, 107.1, 105.2, 101.7, 61.36, 13.68. HRMS (ESI) calcd for
carboxylate (3r). Following the general procedure, 3r was obtained
1
as a yellow solid (66.5 mg, 93% yield): H NMR (600 MHz, CDCl
3
) δ
+
+
19 2 5
[M+H] [C25H N O ] 427.1288, found 427.1287.
8
.99 (dd, J = 8.4, 1.2 Hz, 1H), 8.01 (d, J = 7.8 Hz, 1H), 7.66 (d, J = 1.2
Methyl 6-(4-fluorophenyl)-12-oxo-12H-indazolo[2,1-a]cinnoline-5- Hz, 1H), 7.48 (dd, J = 7.8, 1.2 Hz, 1H), 7.36 (t, J = 7.8 Hz, 2H), 7.24 (t,
carboxylate (3m). Following the general procedure, 3m was J = 7.2 Hz, 1H), 7.19 (td, J = 7.8, 1.2 Hz, 1H), 6.74 (d, J = 3.0 Hz, 1H),
1
13
obtained as a yellow solid (71.8 mg, 93% yield): H NMR (600 MHz, 6.63 (dd, J = 3.3, 1.8 Hz, 1H), 5.73 (d, J = 8.4 Hz, 1H), 3.63 (s, 3H).
CDCl ) δ 9.04 (d, J = 7.8 Hz, 1H), 8.03 (m, 1H), 7.49 – 7.40 (m, 3H), NMR (150 MHz, CDCl ) δ 165.6, 157.6, 144.3, 144.2, 142.7, 136.3,
.38 (t, J = 7.8 Hz, 1H), 7.28 (m, 1H), 7.25 – 7.18 (m, 4H), 5.91 – 5.51 134.7, 132.0, 131.8, 129.3, 129.1, 125.9, 124.5, 123.6, 122.7, 119.4,
C
3
3
7
1
3
(
3
m, 1H), 3.53 (s, 3H). C NMR (150 MHz, CDCl ) δ 165.8, 163.8 (d, J 116.4, 116.1, 114.5, 113.4, 112.0, 111.5, 52.3. HRMS (ESI) calcd for
+
+
=
1
1
250.7 Hz), 157.3, 138.2, 136.2, 133.9, 132.0 (d, J = 8.4 Hz), 131.4, [M+H] [C21
H
15
N
2
O
4
] 359.1026, found 359.1031.
Ethyl 6-methyl-12-oxo-12H-indazolo[2,1-a]cinnoline-5-carboxylate
3s). Following the general procedure, 3s was obtained as a yellow
28.6, 127.4 (d, J = 3.5 Hz), 125.9, 123.8 (d, J = 35.1 Hz), 122.7,
19.8, 116.7, 116.6, 116.4, 116.1, 112.7, 110.8, 51.9. HRMS (ESI)
(
+
+
calcd for [M+H] [C23
Methyl 6-(4-iodophenyl)-12-oxo-12H-indazolo[2,1-a]cinnoline-5- 8.4 Hz, 1H), 8.07 (d, J = 8.4 Hz, 1H), 7.63 (m, 2H), 7.34 (t, J = 7.2 Hz,
carboxylate (3n). Following the general procedure, 3n was obtained 1H), 7.32 – 7.28 (m, 1H), 7.26 (dd, J = 7.2, 1.2 Hz, 1H), 7.21 – 7.17
H16FN
2
O
3
] 387.1139, found 387.1146.
1
3
solid (55.5 mg, 87% yield): H NMR (600 MHz, CDCl ) δ 8.92 (d, J =
1
3
as a yellow solid (90.9 mg, 92% yield): H NMR (600 MHz, CDCl ) δ (m, 1H), 4.42 (q, J = 7.2 Hz, 2H), 2.68 (s, 3H), 1.41 (t, J = 7.2 Hz, 3H).
1
3
9
2
3
.01 (d, J = 8.4 Hz, 1H), 8.01 (d, J = 7.8 Hz, 1H), 7.89 (d, J = 7.8 Hz,
3
C NMR (150 MHz, CDCl ) δ 166.7, 157.0, 138.1, 136.9, 133.3,
H), 7.44 (d, J = 7.8 Hz, 1H), 7.36 (t, J = 7.8 Hz, 1H), 7.26 – 7.19 (m, 131.9, 127.8, 125.8, 124.1, 123.6, 122.9, 120.3, 117.3, 116.2, 113.7,
1
3
C
+
+
H), 7.17 (d, J = 8.4 Hz, 2H), 5.75 (d, J = 7.8 Hz, 1H), 3.51 (s, 3H).
17 2 3
109.6, 61.5, 18.4, 14.3. HRMS (ESI) calcd for [M+H] [C19H N O ]
NMR (150 MHz, CDCl
3
) δ 165.7, 157.3, 138.4, 138.2, 136.3, 134.0, 321.1234, found 321.1228.
1
31.5, 131.4, 130.9, 128.7, 125.9, 124.0, 123.8, 122.7, 119.8, 116.7,
Ethyl 1-methoxy-6-methyl-12-oxo-12H-indazolo[2,1-a]cinnoline-5-
+
116.1, 112.8, 110.7, 96.9, 52.0. HRMS (ESI) calcd for [M+H]
carboxylate (3t). Following the general procedure, 3t was obtained
+
[C
23
H
16IN
2
O
3
] 495.0200, found 495.0208.
1
as a yellow solid (56.7 mg, 81% yield): H NMR (600 MHz, CDCl
3
) δ
Methyl
12-oxo-6-(p-tolyl)-12H-indazolo[2,1-a]cinnoline-5- 8.01 (d, J = 7.8 Hz, 1H), 7.60 (ddd, J = 8.4, 7.2, 1.2 Hz, 1H), 7.51 (d, J
carboxylate (3o). Following the general procedure, 3o was obtained = 7.8 Hz, 1H), 7.40 (t, J = 7.2 Hz, 1H), 7.24 (dd, J = 16.2, 8.4 Hz, 1H),
1
3
as a yellow solid (72.6 mg, 95% yield): H NMR (600 MHz, CDCl ) δ 6.94 (d, J = 7.8 Hz, 1H), 6.87 (dd, J = 7.8, 0.6 Hz, 1H), 4.36 (q, J = 7.2
1
3
9
7
3
1
1
.05 (d, J = 7.8 Hz, 1H), 8.05 – 7.92 (m, 1H), 7.42 (d, J = 7.8 Hz, 1H), Hz, 2H), 3.94 (s, 3H), 2.50 (s, 3H), 1.36 (t, J = 7.2 Hz, 3H). C NMR
.38 – 7.28 (m, 5H), 7.22 – 7.12 (m, 3H), 5.76 – 5.61 (m, 1H), 3.49 (s, (150 MHz, CDCl ) δ 166.7, 157.7, 151.2, 144.1, 141.3, 131.2, 128.1,
) δ 166.1, 157.3, 140.8, 126.9, 124.7, 123.7, 120.5, 119.5, 116.0, 115.5, 112.5, 110.3, 61.3,
3
1
3
H), 2.49 (s, 3H). C NMR (150 MHz, CDCl
3
+
+
39.2, 136.3, 133.9, 131.2, 129.8, 129.6, 128.4, 128.3, 125.8, 123.8, 56.3, 17.6, 14.2. HRMS (ESI) calcd for [M+H] [C20
19 2 4
H N O ]
23.5, 122.4, 120.0, 116.5, 116.1, 113.1, 110.3, 51.8, 21.6. HRMS 351.1339, found 351.1346.
+
+
(ESI) calcd for [M+H] [C24
19 2 3
H N O ] 383.1390, found 383.1393.
Methyl 6-methyl-12-oxo-12H-indazolo[2,1-a]cinnoline-5-carboxylate
Methyl 6-(4-methoxyphenyl)-12-oxo-12H-indazolo[2,1-a]cinnoline- (3u). Following the general procedure, 3u was obtained as a yellow
1
5
-carboxylate (3p). Following the general procedure, 3p was solid (51.5 mg, 84% yield): H NMR (600 MHz, CDCl
3
) δ 8.91 (dd, J =
obtained as a yellow solid (73.4 mg, 92% yield): H NMR (600 MHz, 8.4, 0.6 Hz, 1H), 8.07 (d, J = 7.8 Hz, 1H), 7.62 (m, 2H), 7.36 – 7.32 (m,
CDCl ) δ 9.04 (dd, J = 8.4, 0.6 Hz, 1H), 8.02 – 7.94 (m, 1H), 7.41 (dd, J 1H), 7.32 – 7.28 (m, 1H), 7.23 (dd, J = 7.8, 1.2 Hz, 1H), 7.20 – 7.16
1
3
13
=
7.8, 1.2 Hz, 1H), 7.37 – 7.31 (m, 3H), 7.23 – 7.15 (m, 3H), 7.07 – (m, 1H), 3.94 (s, 3H), 2.66 (s, 3H). C NMR (150 MHz, CDCl
3
) δ
.01 (m, 2H), 5.91 – 5.60 (m, 1H), 3.92 (s, 3H), 3.51 (s, 3H). C NMR 167.2, 157.0, 138.6, 136.9, 133.3, 131.9, 127.8, 125.8, 124.1, 123.7,
) δ 166.2, 161.1, 157.4, 138.9, 136.3, 133.9, 131.2, 122.9, 120.2, 117.4, 116.2, 113.7, 109.3, 52.3, 18.4. HRMS (ESI)
13
7
(150 MHz, CDCl
3
+
+
1
15 2 3
31.2, 128.3, 125.8, 123.7, 123.5, 123.3, 122.4, 120.1, 116.5, 116.1, calcd for [M+H] [C18H N O ] 307.1077, found 307.1073.
6
| J. Name., 2012, 00, 1-3
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