Diazuleno[2,1-a:1,2-c]naphthalenes
H5′,7′ and H5′′,7′′), 7.39 (s, 2H, H1′,3′), 7.54 (dd, J ) 9.6, 9.6 Hz,
2H, H6′ and H6′′), 7.77 (s, 2H, H1′,3′), 8.23 (d, J ) 9.6 Hz, 2H,
(C8′a), 139.3 (C6′), 138.2 (C8′), 138.1 (C4′), 132.7 (C2′), 128.6 (C7′),
127.5 (C5′), 123.2 (C3′), 117.1 (C1′), 97.6 (C1,2), 51.3 (q, 1′-
COOMe). Anal. Calcd for C26H18O4: C, 79.17; H, 4.60. Found:
C, 79.47; H, 4.90.
H
4′,8′), 8.36 (d, J ) 9.6 Hz, 2H, H4′′,8′′); 13C NMR (22.5 MHz,
CDCl3) δ 197.1, 149.6, 141.8, 141.6, 141.2, 140.7, 140.3, 137.5,
137.1, 124.3, 123.6, 118.8, 116.5, 74.3. Anal. Calcd for C22H16O2;
C, 84.59; H, 5.16. Found: C, 84.89; H, 5.32.
Di-2-a zu len yld ia cetylen e (14a ). A solution of 13a (51 mg,
0.34 mmol), PdCl2(PPh3)2 (8.2 mg, 0.012 mmol), CuI (2.0 mg,
0.011 mmol), and triethylamine (1.5 mL) in toluene (3 mL)
was stirred at room temperature for 1 h under an O2
atmosphere. After workup, the residue was purified by column
chromatography on silica gel with CH2Cl2 to afford 14a (35
mg, 69%) as green needles: mp 222.0-223.0 °C dec. (ethyl
acetate/hexane); MS (70 eV; m/z (relative intensity)) 302 (M+,
100); IR (KBr disk) νmax 2186 (w, CtC) cm-1; UV-vis (CH2-
Cl2; λmax (log ꢀ)) 266 (4.65), 317 (4.95), 407 (4.70), 443 (4.76),
Di-2-a zu len yleth a n ed ion e (17). A mixture of 16 (81 mg,
0.26 mmol) and activated MnO2 (113 mg, 1.30 mmol) in
benzene (80 mL) was stirred at room temperature for 18 h.
From the reaction mixture, excess MnO2 was removed by
filtration. The organic layer was concentrated and the residue
was purified by column chromatography on silica gel with
benzene to give 17 (73 mg, 91%) as green plates: mp 209-
210 °C; MS (70 eV; m/z (relative intensity)) 310 (M+, 9), 155
(M+/2, 100), 127 (C10H7+, 54); IR (KBr disk) νmax 1652 (CdO)
1
587 (3.05), 629 (3.04) nm; H NMR (400 MHz, CDCl3) δ 8.26
1
cm-1; H NMR (300 MHz, CDCl3) δ 8.45 (d, J ) 9.8 Hz, 4H,
(d, J ) 9.5 Hz, 4H, H4′,8′), 7.56 (t, J ) 9.9 Hz, 2H, H6′), 7.50 (s,
4H, H1′,3′), 7.20 (dd, J ) 9.9, 9.5 Hz, 4H, H5′,7′); 13C NMR (100
MHz, CDCl3) δ 140.2 (C3′a,8′a), 138.3 (C6′), 137.2 (C4′,8′), 128.5
(C2′), 124.3 (C5′,7′), 121.6 (C1′,3′), 82.4 (C1,4), 80.2 (C2,3). Anal.
Calcd for C24H14‚0.5toluene: C, 94.76; H, 5.21. Found: C,
94.67; H, 4.98.
H
4′,8′), 7.89 (s, 4H, H1′,3′), 7.68 (dd, J ) 9.8, 9.8 Hz, 2H, H6′),
7.19 (dd, J ) 9.8, 9.8 Hz, 4H, H5′,7′); 13C NMR (75 MHz, CDCl3)
δ 192.3 (C1,2), 142.5 (C4′,8′), 141.8 (C6′), 140.6 (C3′a,8′a), 140.2 (C2′),
124.5 (C5′,7′), 119.7 (C1′,3′). Anal. Calcd for C22H14O2: C, 85.14;
H, 4.55. Found: C, 85.32; H, 4.53.
Di-2-azu len yleth an edion e Dih ydr azon e (18). The ethane-
dione 17 (210 mg, 0.677 mmol) and 80% hydrazine mono-
hydrate (340 mg, 5.4 mmol) in ethanol (16 mL) was refluxed
for 3 days. After workup, the residue was purified by column
chromatography on silica gel with CH2Cl2 to afford 18 (211
mg, 92%) as green plates: mp 202 °C dec.; MS (70 eV; m/z
(relative intensity)) 338 (M+, 60), 278 (M+ - N4H4, 81), 127
(C10H7+, 100); IR (KBr disk) νmax 3380, 3320, 3265, 3170
(NNH2) cm-1. NMR data could not be obtained due to the low
Bis(1-m eth oxyca r bon yl-2-a zu len yl)d ia cetylen e (14b).
The same procedure used for the preparation of 14a was
adopted. The oxidation of 13b (106 mg, 0.504 mmol) in the
presence of PdCl2(PPh3)2 (11 mg, 0.016 mmol), CuI (3.1 mg,
0.016 mmol), and triethylamine (2.5 mL) in toluene (5 mL)
for 1.5 h followed by column chromatography on silica gel with
10% ethyl acetate/CH2Cl2 afforded 14b (80 mg, 76%) as dark
green prisms: mp 205.0-205.3 °C (toluene); MS (70 eV; m/z
(relative intensity)) 418 (M+, 100), 403 (M+ - CH3, 31), 178
((M+ - 2OCH3)/2, 24); IR (KBr disk) νmax 1692 (s, CdO) cm-1
;
solubility. Anal. Calcd for
Found: C, 78.25; H, 5.35.
C22H18N4: C, 78.08; H, 5.36.
UV-vis (CH2Cl2; λmax (log ꢀ)) 270 (4.19), 335 (4.56), 383 (4.06),
409 (4.30), 446 (4.38), 553 (3.39), 584 (3.41) nm; 1H NMR (500
MHz, CDCl3) δ 9.59 (d, J ) 9.9 Hz, 2H, H8′), 8.37 (d, 2H, J )
9.3 Hz, H4′), 7.77 (dd, 2H, J ) 10.0, 9.7 Hz, H6′), 7.57 (dd, J )
9.9, 9.7 Hz, 2H, H7′), 7.53 (s, 2H, H3′), 7.45 (dd, J ) 10.0, 9.3
Hz, 2H, H5′), 4.05 (s, 6H, 1′-COOMe); 13C NMR (125 MHz,
CDCl3) δ 165.1 (s, 1′-COOMe), 143.1 (C3′a), 141.4 (C8′a), 139.9
(C6′), 138.6 (C8′), 138.5 (C4′), 130.8 (C2′), 128.8 (C7′), 127.7 (C5′),
124.1 (C3′), 117.9 (C1′), 83.8 (C2,3), 83.1 (C1,4), 51.4 (q, 1′-
COOMe). Anal. Calcd for C28H18O4: C, 80.37; H, 4.34. Found:
C, 80.55; H, 4.45.
7,8,9,10-Tetr a p h en yld ia zu len o[2,1-a :1,2-c]n a p h th a len e
(3a ). A solution of 4a (418 mg, 1.50 mmol) and 5 (4.03 g,
10.5 mmol) in diphenyl ether (33 mL) was stirred at 160 °C
for 20 h under an Ar atmosphere. The reaction mixture was
purified by column chromatography on silica gel with hexane
and 50% CH2Cl2/hexane and GPC with CHCl3 to afford the
recovered 4a (69 mg, 17%) and 3a (373 mg, 47%) as ocher
needles: mp 293.9-295.0 °C dec. (toluene); MS (70 eV; m/z
(relative intensity)) 632 (M+, 100); UV-vis (CH2Cl2; λmax
(log ꢀ)) 273 (4.71), 323 (4.74), 388 (4.58), 416 (4.59), 461 (3.97),
639 (2.93), 831 (2.70), 942 (2.50) nm; 1H NMR (600 MHz,
CDCl3 + Et3N) δ 9.28 (d, J ) 9.3 Hz, 2H, H8′), 7.96 (d, J ) 9.9
Hz, 2H, H4′), 7.49 (dd, J ) 10.2, 9.3 Hz, 2H, H6′), 7.31-7.28
(m, 10H, H2′′,3′′,4′′,5′′), 7.10 (dd, J ) 10.2, 9.3 Hz, 2H, H7′), 6.98
(dd, J ) 9.9, 9.3 Hz, 2H, H5′), 6.91-6.88 (m, 6H, H3′′′,4′′′,5′′′),
6.83-6.82 (m, 4H, H2′′′,6′′′), 6.41 (s, 2H, H3′); 13C NMR (150 MHz,
CDCl3 + Et3N) δ 142.6 (C3,6 or C1′′), 140.9 (C2′), 140.8 (C1′′′),
140.4 (C4,5), 139.5 (C1′′ or C3,6), 137.7 (C4′), 137.5 (C3′a), 137.4
(C6′), 134.3 (C8′a), 134.1 (C8′), 131.8 (C2′′,6′′), 131.5 (C2′′′,6′′′), 129.1
(C1,2), 128.2 (C3′′,5′′), 126.8 (C4′′), 126.6 (C3′′′,5′′′), 125.3 (C4′′′), 123.4
(C1′), 122.3 (C5′ and C7′), 118.3 (C3′). Anal. Calcd for C50H32: C,
94.90; H, 5.10. Found: C, 94.60; H, 5.26.
Di-2-a zu len yla cetylen e (4a ), Meth od 1. To a degassed
solution of 13a (760 mg, 4.99 mmol), 7b (1.27 g, 5.00 mmol),
and CuI (96 mg, 0.50 mmol) in triethylamine (50 mL) and
toluene (100 mL) was added Pd(PPh3)4 (288 mg, 0.249 mmol).
The resulting mixture was stirred at room temperature for
1.5 h under an Ar atmosphere. After workup, the residue was
purified by recrystallization from toluene to afford 4a (1.34 g,
96%) as green needles.
Di-2-a zu len yla cetylen e (4a ), Meth od 2. The dihydrazone
18 (135 mg, 0.399 mmol) and copper(II) acetate monohydrate
(319 mg, 1.60 mmol) in methanol (84 mL) and CH2Cl2 (35 mL)
was stirred at room temperature for 20 h. After workup, the
residue was purified by column chromatography on silica gel
with toluene to afford 4a (84 mg, 76%).
Com p ou n d 4a . Mp 252.0-257.0 °C dec.; MS (70 eV; m/z
(relative intensity)) 278 (M+, 100); Raman (Ar laser, 5145 Å)
2190 (CtC) cm-1; UV-vis (CH2Cl2; λmax (log ꢀ)) 263 (4.51), 318
(4.97), 413 (4.62), 438 (4.78), 584 (3.02), 625 (2.99) nm; 1H NMR
(400 MHz, CDCl3) δ 8.28 (d, J ) 9.5 Hz, 4H, H4′,8′), 7.55 (t, J
) 9.9 Hz, 2H, H6′), 7.55 (s, 4H, H1′,3′), 7.19 (dd, J ) 9.9, 9.5 Hz,
4H, H5′,7′); 13C NMR (100 MHz, CDCl3) δ 140.4 (C3′a,8′a), 137.6
(C6′), 136.7 (C4′,8′), 130.5 (C2′), 124.0 (C5′,7′), 120.8 (C1′,3′), 94.3
(C1,2). Anal. Calcd for C22H14‚0.5toluene: C, 94.41; H, 5.59.
Found: C, 94.11; H, 5.18.
Bis(1-m eth oxyca r bon yl-2-a zu len yl)a cetylen e (4b). The
same procedure used for the preparation of 4a was adopted.
The reaction of 13b (106 mg, 0.504 mmol) with 10b (157 mg,
0.503 mmol), CuI (13 mg, 0.068 mmol), and Pd(PPh3)4 (28 mg,
0.024 mmol) in triethylamine (5 mL) and toluene (10 mL) at
50 °C for 1 h followed by recrystallization from toluene afforded
4b (165 mg, 83%) as green prisms: mp 234.0-234.3 °C; MS
(70 eV; m/z (relative intensity)) 394 (M+, 100), 363 (M+
-
OCH3, 62), 348 (M+ - OCH3 - CH3, 60); IR (KBr disk) νmax
1682 (s, CdO) cm-1; UV-vis (CH2Cl2; λmax (log ꢀ)) 257 (4.43),
279 (4.25), 329 (4.85), 415 (4.54), 439 (4.70), 584 (3.37) nm; 1H
NMR (500 MHz, CDCl3) δ 9.60 (d, J ) 10.1 Hz, 2H, H8′), 8.39
(d, J ) 9.6 Hz, 2H, H4′), 7.76 (dd, J ) 9.9, 9.8 Hz, 2H, H6′),
7.58 (s, 2H, H3′), 7.57 (dd, J ) 10.1, 9.8 Hz, 2H, H7′), 7.45 (dd,
J ) 9.9, 9.6 Hz, 2H, H5′), 4.07 (s, 6H, 1′-COOMe); 13C NMR
(125 MHz, CDCl3) δ 165.5 (s, 1′-COOMe), 143.2 (C3′a), 141.6
1,2-Bis(1-m et h oxyca r b on yl-2-a zu len yl)-3,4,5,6-t et r a -
p h en ylben zen e (6b). The same procedure used for the
preparation of 3a was adopted. The reaction of 4b (198 mg,
0.502 mmol) with 5 (1.36 g, 3.54 mmol) in diphenyl ether (11
mL) for 2 days followed by column chromatography on silica
gel with hexane and CH2Cl2 and GPC with CHCl3 afforded
6b (192 mg, 51%) as purple prisms: mp 161.0-161.7 °C (ethyl
acetate); MS (FAB; m/z (relative intensity)) 750 (M+, 100), 719
J . Org. Chem, Vol. 67, No. 21, 2002 7301