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General Procedure.
In freshly distilled and degassed toluene (20 mL) was placed Pd(OAc)2 (5% molar) under an inert atmosphere. Then tri-tert-butylphosphine was added (15%) and the solution was allowed to stir 10 min. Dibromobenzene derivative (5 mmol), methyl anthranilate derivative (12 mmol) and Cs2CO3 (15 mmol) were successively added. After overnight reflux, crude mixture was allowed to cool and was then quenched by 50 mL NH4Cl (1 M) solution. About 100 mL CH2Cl2 were added and the biphasic mixture separated. The aqueous phase was extracted twice by CH2Cl2. Organic phases were dried on Na2SO4 and evaporated to dryness. The resulting brown oil was purified by column chromatography, using an CH2Cl2-n-hexane (1:1) mixture as eluant, affording a yellow powder.
Spectroscopic data for selected compounds.
Compound 5: yellow solid; mp 85-88 °C; R
f
= 0.35 (CH2Cl2-n-hexane, 1:1). 1H NMR (DMSO-d
6): δ = 9.47 (s, 1 H), 9.33 (s, 1 H), 7.89 (dd, J = 1.8, 8.1 Hz, 1 H), 7.71 (s, 1 H), 7.41 (s, 1 H), 7.26 (s, 4 H), 7.13-7.23 (m, 3 H), 6.75-6.80 (m, 1 H), 3.86 (s, 3 H), 3.85 (s, 3 H), 2.23 (s, 3 H). 13C NMR (DMSO-d
6): δ = 168.6, 148.0, 145.2, 137.2, 135.8, 134.8, 131.8, 131.3, 126.7, 124.2, 123.1, 117.6, 115.0, 114.0, 112.3, 111.8, 52.4, 20.1. DCI-MS: m/z (%) = 391 (100), 392 (26), 393 (5).
Coumpound 6b: yellow solid; mp 97-98 °C; R
f
= 0.37 (CH2Cl2-n-hexane, 1:1). 1H NMR (DMSO-d
6
): δ = 9.26 (s, 1 H), 9.18 (s, 1 H), 7.95 (d, J = 1.5 Hz, 1 H), 7.92 (d, J = 1.5 Hz, 1 H), 7.25-7.36 (m, 4 H), 7.13 (dd, J = 8.4, 1.5 Hz, 1 H), 6.99 (m, 2 H), 6.74 (m, 2 H), 3.86 (s, 3 H), 3.84 (s, 3 H), 2.39 (s, 3 H). 13C NMR (CDCl3): δ = 168.7, 168.5, 150.8, 148.5, 135.3, 134.9, 134.1, 134.0, 133.9, 131.7, 131.5, 131.4, 125.1, 124.3, 117.2, 116.8, 114.6, 114.2, 112.7, 112.1, 51.7, 51.6, 21.1. DCI-MS: m/z (%) = 391 (100) [M+], 392 (26), 393 (4).
18 In the ortho series, reaction with POCl3 leads to intractable mixture. Nevertheless, dichloroquinacridines are preferred over quinacridones since they are more soluble and less hygroscopic.
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21 In our hands, a 29:71 molar ratio of quinacridine 2b (R2 = CH3, R1 = R3 = H) and dihydroquinacridine(9b) mixture was brought up only to 73:27 (2b:9b). Increasing the catalytic load to 7% and the reaction time from 45 min to 16 h led to a similar result.
22a
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22c In all cases, quantitative aromatization was observed on the crude mixture NMR analysis.
23
General Procedure.
The amount of hydrogenated quinacridines in the mixture was estimated my NMR, based on the relative peak inten-sities. Characteristic peaks of hydrogenated quinacridines were located at δ = 4.5 ppm (methylene group), whereas those of quinacridine are the more downfield-shifted at δ = 9.4 ppm (para) or δ = 8.6 ppm (ortho). Lateral methyl groups are also of relevant importance and are situated in the 2.3-3.1 ppm zone, those borne by hydrogenated products being shifted more upfield. Such a mixture (300 µmol in hydro-genated compounds) was dissolved in AcOH (10 mL), TrBF4 (330 µmol) was added and the mixture was heated to reflux. Crude mixture was poured in cold H2O ca. 10 min later. The pH value was adjusted to neutrality and the brown suspension was filtered and dried. The mixture was purified by column chromatography using a gradient of MeOH in CH2Cl2 (1-3% v/v).
24
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26 Adding SeO2 twice in the same flask seems to be preferable than an unique initial load. Selenium dioxide was firstly reacted in a flask containing both substrate 9d and AcOH. Then, 80 min later, AcOH was evaporated, naphthalene added, SeO2 newly added and mixture heated to 230 °C. When both loads of SeO2 were initially mixed with substrate and acid, a 72:28 ratio was obtained.
27
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30 Compound 11: white solid; mp 236-238 °C; R
f
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31a X-ray structure of intermediate 7c (R = CH3) showed that the molecule exhibits a dihedral angle of 35.9° (Cesario, M.; Baudoin, O.; Teulade-Fichou, M.-P. unpublished results).
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