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Current Organic Synthesis

Editor-in-Chief

ISSN (Print): 1570-1794
ISSN (Online): 1875-6271

Research Article

A Brief Synthesis of 2,2’-Arylmethylene Bis(3-hydroxy-5,5-dimethyl-2-cyclohexene-1- one) Catalyzed by TEAOH in Various Solvents

Author(s): Hui Gao , Xiaobi Yang, Xinyu Tang, Pengcheng Yin and Zewei Mao*

Volume 16 , Issue 7 , 2019

Page: [1032 - 1039] Pages: 8

DOI: 10.2174/1570179416666190723122816

Price: $65

Abstract

Aims and Objectives: 2,2’-Arylmethylene bis(3-hydroxy-5,5-dimethyl-2-cyclohexene-1-one) having four carbonyl functionalities along with their tautomeric keto-enol forms, is an important biologically active compound and important synthetic intermediate in the synthesis of xanthenes. This study was conducted in order to develop a new and concise method of synthesis of 2,2’-arylmethylene bis (3-hydroxy-5,5-dimethyl-2- cyclohexene-1-one) derivatives.

Materials and Methods: TEAOH (20 mol %) was fond to be as a simple and efficient catalyst for the preparation of 2,2’-arylmethylene bis(3-hydroxy-5,5-dimethyl-2-cyclohexene-1-one) derivatives by the Knoevenagel condensation/Michael addition tandem reactions.

Results: A concise and practical method was developed for one-pot synthesis of 2,2’-arylmethylene bis(3- hydroxy-5,5-dimethyl-2-cyclohexene-1-one) derivatives catalyzed by TEAOH at room temperature in various solvents.

Conclusion: This strategy provides several advantages over the traditional synthetic method, and is applicable to a wide variety of aromatic and heteroaromatic aldehydes at room temperature in various solvents.

Keywords: Concise synthesis, TEAOH, cyclohexanedione, aromatic aldehyde, heteroaromatic aldehyde, traditional synthetic method.

Graphical Abstract
[1]
(a) Li, Z.; Wang, W.; Jian, H.; Li, W.; Dai, B.; He, L. Synthesis of 9-phenol-substituted xanthenes by cascade O-insertion/1,6-conjugate addition of benzyne with ortho-hydroxyphenyl substituted para-quinone methides. Chin. Chem. Lett., 2019, 30, 386-388.
[http://dx.doi.org/10.1016/j.cclet.2018.04.003]
(b) Hirata, R.; Torii, A.; Kawano, K.; Futaki, S.; Imayoshi, A.; Tsubaki, K. Development of xanthene dyes containing arylacetylenes: The role of acetylene linker and substituents on the aryl group. Tetrahedron, 2018, 74, 3608-3615.
[http://dx.doi.org/10.1016/j.tet.2018.05.019]
(c) Yamagami, A.; Kawano, K.; Futaki, S.; Kuramochi, K.; Tsubaki, K. Syntheses and properties of second-generation V-shaped xanthene dyes with piperidino groups. Tetrahedron, 2017, 73, 7061-7066.
[http://dx.doi.org/10.1016/j.tet.2017.10.064]
(d) Romieu, A.; Dejouy, G.; Valverde, I.E. Quest for novel fluorogenic xanthene dyes: Synthesis, spectral properties and stability of 3-imino-3H-xanthen-6-amine(pyronin) and its silicon analog. Tetrahedron Lett., 2018, 59, 4574-4581.
[http://dx.doi.org/10.1016/j.tetlet.2018.11.031]
[2]
(a) Maharvi, G.M.; Ali, S.; Riaz, N.; Afza, N.; Malik, A.; Ashraf, M.; Iqbal, L.; Lateef, M. Mild and efficient synthesis of new tetraketones as lipoxygenase inhibitors and antioxidants. J. Enzyme Inhib. Med. Chem., 2008, 23(1), 62-69.
[http://dx.doi.org/10.1080/14756360701408754] [PMID: 18341255]
(b) Suresh, D.K.; Kumar, D.; Sandhu, J.S. An efficient green protocol for the production of 1,8-dioxo-octahydroxanthenes in triethylammonium acetate (TEAA) a recyclable inexpensive ionic liquid. Rasayan J. Chem., 2009, 2, 937-940.
(c) Khan, K.M.; Maharvi, G.M.; Nawaz, S.A.; Perveen, S.; Choudhary, M.I. An alternative method for the synthesis of tetraketones and their lipoxygenase inhibiting and antioxidant properties. Lett. Drug Des. Discov., 2007, 4, 272-278.
[http://dx.doi.org/10.2174/157018007784620004]
(d) Silva, M.L.; Teixeira, R.R.; Santos, L.A.; Martins, F.T.; Ramalho, T.C. Structural analysis of two tetraketones and theoretical investigation of the reactions involved in their preparation. J. Mol. Struct., 2018, 1156, 700-711.
[http://dx.doi.org/10.1016/j.molstruc.2017.11.105]
[3]
(a) Ilangovan, A.; Muralidharan, S.; Sakthivel, P.; Malayappasamy, S.; Karuppusamy, S.; Kaushik, M.P. Simple and cost effective acid catalysts for efficient synthesis of 9-aryl-1,8-dioxooctahydroxanthene. Tetrahedron Lett., 2013, 54, 491-494.
[http://dx.doi.org/10.1016/j.tetlet.2012.11.058]
(b) Kumar, A.; Maurya, R.A. Bakers’ yeast catalyzed synthesis of polyhydroquinoline derivatives via an unsymmetrical Hantzsch reaction. Tetrahedron Lett., 2007, 48, 3887-3890.
[http://dx.doi.org/10.1016/j.tetlet.2007.03.130]
(c) Nemati, F.; Heravi, M.M.; Saeedi Rad, R. Nano-Fe3O4-encapsulated-silica particles bearing sulfonic acid groups as a magnetically separable catalyst for highly efficient knoevenagel condensation and michael addition reactions of aromatic aldehydes with 1, 3-cyclic diketones. Chin. J. Catal., 2012, 33, 1825-1831.
[http://dx.doi.org/10.1016/S1872-2067(11)60455-5]
[4]
(a) Fan, X.S.; Li, Y.Z.; Zhan, X.Y.; Hu, X.Y.; Wang, J.J. FeCl3.6H2O Catalyzed reaction of aromatic aldehydes with 5,5-dimethyl-1,3-cyclohexandione in ionic liquids. Chin. Chem. Lett., 2005, 16, 897-899.
(b) Maghsoodlou, M.T.; Habibi-Khorassani, S.M.; Shahkarami, Z.; Maleki, N.; Rostamizadeh, M. An efficient synthesis of 2,2′-arylmethylene bis(3-hydroxy-5,5-dimethyl-2-cyclohexene-1-one) and 1, 8-dioxooctahydroxanthenes using ZnO and ZnO–acetyl chloride. Chin. Chem. Lett., 2010, 21, 686-689.
[http://dx.doi.org/10.1016/j.cclet.2010.02.005]
(c) Bayat, M.; Imanieh, H.; Hossieni, S.H. Synthesis of 2,2′-arylmethylene bis(3-hydroxy-5,5-dimethyl-2-cyclohexene-1-one) in aqueous medium at room temperature. Chin. Chem. Lett., 2009, 20, 656-659.
[http://dx.doi.org/10.1016/j.cclet.2008.12.050]
[5]
(a) Li, J.T.; Li, Y.W.; Song, Y.L.; Chen, G.F. Improved synthesis of 2,2′-arylmethylene bis(3-hydroxy-5,5-dimethyl-2-cyclohexene-1-one) derivatives catalyzed by urea under ultrasound. Ultrason. Sonochem., 2012, 19(1), 1-4.
[http://dx.doi.org/10.1016/j.ultsonch.2011.05.001] [PMID: 21622016]
(b) Yu, J.J.; Wang, L.M.; Liu, J.Q.; Guo, F.L.; Liu, Y.; Jiao, N. Synthesis of tetraketones in water and under catalyst-free conditions. Green Chem., 2010, 12, 216-219.
[http://dx.doi.org/10.1039/B913816A]
(c) Jiang, L.; Wang, B.; Li, R.R.; Shen, S.; Yu, H.W.; Ye, L.D. “Amano” lipase DF-catalyzed efficient synthesis of 2,2′-arylmethylene dicyclohexane-1,3-dione derivatives in anhydrous media. Chin. Chem. Lett., 2014, 25, 1190-1192.
[http://dx.doi.org/10.1016/j.cclet.2014.04.007]
[6]
Jung, D.H.; Lee, Y.R.; Kim, S.H.; Lyoo, W.S. New and general methods for the synthesis of arylmethylene bis(3-hydroxy-2-cyclohexene-1-ones) and xanthenediones by EDDA and In(OTf)3 catalyzed one-pot domino Knoevenagel/Michael or Koevenagel/Michael/cyclodehydration reactions. Bull. Korean Chem. Soc., 2009, 30, 1989-1995.
[http://dx.doi.org/10.5012/bkcs.2009.30.9.1989]
[7]
Kantevari, S.; Bantu, R.; Nagarapu, L. HClO4–SiO2 and PPA–SiO2 catalyzed efficient one-pot Knoevenagel condensation, Michael addition and cyclodehydration of dimedone and aldehydes in acetonitrile, aqueous and solvent free conditions: Scope and limitations. J. Mol. Catal. Chem., 2007, 269, 53-57.
[http://dx.doi.org/10.1016/j.molcata.2006.12.039]
[8]
(a) Rad, F.K.; Behbahani, F.K. Tetraketones, Synthesis and their Applications. Curr. Org. Synth., 2017, 14, 22-39.
(b) Sepideh, H.B.; Mohammad, G.D.; Amene, Y. Selective and highly efficient synthesis of xanthenedione or tetraketone derivatives catalyzed by ZnO nanorod-decorated graphene oxide. New J. Chem., 2018, 42, 14246-14262.
[http://dx.doi.org/10.1039/C8NJ01053F]
[9]
(a) Nandre, K.P.; Patil, V.S.; Bhosale, S.V. CsF mediated rapid condensation of 1,3-cyclohexadione with aromatic aldehydes: Comparative study of conventional heating vs. ambient temperature. Chin. Chem. Lett., 2011, 22, 777-780.
[http://dx.doi.org/10.1016/j.cclet.2011.01.002]
(b) Kumar, D.; Sandhu, J.S. Efficient, solvent-free, microwave-enhanced condensation of 5,5-dimethyl-1,3-cyclohexanedione with aldehydes and imines using libr as inexpensive, mild catalyst. Synth. Commun., 2010, 40, 510-517.
[http://dx.doi.org/10.1080/00397910902987792]
[10]
Cravotto, G.; Demetri, A. Nano, Gian M.; Palmisano, G.; Penoni, A.; Tagliapietra, S. The Aldol reaction under high-intensity ultrasound: A novel approach to an old reaction. Eur. J. Org. Chem., 2003, 2003, 4438-4444.
[http://dx.doi.org/10.1002/ejoc.200300369]
[11]
(a) Elanany, M.; Su, B.L.; Vercauteren, D.P. Strong templating effect of TEAOH in the hydrothermal genesis of the AlPO4-5 molecular sieve: Experimental and computational investigations. J. Mol. Catal. Chem., 2007, 270, 295-301.
[http://dx.doi.org/10.1016/j.molcata.2007.02.015]
(b) Kim, D.; Shete, M.; Tsapatsis, M. Large-grain, oriented, and thin zeolite mfi films from directly synthesized nanosheet coatings. Chem. Mater., 2018, 30, 3545-3551.
[http://dx.doi.org/10.1021/acs.chemmater.8b01346]
(c) Xu, W.; Wang, X.; Zhong, Z.; Song, A.; Hao, J. Influence of counterions on lauric acid vesicles and theoretical consideration of vesicle stability. J. Phys. Chem. B, 2013, 117(1), 242-251.
[http://dx.doi.org/10.1021/jp306630n] [PMID: 23231352]
[12]
Navarro, C.A.; Sierra, C.A.; Ochoa-Puentes, C. Evaluation of sodium acetate trihydrate–urea DES as a benign reaction media for the Biginelli reaction. Unexpected synthesis of methylene bis(3-hydroxy-5,5-dimethylcyclohex-2-enones), hexahydroxanthene-1, 8-diones and hexahydroacridine-1, 8-diones. RSC Advances, 2016, 6, 65355-65365.
[http://dx.doi.org/10.1039/C6RA13848A]

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