RSS-Feed abonnieren
DOI: 10.1055/s-2006-947339
A New LiBr-Catalyzed, Facile and Efficient Method for the Synthesis of 14-Alkyl or Aryl-14H-dibenzo[a,j]xanthenes and Tetrahydrobenzo[b]pyrans under Solvent-Free Conventional and Microwave Heating
Publikationsverlauf
Publikationsdatum:
24. Juli 2006 (online)
Abstract
An efficient method for the synthesis of 14-alkyl or aryl-14H-dibenzo[a,j]xanthenes and tetrahydrobenzo[b]pyrans under solvent-free conventional and microwave heating using lithium bromide, is described.
Key words
xanthenes - tetrahydrobenzo[b]pyrans - solvent-free - lithium bromide - microwave irradiation
- 1
Green GR.Evans JM.Vong AK. In Comprehensive Heterocyclic Chemistry II Vol. 5:Katritzky AR.Rees CW.Scriven EFV. Pergamon Press; Oxford: 1995. p.469 -
2a
Sirkeciolgu O.Talini N.Akar A. J. Chem. Res., Synop. 1995, 502 -
2b
Ahmad M.King TA.Ko D.-K.Cha BH.Lee J. J. Phys. D: Appl. Phys. 2002, 35: 1473 -
2c
Ion RM.Fara VL. Proc. Indian Acad. Sci. 1999, 107: 825 -
3a
Ion RM. Progr. Catal. 1997, 2: 55 -
3b
Ion RM.Frackowiak D.Planner A.Wiktorowicz K. Acta Biochim. Pol. 1998, 45: 833 - 4
Hideo T. inventors; Jpn. Tokkyo Koho JP56005480. ; Chem. Abstr. 1981, 95, 80922b - 5
Lambert RW,Martin JA,Merrett JH,Parkes KEB, andThomas GJ. inventors; PCT Int. Appl. WO9706178. ; Chem. Abstr. 1997, 126, 212377y - 6
Poupelin JP.Saint-Ruf G.Foussard-Blanpin O.Narcisse G.Uehida-Ernouf G.Lacroix R. Eur. J. Med. Chem. 1978, 13: 67 - 7
Callan JF.De Silva P.Magri DC. Tetrahedron 2005, 61: 8551 -
8a
Knight DW.Little PB. Synlett 1998, 1141 -
8b
Knight DW.Little PB. J. Chem. Soc., Perkin Trans. 1 2001, 14: 1771 - 9
Jha A.Beal J. Tetrahedron Lett. 2004, 45: 8999 -
10a
Sarma RJ.Baruah JB. Dyes Pigm. 2005, 64: 91 -
10b
Bekaert A.Andrieux J.Plat M. Tetrahedron Lett. 1992, 33: 2805 -
10c
Buechler CA.Cooper DE.Scrudder EO. J. Org. Chem. 1943, 8: 316 - 11
Papini P.Cimmarusti RE. Gazz. Chim. Ital. 1947, 77: 142 - 12
Ota K.Kito T. Bull. Chem. Soc. Jpn. 1976, 49: 1167 - 13
Van Allan JA.Giannini DD.Whitesides TH. J. Org. Chem. 1982, 47: 820 - 14
Sen RN.Sarkar NN. J. Am. Chem. Soc. 1925, 47: 1079 -
15a
Ono F.Negoro R.Sato T. Synlett 2001, 1581 -
15b
Pushin AN.Trachentro SE.Martynov IV. Dokl. Akad. Nauk SSSR 1988, 299: 154 -
15c
Seeback D.Thaler A.Blaser D.Ko SY. Helv. Chem. Acta 1991, 74: 1102 -
15d
Prajapati D.Lekhok KR.Sandhu JS.Ghosh AC. J. Chem. Soc., Perkin Trans. 1 1996, 959 -
15e
Baruah PP.Gadhwal S.Prajapati D.Sandhu JS. Synlett 2002, 1038 -
15f
Laskar DD.Prajapati D.Sandhu JS. Synth. Commun. 2001, 1427 -
16a
Firouzabadi H.Karimi B.Eslami S. Tetrahedron Lett. 1999, 4055 -
16b
Firouzabadi H.Iranpoor N.Karimi M. Synthesis 1999, 58 -
17a
Kappe CO. Angew. Chem. Int. Ed. 2004, 43: 6250 -
17b
Hayes BL. Aldrichimica Acta 2004, 37: 66 -
17c
Nüchter M.Ondruschka B.Bonrath W.Gum A. Green Chem. 2004, 4: 128 -
17d
Mavanadadi F.Lidstrom P. Curr. Top. Med. Chem. 2004, 4: 773 -
17e
Al-Obeidi F.Austin RE.Okonya JF.Bond DRS. Mini Rev. Med. Chem. 2003, 3: 449 -
17f
Wilson NS.Roth GP. Curr. Opin. Drug Discovery Dev. 2002, 5: 620 -
17g
Lidstrom P.Tierney J.Wathey B.Westman J. Tetrahedron 2001, 57: 9225 -
18a
Laskar DD.Gohain M.Prajapati D.Sandhu JS. New J. Chem. 2002, 193: -
18b
Sarmah U.Boruah RC.Sandhu JS. Tetrahedron Lett. 2002, 43: 143 -
18c
Laskar DD.Prajapati D.Sandhu JS. Chem. Res., Synop. 2001, 313 -
18d
Thakuria JA.Baruah M.Sandhu JS. Chem. Lett. 1999, 995 -
18e
Gadhwal S.Baruah M.Sandhu JS. Synlett 1999, 1573 -
18f
Karmakar D.Prajapati D.Sandhu JS. J. Chem. Res., Synop. 1998, 382 -
18g
Borah HN.Boruah RC.Sandhu JS. J. Chem. Res., Synop. 1998, 272 -
18h
Konwar D.Boruah RC.Sandhu JS. Tetrahedron Lett. 1997, 38: 4267 -
18i
Baruah B.Prajapati D.Baurah A.Sandhu JS. Tetrahedron Lett. 1997, 38: 449 -
21a
Wang XS.Shi DQ.Tu SJ.Yao CS. Synth. Commun. 2003, 33: 119 -
21b
Selected Characterization Data. 14-Phenyl-14 H -dibenzo[ a,j ]xanthene (3a, Table 1, Entry 1).
Mp 184-85 °C. IR (KBr): 3030, 1612, 1242 cm-1. 1H NMR (200 MHz, CDCl3): δ = 6.75 (s, 1 H), 7.10-8.10 (m, 17 H). Anal. Calcd for C27H18O: C, 90.47; H, 5.06. Found: C, 90.55; H, 5.15.
14-(4-Methoxyphenyl)14- H -dibenzo[ a,j ]xanthene (3c, Table 1, Entry 3).
Mp 203-04 °C. IR (KBr): 3035, 1621, 1581, 1252. cm-1. 1H NMR (200 MHz, CDCl3): δ = 3.50 (s, 3 H), 6.45 (s, 1 H), 6.73 (d, J = 9.3 Hz, 2 H), 7.36-7.92 (m, 12 H), 8.36 (d, J = 9.3 Hz, 2 H). Anal. Calcd for C28H20O2: C, 86.57; H, 5.19. Found: C, 86.35; H, 5.29.
14-(3-Bromophenyl)-14- H -dibenzo[ a,j ]xanthene (3d, Table 1, Entry 4).
Mp 190-92 °C. IR (KBr): 3040, 1613, 1245. cm-1. 1H NMR (200 MHz, CDCl3): δ = 6.62 (s, 1 H), 7.21-20 (m, 16 H). Anal. Calcd for C27H17BrO: C, 74.15; H, 3.92. Found: C, 74.21; H, 3.86. UV (CHCl3): λmax = 245, 266, 335 nm.
14-(4-Nitrophenyl)-14 H -dibenzo[ a,j ]xanthene (3g, Table 1, Entry 7).
Mp 309-10 °C. IR (KBr): 3070, 1615, 1540, 1355, 1245. cm-1. 1H NMR (200 MHz, CDCl3): δ = 7.20-7.90 (m, 12 H), 8.15 (d, J = 9.0 Hz, 2 H), 8.55 (d, J = 9.0 Hz, 2 H). Anal. Calcd for C27H17NO3: C, 80.38; H, 4.25; N, 3.47. Found: C, 80.29; H, 4.10; N, 3.55. UV (CHCl3): λmax 245, 259, 335 nm.
14-(4-Methylphenyl)-14 H -dibenzo[ a,j ]xanthene (3i, Table 1, Entry 9).
Mp 227-29 °C. IR (KBr): 3038, 1618, 1240 cm-1. 1H NMR (200 MHz, CDCl3): δ = 2.30 (s, 3 H), 6.55 (s, 1 H), 7.15-7.95 (m, 16 H). Anal. Calcd for C28H20O: C, 90.29; H, 5.41. Found: C, 90.41; H, 5.49.
14-Ethyl-14 H -dibenzo[ a,j ]xanthene (3j, Table 1, Entry 10).
Mp 112-13 °C. IR (KBr): 3045,2901, 1615, 1221 cm-1. 1H NMR (200 MHz, CDCl3): δ = 0.98 (t, J = 6.1 Hz, 3 H) 1.64 (d, J = 6.1 Hz, 3 H), 5.60 (q, J = 6.1 Hz, 1 H) 7.09-7.97 (m, 12 H). Anal. Calcd for C23H18O: C, 89.00; H, 5.85. Found: C, 89.12; H, 5.76.
2-Amino-3-cyano-4-phenyl-7,7-dimethyl-5-oxo-4 H -5,6,7,8-tetrahydrobenzo[ b ]pyran (6a, Table 2, Entry 1).
Mp 232-234 °C. IR (KBr): 3392, 3288, 2934, 2198, 1685, 1601 cm-1. 1H NMR (200 MHz, CDCl3): δ = 0.97 (s, 3 H), 1.04 (s, 3 H), 2.18 (d, J = 14.5 Hz, 1 H), 2.23 (d, J = 14.5 Hz, 1 H), 2.50-2.60 (br s, 2 H), 4.30 (s, 1 H), 6.10 (s, 2 H), 7.20-7.40 (m, 5 H). Anal. Calcd for C18H18N2O2: C, 73.45; H, 6.16; N, 9.52. Found: C, 73.58; H, 6.08; N, 9.40.
Ethyl-2-Amino-4-phenyl-7,7-dimethyl-5-oxo-4 H -5,6,7,8-tetrahydrobenzo[ b ]pyran Carboxlate (6d, Table 2, Entry 4).
Mp 191-193 °C. IR (KBr): 3420, 2960, 2925, 1749, 1598, 1358 cm-1. 1H NMR (200 MHz, CDCl3): δ = 1.0 (s, 3 H), 1.06 (s, 3 H), 1.21 (t, J = 7.5 Hz), 2.14 (d, J = 14.0 Hz, 1 H), 2.25 (d, J = 14.0 Hz, 1 H), 2.49 (br s, 2 H), 4.19 (q, J = 7.5 Hz), 4.27 (s, 1 H), 5.84 (s, 2 H), 7.10-7.35 (m, 5 H). Anal. Calcd for C20H23NO4: C, 70.38; H, 6.74; N, 4.11. Found: C, 70.30; H, 6.83; N, 4.07.
References and Notes
General Procedure for the Synthesis of 14-Alkyl or Aryl Dibenzo[
a,j
]xanthenes - Method A.
A mixture of aldehyde (2 mmol), β-naphthol (4 mmol) and LiBr (0.3 mmol) were mixed and stirred for 5 min at r.t. and then temperature was raised to 130 °C and maintained for the appropriate time given in Table
[1]
. After completion of reaction (TLC), the reaction mixture was cooled to r.t. and H2O (20 mL) was added and the mixture stirred for 5 min. The solid thus obtained was filtered and the crude product obtained was purified by recrystallization from EtOH.
Method B.
A mixture of aldehyde (2 mmol,), β-naphthol (4 mmol) and LiBr (0.3 mmol) were irradiated in a domestic microwave oven at 500 W for the appropriate time according to Table
[1]
. After completion of reaction (TLC), the reaction mixture was cooled to r.t. and H2O (20 mL) was added and the mixture stirred for 5 min. The solid thus obtained was filtered and the crude product obtained was purified by recrystallization from EtOH.
General Procedure for the Synthesis of Tetrahydrobenzo[
b
]pyran - Method A.
A mixture of aldehyde (2 mmol,), 5,5-dimethyl-1,3-cyclo-hexanedione (2 mmol), active methylene compound (2 mmol) and LiBr (0.6 mmol) was mixed and stirred for 5 min at r.t. and then heated at 90 °C for the appropriate time given in Table
[2]
. After completion of reaction (TLC), the reaction mixture was cooled to r.t., H2O (20 mL) was added and the mixture stirred for 5 min. The solid thus obtained was filtered and the crude product obtained was purified by recrystallization from EtOH.
Method B.
A mixture of aldehyde (2 mmol), 5,5-dimethyl-1,3-cyclo-hexanedione (2 mmol), active methylene compound (2 mmol) and LiBr (0.6 mmol) was irradiated in a domestic microwave oven at 500 W for the appropriate time according to Table
[2]
. After completion of reaction (TLC), the reaction mixture was cooled to r.t., H2O (20 mL) was added and the mixture stirred for 5 min. The solid thus obtained was filtered and the crude product obtained was purified by recrystallization from EtOH.