One-Pot Synthesis of 1,8-Dioxo-Octahydroxanthene Derivatives Using Zn(No₃)₂ Under Solvent-Free Conditions

 INTRODUCTION

Multicomponent reactions (MCRs) refers to a reaction in which two or more ingredients are combined within a single process and the products they create, which is part of all the components are present^1-3. Since the multi-component reactions for the synthesis of organic compounds and these compounds can be used as a drug and precursor multicomponent reactions, so to investigate them out is important⁴.

In our ongoing research prompted by our interest in multiple component reactions and as part of programs in the area of heterocyclic compounds containing oxygen, and due to the resultant pharmacological interest in compounds which belong to the xanthene Derivatives, although this reaction done⁵.

Xanthene derivatives are one of the important classes of organic compounds which are biologically important drug intermediates in the field of medicinal chemistry for their biologically active properties, such as antimalarial, antibacterial, antiinflammatory, and antiviral properties and have been used as dyes, fluorescent material and in laser technologies^6-9. Recently, several improved methodologies have been developed that use triethylbenzyl ammonium chloride¹⁰, p-dodecyl benzenesulfonic acid¹¹, phosphomolybdic acid supported on silica gel¹², sulfonic acid on silica gel¹³, HClO₄–SiO₂ ¹⁴ and ZnO ¹⁵ among others. Previously, we have synthesized a number of heterocyclic compounds^16-26.

In this study, we have used of Zn(NO₃)₂ as a catalysts to develop a new and easy methodology for the synthesis of xanthene derivatives. The experiments were started with the study of one pot reaction, a short time with high yields, easy separation of product, and a 3-component method, mild and efficient method for the preparation of the xanthenes by using Zn(NO₃)₂ as a catalyst (Scheme1).

 

Scheme 1 Click here to View Scheme

 

EXPERIMENTAL

All chemicals were obtained from Merck or Fluka without further purification. Silica gel SILG/UV 254 plates were used for TLC. IR spectra were measured on a Shimadzu IR-470 Spectrophotometer. ¹H NMR spectra were determined on Bruker 400 DRX AVANCE instrument at 400 MHz, respectively.

General procedure for preparation of A1

A mixture of aldehyde (1 mmol), dimedone (2 mmol), and Zn(NO₃)₂ (6 mol %) as a catalyst was stirred at 110 ^oC for 10 min. The progress of reaction was monitored by TLC. After finishing, recrystallized from ethanol 95% to give pure products (A1)

Spectral data

3,4,6,7-tetrahydro-3,3,6,6-tetramethyl-9-(3-nitrophenyl)-2H-xanthene-1,8(5H,9H)-dione (A1)

White crystals, Yield: (90%), mp 171-174^oC. IR (ν_max/cm^-1) (KBr): 3074 (arom. CH Str.); 2990 (aliph. CH Str.); 1660 (C=O Str.); 1622 (C=C Str.); 1500, 1360 (NO2,Str). ¹H NMR (400.22 MHz CDCl₃): δ=1.00 (6H, s, 2CH₃); 1.12 (6H, s, 2CH₃); 2.19 (4H, ABq, ³J=16.4Hz, 2CH₂); 2.52 (4H, s, 2CH₂); 4.84 (H, s, CH); 7.28 8.04- (4H, m, CH).

RESULTS AND DISCUSSION

 We have been able to introduce an efficient and environmentally friendly for the synthesis of xanthene derivatives via condensation of dimedone with various aromatic aldehydes and ammonium acetate. Therefore, reported Zn(NO₃)₂ as catalyst which could provide an efficient, cheap, easy separation, high yield and simple route under solvent-free condition for the synthesis of 1,8-Dioxo-octahydroxanthenes.

ACKNOWLEDGEMENTS

We gratefully acknowledge the financial support from the Research Council of Tonekabon Branch Islamic Azad University.

REFERENCES

1. Domling A., Chem. Rev., 106: 17 (2006).
2. Khan A. J and Basheer M., Orient. J.Chem., 27(4): 1759-1762 (2011).
3. Setamdideh D., Karimi Z and Rahimi F., Orient. J.Chem., 27(4): 1621-1634 (2011).
4. Kalinski C., Lemoine H., Schmidt J., Burdack C., Kolb J., Umkehrer M. and Ross G., Syn. lett., 24: 4007 (2008).
5. Peet N. P., Huber, E.W. and Huffman, J. C., J. Heterocycl. Chem., 32: 33 (1995).
6. Schumacher K., Ravikovitch P.I., Du Chesne A., Neimark A. and Unger K. K., Langmuir 16: 4648(2000)
7. Chibale K., Visser M., Schalkwyk D. V., Smith P. J., Saravanamuthu A. and Fairlamb A. H., Tetrahedron 59(13): 2289 (2003)
8. Hideo T.,  Jpn. Tokkyo Koho JP 56005480., Chem. Abst., 95: 80922b (1981).
9. Poupelin J. P., Saint-Rut G., Fussard-Blanpin O., Narcisse G., Uchida-Ernouf G. and Lakroix R., Eur. J. Med. Chem., 13: 67 (1978).
10. Wang X. S., Shi D. Q., Li Y. L., Chen H., Wei X. Y. and Zong Z. M., Synth Commun., 35, 97 (2005).
11. Jin T. S., Zhang J. S., Xiao J. C., Wang A. Q. and Li T. S., Synlett., 866 (2004) .
12. Srihari P., Mandal S. S., Reddy J. S. S., Srinivasa Rao R. and Yadav J. S., Chin Chem Lett., 19, 771 (2008).
13. Mahdavi G. H., Bigdeli M. A. and Saeidi Hayeniaz Y., Chin Chem Lett., 20, 539 (2009).
14.  Kantevari S., Bantu R. and Nagarapu L., J Mol Catal A: Chem., 269, 53 (2007).
15. Maghsoodlou M. T., Habibi-Khorassani S. M., Shahkarami Z., Maleki N. and Rostamizadeh M., Chin Chem Lett., 21, 686 (2010).
16. Azizian J., Hatamjafari F., Karimi A. R. and Shaabanzadeh M., Synthesis. 5: 765 (2006).
17. Azizian J., Shaabanzadeh M., Hatamjafari F. and Mohammadizadeh M.R., Arkivoc. (xi): 47 (2006).
18. Hatamjafari F., Synthetic Communications. 36: 3563 (2006).
19. Azizian J., Hatamjafari F. and Karimi A. R., Journal of Heterocyclic Chemistry. 43: 1349 (2006).
20. Hatamjafari F and Montazeri N., Turkish Journal of Chemistry. 33: 797 (2009).
21. Hatamjafari F., Orient. J. Chem., 28: 141(2012).
22. Hatamjafari F., Orient. J. Chem., 29: 93(2013).
23. Hatamjafari F and Alijanichakoli F., Orient. J.Chem., 29: 145(2013).
24. Hatamjafari F and Hosseinian A., Orient. J.Chem., 29: 109(2013).
25. Hatamjafari F and Khojastehkouhi H., Orient. J. Chem., 30: (2014 in press).
26. Hatamjafari F and Germani Nezhad F., Orient. J. Chem., 30: (2014 in press).

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