F. Catti et al. / Tetrahedron 64 (2008) 9561–9566
9565
(CH), 128.7 (C), 126.7 (C), 126.0 (CH), 114.5 (CH), 114.2 (CH), 77.6
4.2.3. 4-(40-Methylbenzylidene)-12-(400-tolyl)-1,2,3,4-
(CH), 70.2 (CH2), 68.1 (CH2), 55.7 (CH3), 55.6 (CH3), 53.8 (CH), 42.0
(CH3); IR (KBr) nmax: 2832, 1600, 1459, 1102 cmꢂ1; LRMS (ESþ)
(MeOH): m/z 387.21 [MþNa]þ (100%), 365.23 [MþH]þ (20%); HRMS
(ESþ): m/z calcd for C22H24N2O3 [MþH]þ: 365.1865, found:
365.1866.
tetrahydrobenzo[b]acridine-6,11-dione (15)
Isolated as an orange solid (45.0 mg, 0.10 mmol, 20%); mp
246.5–247.5 ꢀC; 1H NMR (500 MHz, CDCl3)
: 8.44 (s, 1H, H13), 8.35
(d, 1H, J¼7.5 Hz, H7/10), 8.09 (d, 1H, J¼7.5 Hz, H7/10), 7.79–7.70 (m,
d
0
00
2H, H8,9), 7.42 (d, 2H, J¼7.9 Hz, H2 ), 7.33 (d, 2H, J¼7.8 Hz, H2 ), 7.22
0
00
(d, 2H, J¼7.9 Hz, H3 ), 7.02 (d, 2H, J¼7.8 Hz, H3 ), 2.92 (t, 2H,
4.1.2. 7-(12-Methoxybenzylidene)-3-(40-methoxyphenyl)-2-
methyl-2,3,3a,4,6,7-hexahydro-thiopyrano[4,3-c]pyrazole (24)
Isolated as a white solid (1.43 g, 3.77 mmol, 76%); mp 152.0–
0
J¼5.5 Hz, H3), 2.53 (t, 2H, J¼6.2 Hz, H1), 2.48 (s, 3H, H5 ), 2.39 (s, 3H,
0
H5 ), 1.75 (m, 2H, H2); 13C NMR (125.5 MHz, CDCl3)
d
: 183.1 (C),
00
182.3 (C), 158.0 (C), 151.5 (C), 147.4 (C), 137.6 (C), 137.1 (C), 135.5
(C), 134.4 (C), 134.3 (CH), 134.2 (C), 133.8 (CH), 133.1 (CH), 132.9 (C),
130.1 (CH), 128.5 (CH), 128.7 (CH), 127.3 (CH), 127.1 (CH), 126.7 (CH),
125.9 (C), 28.3 (CH2), 27.6 (CH2), 22.1 (CH2), 21.5 (CH3), 21.4 (CH3);
IR (KBr) nmax: 1677,1544,1519,1298 cmꢂ1; LRMS (ESþ) (MeOH): m/z
456.22 [MþH]þ (100%), 933.45 [2MþNa]þ (70%); HRMS (ESþ): m/z
calcd for C32H26NO2 [MþH]þ: 456.1964, found: 456.1962.
153.0 ꢀC; 1H NMR (300 MHz, CDCl3)
d
: 7.34 (d, 2H, J¼8.4 Hz, H2 ),
7.23 (d, 2H, J¼8.4 Hz, H10), 7.15 (s, 1H, H8), 6.90 (dd, 4H, J¼15.5,
0
8.4 Hz, H3 ,11), 3.82–3.77 (m, 7H, OCH3 and H6b), 3.61–3.55 (m, 2H,
H6a,3), 3.21 (ddd, 1H, J¼14.5, 10.7, 6.1 Hz, H3a), 2.87–2.69 (m, 2H,
H4a,b), 2.76 (s, 3H, NCH3); 13C NMR (75.5 MHz, CDCl3)
d: 159.9 (CH),
159.4 (CH), 153.2 (C), 131.3 (CH), 130.6 (C), 129.0 (CH), 128.9 (C),
127.2 (C), 127.0 (CH), 114.6 (CH), 114.2 (CH), 79.9 (CH), 56.8 (CH),
55.7 (CH3), 55.6 (CH3), 42.1 (CH3), 31.7 (CH2), 30.0 (CH2); IR (KBr)
nmax: 2833, 2787, 1602, 1455 cmꢂ1; LRMS (ESþ) (MeOH): m/z 403.17
[MþNa]þ (100%); HRMS (ESþ): m/z calcd for C22H25N2O2S [MþH]þ:
381.1637, found: 381.1640.
4.2.4. 4-(20-Bromobenzylidene)-12-(200-bromophenyl)-1,2,3,4-
tetrahydrobenzo[b]acridine-6,11-dione (21)
Isolated as
a
green/yellow crystalline solid (137.0 mg,
0.23 mmol, 47%); mp 212.5–213.0 ꢀC; 1H NMR (300 MHz, CDCl3)
d
:
8.45 (br s,1H, H13), 8.39–8.33 (m,1H, H7/10), 8.13–8.07 (m,1H, H7/10),
7.83–7.70 (m, 3H, H8,9 and ArH), 7.65 (dd, 1H, J¼7.8, 1.0 Hz, ArH),
7.48 (dt, 1H, J¼7.5, 1.2 Hz, ArH), 7.29–7.19 (m, 3H, ArH), 7.18–7.17 (m,
1H, ArH), 7.10 (dd,1H, J¼7.5,1.6 Hz, ArH), 2.83–2.64 (m, 2H, H3), 2.51
(dd, 2H, J¼6.7, 6.7 Hz, H1), 1.86–1.75 (m, 2H, H2); 13C NMR
4.2. General procedure for aza-Diels–Alder reaction
A mixture of the substituted indazole (0.5 mmol) and 1,4-
naphthoquinone (1 mmol) was allowed to react in a sealed Schlenk
tube in the dark for 6 days at 105 ꢀC in freshly distilled and
degassed toluene (5 mL). Evaporation of the solvent, purification by
column chromatography and recrystallisation from acetonitrile
gave the desired product.
(75.5 MHz, CDCl3) d: 182.7 (C), 181.8 (C), 157.8 (C), 149.8 (C), 147.5
(C), 139.4 (C), 137.6 (C), 136.7 (C), 136.1 (C), 134.3 (CH), 134.1 (CH),
133.7 (C), 133.1 (C), 132.8 (CH), 132.7 (CH), 132.4 (CH), 130.8
(CH), 129.3 (CH), 128.9 (CH), 128.1 (CH), 127.9 (CH), 127.3 (CH), 127.3
(CH), 126.8 (CH), 126.0 (C), 125.0 (C), 121.3 (C), 27.7 (CH2), 27.2 (CH2),
22.0 (CH2); IR (KBr) nmax: 3065, 2951, 1671, 1547, 1524, 723 cmꢂ1
;
4.2.1. 4-(E)-Benzylidene-12-phenyl-1,2,3,4-tetrahydro-
benzo[b]acridine-6,11-dione (11)
LRMS (ESþ) (MeOH): m/z 605.93 ([MþNa]þ 79Br) (10%), 607.94
[MþNa]þ (100%), 609.95 ([MþNa]þ 81Br) (10%); HRMS (ESþ): m/z
calcd for C30H19NO2Na79Br81Br [MþNa]þ: 607.9660, found: 607.9663.
Isolated as yellow needles (64.0 mg, 0.15 mmol, 30%); mp
244.5–245.5 ꢀC; 1H NMR (300 MHz, CDCl3)
d: 8.47 (s, 1H, H13), 8.38–
8.33 (m, 1H, H7/10), 8.10–8.05 (m, 1H, H7/10), 7.81–7.69 (m, 2H, H8,9),
7.58–7.47 (m, 5H, ArH), 7.45–7.37 (m, 2H, ArH), 7.34–7.27 (m, 1H,
ArH), 7.17–7.11 (m, 2H, ArH), 2.96–2.88 (m, 2H, H3), 2.53 (t, 2H,
J¼6.2 Hz, H1), 1.76 (tt, 2H, J¼12.3, 6.2 Hz, H2); 13C NMR (125.5 MHz,
4.2.5. 4-(40-Methoxybenzylidene)-12-(400-methoxyphenyl)-3,4-
dihydro-1H-2-oxa-5-aza-naphthacene-6,11-dione (23)
Isolated as a green/yellow solid (59.0 mg, 0.12 mmol, 24%); mp
260.5–261.0 ꢀC; 1H NMR (300 MHz, CDCl3)
d: 8.42 (s 1H, H13), 8.39–
CDCl3) d: 183.0 (C), 182.2 (C), 157.9 (C), 151.3 (C), 147.3 (C), 138.5 (C),
8.32 (m, 1H, H7/10), 8.13–8.07 (m, 1H, H7/10), 7.83–7.70 (m, 2H, H8,9),
0
0
00
00
137.2 (C), 137.0 (C), 134.8 (C), 134.3 (CH), 134.0 (C), 133.9 (CH), 133.1
(CH), 132.9 (C), 130.0 (CH), 128.7 (CH), 128.2 (CH), 127.6 (CH), 127.5
(CH), 127.3 (CH), 127.1 (CH), 126.8 (CH), 125.9 (C), 28.3 (CH2), 27.5
(CH2), 22.1 (CH2); IR (KBr) nmax: 2933, 1672, 1545, 1520, 1301, 1252,
978 cmꢂ1; LRMS (ESþ) (MeOH): m/z 450.16 [MþNa]þ (10%), 877.29
[2MþNa]þ (100%); HRMS (ESþ): m/z calcd for C30H21NO2Na
[MþNa]þ: 450.1470, found: 450.1466. Anal. calcd for C30H21NO2:
84.29% C, 4.95% H, 3.28% N; found: 84.04% C, 4.64% H, 3.13% N.
7.34 (d, 2H, H2 ), 7.10–7.02 (m, 4H, H3 ,2 ), 6.99–6.94 (m, 2H, H3 ),
4.90 (d, 2H, J¼1.5 Hz, H3), 4.51 (s, 2H, H1), 3.90 (s, 3H, OCH3), 3.85 (s,
3H, OCH3); 13C NMR (75.5 MHz, CDCl3)
d: 182.9 (C), 182.1 (C), 159.8
(C), 159.3 (C), 154.8 (C), 148.6 (C), 134.4 (CH), 134.0 (CH), 133.9 (CH),
132.8 (C), 131.9 (CH), 131.7 (CH), 128.9 (C), 128.5 (C), 128.0 (CH),
127.2 (CH), 114.2 (CH), 114.0 (CH), 67.4 (CH2), 66.8 (CH2), 55.3 (CH3),
55.2 (CH3); IR (KBr) nmax: 2924, 1684, 1668, 1597, 1509, 1114 cmꢂ1
;
LRMS (ESþ) (MeOH): m/z 512.13 [MþNa]þ (100%); HRMS (ESþ): m/z
calcd for C31H23NO5Na [MþNa]þ: 512.1474, found: 512.1478.
4.2.2. 4-(40-Methoxybenzylidene)-12-(400-methoxyphenyl)-1,2,3,4-
tetrahydro-benzo[b]acridine-6,11-dione (13)
4.2.6. 4-(400-Methoxybenzylidene)-12-(40-methoxyphenyl)-3,4-
dihydro-2-thia-5-aza-naphthacene-6,11-dione (25)
Isolated as an orange solid (102.0 mg, 0.21 mmol, 42%); mp
249.5–250.5 ꢀC; 1H NMR (300 MHz, CDCl3)
d
: 8.41 (br s, 1H, H13),
Isolated as a green solid (30.0 mg, 0.06 mmol, 12%); mp 263.0–
8.37–8.32 (m, 1H, H7/10), 8.12–8.05 (m, 1H, H7/10), 7.80–7.69 (m, 2H,
264.0 ꢀC; 1H NMR (300 MHz, CDCl3)
d
: 8.40 (br s,1H, H13), 8.37–8.33
0
00 00
H8,9), 7.53–7.46 (m, 2H, H2 ), 7.04 (s, 4H, H2 ,3 ), 6.98–6.92 (m, 2H,
(m,1H, H7/10), 8.12–8.08 (m,1H, H7/10), 7.82–7.71 (m, 2H, H8,9), 7.46–
0
0
00 00
0
H3 ), 3.90 (s, 3H, OCH3), 3.85 (s, 3H, OCH3), 2.96–2.89 (m, 2H, H3),
7.40 (m, 2H, H2 ), 7.07 (br s, 4H, H2 ,3 ), 6.99–6.94 (m, 2H, H3 ), 3.95
(br s, 2H, H3), 3.91 (s, 3H, OCH3), 3.86 (s, 3H, OCH3), 3.58 (br s, 2H,
2.45 (t, 2H, J¼6.2 Hz, H1), 1.69 (tt, 2H, J¼6.2, 6.0 Hz, H2); 13C NMR
(75.5 MHz, CDCl3)
d: 183.2 (C), 182.4 (C), 159.1 (C), 158.9 (C), 158.1
H1); 13C NMR (100 MHz, CDCl3)
d: 183.0 (C), 181.9 (C), 159.6 (C),
(C), 151.0 (C), 147.4 (C), 137.2 (C), 134.3 (C), 134.2 (C), 133.8 (CH),
133.1 (C), 132.9 (C), 132.8 (CH), 131.6 (CH), 130.5 (C), 129.9 (C), 128.1
(CH), 127.2 (CH), 127.1 (CH), 114.1 (CH), 113.7 (CH), 55.3 (CH3), 55.2
(CH3), 28.3 (CH2), 27.7 (CH2), 22.2 (CH2); IR (KBr) nmax: 2953, 2238,
1677, 1603, 1509 cmꢂ1; LRMS (ESþ) (MeOH): m/z 488.20 [MþH]þ
(100%); HRMS (ESþ): m/z calcd for C32H26NO4 [MþH]þ: 488.1862,
found: 488.1856.
159.3 (C), 157.7 (C), 150.1 (C), 147.5 (C), 134.7 (C), 134.4 (CH), 134.2
(CH), 133.9 (CH), 132.9 (CH), 131.6 (CH), 130.4 (C), 129.5 (C), 129.0
(C), 128.2 (CH), 127.3 (CH), 127.2 (CH), 125.8 (C), 114.4 (CH), 113.9
(CH), 55.5 (CH3), 55.2 (CH3), 29.4 (CH2), 29.1 (CH2); IR (KBr) nmax
:
2934, 1666, 1597, 1509 cmꢂ1; LRMS (ESþ) (MeOH): m/z 506.15
[MþH]þ (100%); HRMS (ESþ): m/z calcd for C31H24NO4S [MþH]þ:
506.1426, found: 506.1420.