Hostname: page-component-7b9c58cd5d-hxdxx Total loading time: 0 Render date: 2025-03-15T09:34:08.710Z Has data issue: false hasContentIssue false
  • English
  • Français

Synthesis and X-ray diffraction data of 5-acryloyloxy-trans-2-(4-methoxyphenyl)-3-methyl-2,3-dihydrobenzo[b]furan

Published online by Cambridge University Press:  17 August 2012

Mónica V. Sandoval ,
J. A. Henao ,
Arnold R. Romero Bohórquez  and
Vladimir V. Kouznetsov
Mónica V. Sandoval
Affiliation:
Grupo de Investigación en Química Estructural (GIQUE), Escuela de Química, Facultad de Ciencias, Universidad Industrial de Santander, A.A. 678, Carrera 27, Calle 9 Ciudadela Universitaria, Bucaramanga, Colombia
J. A. Henao*
Affiliation:
Grupo de Investigación en Química Estructural (GIQUE), Escuela de Química, Facultad de Ciencias, Universidad Industrial de Santander, A.A. 678, Carrera 27, Calle 9 Ciudadela Universitaria, Bucaramanga, Colombia
Arnold R. Romero Bohórquez
Affiliation:
Laboratorio de Química Orgánica y Biomolecular (LQOBio), Centro de Investigación en Biomoléculas, (CIBIMOL), Escuela de Química, Facultad de Ciencias, Universidad Industrial de Santander, A.A. 678, Carrera 27, Calle 9 Ciudadela Universitaria, Bucaramanga, Colombia
Vladimir V. Kouznetsov
Affiliation:
Laboratorio de Química Orgánica y Biomolecular (LQOBio), Centro de Investigación en Biomoléculas, (CIBIMOL), Escuela de Química, Facultad de Ciencias, Universidad Industrial de Santander, A.A. 678, Carrera 27, Calle 9 Ciudadela Universitaria, Bucaramanga, Colombia
*
a)Author to whom correspondence should be addressed. Electronic mail: jahenao@uis.edu.co
Rights & Permissions [Opens in a new window]

Abstract

The compound O-acryloylated 2,3-dihydrobenzo[b]furan-5-ol (2) described in the title (chemical formula C19H18O4) was synthesized through the acryloylation reaction in anhydrous dichloromethane from the corresponding trans-2-(4-methoxyphenyl)-3-methyl-2,3-dihydrobenzo[b]furan-5-ol derivative (1), an adduct easily obtained using the Lewis acid-promoted formal [3 + 2] cycloaddition reaction. Molecular characterization was performed by Fourier Transform-Infrared (FT-IR), Gas Chromatography-Mass Spectrometry (GC-MS), 1H and 13C NMR and crystallographic characterization was carried out by X-ray diffraction (XRD) of polycrystalline samples. The title compound crystallized in a monoclinic system and unit-cell parameters are reported [a = 8.067(2) Å, b = 8.803(2) Å, c = 22.405(5) Å, β = 91.62(3)°, unit-cell volume V = 1590.7(6) Å3 and Z = 4]. All measured lines were indexed with the P21/c (No. 14) space group.

Keywords

dihydrobenzofuranX-ray powder diffraction dataO-acryloylation reaction
Type
New Diffraction Data
Information
Powder Diffraction , Volume 27 , Issue 3 , September 2012 , pp. 211 - 214
Copyright
Copyright © International Centre for Diffraction Data 2012

I. INTRODUCTION

Benzofuran and dihydrobenzofuran derivatives are natural and synthetic medicinally important heterocyclic molecules (Benavides et al., Reference Benavides, Sartorelli and Kato1999; Apers et al., Reference Apers, Vlietinck and Pieters2003). The chemistry of these compounds has been very interesting for organic chemists, owing to the presence of scaffolds on the skeletons of numerous natural products and pharmaceutical agents (Tsai et al., Reference Tsai, Hsieh and Duh1998; Chen et al., Reference Chen, Shaw, Chen and Tsai2002). A large number of reports have shown that these compounds exhibit a broad spectrum with potential bioactivities, such as antiplasmodial (Rakotondramanana et al., Reference Rakotondramanana, Delomenède, Baltas, Duran, Bedos-Belval, Rasoanaivo, Negre-Salvayre and Gornitzka2007), antileishmanial (Van Miert et al., Reference Van Miert, Van Dyck, Schmidt, Brun, Vlietinck, Lemière and Pieters2005), antimicrobial (Kossakowski et al., Reference Kossakowski, Ostrowska, Struga and Stefanska2009) and anti-inflammatory (Wu et al., Reference Wu, Chang, Wang, Hwang, Lee, Chen, Wu and Wu2011). In general, many synthetic methods for the synthesis of (dihydro)benzofuran systems have been developed (Bertolini and Pineschi, Reference Bertolini and Pineschi2009). Among them, the Lewis acid-promoted formal [3 + 2] cycloaddition reaction is a powerful and successful synthetic tool to rapidly construct this ring system (Engler et al., Reference Engler, Wei, Letavic, Combrink and Reddy1994, Reference Engler, Meduna, LaTessa and Chai1996; Engler and Lyenyar, Reference Engler and Lyenyar1998). Interesting chemical transformation with propenylbenzenes is this cycloaddition catalyzed by Fe(ClO4)3 (Ohara et al., Reference Ohara, Kiyokane and Itoh2002, Reference Ohara, Kawai, Hayase and Itoh2003), InCl3 (Yadav et al., Reference Yadav, Reddy and Kondaji2003) for obtaining the trans-2,3-dihydrobenzo[b]furan-5-ols derivatives have been reported. We have also described the diastereoselective synthesis of corresponding trans-2-(4-methoxyphenyl)-3-methyl-2,3-dihydrobenzo[b]furan-5-ol (1) using BF3.OEt2 as catalyst and PEG-400 as a green and reusable solvent (Kouznetsov et al., Reference Kouznetsov, Merchan and Romero2008). However, few crystallographic studies by X-ray diffraction (XRD) of this type of derivative have been reported.

In this regard, our ongoing research program focused on the bioactive dihydrobenzofuran derivatives with anethole fragments and its X-ray crystallographic study. Here, we discuss a simple methodology for preparation of compound 5-acryloyloxy-trans-2-(4-methoxiphenyl)-3-methyl-2,3-dihydrobenzo[b]furan (2) through the acryloylation reaction starting from the corresponding 2,3-dihydrobenzo[b]furan-5-ol (1) and report the results of the molecular characterization (FT-IR, GC-MS, 1H-NMR and 13C-NMR) and X-ray powder diffraction (XRPD) data.

II. EXPERIMENTAL

A. Synthesis

As shown in Figure 1, the title compound was synthesized as follows: a mixture of trans-2-(4-methoxyphenyl)-3-methyl-2,3-dihydrobenzo[b]furan-5-ol (1) (0.50 g, 1.95 mmol) and triethylamine (0.39 g, 3.91 mmol) in CH2Cl2 (30 ml) was stirred at room temperature, after 10 min the system was cooled to 0 °C and a solution of acryloyl chloride (0.35 g, 3.91 mmol) was added dropwise via syringe for 5 min into the mixture. The resulting mixture was stirred vigorously at room temperature overnight (about 14–16 h). After completion of the reaction as indicated by Thin Layer Chromatography (TLC), the final reaction mixture was placed at 0 °C and was carefully diluted with water (20 ml) and extracted with dichloromethane (3 × 15 ml). The organic layer was separated and dried (Na2SO4), concentrated in vacuo and the crude product was purified by column chromatography using silica gel (60–120 mesh) and eluted with petroleum ether – ethyl acetate to afford pure dihydrobenzofuran (2) (yield 82%). The melting point was between 99 and 101 °C.

Figure 1. Synthesis of the 5-acryloyloxy-trans-2-(4-methoxiphenyl)-3-methyl-2,3-dihydrobenzo[b]furan (2) via acryloylation reaction.

The molecular characterization that was carried out with infrared (IR) spectrometry showed the following characteristic signals: 3007, 2953, 2884, 1734, 1610 and 1515 cm−1; Mass Spectrometry (MS) gave a molecular peak m/z = 310 (60, M +); nuclear magnetic resonance on protons 1H NMR (400 MHz, CDCl3 Me4Si) showed δ (ppm) to be 1.39 (3H, d, J = 6.8 Hz, −CH3), 3.47 (1H, m, 3-H), 3.82 (3H, s, CH3O-Ar), 5.15 (1H, d, J = 9.3 Hz, 2-H), 6.00 (1H, dd, J = 9.3, 1.1 Hz, Hvinyl), 6.33 (1H, dd, J = 17.3, 10.4 Hz, Hvinyl), 6.61 (1H, dd, J = 17.3, 1.1 Hz, Hvinyl), 6.83 (1H, d, J = 8.3 Hz, 6-H), 6.92 (4H, m, 4-H, 7-H y 2-HAr) and 7.37 (2H, d, J = 8.6 Hz, 3-HAr); nuclear magnetic resonance on carbons 13C-NMR (100 Hz, CDCl3 Me4Si), δ (ppm), presents the following data: 165.1, 159.7, 156.8, 144.4, 133.1, 132.2, 132.2, 128.0, 127.6 (2C), 120.9, 117.0, 114.0 (2C), 109.5, 93.0, 55.2, 45.4, and 17.4.

B. Powder data collection

The title compound was ground and sieved to grain size less than 38 µm. The compound was mounted on a zero-background specimen holder. The diffraction pattern was collected at room temperature (298 K) in the 2θ range from 2 to 70° 2θ with a step size of 0.02° 2θ and a count time of 0.4 s per step, using a D8 FOCUS BRUKER diffractometer operating in Bragg–Brentano geometry quipped with an X-ray tube (CuKα radiation: λ = 1.5406 Å, 40 kV and 40 mA) with a nickel filter and a one-dimensional LynxEye detector. A fixed anti-scatter slit of 8 mm, receiving slit of 1 mm, soller slits of 2.5° and a detector slit of 3 mm were used.

PowderX program (Dong, Reference Dong1999) was used to remove the background (Sonneveld and Visser, Reference Sonneveld and Visser1975), smoothing (Savitzky and Golay, Reference Savitzky and Golay1964), to eliminate the Kα 2 component (Rachinger, Reference Rachinger1948) and the second derivative method was used to determine the peak observed positions and intensities.

III. RESULTS AND DISCUSSION

The experimental XRPD pattern is depicted in Figure 2. XRPD data for the title compound are given in Table I. Indexing of the experimental XRPD pattern was done using the DICVOL06 program (Boultif and Louër, Reference Boultif and Loüer2006) with an absolute error of 0.03° 2θ. The title compound crystallized in a monoclinic system with space group P21/c (No. 14) estimated by the CHEKCELL program (Laugier and Bochu, Reference Laugier and Bochu2002), which was compatible with the systematic absence and with the crystal density (1.447 g cm−3). The unit-cell parameters were refined with the NBS*AIDS83 program (Mighell et al., Reference Mighell, Hubberd and Stalick1981). Unit-cell data, values of M 20 (de Wolff, Reference de Wolff1968) and F 30 (Smith and Snyder, Reference Smith and Snyder1979) are presented in Table II.

Figure 2. XRPD pattern of 5-acryloyloxy-trans-2-(4-methoxiphenyl)-3-methyl-2,3-dihydrobenzo[b]furan (2).

TABLE I. XRPD data of 5-acryloyloxy-trans-2-(4-methoxiphenyl)-3-methyl-2,3-dihydrobenzo[b]furan (2).

Table II. Crystal-structure data for 5-acryloyloxy-trans-2-(4-methoxiphenyl)-3-methyl-2,3-dihydrobenzo[b]furan (2).

ACKNOWLEDGEMENTS

This work was supported by grant RC-245-2011 Colciencias (Patrimonio Autónomo del Fondo Nacional de Financiamiento para la Ciencia, la Tecnología y la Innovación, Francisco José de Caldas). The authors would like to acknowledge Miguel A. Ramos from the Instituto Zuliano de Investigaciones Tecnológicas, INZIT (Maracaibo-Venezuela) for data collection. Arnold R. Romero Bohórquez thanks COLCIENCIAS for the PhD fellowship studies (2005–2010). Mónica V. Sandoval thanks COLCIENCIAS and the Universidad Industrial de Santander for the scholarship (Programa Jóvenes Investigadores e Innovadores año 2010).

References

Apers, S., Vlietinck, A., and Pieters, L. (2003). “Lignans and neolignans as lead compounds,” Phytochem. Rev. 2, 201–217.CrossRefGoogle Scholar
Benavides, P. J. C., Sartorelli, P., and Kato, M. J. (1999). “Phenylpropanoids and neolignans from Piper regnellii,” Phytochemistry 52, 339–343.CrossRefGoogle Scholar
Bertolini, F. and Pineschi, M. (2009). “Recent progress in the synthesis of 2,3-dihydrobenzofurans,” Org. Prep. Proced. Int. 41, 385–418.CrossRefGoogle Scholar
Boultif, A. and Loüer, D. (2006). “Indexing of powder diffraction patterns of low symmetry lattices by successive dichotomy method,” J. Appl. Crystallogr. 37, 724–731.CrossRefGoogle Scholar
Chen, C.-H., Shaw, C.-Y., Chen, C.-C., and Tsai, Y.-C. (2002). “2,3,4-Trimethyl-5,7-dihydroxy-2,3-benzofuran, a novel antioxidant, from Penicillium citrinum F5,” J. Nat. Prod. 65, 740–741.CrossRefGoogle Scholar
de Wolff, P. M. (1968). “A simplified criterion for the reliability of a powder pattern,” J. Appl. Crystallogr. 1, 108–113.CrossRefGoogle Scholar
Dong, C. (1999). “PowderX: Windows-95-based program for poder X-ray diffraction data processing,” J. Appl. Crystallogr. 32, 838–838.CrossRefGoogle Scholar
Engler, T. and Lyenyar, R. (1998). “Lewis acid-directed reactions of quinones with styrenyl systems: the case of 2-methoxy-3-methyl-1,4-benzoquinone,” J. Org. Chem. 63, 1929–1934.CrossRefGoogle Scholar
Engler, T., Meduna, S., LaTessa, K., and Chai, W. (1996). “Lewis acid-promoted reactions of styrenyl systems with benzoquinone bisimines: new regioselective syntheses of substituted 2-aryl-2,3-dihydroindoles and 2-arylindoles,” J. Org. Chem. 61, 8598–8603.CrossRefGoogle Scholar
Engler, T. A., Wei, D., Letavic, M. A., Combrink, K. D., and Reddy, J. P. (1994). “Regioselective lewis acid-directed reactions of 2-alkoxy-5-alkyl-1,4-benzoquinones with styrenes: synthesis of burchellin and guianin neolignans,” J. Org. Chem. 59, 6588–6599.CrossRefGoogle Scholar
Kossakowski, J., Ostrowska, K., Struga, M., and Stefanska, J. (2009). “Synthesis of new derivatives of 2,2-dimethyl-2,3-dihydro-7-benzo[b]furanol with potential antimicrobial activity,” Med. Chem. Res. 18, 555–565.CrossRefGoogle Scholar
Kouznetsov, V. V., Merchan, A. D., and Romero, B. A. R. (2008). “PEG-400 as green reaction medium for Lewis acid-promoted cycloaddition reactions with isoeugenol and anethole,” Tetrahedron Lett. 49, 3097–3100.CrossRefGoogle Scholar
Laugier, J. and Bochu, B. (2002). CHEKCELL. “LMGP-Suite Suite of Programs for the interpretation of X-ray. Experiments,” ENSP/Laboratoire des Matériaux et du Génie Physique, BP 46. 38042 Saint Martin d'Hères, France. http://www.inpg.fr/LMGP and http://www.ccp14.ac.uk/tutorial/lmgp/.Google Scholar
Mighell, A. D., HubberdC, R. C, R., and Stalick, J. K. (1981). “NBS* AIDS80: A FORTRAN program for crystallographic data evaluation,” National Bureau of Standards (USA), Technical Note 1141.CrossRefGoogle Scholar
Ohara, H., Kiyokane, H., and Itoh, T. (2002). “Cycloaddition of styrene derivatives with quinone catalyzed by ferric ion; remarkable acceleration in an ionic liquid solvent system,” Tetrahedron Lett. 43, 3041–3044.CrossRefGoogle Scholar
Ohara, H., Kawai, K., Hayase, S., and Itoh, T. (2003). “Synthesis of optically active 2,3-dihydrobenzofuran derivatives through a combination strategy of iron(III)-catalyzed reaction and enzymatic reaction,” Tetrahedron Lett. 44, 4081–4084.Google Scholar
Rachinger, W. A. (1948). “A correction for the α 1α 2 doublet in the measurement of widths of X-ray diffraction lines,” J. Sci. Instrum. 25, 254.Google Scholar
Rakotondramanana, D. L. A., Delomenède, M., Baltas, M., Duran, H., Bedos-Belval, F., Rasoanaivo, P., Negre-Salvayre, A., and Gornitzka, H. (2007). “Synthesis of ferulic ester dimers, functionalisation and biological evaluation as potential antiatherogenic and antiplasmodial agents,” Bioorg. Med. Chem. 15, 6018–6026.CrossRefGoogle ScholarPubMed
Savitzky, A. and Golay, M. J. (1964). “Smoothing and differentiation of data by simplified least squares procedures,” Anal. Chem. 36, 1627–1639.CrossRefGoogle Scholar
Smith, G. S. and Snyder, R. L. (1979). “F N: a criterion for rating powder diffraction patterns and evaluating the reliability of powder-pattern indexing,” J. Appl. Crystallogr. 12, 60–65.CrossRefGoogle Scholar
Sonneveld, E. J. and Visser, J. W. (1975). “Automatic collection of powder diffraction data from photographs,” J. Appl. Crystallogr. 8, 1–7.CrossRefGoogle Scholar
Tsai, I.-L., Hsieh, C.-F., and Duh, C.-Y. (1998). “Additional citotoxic neolignans from Persea Obovatifolia,” Phytochemistry 48, 1371–1375.CrossRefGoogle Scholar
Van Miert, S., Van Dyck, S., Schmidt, T. J., Brun, R., Vlietinck, A., Lemière, G., and Pieters, L. (2005). “Antileishmanial activity, cytotoxicity and QSAR analysis of synthetic dihydrobenzofuran lignans and related benzofurans,” Bioorg. Med. Chem. 13, 661–669.CrossRefGoogle ScholarPubMed
Wu, S. F., Chang, F. R., Wang, S. Y., Hwang, T. L., Lee, C. L., Chen, S. L., Wu, C. C., and Wu, Y. C. (2011). “Anti-inflammatory and cytotoxic neoflavonoids and benzofurans from Pterocarpus santalinus,” J. Nat. Prod. 74, 989–996.CrossRefGoogle ScholarPubMed
Yadav, J. S., Reddy, B. V. S., and Kondaji, G. (2003). “InCl3-catalyzed [3 + 2] cycloaddition reactions: a facile synthesis of trans-dihydrobenzofurans and substituted cyclobutane derivatives,” Synthesis. 34, 1100–1104.CrossRefGoogle Scholar
Figure 0

Figure 1. Synthesis of the 5-acryloyloxy-trans-2-(4-methoxiphenyl)-3-methyl-2,3-dihydrobenzo[b]furan (2) via acryloylation reaction.

Figure 1

Figure 2. XRPD pattern of 5-acryloyloxy-trans-2-(4-methoxiphenyl)-3-methyl-2,3-dihydrobenzo[b]furan (2).

Figure 2

TABLE I. XRPD data of 5-acryloyloxy-trans-2-(4-methoxiphenyl)-3-methyl-2,3-dihydrobenzo[b]furan (2).

Figure 3

Table II. Crystal-structure data for 5-acryloyloxy-trans-2-(4-methoxiphenyl)-3-methyl-2,3-dihydrobenzo[b]furan (2).