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Short Note

Trimethyl 4,6-Dicyano-5-hydroxybenzene-1,2,3-tricarboxylate

by
Afsaneh Zonouzi
1,*,
Roghieh Mirzazadeh
1 and
Seik Weng Ng
2
1
School of Chemistry, University College of Science, University of Tehran, Tehran, 14174, Iran
2
Department of Chemistry, University of Malaya, Kuala Lumpur, 50603, Malaysia
*
Author to whom correspondence should be addressed.
Molbank 2012, 2012(3), M775; https://doi.org/10.3390/M775
Submission received: 28 April 2012 / Accepted: 1 August 2012 / Published: 28 August 2012

Abstract

:
A novel synthesis of a fully substituted fluorescent phenol by a one-pot reaction of dimethyl acetylendicarboxylate and malononitrile in the presence of catalysts has been developed. The structure of the synthesized compound was assigned on the basis of its elemental analysis, 1H-NMR, 13C-NMR, IR, mass spectral and X-ray data. The photophysical data of the new compound are reported.

Graphical Abstract

Optoelectronic devices such as optical fibers, switches, tunable lasers and amplifiers, modulators with various applications need compounds emitting in the blue spectral region [1]. Multi-component reactions (MCRs) are of increasing significance in organic and medicinal chemistry. MCRs allow organic compounds to be synthesized in a few steps or in a one-pot operation [2].
Substituted phenols are of great importance in biosynthesis and also as building blocks in organic synthesis [3,4]. There are a few reports on the synthesis of highly substituted phenols [5]. So the development of a multi-component one-pot procedure for the synthesis of fluorescent poly-functionalized phenol can be seen as urgently interesting for technology upgrading. In continuation of our quest for developing one-pot procedures, here we wish to report a novel one-pot condensation reaction of dimethyl acetylenedicarboxylate 1 and malononitrile in the presence of Ph3P (triphenylphosphine) and p-toluenesulfonic acid (p-TSA) for the synthesis of fully substituted phenol 2 with bright fluorescence property (Scheme 1).
Easy, rapid and mild reaction conditions and also high atom economy of this one-pot procedure make the present method useful for the synthesis of highly functionalized phenols.
Structure 2 was assigned on the basis of its elemental analysis, 1H-NMR, 13C-NMR, IR and mass spectral data. The light green crystals of 2 were obtained by slow crystallization from ethyl acetate and its X-ray structure was determined to confirm unambiguously its structure [6] (Figure 1).
A possible mechanism for the synthesis of 2 is shown in Scheme 2. It is suggested that the zwitterion 3 is produced at first by addition of Ph3P to the acetylenic ester. Then the zwitterion 3 condenses with another ester molecule to produce zwitterion 4. Attack of the malononitrile anion at 4, fallowed by loss of Ph3P and intramolecular cyclization affords 5. Elimination of CN from C2 and addition of CN to C6 in the presence of OTS can produce the intermediate 6. Finally, 6 can be aromatized to 2 by keto-enol tautomerization. Intermediate 6 was detected in the early stage of the reaction by 1H-NMR and IR spectra. The proton adjacent to the CN group appears at δ = 4.53 for 6 in the 1H-NMR spectrum and the carbonyl group of 6 has been detected at νmax = 1,801 cm−1 in the IR spectrum of the reaction mixture. At the end of this transformation (after 24 h), there was no carbonyl absorption detectable in the IR spectrum. Probably, the stability gained from aromatic ring generation drives this keto-enol tautomerization.
Compound 2 is fluorescent and its photophysical data including λAbs. (nm), λFlu. (nm) have been measured for 0.002 M solutions in CH3OH, CH3CN and CHCl3 (Table 1).
Figure 2 shows photographs of compound 2 solutions in CH3OH, CH3CN and CH3Cl (a): under visible light and (b): under a UV lamp with λ = 366 nm (Philips TL8W/08F8T5/BLC).

Experimental

Elemental analysis for C, H and N was performed using a Thermo Finnigan Flash EA1112 instrument. 1H-NMR and 13C-NMR spectra were determined on a Bruker 500 spectrometer. IR spectra were measured on a Bruker EQUINOX 55 spectrophotometer with the ATR method. Mass spectra were recorded on a Finnigan-MAT 8430 spectrometer. Photophysical data measurements were made with a Cary Eclipse Fluorescence spectrophotometer.
Trimethyl 4,6-dicyano-5-hydroxybenzene-1,2,3-tricarboxylate (2). To a magnetically stirred solution of dimethyl acetylenedicarboxylatae (0.28 g, 2 mmol) in 3 mL of CH2Cl2, Ph3P (0.26 g, 1 mmol) and malononitrile (0.1 g, 1.5 mmol) in 3 mL of CH2Cl2 were added dropwise by two dropping funnels at −10 °C over 40 min and stirring was continued at this temperature for 2 h. Then, 0.069 g (40 mol%) p-TSA were added. The reaction mixture was warmed up to room temperature and stirred for 24 h. The solvent was removed under reduced pressure and the residue was purified by column chromatography on silica gel, using n-hexane/ethyl acetate (3/1) as the mobile phase. The product was obtained as light green crystals, 0.26 g, 83%. Melting point: 129–130 °C.

Structural Characterization

IR, νmax: 3419, 3348, 3252, 2961, 2232, 1728, 1651, 1573, 1430, 1370, 1303, 1240, 1173, 1015 cm−1; δH (500 MHz, CDCl3): 3.78 (3H, s, CH3), 3.91 (6H, s, 2CH3), 8.03 (1H, br s, OH) ppm; δC (125 MHz, CDCl3): 54.2, 54.6 (CH3), 96.5 (CN), 113.9, 114.2, 114.4, 155.0 (Ar), 163.7, 165.8 (CO) ppm; MS: m/z = 318 (M+), 317, 214, 156, 141, 59, 45; Anal. Calcd for C14H10N2O7: C, 52.84; H, 3.17; N, 8.80; Found: C, 52.79; H, 3.15; N, 8.62.

Supplementary materials

Supplementary File 1Supplementary File 2Supplementary File 3

Acknowledgements

Support of this study by the Research Council at the University of Tehran is gratefully acknowledged.

References and Notes

  1. Lakowicz, J.R. Principle of Fluorescence Spectroscopy, 3rd ed.; Springer: New York, NY, USA, 2006. [Google Scholar]
  2. Hussain, H.H.; Babic, G.; Durst, T.; Wright, J.S.; Flueraru, M.; Chichirau, A.; Chepelev, L.L. Development of novel antioxidants: Design, synthesis, and reactivity. J. Org. Chem. 2003, 68, 7023–7032. [Google Scholar] [CrossRef] [PubMed]
  3. Vosooghi, M.; Rajabalian, S.; Sorkhi, M.; Badinloo, M.; Nakhjiri, M.; Negahbani, A.S.; Asadipour, A.; Mahdavi, M.; Shafiee, A.; Foroumadi, A. Synthesis and cytotoxic activity of some 2-amino-4-aryl-3-cyano-7-(dimethylamino)-4H-chromenes. Res. Pharm. Sci. 2010, 5, 9–14. [Google Scholar] [PubMed]
  4. Wright, J.S.; Johnson, E.R.; DiLiabio, G.A. Predicting the activity of phenolic antioxidants: Theoretical method, analysis of substituent effects, and application to major families of antioxidants. J. Am. Chem. Soc. 2001, 123, 1173–1183. [Google Scholar] [CrossRef] [PubMed]
  5. Samshuddin, S.; Narayana, B.; Sarojini, B.K. Ethyl 4,4''-difluoro-5'-hydroxy-1,1':3',1''-terphenyl-4'-carboxylate. Molbank 2011, 2011, M745. [Google Scholar] [CrossRef]
  6. Crystallographic data for compound 2 reported in this paper have been deposited with the Cambridge Crystallographie Data Center as supplementary publication CCDC No. 842814. These data can be obtained free of charge via www.ccdc.com.ac.uk/data_request/cif.
Scheme 1. Synthesis of trimethyl 4,6-dicyano-5-hydroxybenzene-1,2,3-tricarboxylate.
Scheme 1. Synthesis of trimethyl 4,6-dicyano-5-hydroxybenzene-1,2,3-tricarboxylate.
Molbank 2012 m775 sch001
Figure 1. X-Ray crystal structure of 2.
Figure 1. X-Ray crystal structure of 2.
Molbank 2012 m775 g001
Scheme 2. A possible mechanism for the formation of 2.
Scheme 2. A possible mechanism for the formation of 2.
Molbank 2012 m775 sch002
Figure 2. Photographs of solutions of 2, from left to right in CH3OH, CH3CN and CH3Cl, respectively.
Figure 2. Photographs of solutions of 2, from left to right in CH3OH, CH3CN and CH3Cl, respectively.
Molbank 2012 m775 g002
Table 1. Photophysical data: electronic absorption (Abs.) and fluorescence (Flu.) of 2.
Table 1. Photophysical data: electronic absorption (Abs.) and fluorescence (Flu.) of 2.
CH3OHCH3CNCHCl3
Comp.λAbs.λFlu.λAbs.λFlu.λAbs.λFlu.
2237469226459335455

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MDPI and ACS Style

Zonouzi, A.; Mirzazadeh, R.; Ng, S.W. Trimethyl 4,6-Dicyano-5-hydroxybenzene-1,2,3-tricarboxylate. Molbank 2012, 2012, M775. https://doi.org/10.3390/M775

AMA Style

Zonouzi A, Mirzazadeh R, Ng SW. Trimethyl 4,6-Dicyano-5-hydroxybenzene-1,2,3-tricarboxylate. Molbank. 2012; 2012(3):M775. https://doi.org/10.3390/M775

Chicago/Turabian Style

Zonouzi, Afsaneh, Roghieh Mirzazadeh, and Seik Weng Ng. 2012. "Trimethyl 4,6-Dicyano-5-hydroxybenzene-1,2,3-tricarboxylate" Molbank 2012, no. 3: M775. https://doi.org/10.3390/M775

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