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Synlett 2010(13): 1909-1914  
DOI: 10.1055/s-0030-1258496
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

One-Pot Synthesis of Pyrano[3,4-b]chromones from Chromone-3-­carbaldehyde

Suman Kalyan Panja, Sourav Maiti, Subhabrata Banerjee, Chandrakanta Bandyopadhyay*
Department of Chemistry, R. K. Mission Vivekananda Centenary College, Rahara, Kolkata 700 118, West Bengal, India
e-Mail: kantachandra@rediffmail.com;
Further Information

Publication History

Received 14 January 2010
Publication Date:
16 July 2010 (online)

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Abstract

3-Formylchromone reacts with cyclohexyl isocyanide to produce pyrano[3,4-b]chromone, which rearranges to 1-benzopyrano[2,3-c]pyridine when heated with HCl in ethanol.

Key words

3-formylchromone - 1-benzopyran - isocyanide - pyrano[3,4-b]chromone - furo[3,4-b]chromone - molecular rearrangement - fluorophore - heterocycles - benzopyrano[2,3-c]pyridine

    References and Notes

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9

Analytical Data of 1 H -Furo[3,4- b ]-1-benzopyran-3,9-dione (3a) White crystalline solid, mp 240-42 ˚C (lit.¹¹ 242-43 ˚C). IR (KBr): 2978, 1775, 1642 cm-¹. ¹H NMR (300 MHz, CDCl3): δ = 5.23 (s, 2 H, CH2), 7.56 (br t, J = 7.2 Hz, 1 H, 7-H), 7.69 (br d, J = 8.4 Hz, 1 H, 5-H), 7.81-7.87 (m, 1 H, 6-H), 8.30 (br d, J = 7.2 Hz, 1 H, 8-H).

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Preparation of 2-(4-Oxo-4 H -1-benzopyran-3-yl)-4-( N -cyclohexylimino)pyrano[3,4- b ]-1-benzopyran-10-ones 4a-c Cyclohexyl isocyanide (0.065 g, 0.6 mmol) was added to a solution of 1 (1 mmol) in MeCN (15 mL). The resultant mixture was heated under reflux for 30 min when a solid began to separate. The reaction mixture was cooled, and the separated solid was filtered off. The solid was further crystallised from chloroform-light PE (4:1) to afford a yellowish green solid.
Compound 4a: yield 0.15 g (68%); mp 274-76 ˚C. IR (KBr): 3070, 2931, 1664, 1611 cm-¹. ¹H NMR (300 MHz, CDCl3): δ = 1.27-1.35 (m, 1 H, cyclohexyl H), 1.39-1.52 (m, 2 H, cyclohexyl H), 1.58-1.66 (m, 2 H, cyclohexyl H), 1.77-1.95 (m, 5 H, cyclohexyl H), 3.89-4.02 (m, 1 H, NCH), 7.18 (s, 1 H, 1-H), 7.41-7.45 (m, 1 H, ArH), 7.48-7.50 (m, 2 H, ArH), 7.65-7.76 (m, 3 H, ArH), 8.31 (br d, J = 8.0 Hz, 1 H, 5′-H), 8.34 (br d, J = 7.8 Hz, 1 H, 9-H), 8.73 (s, 1 H, 2′-H). ¹³C NMR (75 MHz, CDCl3): δ = 24.9 (3′′-C, 5′′-C), 25.7 (4′′-C), 33.6 (2′′-C, 6′′-C), 58.1 (1′′-C), 97.0 (1-C), 118.1 (8′-C), 119.0 (6-C), 119.7 (10a-C), 120.2 (3′-C), 123.8 (4′a-C), 124.9 (9a-C), 125.2 (6′-C), 126.1 (8-C), 126.5 (5′-C, 9-C), 133.6 (7′-C), 134.5 (7-C), 144.2 (2′-C), 146.9 (2-C), 153.1 (4a-C), 155.7 (4-C), 155.9 (5a-C), 156.4 (8′a-C), 172.2 (10-C), 174.8 (4′-C). MS: m/z = 440 [M+ + H], 462 [M+ + Na]. Anal. Calcd for C27H21NO5: C, 73.79; H, 4.82; N, 3.19. Found: C, 73.90; H, 4.89; N, 3.11.
Compound 4b: yield 0.16 g (70%); mp 300-302 ˚C. IR (KBr): 3059, 2925, 1669, 1616 cm-¹. ¹H NMR (300 MHz, CDCl3): δ = 1.30-1.77 (m, 6 H, cyclohexyl H), 1.88-1.97 (m, 4 H, cyclohexyl H), 2.47 (s, 3 H, ArCH3), 2.50 (s, 3 H, ArCH3), 3.88-3.95 (m, 1 H, NCH), 7.17 (s, 1 H, 1-H), 7.38 (d, J = 8.7 Hz, 1 H, 6-H), 7.47 (br d, J = 8.7 Hz, 1 H, 7-H), 7.54 (d, J = 8.4 Hz, 1 H, 8′-H), 7.60 (br d, J = 8.4 Hz, 1 H, 7′-H), 8.08 (br s, 1 H, 9-H), 8.12 (br s, 1 H, 5′-H), 8.71 (s, 1 H, 2′-H). ¹³C NMR (75 MHz, CDCl3): δ = 20.9 (2 × CH3), 24.9 (3′′-C, 5′′-C), 25.6 (4′′-C), 33.5 (2′′-C, 6′′-C), 58.1 (1′′-C), 97.1 (1-C), 117.8 (8′-C), 118.8 (6-C), 119.4 (10a-C), 120.0 (3′-C), 123.3 (4′a-C), 124.4 (9a-C), 125.8 (5′-C), 125.9 (9-C), 134.9 (7′-C), 135.3 (7-C), 135.9 (6′-C), 136.3 (8-C), 144.0 (2′-C), 147.2 (2-C), 153.1 (4a-C), 154.1 (8′a-C), 154.6 (5a-C), 155.7 (4-C), 172.4 (10-C), 175.1 (4′-C). MS: m/z = 468 [M+ + H], 490 [M+ + Na]. Anal. Calcd for C29H25NO5: C, 74.50; H, 5.39; N, 3.00. Found: C, 74.39; H, 5.42; N, 2.93.
Compound 4c: yield 0.19 g (75%); mp 296-298 ˚C. IR (KBr): 3061, 2929, 1672, 1606 cm-¹. ¹H NMR (300 MHz, CDCl3): δ = 1.26-1.77 (m, 6 H, cyclohexyl H), 1.89-1.93 (m, 4 H, cyclohexyl H), 3.88-3.95 (m, 1 H, NCH), 7.10 (s, 1 H, 1-H), 7.45 (d, J = 8.7 Hz, 1 H, 6-H), 7.61 (dd, J = 8.7, 1.8 Hz, 1 H, 7-H), 7.65-7.69 (m, 2 H, ArH), 8.24 (d, J = 1.8 Hz, 1 H, 9-H), 8.27 (br s, 1 H, 5′-H), 8.70 (s, 1 H, 2′-H). ¹³C NMR (75 MHz, CDCl3): δ = 24.8 (3′′-C, 5′′-C), 25.6 (4′′-C), 33.5 (2′′-C, 6′′-C), 58.3 (1′′-C), 96.9 (1-C), 119.6 (8′-C), 119.9 (6-C), 120.0 (10a-C), 120.7 (3′-C), 124.5 (4′a-C), 125.7 (9a-C), 125.9 (8-C, 6′-C), 131.4 (5′-C), 132.4 (9-C), 134.0 (7′-C), 134.9 (7-C), 144.1 (2′-C), 146.6 (2-C), 153.2 (4a-C), 154.1 (8′a-C), 154.6 (5a-C), 155.8 (4-C), 171.1 (10-C), 173.8 (4′-C). MS: m/z = 512 [M+ + 4], 510 [M+ + 2], 508 [M+]. Anal. Calcd for C27H19NCl2O5: C, 63.79; H, 3.77; N, 2.76. Found: C, 63.68; H, 3.72; N, 2.67.

15

2-(7-Hydroxy-4-oxo-4 H -1-benzopyran-3-yl)-7-hydroxy-4-( N -cyclohexylimino)pyrano[3,4- b ]-1-benzopyran-10-one (13) Yield 51%; mp 310-312 ˚C. IR (KBr): 3436, 1660, 1629, 1458 cm-¹. ¹H NMR (300 MHz, DMSO-d 6): δ = 1.14-1.28 (m, 1 H, cyclohexyl H), 1.30-1.52 (m, 4 H, cyclohexyl H), 1.57-1.72 (m, 1 H, cyclohexyl H), 1.80-1.97 (m, 4 H, cyclohexyl H), 3.86-4.06 (m, 1 H, NCH), 6.87 (s, 1 H, 1-H), 6.91 (br s, 1 H, 8′-H), 6.95 (br d, J = 8.7 Hz, 1 H, 6′-H), 7.02 (br d, J = 8.4 Hz, 1 H, 8-H), 7.05 (br s, 1 H, 6-H), 7.98 (d, J = 8.7 Hz, 1 H, 5′-H), 8.04 (d, J = 8.4 Hz, 1 H, 9-H), 8.70 (s, 1 H, 2′-H), 11.01 (br s, 2 H, 2 × OH). MS: m/z = 472 [M+ + H], 494 [M+ + Na]. Anal. Calcd for C27H21NO7: C, 68.78; H, 4.49; N, 2.97. Found: C, 68.97; H, 4.35; N, 2.90.

16

3-Cyclohexyl-8-methyl-2-(6-methyl-4-oxo-4 H -1-benzopyran-3-yl)-1-benzopyrano[2,3- c ]pyridine-4,10-dione (17b) Yield 35%; mp 260-262 ˚C. IR (KBr): 2924, 1715, 1664, 1611, 1482 cm-¹. ¹H NMR (300 MHz, CDCl3): δ = 1.25-1.50 (m, 3 H, cyclohexyl H), 1.73-1.76 (m, 1 H, cyclohexyl H), 1.88-2.92 (m, 4 H, cyclohexyl H), 2.34-2.48 (m, 2 H, cyclohexyl H), 2.35 (s, 3 H, ArCH3), 2.49 (s, 3 H, ArCH3), 4.12-4.29 (m, 1 H, NCH), 6.83 (s, 1 H, 1-H), 7.44 (d, J = 8.4 Hz, 1 H, 6-H), 7.50-7.59 (m, 3 H, ArH), 7.78 (s, 1 H, 2′-H), 7.96 (br s, 1 H, 9-H), 8.07 (br s, 1 H, 5′-H). ¹³C NMR (75 MHz, CDCl3): δ = 20.9 (CH3), 21.0 (CH3), 25.1 (4′′-C), 26.2 (3′′-C, 5′′-C), 29.9 (2′′-C, 6′′-C), 54.2 (1′′-C), 107.6 (1-C), 117.7 (3′-C), 118.1 (6-C), 118.4 (8′-C), 120.0 (10a-C), 123.5 (9a-C), 125.0 (4′a-C), 125.4 (9-C), 126.3 (5′-C), 132.0 (2-C), 134.8 (7-C), 135.3 (8-C), 135.5 (7′-C), 136.1 (6′-C), 153.3 (5a-C), 154.6 (8′a-C), 155.3 (4a-C), 155.4 (2′-C), 159.5 (4-C), 171.7 (10-C), 176.6 (4′-C). MS: m/z = 468 [M+ + H], 490 [M+ + Na]. Anal. Calcd for C29H25NO5: C, 74.50; H, 5.39; N, 3.00. Found: C, 74.70; H, 5.52; N, 2.88.