The Journal of Organic Chemistry
Article
13
1
3H); 13C{ H} NMR (100 MHz, CDCl ) δ 162.0, 149.1, 142.3, 142.2,
1
C{ H} NMR (100 MHz, CDCl ) δ 160.9, 148.5, 143.0, 142.7,
3
3
1
1
1
41.3, 141.1, 136.3, 134.8, 134.5, 134.1, 132.6, 131.9, 130.6, 129.9,
141.1, 139.6, 136.8, 131.4, 127.8, 124.2, 123.8, 115.8, 108.7, 17.2,
−
1
29.5, 128.3, 128.0, 125.0, 124.95, 116.0, 115.9; IR (film): 2642,
15.3; IR (film): 2952, 1706, 1615, 1574, 1195, 1092, 738 cm ;
−
1
+
+
641, 1573, 1322, 1161, 1065, 717 cm ; HRMS (EI) m/z: [M]
HRMS (EI) m/z: [M] Calcd for C15H O 224.0837; Found
12 2
Calcd for C H Cl O 416.0371; Found 416.0367.
224.0834.
25
14
2
2
3
,4-Bis(3-bromophenyl)-1H-azuleno[2,1-c]pyran-1-one (3i).
3,4-Diethyl-1H-azuleno[2,1-c]pyran-1-one (3o). Yield: 35.8 mg
(71%); R = 0.2 (CH Cl /hexane = 2:1); green solid; melting point:
135−137 °C; H NMR (400 MHz, CDCl ) δ 8.73 (d, J = 9.5 Hz,
Yield: 60.5 mg (60%); R = 0.3 (CH Cl /hexane = 2:1); brown
f
2
2
f
2
2
1
1
solid; melting point: 239−241 °C; H NMR (400 MHz, CDCl ) δ
3
3
8
7
=
1
1
1
7
5
.46 (d, J = 10.0 Hz, 1H), 7.93 (s, 1H), 7.68−7.59 (m, 5H), 7.41−
1H), 8.34 (d, J = 10.0 Hz, 1H), 7.81 (s, 1H), 7.61 (t, J = 9.8 Hz, 1H),
7.13 (t, J = 10.0 Hz, 1H), 7.04 (t, J = 9.6 Hz, 1H), 3.00 (q, J = 7.5 Hz,
2H), 2.74 (q, J = 7.5 Hz, 2H), 1.37 (t, J = 7.5 Hz, 3H), 1.32 (t, J = 7.5
.35 (m, 3H), 7.19−7.13 (m, 2H), 7.06 (t, J = 7.9 Hz, 1H), 6.87 (t, J
10.0 Hz, 1H); 13C{ H} NMR (100 MHz, CDCl ) δ 160.8, 147.9,
1
3
1
3
1
43.1, 142.7, 141.4, 141.2, 137.7, 136.2, 135.2, 134.0, 132.3, 132.0,
31.6, 131.0, 130.0, 129.4, 129.1, 128.1, 127.9, 125.2, 125.1, 123.4,
22.2, 116.2, 116.1; IR (film): 3052, 2359, 1721, 1644, 1568, 1391,
61, 566 cm ; HRMS (EI) m/z: [M] Calcd for C H Br O
03.9361, C H Br O 507.9321; Found 503.9358, 507.9306.
Hz, 3H); C{ H} NMR (100 MHz, CDCl ) δ 162.1, 154.1, 142.3,
3
142.2, 140.7, 140.0, 135.7, 130.0, 128.5, 124.2, 123.9, 116.3, 114.1,
23.9, 20.8, 14.5, 13.4; IR (film): 2967, 1713, 1643, 1391, 1190, 990,
−
1
+
79
−1
+
735 cm ; HRMS (EI) m/z: [M] Calcd for C17H O 252.1150;
2
5
14
2
2
16 2
81
14
Found 252.1152.
2
5
2
2
3
,4-Bis(4-bromophenyl)-1H-azuleno[2,1-c]pyran-1-one (3j).
3,4-Dibutyl-1H-azuleno[2,1-c]pyran-1-one (3p). Yield: 40.7 mg
(66%); R = 0.4 (CH Cl /hexane = 2:1); green solid; melting point:
90−92 °C; H NMR (400 MHz, CDCl ) δ 8.69 (d, J = 9.5 Hz, 1H),
Yield: 82.6 mg (82%); R = 0.3 (CH Cl /hexane = 2:1); brown
f
2
2
f
2
2
1
1
solid; melting point: 269−271 °C; H NMR (400 MHz, CDCl ) δ
3
3
8
=
(
.44 (d, J = 10.0 Hz, 1H), 7.91 (s, 1H), 7.65−7.58 (m, 4H), 7.35 (d, J
8.33 (d, J = 10.0 Hz, 1H), 7.81 (s, 1H), 7.61 (t, J = 9.8 Hz, 1H), 7.12
(t, J = 9.9 Hz, 1H), 7.03 (t, J = 7.0 Hz, 1H), 2.94 (t, J = 8.1 Hz, 2H),
2.70 (t, J = 7.8 Hz, 2H), 1.78−1.68 (m, 4H), 1.60−1.51 (m, 2H),
1.48−1.39 (m, 2H), 1.03 (t, J = 7.3 Hz, 3H), 0.97 (t, J = 7.3 Hz, 3H);
8.6 Hz, 2H), 7.29 (d, J = 8.3 Hz, 2H), 7.19 (d, J = 8.6 Hz, 2H), 7.13
1
3
1
t, J = 9.7 Hz, 1H), 6.87 (t, J = 10.0 Hz, 1H); C{ H} NMR (100
MHz, CDCl ) δ 160.9, 148.4, 143.0, 142.7, 141.3, 141.1, 136.3, 134.6,
32.90, 132.85, 132.4, 131.3, 130.9, 129.4, 128.0, 125.04, 124.99,
3
1
3
1
1
C{ H} NMR (100 MHz, CDCl ) δ 162.1, 153.3, 142.3, 142.2,
3
1
1
23.0, 122.9, 116.1, 116.0; IR (film): 2359, 1644, 1483, 1391, 1181,
140.7, 140.0, 135.8, 130.2, 128.5, 124.1, 123.9, 116.3, 113.2, 31.9,
−
1
+
009, 743, 606 cm ; HRMS (EI) m/z: [M] Calcd for
30.8, 30.4, 27.4, 22.9, 22.7, 14.1, 14.0; IR (film): 2956, 2929, 2870,
7
9
81
−1
+
C H
Br O2 503.9361, C H
Br O 507.9321; Found
2359, 1718, 1572, 1187, 735 cm ; HRMS (EI) m/z: [M] Calcd for
2
5
14
2
25 14
2
2
5
03.9359, 507.9323.
,4-Bis(4-(trifluoromethyl)phenyl)-1H-azuleno[2,1-c]pyran-1-
one (3k). Yield: 65.8 mg (68%); R = 0.3 (CH Cl /hexane = 2:1);
C H O 308.1776; Found 308.1773.
4-Methyl-3-phenyl-1H-azuleno[2,1-c]pyran-1-one (3q). Yield:
46.9 mg (82%); data for the major isomer 3r-1; R = 0.3 (CH Cl /
2
1
24
2
3
f
2
2
f
2
2
1
1
brown solid; melting point: 244−246 °C; H NMR (400 MHz,
CDCl ) δ 8.48 (d, J = 10.0 Hz, 1H), 7.95 (s, 1H), 7.79 (d, J = 8.0 Hz,
hexane = 2:1); brown solid; melting point: 208−210 °C; H NMR
3
(400 MHz, CDCl ) δ 8.92 (d, J = 9.4 Hz, 1H), 8.35 (d, J = 10.0 Hz,
3
2
5
H), 7.64 (t, J = 9.8 Hz, 1H), 7.59 (d, J = 8.0 Hz, 2H), 7.51−7.41 (m,
1H), 7.81 (s, 1H), 7.65−7.59 (m, 3H), 7.49−7.39 (m, 3H), 7.15 (t, J
= 9.9 Hz, 1H), 7.07 (t, J = 9.7 Hz, 1H), 2.68 (s, 3H); C{ H} NMR
1
3
1
13
1
H), 7.19 (t, J = 9.7 Hz, 1H), 6.86 (t, J = 10.0 Hz, 1H); C{ H}
NMR (100 MHz, CDCl ) δ 160.7, 147.9, 143.2, 142.9, 141.4, 141.1,
(100 MHz, CDCl ) δ 161.6, 150.5, 142.5, 142.3, 141.2, 140.3, 137.3,
3
3
1
39.5, 136.8, 136.2, 131.8, 130.8 (q, J = 61.3 Hz), 130.7 (q, J = 39.4
133.8, 131.1, 130.0, 128.9, 128.28, 128.27, 124.6, 124.4, 116.0, 110.0,
−1
Hz), 129.6, 128.7, 128.3, 124.0 (q, J = 272.3 Hz), 126.6 (q, J = 3.6
Hz), 125.4, 125.2, 125.1 (q, J = 3.7 Hz), 122.6, 116.7, 116.2;
16.7; IR (film): 3064, 2921, 2851, 1722, 1643, 1572, 1185, 703 cm ;
1
9
+
F
HRMS (EI) m/z: [M] Calcd for C H O 286.0994; Found
2
0
14
2
NMR (376 MHz, CDCl ) δ −62.49, −62.82; IR (film): 2908, 1718,
286.0992. Data for the minor isomer 3r-2; R = 0.4 (CH Cl /hexane =
3
f
2
2
−
1
+
1
1
636, 1568, 1488, 1182, 1015, 764 cm ; HRMS (EI) m/z: [M]
2:1); brown solid; melting point: 208−210 °C; H NMR (400 MHz,
Calcd for C H F O 484.0898; Found 484.0900.
CDCl ) δ 8.35 (d, J = 9.9 Hz, 1H), 7.84 (s, 3H), 7.57−7.51 (m, 3H),
27
14
6
2
3
3
,4-Di(thiophen-2-yl)-1H-azuleno[2,1-c]pyran-1-one (3l). Yield:
7.47 (d, J = 9.5 Hz, 2H), 7.41−7.38 (m, 2H), 7.01 (t, J = 9.7 Hz, 1H),
1
3
1
3
6.7 mg (51%); R = 0.3 (CH Cl /hexane = 2:1); brown solid;
6.70 (t, J = 9.9 Hz, 1H), 2.17 (s, 3H); C{ H} NMR (100 MHz,
f
2
2
1
melting point: 241−243 °C; H NMR (400 MHz, CDCl ) δ 8.36 (d,
J = 10.0 Hz, 1H), 7.85 (s, 1H), 7.71 (d, J = 5.0 Hz, 1H), 7.58−7.52
CDCl ) δ 161.9, 150.4, 142.4, 142.3, 141.4, 139.9, 136.2 135.6, 130.8,
3
3
130.5, 129.4 128.4, 127.4, 124.4, 124.0, 115.7, 115.5, 17.7; IR (film):
−
1
(
(
9
1
1
m, 2H), 7.40 (d, J = 2.3 Hz, 1H), 7.34 (t, J = 4.1 Hz, 1H), 7.27−7.26
2359, 2088, 1643, 1499, 1183, 1085, 770 cm ; HRMS (EI) m/z:
+
m, 2H), 7.05 (t, J = 9.5 Hz, 1H), 6.97 (t, J = 4.2 Hz, 1H), 6.84 (t, J =
[M] Calcd for C H O 286.0994; Found 286.0993.
2
0
14
2
.9 Hz, 1H); 13C{ H} NMR (100 MHz, CDCl ) δ 160.2, 146.9,
1
3
4-Butyl-3-phenyl-1H-azuleno[2,1-c]pyran-1-one (3r). Yield: 55.8
mg (85%); Data for the major isomer 3s-1; R = 0.3 (CH Cl /hexane
43.0, 142.6, 141.7, 141.0, 136.3, 135.53, 135.50, 130.8, 130.7, 129.3,
28.8, 128.7, 128.5, 127.1, 127.0, 125.3, 124.8, 116.0, 107.1; IR
f
2
2
1
= 2:1); green solid; melting point: 147−149 °C; H NMR (400 MHz,
−
1
(
film): 2359, 1791, 1638, 1428, 1222, 1017, 778 cm ; HRMS (EI)
CDCl ) δ 8.79 (d, J = 9.5 Hz, 1H), 8.42 (d, J = 10.0 Hz, 1H), 7.90 (s,
3
+
m/z: [M] Calcd for C H O S 360.0279; Found 360.0281.
1H), 7.68 (t, J = 9.8 Hz, 1H), 7.59−7.56 (m, 2H), 7.49−7.43 (m,
3H), 7.20 (t, J = 9.9 Hz, 1H), 7.13 (t, J = 9.7 Hz, 1H), 3.02 (t, J = 8.0
Hz, 2H), 1.80−1.72 (m, 2H), 1.43−1.37 (m, 2H), 0.88 (t, J = 7.4 Hz,
2
1
12
2 2
3
,4-Di(pyridin-3-yl)-1H-azuleno[2,1-c]pyran-1-one (3m). Yield:
3
5.0 mg (50%); R = 0.3 (CH Cl /hexane = 2:1); green solid;
f
2
2
1
13
1
melting point: 252−254 °C; H NMR (400 MHz, CDCl ) δ 8.78 (dd,
J = 4.9 Hz, J = 1.7 Hz, 1H), 8.69 (dd, J = 2.2 Hz, J = 0.8 Hz, 2H),
3H); C{ H} NMR (100 MHz, CDCl ) δ 161.6, 150.7, 142.6, 142.4,
3
3
140.9, 140.6, 136.2, 134.2, 129.8, 129.6, 129.2, 129.0, 128.4, 124.5,
8
1
.50−8.45 (m, 3H), 7.95 (s, 1H), 7.78 (dt, J = 7.8 Hz, J = 2.0 Hz,
124.4, 116.5, 115.0, 32.1, 28.0, 22.6, 13.9; IR (film): 2359, 1868,
−
1
+
H), 7.69 (dt, J = 8.0 Hz, J = 2.0 Hz, 1H), 7.67−7.62 (m, 1H), 7.60
1639, 1466, 1293, 1183, 771 cm ; HRMS (EI) m/z: [M] Calcd for
C H O 328.1463; Found 328.1465. Data for the minor isomer 3s-
(
d, J = 9.6 Hz, 1H), 7.47 (ddd, J = 7.8 Hz, J = 4.9 Hz, J = 0.8 Hz, 1H),
2
3
20
2
1
3
1
7
.22−7.17 (m, 2H), 6.87 (t, J = 9.9 Hz, 1H); C{ H} NMR (100
2; R = 0.4 (CH Cl /hexane = 2:1); green solid; melting point: 147−
f
2
2
1
MHz, CDCl ) δ 160.6, 151.7, 150.2, 150.1, 149.3, 147.6, 143.3, 142.9,
149 °C; H NMR (400 MHz, CDCl ) δ 8.35 (d, J = 10.0 Hz, 1H),
3
3
1
1
1
41.3, 141.0, 138.8, 136.6, 136.2, 131.3, 129.4, 128.7, 128.1, 125.4,
25.2, 124.1, 123.0, 116.2, 114.6; IR (film): 3082, 2359, 1720, 1568,
393, 1194, 1020, 721 cm ; HRMS (EI) m/z: [M] Calcd for
7.84 (s, 1H), 7.56−7.37 (m, 7H), 7.00 (t, J = 9.7 Hz, 1H), 6.69 (t, J =
9.9 Hz, 1H), 2.42 (t, J = 7.6 Hz, 2H), 1.70−1.58 (m, 2H), 1.32-1.22
−
1
+
13
1
(m, 2H), 0.82 (t, J = 7.3 Hz, 3H); C{ H} NMR (100 MHz, CDCl )
3
C H N O 350.1055; Found 350.1053.
δ 162.1, 154.1, 142.4, 142.2, 141.4, 140.0, 136.1, 135.8, 130.9, 130.6,
129.3, 128.4, 127.4, 124.0, 115.6, 115.5, 30.8, 30.5, 22.4, 13.9; IR
23
14
2
2
3,4-Dimethyl-1H-azuleno[2,1-c]pyran-1-one (3n). Yield: 32.3 mg
−
1
(
72%); R = 0.1 (CH Cl /hexane = 2:1); brown solid; melting point:
(film): 2958, 2869, 2339, 1724, 1643, 1180, 1017, 703 cm ; HRMS
f
2
2
1
+
2
1
7
26−228 °C; H NMR (400 MHz, CDCl ) δ 8.85 (d, J = 9.4 Hz,
H), 8.32 (d, J = 10.0 Hz, 1H), 7.76 (s, 1H), 7.59 (t, J = 9.8 Hz, 1H),
.09 (t, J = 9.9 Hz, 1H), 7.02 (t, J = 9.7 Hz, 1H), 2.57 (s, 3H), 2.42 (s,
(EI) m/z: [M] Calcd for C H O 328.1463; Found 328.1465.
3
23 20
2
Ethyl 4-methyl-1-oxo-1H-azuleno[2,1-c]pyran-3-carboxylate
(3s). Yield: 44.0 mg (78%); data for the major isomer 3q-1; R =
f
I
J. Org. Chem. XXXX, XXX, XXX−XXX