G
Synthesis
Y. E. Sabutskii et al.
Paper
1
13
H NMR (700 MHz, CDCl ): δ = 1.08 (t, J = 7.4 Hz, 3 H, CH CH ), 1.93
C NMR (176 MHz, CDCl ): δ = 13.6, 19.1, 30.2, 69.8, 110.6, 110.7,
3
2
3
3
(
m, 2 H, CH CH ), 3.97 (t, J = 6.6 Hz, 2 H, OCH CH ), 6.12 (s, 1 H, ArH),
111.7, 128.1, 130.6, 156.9, 158.4, 160.5, 182.7, 188.5.
2
3
2
2
7
.23 (dd, J = 2.5, 7.1 Hz, 1 H, ArH), 7.62 (m, 2 H, 2 ArH), 11.79 (s, 1 H,
+
HRMS (EI): m/z [M] calcd for C14H14O : 262.0841; found: 262.0851.
5
5-OH).
1
3
C NMR (176 MHz, CDCl ): δ = 10.3, 21.7, 71.2, 110.7, 114.4, 118.8,
3
5,8-Dihydroxy-2-(pentyloxy)naphthalene-1,4-dione (27)
1
23.7, 132.1, 137.0, 159.5, 161.9, 184.1, 185.1.
Red solid; yield: 254 mg (92%); mp 122–125 °C; R = 0.67 (system A).
f
+
HRMS (EI): m/z [M] calcd for C13H12O : 232.0735; found: 232.0746
4
IR (CHCl ): 2960, 2933, 2875, 1614, 1572, 1457, 1410, 1378, 1312,
3
–1
1
295, 1270, 1243, 1183, 1071 cm .
2
-Butoxy-8-hydroxynaphthalene-1,4-dione (23)
Yellow crystals; yield: 220 mg (89%); mp 127–129 °C; Rf = 0.59
system A).
IR (CHCl ): 2963, 2930, 2877, 1645, 1606, 1579, 1485, 1458, 1376,
1
H NMR (700 MHz, CDCl ): δ = 0.95 (t, J = 7.3 Hz, 3 H, CH CH ), 1.40
3
2
3
(m, 2 H, CH CH ), 1.47 (m, 2 H, OCH CH CH ), 1.91 (m, 2 H, OCH CH ),
2
3
2
2
2
2
2
(
4
.03 (t, J = 6.6 Hz, 2 H, OCH CH ), 6.14 (s, 1 H, ArH), 7.20 (d, J = 9.4 Hz,
2 2
1 H, ArH), 7.27 (d, J = 9.4 Hz, 1 H, ArH), 12.21 (s, 1 H, α-OH), 12.65 (s, 1
H, α-OH).
3
1
361, 1306, 1291, 1243, 1170, 1067, 1028 cm–1
.
1
13
H NMR (700 MHz, CDCl ): δ = 1.00 (t, J = 7.4 Hz, 3 H, CH CH ), 1.52
C NMR (176 MHz, CDCl ): δ = 13.9, 22.3, 27.9 (2 C), 70.1, 110.5,
3
2
3
3
(
m, 2 H, CH CH ), 1.88 (m, 2 H, OCH CH ), 4.01 (t, J = 6.6 Hz, 2 H,
110.7, 111.6, 128.1, 130.6, 156.9, 158.4, 160.5, 182.7, 188.5.
2
3
2
2
OCH CH ), 6.12 (s, 1 H, ArH), 7.22 (dd, J = 2.5, 7.1 Hz, 1 H, ArH), 7.62
+
2
2
HRMS (EI): m/z [M] calcd for C15H16O : 276.0998; found: 276.0984.
5
(m, 2 H, 2 ArH), 11.79 (s, 1 H, 5-OH).
1
3
C NMR (176 MHz, CDCl ): δ = 13.7, 19.1, 30.2, 69.6, 110.7, 114.4,
3
5,8-Dihydroxy-6,7-dimethyl-2-propoxynaphthalene-1,4-dione
1
18.8, 123.7, 132.1, 137.0, 159.5, 162.0, 184.1, 185.1.
(28)
+
HRMS (EI): m/z [M] calcd for C14H14O : 246.0892; found: 246.0883.
Red solid; yield: 232 mg (84%); mp 157–159 °C; R = 0.67 (system A).
4
f
IR (CHCl ): 2972, 2941, 2882, 1599, 1576, 1457, 1394, 1314, 1267,
3
8
-Hydroxy-2-(pentyloxy)naphthalene-1,4-dione (24)
Yellow crystals; yield: 231 mg (89%); mp 94–97 °C; Rf = 0.62
system A).
IR (CHCl ): 2960, 2932, 2875, 1646, 1606, 1579, 1458, 1375, 1361,
–1
1164, 1085 cm
.
1
H NMR (700 MHz, CDCl ): δ = 1.08 (t, J = 7.4 Hz, 3 H, CH CH ), 1.94
3
2
3
(
(
m, 2 H, OCH CH ), 2.26 (s, 3 H, ArCH ), 2.27 (s, 3 H, ArCH ), 4.00 (t,
2 2 3 3
J = 6.6 Hz, 2 H, OCH CH ), 6.16 (s, 1 H, ArH), 13.02 (s, 1 H, α-OH), 13.34
3
2
2
1
307, 1291, 1243, 1170, 1065, 1029 cm–1
.
(s, 1 H, α-OH).
1
13
H NMR (500 MHz, CDCl ): δ = 0.95 (t, J = 7.2 Hz, 3 H, CH CH ), 1.41
C NMR (176 MHz, CDCl ): δ = 10.3, 12.2, 12.6, 21.8, 71.2, 107.4,
3
2
3
3
(
m, 2 H, CH CH ), 1.46 (m, 2 H, OCH CH CH ), 1.90 (m, 2 H, OCH CH ),
109.5, 109.7, 137.7, 140.7, 160.0, 160.8, 162.6, 177.4, 184.0.
2
3
2
2
2
2
2
4
6
.01 (t, J = 6.6 Hz, 2 H, OCH CH ), 6.12 (s, 1 H, ArH), 7.23 (dd, J = 3.2,
.4 Hz, 1 H, ArH), 7.62 (m, 2 H, 2 ArH), 11.79 (s, 1 H, 5-OH).
+
2
2
HRMS (EI): m/z [M] calcd for C15H16O : 276.0997; found: 276.0986.
5
1
3
C NMR (125 MHz, CDCl ): δ = 13.9, 22.3, 28.0 (2 C), 69.9, 110.7,
3
2-Butoxy-5,8-dihydroxy-6,7-dimethylnaphthalene-1,4-dione (29)
1
14.4, 118.8, 123.7, 132.1, 137.0, 159.5, 161.9, 184.1, 185.0.
Red solid; yield: 268 mg (92%); mp 133–134 °C; R = 0.72 (system A).
f
+
HRMS (EI): m/z [M] calcd for C15H16O : 260.1048; found: 260.1036.
4
IR (CHCl ): 2963, 2933, 2877, 1599, 1578, 1458, 1396, 1312, 1266,
3
–1
1
192, 1164, 1098, 1085 cm .
5
,8-Dihydroxy-2-propoxynaphthalene-1,4-dione (25)
1
H NMR (500 MHz, CDCl ): δ = 1.00 (t, J = 7.4 Hz, 3 H, CH CH ), 1.53
3
2
3
Red solid; yield: 211 mg (85%); mp 167–170 °C; R = 0.58 (system A)
f
(m, 2 H, CH CH ), 1.89 (m, 2 H, OCH CH ), 2.25 (s, 3 H, ArCH ), 2.27 (s,
2 3 2 2 3
IR (CHCl ): 2972, 2941, 2883, 1614, 1572, 1456, 1409, 1348, 1312,
3 H, ArCH ), 4.03 (t, J = 6.6 Hz, 2 H, OCH CH ), 6.16 (s, 1 H, ArH), 13.01
(s, 1 H, α-OH), 13.34 (s, 1 H, α-OH).
3
3
2
2
1
295, 1270, 1242, 1183, 1072 cm–1
.
1
13
H NMR (700 MHz, CDCl ): δ = 1.08 (t, J = 7.5 Hz, 3 H, CH CH ), 1.94
C NMR (125 MHz, CDCl ): δ = 12.2, 12.6, 13.7, 19.1, 30.3, 69.6, 107.4,
3
2
3
3
(
m, 2 H, CH CH ), 4.00 (t, J = 6.6 Hz, 2 H, OCH CH ), 6.14 (s, 1 H, ArH),
109.4, 109.7, 137.7, 140.7, 160.0, 160.7, 162.6, 177.5, 184.1.
2
3
2
2
7
.20 (d, J = 9.4 Hz, 1 H, ArH), 7.27 (d, J = 9.4 Hz, 1 H, ArH), 12.21 (s, 1 H,
+
HRMS (EI): m/z [M] calcd for C16H18O : 290.1154; found: 290.1143.
5
α-OH), 12.65 (s, 1 H, α-OH).
1
3
C NMR (176 MHz, CDCl ): δ = 10.3, 21.7, 71.5, 110.6, 110.7, 111.6,
3
5,8-Dihydroxy-6,7-dimethyl-2-(pentyloxy)naphthalene-1,4-dione
1
28.2, 130.6, 156.8, 158.4, 160.4, 182.7, 188.5.
(30)
+
HRMS (EI): m/z [M] calcd for C13H12O : 248.0684; found: 248.0697.
Red solid; yield: 265 mg (87%); mp 145–147 °C; R = 0.74 (system A).
5
f
IR (CHCl ): 2960, 2930, 2874, 1599, 1577, 1459, 1396, 1312, 1267,
3
2
-Butoxy-5,8-dihydroxynaphthalene-1,4-dione (26)
–1
1163, 1085 cm
.
Red solid; yield: 218 mg (83%); mp 123–125 °C (Lit.24 116–120 °C);
Rf = 0.63 (system A).
1
H NMR (700 MHz, CDCl ): δ = 0.94 (t, J = 7.4 Hz, 3 H, CH CH ), 1.41
3
2
3
(m, 2 H, CH CH ), 1.47 (m, 2 H, CH CH CH ), 1.91 (m, 2 H, OCH CH ),
2
3
2
2
3
2
2
IR (KBr): 2964, 2963, 2876, 1613, 1573, 1456, 1348, 1311, 1294, 1270,
2.26 (s, 3 H, ArCH ), 2.27 (s, 3 H, ArCH ), 4.02 (t, J = 6.6 Hz, 2 H,
OCH CH ), 6.16 (s, 1 H, ArH), 13.01 (s, 1 H, α-OH), 13.34 (s, 1 H, α-OH).
2 2
3
3
–1
1241, 1185, 1073 cm
.
1
13
H NMR (700 MHz, CDCl ): δ = 1.00 (t, J = 7.4 Hz, 3 H, CH CH ), 1.53
C NMR (176 MHz, CDCl ): δ = 12.2, 12.6, 13.9, 22.3, 28.0, 28.1, 69.9,
3
3
2
3
(
m, 2 H, CH CH ), 1.89 (m, 2 H, OCH CH ), 4.04 (t, J = 6.6 Hz, 2 H,
107.4, 109.4, 109.7, 137.7, 140.7, 160.0, 160.7, 162.6, 177.5, 184.1.
2
3
2
2
OCH CH ), 6.12 (s, 1 H, ArH), 7.20 (d, J = 9.2 Hz, 1 H, ArH), 7.27 (d,
J = 9.2 Hz, 1 H, ArH), 12.21 (s, 1 H, α-OH), 12.65 (s, 1 H, α-OH).
+
2
2
HRMS (EI): m/z [M] calcd for C17H20O : 304.1310; found: 304.1319.
5
©
Georg Thieme Verlag Stuttgart · New York — Synthesis 2018, 50, A–K