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Synlett 2011(10): 1403-1406  
DOI: 10.1055/s-0030-1260567
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Synthesis of Novel 1-Aryl-9H-xanthen-9-ones

Cátia I. C. Estevesa, Clementina M. M. Santosb, Cristela M. Britoa, Artur M. S. Silva*a, José A. S. Cavaleiroa
a Department of Chemistry & QOPNA, University of Aveiro, Campus Universitário de Santiago, 3810-193 Aveiro, Portugal
Fax: +351(234)370084; e-Mail: artur.silva@ua.pt;
b Department of Vegetal Production and Technology, School of Agriculture, Campus de Santa Apolónia, 5301-855 Bragança, Portugal
Further Information

Publication History

Received 28 February 2011
Publication Date:
16 May 2011 (online)

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Abstract

A novel route for the synthesis of 1-aryl-9H-xanthen-9-ones is reported. This methodology involves the condensation of 2-methylchromone with cinnamaldehydes leading to (E,E)-2-(4-arylbuta-1,3-dien-1-yl)-4H-chromen-4-ones. The final steps involved electrocyclization and oxidation of the latter compounds, in an one-pot synthesis, giving the desired 1-aryl-9H-xanthen-9-ones.

Key words

1-arylxanthones - 2-methylchromone - aldol condensation - electrocyclization - oxidation

    References and Notes

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18

Typical Experimental Procedure
Sodium (0.11 g, 4.8 mmol) was gradually added to dry EtOH (5 mL), and the mixture was stirred until it reached r.t. 2-Methylchromone (2, 0.2 g, 1.2 mmol) and the appropriate cinammaldehyde 4a-e (1.5 mmol) were added and the reaction mixture allowed to stand at r.t. until complete disappearance of chromone 2 (TLC). The solution was then poured into ice (20 g) and H2O (30 mL) and adjusted to pH 4 with dilute HCl. The solid was removed by filtration, dissolved in CH2Cl2, and purified by silica gel column chromatography using CH2Cl2 as eluent. The solvent was evaporated the residue were recrystallized from EtOH to give the (E,E)-2-(4-arylbuta-1,3-dien-1-yl)-4H-chromen-4-ones 5a-e in good yields (Table  [¹] ).

19

Physical Data of ( E , E )-2-[ - 4-(4-methoxyphenyl)buta-1,3-dien-1-yl]-4 H -chromen-4-one (5c)
Mp 137-139 ˚C. ¹H NMR (300,13 MHz, CDCl3): δ = 3.84 (s, 3 H, OCH3), 6.24 (s, 1 H, H-3), 6.32 (d, 1 H, J = 15.3 Hz, H-α), 6.84-6.87 (m, 1 H, H-δ), 6.90 (d, 2 H, J = 8.8 Hz, H-3′,5′), 6.90-6.96 (m, 1 H, H-γ), 7.38 (ddd, 1 H, J = 8.2, 7.1, 0.9 Hz, H-6), 7.41-7.44 (m, 1 H, H-β), 7.43 (d, 2 H, J = 8.8 Hz, H-2′,6′), 7.49 (d, 1 H, J = 8.1 Hz, H-8), 7.67 (ddd, 1 H, J = 8.1, 7.1, 1.7 Hz, H-7), 8.18 (dd, 1 H, J = 8.2, 1.7 Hz, H-5). ¹³C NMR (75.47 MHz, CDCl3): δ = 55.3 (OCH3), 109.9 (C-3), 114.3 (C-3′-5′), 117.7 (C-8), 122.3 (C-α), 124.1 (C-10), 124.8 (C-6), 125.0 (C-γ), 125.5 (C-5), 128.5 (C-2′,6′), 128.6 (C-1′), 133.6 (C-7), 137.8 (C-β), 138.9 (C-δ), 140.4 (C-9), 160.3 (C-4′), 162.0 (C-2), 178.4 (C-4). ESI-MS: m/z (rel. int.) = 305 (100) [M + H]+, 327 (110) [M + Na]+, 343 (20) [M + K]+, 631 (11) [2 M + Na]+. Anal. Calcd for C20H16O3: C, 78.93; H, 5.30. Found: C, 78.86; H, 5.30.

20

Physical Data of 1,4-Dihydro-1-phenyl-9 H -xanthen-9-one (7a)
Yellow oil. ¹H NMR (300.13 MHz, CDCl3): δ = 2.76 (ddd, 1 H, J = 18.6, 5.8, 1.3 Hz, H-4 trans ), 3.01 (ddd, 1 H, J = 18.6, 9.7, 2.8 Hz, H-4 cis ), 4.56 (d, 1 H, J = 9.7 Hz, H-1), 6.39 (dd, 1 H, J = 9.7, 2.8 Hz, H-2), 6.44-6.51 (m, 1 H, H-3), 7.14-7.26 (m, 3 H, H-3′,4′,5′), 7.33-7.35 (m, 2 H, H-2′,6′), 7.33-7.37 (m, 1 H, H-7), 7.45 (d, 1 H, J = 7.9 Hz, H-5), 7.62 (ddd, 1 H, J = 7.9, 7.7, 1.6 Hz, H-6), 8.17 (dd, 1 H, J = 7.9, 1.6 Hz, H-8). ¹³C NMR (75.47 MHz, CDCl3): δ = 31.5 (C-4), 33.4 (C-1), 116.6 (C-9b), 117.9 (C-5), 121.9 (C-2), 124.3 (C-8a), 124.8 (C-7), 125.9 (C-8), 125.9 (C-4′), 127.1 (C-2′,6′), 128.4 (C-3′,5′), 133.1 (C-6), 138.4 (C-3), 143.3 (C-1′), 155.4 (C-4b), 159.3 (C-4a), 176.4 (C-9).

21

Typical Experimental Procedure
Iodine (18 mg, 0.07 mmol) was added to a solution of the appropriated chomone 5a-e (0.35 mmol) in 1,2-4-trichlorobenzene (5 mL), and the mixture was refluxed for 48 h. After this period the solution was directly purified by silica gel column chromatography using light PE as eluent to remove 1,2,4-trichlorobenzene and then CH2Cl2 to recover the product. The solvent was evaporated to dryness and the residue were recrystallized from EtOH to give the 1-aryl-9H-xanthen-9-ones 6a-e in moderated yields (Table  [¹] ).

22

Physical Data of 1-Phenyl-9 H -xanthen-9-one (6a)
Mp 177-179 ˚C. ¹H NMR (300.13 MHz, CDCl3): δ = 7.18 (dd, 1 H, J = 7.2, 1.2 Hz, H-2), 7.31 (ddd, 1 H, J = 7.8, 7.5, 1.1 Hz, H-7), 7.33-7.36 (m, 2 H, H-2′,6′), 7.41-7.45 (m, 3 H, H-3′,4′,5′), 7.48 (d, 1 H, J = 8.6 Hz, H-5), 7.53 (dd, 1 H, J = 8.4, 1.2 Hz, H-4), 7.67-7.80 (m, 2 H, H-3 and H-6), 8.18 (dd, 1 H, J = 7.8, 1.7 Hz, H-8). ¹³C NMR (75.47 MHz, CDCl3): δ = 117.4 (C-5), 117.7 (C-4), 119.3 (C-9b), 122.7 (C-8a), 123.8 (C-7), 127.0 (C-8), 127.1 (C-4′), 127.2 (C-2), 127.5 (C-3′,5′), 128.4 (C-2′,6′), 133.4 (C-3), 134.5 (C-6), 141.8 (C-1′), 144.2 (C-1), 155.4 (C-4b), 157.3 (C-4a), 176.9 (C-9). ESI-MS: m/z (rel. int.) = 273 (100) [M + H]+, 295 (76) [M + Na]+, 311 (12) [[M + K]+, 567 (4) [2 M + Na]+. Anal. Calcd for C19H12O2: C, 83.81; H, 4.44. Found: C, 83.57; H, 4.13.