Abstract
A simple, clean and highly efficient method for the preparation of polyhydroxyl aromatic compounds is described from the reaction of 2,6-bis(methylol)phenols and different substituted phenols in the presence of silica sulfuric acid (SSA) as a heterogeneous catalyst. SSA afforded the clean synthesis of target compounds in much higher yields than traditional catalysts. The established method is also suitable for the synthesis of phloroglucinol derivatives (Phloroglucides) and other polyhydric phenols. Besides the easy work-up of the reaction mixture, the comfortable purification of the products is another advantage of this method.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Widen CJ, Fraser-Jenkins CR, Lounasmaa M, Eaw JV, Reichstein T (1971) Die phloroglucide von dryopteris caucasica (A.Br.). Helv Chim Acta 56: 831–838. doi:10.1002/hlca.19730560304
Appendino G, Ottino M, Marquez N, Bianchi F, Giana A, Ballero M, Sterner O, Fiebich BL, Munoz E (2007) Arzanol, an anti-inflammatory and anti-HIV-1 phloroglucinol α-pyrone from Helichrysum italicum ssp. microphyllum. J Nat Prod 70: 608–612. doi:10.1021/np060581r
Closse A, Sigg H-P (1973) Isolierung und strukturaufklarüng von cryptosporin. Helv Chim Acta 56: 619–625. doi:10.1002/hlca.19730560207
Albert A (1953) Avidity of terramycin and aureomycin for metallic cations. Nature 172: 201. doi:10.1038/172201a0
Fu GM, Yu BY, Zhu DN (2006) Two novel phloroglucinol derivatives from Euphorbia ebracteolata hayata. J Asian Nat Prod Res 8: 149–153. doi:10.1080/1028602042000325663
McGarry EJ, Forsyth BA (1981) 2,6-Benzyl substituted phenols. U.S. Patent 4282390
Hakimelahi GH, Moshfegh AA (1981) The synthesis of polyfunctional aromatic ring systems. Structural analogues of phloroglucides, aranciamycin, cryptosporin and terramycin. Helv Chim Acta 64: 599–609. doi:10.1002/hlca.19810640224
Moshfegh AA, Mazandarani B, Nahid A, Hakimelahi GH (1982) The synthesis of hetero-halogenated derivatives of phloroglucide analogues. Helv Chim Acta 65: 1229–1232. doi:10.1002/hlca.19820650412
Moshfegh AA, Badri R, Hojjatie M, Kaviani M, Naderi B, Nazmi AH, Ramezanian M, Roozpeikar B, Hakimelahi GH (1982) The synthesis of 4,11,18,25-tetrachloro[14] metacyclophane-7,14,21,28-tetrol. Structural analogues of phloroglucides. Helv Chim Acta 65: 1221–1228. doi:10.1002/hlca.19820650411
Hwu JR, Tsay S-C, Hakimelahi GH, Lin CC, Tseng WN, Moshfegh AA, Azaripour A, Mottaghian H (2001) Phloroglucidic acid and derivatives as antibacterial agents. U.S. Patent 6288265 B1
Hwu JR, Moshfegh AA, Tsay S-C, Lin CC, Tseng WN, Azaripour A, Mottaghian H, Hakimelahi GH (1997) Cephalosporin 3′-phloroglucide esters and (phloroglucidamido)cephalosporins as novel antibacterial agents. J Med Chem 40: 3434–3441. doi:10.1021/jm960810e
Castillo GM, Choi PY, Snow AD (2007) Polyhydroxylated aromatic compounds for the treatment of amyloidosis and alpha-synuclein fibril formation. U.S. Patent 2007/0191330 A1
Shaw J, Urgaonkar S, Ray-Chaudhuri D, La Pierre H (2007) Synthesis of inhibitors of FtsZ. W.O. Patent 2007/056188
Böhmer V, Marschollek F, Zetta L (1987) Calix[4]arenes with four differently substituted phenolic units. J Org Chem 52: 3200–3205. doi:10.1021/jo00391a005
Kraft D, Cacciapaglia R, Böhmer V, El-Fadl AA, Harkema S, Mandolini L, Reinhoudt DN, Verboom W, Vogt W (1992) New crown ether-like macrocycles containing a nitrophenol unit. Synthesis and metal ion effects on the reactivity of their acetates in transacylation reactions. J Org Chem 57: 826–834. doi:10.1021/jo00029a009
Saitoh A, Osato Y, Kazunori U (2006) Organic luminescence device. U.S. Patent 6998182 B2
Durairaj RB (2005) Resorcinol: chemistry, technology and applications, In: Resorcinol chemistry in photoresist technology. Springer-Verlag, Berlin Heidelberg, pp 717–732, ISBN-10 3-540-25142-1, doi:1007/b982897
Khalafi-Nezhad A, Soltani Rad MN, Hakimelahi GH (2003) Synthesis of polyfunctional aromatic ring systems (phloroglucide analogs) under microwave irradiation. Helv Chim Acta 86: 2396–2403. doi:10.1002/hlca.200390192
Rodia JS (1961) Self catalysis by certain phenols in the synthesis of di- and trinuclear novolacs. J Org Chem 26: 2966–2969. doi:1021/jo01066a082
Sheldon RA, Bekkum HV (2001) Fine chemicals through heterogeneous catalysis, 1st Ed, Wiley-VCH, ISBN-10: 3527299513
Salehi P, Zolfigol MA, Shirini F, Baghbanzadeh M (2006) Silica sulfuric acid and silica chloride as efficient reagents for organic reactions. Curr Org Chem 10: 1–19. doi:10.2174/138527206778742650
Zolfigol MA, Shirini F, Zamani K, Ghofrani E, Ebrahimi S (2004) Silica phosphoric acid/NaNO2 as a novel heterogeneous system for the coupling of thiols to their corresponding disulfides. Phosphorus Sulfur 179: 2177–2182. doi:10.1080/10426500490474842
Prager RH, Yurui Z (1989) Preparation of carboxylate esters of polyhydric alcohols by using a sulfonated charcoal catalyst. Aust J Chem 42: 1003–1005. doi:10.1071/CH9891003
Sharghi H, Jokar M (2009) Al2O3/MeSO3H: a novel and recyclable catalyst for one-pot synthesis of 3,4-dihydropyrimidinones or their sulfur derivatives in biginelli condensation. Synth Commun 39: 958–979. doi:10.1080/00397910802444258
Foster HM, Hein DW (1961) Phenol–formaldehyde condensations. J Org Chem 26: 2539–2541. doi:10.1021/jo01351a609
Kämmerer H, Eberle K, Böhmer V, Großmann M (1975) Darstellung und spektroskopische analyse von oligo{[4-(1,1,3,3-tetramethylbutyl) (bzw. 4-octyl)-2-hydroxy-1,3-phenylen]methylen}en und ihrer ausgangsverbindungen. Macromol Chem 176: 3295–3315. doi:10.1002/macp.1975.021761114
Author information
Authors and Affiliations
Corresponding authors
Rights and permissions
About this article
Cite this article
Khalafi-Nezhad, A., Parhami, A., Bargebid, R. et al. Silica sulfuric acid as mild and efficient catalyst for the preparation of poly-hydroxyl aromatic compounds under mild and heterogeneous conditions. Mol Divers 15, 373–381 (2011). https://doi.org/10.1007/s11030-011-9303-8
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11030-011-9303-8