G
J. F. Cívicos et al.
Paper
Synthesis
13C NMR (100 MHz, CDCl3): δ = 164.03, 155.80, 140.73, 135.72,
130.10, 128.00, 119.91, 72.36, 36.17, 33.96, 31.53, 29.63, 28.66, 24.71.
MS (EI, 70 eV): m/z (%) = 650.30 (M+), 651.31 (M+ + H), 673.29 (M+ +
Na).
1H NMR (400 MHz, CDCl3): δ = 12.47 (s, 1 H), 7.99 (d, J = 8.8 Hz, 1 H),
7.71 (d, J = 8.6 Hz, 1 H), 6.81 (dd, J = 8.8, 2.5 Hz, 1 H), 6.77 (dd, J = 8.6,
2.5 Hz, 1 H), 6.69–6.67 (m, 2 H), 3.84 (s, 3 H), 3.81 (s, 3 H), 3.80 (s, 3
H), 3.76, (s, 3 H), 3.56 (dd, J = 10.3, 4.7 Hz, 1 H), 3.07–2.88 (m, 2 H),
2.79–2.73 (m, 2 H), 2.54 (dd, J = 8.8, 6.6 Hz, 2 H), 2.51–2.40 (m, 1 H),
2.31 (ddd, J = 13.4, 10.5, 4.8 Hz, 1 H).
13C NMR (100 MHz, CDCl3): δ = 191.9, 173.2, 170.9, 165.6, 164.1,
161.6, 146.3, 141.9, 130.4, 126.3, 125.4, 122.9, 113.3, 112.7, 111.8,
94.9, 55.6, 55.4, 54.3, 52.4, 51.6, 28.3, 28.1, 26.6, 20.7.
[trans-N,N-Bis(2-hydroxybenzylidene)cyclohexane-1,2-diami-
no]copper(II) (9a)18
Purple solid; yield: 0.361 g (94%); mp 311 °C.
IR (KBr): 2951, 2864, 2370, 2349, 2320, 1622, 1525, 1431, 1323, 1166,
MS (EI): m/z (%) = 234 (M+), 202, 174, 160, 148, 131, 120, 103, 91, 77,
63, 51.
875, 833, 744 cm–1
.
MS (EI, 70 eV): m/z (%) = 383.08 (M+), 384.08 (M+ + H), 406.07 (M+ +
Na).
Methyl 7-Methoxy-1-oxo-1,2,3,4-tetrahydronaphthalene-2-car-
boxylate (10c)21
[trans-N,N-Bis-(3,5-di-tert-butyl-2-hydroxybenzylidene)cyclohex-
ane-1,2-diamino]copper(II) (9b)
Brown oil; yield: 0.204 g (87%); Rf = 0.32 (hexane/EtOAc 10:1).
IR (KBr): 2995, 2946, 2838, 1746, 1677, 1647, 1598, 1569, 1441, 1322,
Dark green solid; yield: 0.505 g (83%); mp 269 °C.
1264, 1273, 1224, 880, 811, 702 cm–1
.
IR (KBr): 2951, 2886, 2370, 2349, 2318, 1620, 1554, 1523, 1404, 1321,
1H NMR (400 MHz, CDCl3): δ = 12.44 (s, 1 H), 7.50 (d, J = 2.8 Hz, 1 H),
7.33 (d, J = 2.7 Hz, 1 H), 7.15 (d, J = 8.4 Hz, 1 H), 7.06 (dd, J = 8.4, 2.9 Hz,
2 H), 6.87 (dd, J = 8.3, 2.7 Hz, 1 H)., 3.81 (s, 6 H), 3.78 (s, 3 H), 3.77 (s, 3
H), 3.59 (dd, J = 10.3, 4.7 Hz, 1 H), 3.02–2.85 (m, 2 H), 2.72 (t, J = 7.7
Hz, 1 H), 2.53 (dd, J = 8.7, 6.7 Hz, 1 H), 2.46 (ddd, J = 15.1, 9.4, 4.6 Hz, 1
H), 2.37–2.28 (m, 1 H).
13C NMR (100 MHz, CDCl3): δ = 193.51, 173.18, 170.78, 165.13,
156.76, 155.93, 132.76, 131.05, 127.75, 127.15, 126.90, 119.24,
116.81, 114.71, 112.79, 96.80, 55.74, 55.67, 54.13, 52.34, 51.69, 25.65,
21.29, 20.03.
1165, 1049, 877, 746, 619 cm–1
.
MS (EI, 70 eV): m/z (%) = 607.3324 (M+), 608.33 (M+ + H), 630.32 (M+ +
Na).
Methyl 1-Oxo-1,2,3,4-tetrahydronaphthalene-2-carboxylates 10;
General Procedure
A solution of the α-tetralone (10 mmol) in dimethyl carbonate (5 mL)
was added to a stirred suspension of NaH (60% dispersion, 15 mmol)
in dimethyl carbonate (10 mL) under an atmosphere of argon. The
solution was refluxed; when the reaction was complete (TLC moni-
toring) the solvent was evaporated. The resultant solid was dissolved
in 2 M HCl and the phases were separated. The aqueous phase was
extracted with EtOAc (3 × 15 mL). The organic extracts were dried
(MgSO4) and evaporated to dryness. Flash chromatography (10%
EtOAc/hexane) afforded the pure products.
MS (EI): m/z (%) = 234 (M+), 216, 202, 174, 160, 148, 131, 120, 103, 91,
77, 63, 51.
Methyl 6,7-Dimethoxy-1-oxo-1,2,3,4-tetrahydronaphthalene-2-
carboxylate (10d)22
Brown solid; yield: 0.256 g (97%); mp 126–128 °C; Rf = 0.04 (hex-
ane/EtOAc 10:1).
Methyl 1-Oxo-1,2,3,4-tetrahydronaphthalene-2-carboxylate
(10a)19
IR (KBr): 2937, 2830, 1736, 1657, 1509, 1451, 1372, 1273, 1135, 1027
cm–1
.
Brown solid; yield: 0.188 g (92%); mp 66–68 °C; Rf = 0.35 (hex-
1H NMR (400 MHz, CDCl3): δ = 12.56 (s, 1 H), 7.52 (d, J = 1.8 Hz, 1 H),
7.33 (s, 1 H), 6.69 (s, 1 H), 6.67 (d, J = 5.6 Hz, 1 H), 3.94 (s, 3 H), 3.92 (s,
3 H), 3.92 (s, 3 H), 3.91 (s, 3 H), 3.82 (s, 3 H), 3.78 (s, 3 H), 3.58 (dd, J =
9.8, 4.8 Hz, 1 H), 3.05–3.00 (m, 1 H), 3.00–2.88 (m, 9 H), 2.79–2.71 (m,
1 H), 2.60 (dd, J = 11.8, 4.9 Hz, 2 H), 2.57–2.44 (m, 5 H), 2.34 (ddt, J =
13.4, 6.2, 4.7 Hz, 4 H), 2.17–2.08 (m, 2 H).
13C NMR (100 MHz, CDCl3): δ = 191.9, 173.2, 170.9, 165.5, 154.0,
150.9, 148.2, 138.8, 133.3, 124.8, 122.4, 110.5, 110.2, 108.9, 107.3,
94.8, 56.1, 56.0, 53.8, 52.3, 51.6, 27.5, 27.4, 26.8, 20.7.
ane/EtOAc 10:1).
IR (KBr): 2946, 2897, 1728, 1677, 1598, 1451, 1372, 1313, 1156, 949,
900, 732 cm–1
.
1H NMR (400 MHz, CDCl3): δ = 12.41 (s, 1 H), 8.04 (d, J = 7.9 Hz, 1 H),
7.78 (d, J = 7.6 Hz, 1 H), 7.47–7.43 (m, 1 H), 7.30–7.23 (m, 3 H), 7.21
(d, J = 7.6 Hz, 1 H), 7.13 (d, J = 7.1 Hz, 1 H), 3.79 (s, 3 H), 3.75 (s, 3 H),
3.59 (dd, J = 10.5, 4.7 Hz, 1 H), 3.04–2.92 (m, 2 H), 2.77 (dd, J = 10.8,
4.6 Hz, 2 H), 2.57–2.51 (m, 2 H), 2.49–2.42 (m, 1 H), 2.34–2.29 (m, 1
H).
13C NMR (100 MHz, CDCl3): δ = 193.3, 173.2, 170.7, 165.2, 143.8,
139.5, 134.0, 131.8, 130.6, 130.0, 128.9, 127.8, 127.5, 127.0, 126.7,
124.4, 96.9, 54.5, 52.5, 51.8, 27.8, 27.7, 26.5, 20.6.
MS (EI): m/z (%) = 264 (M+), 206, 191, 178, 164, 150, 135, 107, 91, 77,
63, 51.
Methyl 5-(Benzyloxy)-1-oxo-1,2,3,4-tetrahydronaphthalene-2-
carboxylate (10e)8
MS (EI): m/z (%) = 204 (M+), 189, 172, 144, 127, 118, 115, 90, 77, 63,
51.
Brown solid; yield: 0.310 g (100%); mp 72 °C; Rf = 0.35 (hexane/EtOAc
10:1).
Methyl 6-Methoxy-1-oxo-1,2,3,4-tetrahydronaphthalene-2-car-
boxylate (10b)20
IR (KBr): 2951, 2924, 2869, 2851, 1738, 1679, 1573, 1460, 1257, 1204,
993, 751, 700 cm–1
.
Brown solid; yield: 0.229 g (98%); mp 78–80 °C; Rf = 0.10 (hex-
1H NMR (400 MHz, CDCl3): δ = 12.41 (s, 1 H), 7.67 (d, J = 7.4 Hz, 1 H),
7.46 (d, J = 7.7 Hz, 1 H), 7.45–7.32 (m, 10 H), 7.24 (dt, J = 16.5, 8.0 Hz,
2 H), 7.09 (d, J = 7.6 Hz, 1 H), 6.98 (d, J = 7.9 Hz, 1 H), 5.09 (s, 2 H), 5.07
(s, 2 H), 3.81 (s, 3 H), 3.76 (s, 3 H), 3.60 (dd, J = 10.6, 4.7 Hz, 1 H), 3.15
ane/EtOAc 10:1).
IR (KBr): 2957, 2838, 1720, 1668, 1600, 1254, 1214, 1156, 998, 840,
664 cm–1
.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2017, 49, A–I