β-Naphthol in Glycerol: A Versatile Pair for Efficient and Convenient Synthesis of Aminonaphthols, Naphtho-1,3-oxazines, and Benzoxanthenes

Abstract

Three-component Betti reaction was carried out in the environmentally benign, inexpensive, non-toxic solvent glycerol. Even in the absence of a catalyst, the reaction went completion with an unprecedented high rate and the expected Betti bases were obtained in up to 91% yield. The reaction works well for representative cyclic, acyclic, aliphatic, and aromatic amines and aldehydes. A benzoxanthene was also prepared in 93% yield following the same methodology with 20 mol% methanesulfonic acid catalyst.

Key words

glycerol - Betti reaction - one-pot synthesis - naphtho-1,3-oxazine - benzoxanthenes

• References

• 1 Betti M. Gazz. Chim. Ital. 1900; 30: 301
• 2 Gerlach M, Maul C. US 20040147570, 2004
• 3 Mathew BP, Kumar A, Sharma S, Shukla PK, Nath M. Eur. J. Med. Chem. 2010; 45: 1502
• 4 Gyémánt N, Engi H, Schelz Z, Szatmári I, Tóth D, Fülöp F, Molnár J, de Witte PA. M. Br. J. Cancer 2010; 103: 178
• 5 Cheng G, Wang X, Zhu R, Shao C, Xu J, Hu Y. J. Org. Chem. 2011; 76: 2694
• 6 Wang X, Dong Y, Sun J, Xu X, Li R, Hu Y. J. Org. Chem. 2005; 70: 1897
• 7 Dindulkar SD, Puranik VG, Jeong YT. Tetrahedron Lett. 2012; 53: 4376
• 8 Kumar A, Saxena A, Dewan M, De A, Mozumdar S. Tetrahedron Lett. 2011; 52: 4835
• 9 Karmakar B, Banerji J. Tetrahedron Lett. 2011; 52: 4957
• 10 Kumar A, Gupta MK, Kumar M. Tetrahedron Lett. 2010; 51: 1582
• 11 Gu Y. Green Chem. 2012; 14: 2091
• 12 Díaz-Álvarez AE, Francos J, Lastra-Barreira B, Crochet P, Cadierno V. Chem. Commun. 2011; 47: 6208
• 13a Gu Y, Jérôme F. Green Chem. 2010; 12: 1127
• 13b Wolfson A, Dlugy C, Shotland Y. Environ. Chem. Lett. 2007; 5: 67
• 13c Perin G, Mello LG, Radatz CS, Savegnago L, Alves D, Jacob RG, Lenardão EJ. Tetrahedron Lett. 2010; 51: 4354
• 13d Radatz CS, Silva RB, Perin G, Lenardão EJ, Jacob RG, Alves D. Tetrahedron Lett. 2011; 52: 4132
• 14 Crystal data: For compound 12: Molecular formula: C₁₉H₁₇NO, MW = 275.34, monoclinic, space group: P21/n, a = 9.8559(6), b = 5.2439(3), c = 27.8100(16), α = 90.00, β = 98.750(3), γ = 90.00 (CCDC Deposition Number: 903651). The crystal structure of the compound 12 has already been reported: Yang X.-H, Chen X.-L, Diao X.-J, Wu M.-H. Acta Crystallogr., Sect. E: Struct. Rep. Online 2007; 63: o3312
• 15 Giri R, Goodell JR, Xing C, Benoit A, Kaur H, Hiasa H, Ferguson DM. Bioorg. Med. Chem. 2010; 18: 1456
• 16 Chi K.-W, Ahn YS, Shim KT, Park TH, Ahn JS. Bull. Korean Chem. Soc. 1999; 20: 973
• 17a Paul NK, Dietrich L, Jha A. Synth. Commun. 2007; 37: 877
• 17b Sadaphal SA, Sonar SS, Shingate BB, Shingare MS. Green Chem. Lett. Rev. 2010; 3: 213
• 18 Kumar R, Nandi GC, Verma RK, Singh MS. Tetrahedron Lett. 2010; 51: 442