G. Kirsch – St. Deprets · Preparation of Tetracyclic Heteroaromatic Derivatives
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(CH), 55.69 (OCH3). – C17H12O4 (280.37): calcd. C 72.85,
H 4.08; found C 72.60, H 3.90.
4b: 93%, yellow solid, m. p. 162 C (CH2Cl2/C6H6). –
1H NMR (CDCl3): δ = 2.65 (s, SCH3). 7.51 (dd, 9-H, J =
1.87 and 8.57), 7.56 (td, 3-H), 7.63 (d, 5-H, J = 8.75), 7.73
(td, 2-H), 7.74 (d, 6-H, J = 8.82), 7.94 (d, 4-H, J = 8.90),
8.03 (d, 8-H, J = 8.40), 8.36 (d, 11-H, J = 1.77), 8.58 (d, 1-
H, J = 8.17). – 13C NMR (CDCl3): δ = 154.8, 154.5, 132.3,
130.5, 129.9, 125.7, 116.7 (C); 129.2, 128.9, 127.7, 127.3,
124.5, 123.6, 123.3, 112.6, 112.2 (CH), 18.4 (SCH3). –
C17H12OS (264.34): calcd. C 77.24, H 4.58; found C 77.30,
H 4.65.
3b: 89%, yellow solid; m. p. 93 ◦C (CH2Cl2). – IR (KBr):
ν = 1674, 1694. – 1H NMR (CDCl3) δ = 2.46 (s,
SCH3), 7.28 (d, 4-H, J = 1.77), 7.52 (m, 1H), 7.54
(dd, 6-H, J = 1.83 and 8.87), 7.61 (d, 7-H, J = 8.68),
7.71 (m, 1H), 7.81 (m, 1H), 8.16 (dd, 3’-H, J = 1.27
and 8.06), 9.74 (s, CHO), 9.97 (s, CHO). – 13C NMR
(CDCl3): δ = 190.31, 179.26 (CHO), 153.43, 148.95,
135.41, 134.99, 131.11, 129.19, 128.20 (C); 134.13, 132.08,
130.25, 129.99, 119.84, 113.29 (CH); 17.17 (SCH3). –
4c: 67%, colourless solid; m. p. 112 ◦C (CH2Cl2/C6H6). –
C17H12O3 S (296.37): calcd. C 68.90, H 4.08; found C 68.80, 1H NMR (CDCl3): δ = 7.44 (m, 9-H), 7.58 (m, 3-H –
H 3.95.
10-H), 7.71 (m, 12-H), 7.82 (d, 5-H, J = 8.46), 7.96 (d,
6-H, J = 8.58), 8.01 (d, 4-H, J = 8.03), 8.06 (d, 8-H,
J = 7.31), 8.91 (d, 4-H, J = 8.03), 8.06 (d, 8-H, J =
7.31), 8.91 (d, 11-H, J = 8.30), 9.03 (d,1-H, J = 8.46). –
13C NMR (CDCl3): δ = 129.48, 127.61, 126.96, 126.49,
126.41, 125.31, 125.06, 124.84, 123.82, 123.21 (CH). –
C16H10S (234.05): calcd. C 82.01, H 4.30; found C 81.92,
H 4.25.
3c: 72%, orange solid; m. p. 97 ◦C (CH2Cl2). – IR (KBr):
ν = 1648, 1702. – 1H NMR (CDCl3): δ = 7.38 (m, 2H),
7.46 (d, 6’-H, J = 8.19), 7.52 (dd, 4-H, J = 8.04), 7.74
(m, 2H), 8.01 (d, 7-H, J = 7.98), 8.17 (dd, 3’-H, J = 1.31
and 8.06), 9.66 (s, CHO), 9.76 (s, CHO). – 13C NMR
(CDCl3): δ = 190.3, 185.7 (CHO), 146.6, 144.5, 142.9,
142.8, 136.9, 135.6 (C); 134.0, 131.9, 129.8, 128.6, 127.1,
126.5, 125.9 (CH). – C16H10O2S (266.32): calcd. C 72.16,
H 3.78; found C 71.98, H 3.85.
4d: 78%, beige solid; m. p. 141 – 144 ◦C (CH2Cl2/
C6H6). – 1H NMR (CDCl3): δ = 7.43 (m, 9-H), 7.57 (m,
3-H – 10-H), 7.72 (m, 2-H), 7.82 (d, 5-H, J = 8.55), 7.95
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3d: 80%, red solid; m. p. 97 C (CH2Cl2). – IR (KBr):
ν = 1659, 1701. – 1H NMR (CDCl3): δ = 7.40 (m, 2H), 7.50 (d, 6-H, J = 8.59), 8.01 (d, 4-H, J = 7.81), 8.04 (d, 8-H,
J = 7.72), 8.91 (d,1-H, J = 7.81), 9.05 (d, 11-H, J = 8.45). –
C16H10 Se (281.21): calcd. C 68.34, H 3.58; found C 68.12,
(m, 2H), 7.72 (d, 6’-H, J = 7.91), 7.77 (d, 4-H, J = 7.95),
8.01 (d, 7-H, J = 7.70), 8.17 (d, 3’-H, J = 7.31), 9.66
(s, CHO), 9.76 (s, CHO). – C16H10O2Se (313.98): calcd. H 3.49.
C 61.36, H 3.22; found 61.23, H 3.15.
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Synthesis of compounds 5b−d: General procedure
7a: 83%; beige solid; m. p. 187 C (CH2Cl2/MeOH). –
1H NMR (CDCl3/[D6]-DMSO): δ = 6.85 (s, OH), 6.41 (s,
1H, =CH), 7.14 (m, 2H), 7.35 (m, 2H), 8.02 (m, 4-H – 7-
H), 10.33 (s, CHO). – C16H11NO2 (249.26): calcd. C 77.10,
H 4.45, N 5.62; found C 77.20, H 4.30, N 5.50.
To a suspension of zinc powder (7.48 mmol, 485 mg) in
anhydrous THF (5 ml) was added slowly at −10 ◦C 0.35 ml
(3.17 mmol) of TiCl4. Compounds 3b – d (0.569 mmol) dis-
solved in 20 ml of THF were added at −10 ◦C. The reaction
mixture was stirred at room temperature until disappearance
of compound 3 (TLC). The reaction mixture was poured into
an aqueous solution of NaHCO3 and extracted with ether.
After drying and evaporating the solvent, the diols 5 were
precipitated in petroleum ether.
Synthesis of compounds 4a−d: General procedure
To a suspension of zinc powder (7.48 mmol, 485 mg) in
anhydrous THF (5 ml) was added slowly at −10 ◦C 0.35 ml
(3.17 mmol) of TiCl4. The solution was then refluxed and
compounds 3a – d (0.569 mmol) dissolved in THF (20 ml)
5b: yellow oil, purified by column chromatography with
were added. Reflux was maintained until disappearance of CH2Cl2 as eluent. – IR (KBr): ν = 3320. – 1H NMR
3 (TLC). After cooling, the reaction mixture was poured (CDCl3/[D6]-DMSO): δ = 2.65 (s, SCH3), 2.72 (m,OH),
into an aqueous solution of NaHCO3 (10%) and extracted 4.10 (m, 6-H), 5.70 (m, OH), 7.35 (d, 9-H, J = 1.72 and
with ether. Compounds 4a – d were purified by column chro- 8.52), 7.51 (d, 4-H), 7.54 (m, 2-H), 7.71 (m, 3-H), 8.23
matography.
(d, 11-H, J = 1.72), 8.37 (d, 1-H, J = 8.15), 8.44 (d, 8-H,
J = 8.53). – C17H14O3S (282.29): calcd. C 68.44, H 4.73;
found C 68.32, H 4.65.
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4a: 87%, orange solid; m. p. 159 C (CH2Cl2/C6H6). –
1H NMR (CDCl3): δ = 3.98 (s, OCH3), 6.98 (dd, 9-H,
J = 2.46 and 8.98), 7.11 (d, 11-H, J = 2.39), 7.51 (d,
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5c: 82%, colourless solid; m. p. 206 C (pet. ether). –
8-H, J = 8.95), 7.53 (m, 2H), 7.73 (m, 2H), 8.36 (d, 5-H, IR (KBr): ν = 3316. – 1H NMR (CDCl3/[D6]-DMSO):
J = 8.39), 8.47 (d, 6-H, J = 8.36). – 13C NMR (CDCl3): δ = 4.59 (m, 5-H, 6-H), 4.83 (m, OH), 5.26 (m ,OH); 7.14
δ = 156.24, 155.49, ’152.31, 150.61, 129.47, 125.74, 122.09 (m, 4H), 7.62 (d, 8-H, J = 7.12), 7.75 (d, 4-H – 11-H), 8.09
(C); 127.93, 123.23, 123.12, 111.89, 111.65, 105.11, 96.27 (d, 1-H, J = 8.01). – 13C NMR (CDCl3/[D6]-DMSO): δ =
(CH); 52.26 (OCH3). – C17H12O2 (248.28): calcd. C 82.24, 148.24, 141.31, 139.05, 137.50, 131.15, 129.70 (C); 126.80,
H 4.87; found C 82.32, H 4.80.
126.22, 125.83, 125.01, 124.30, 123.84, 122.62 (CH); 74.31,
Unauthenticated
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