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Synthesis and X-ray diffraction data of 4-benzyloxy-1-oxaspiro-[4.6]-undec-3-en-2-one

Published online by Cambridge University Press:  17 December 2013

Jose H. Quintana ,
J. A. Henao ,
Elvis Robles  and
Juan Manuel Urbina
Jose H. Quintana
Affiliation:
Grupo de Investigación en Química Estructural (GIQUE), 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
J. A. Henao
Affiliation:
Grupo de Investigación en Química Estructural (GIQUE), 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
Elvis Robles
Affiliation:
Laboratorio de Química Orgánica y Biomolecular (LQOBio), Escuela de Química, Facultad de Ciencias, Universidad Industrial de Santander, A.A. 678, Carrera 27, Calle 9 Ciudadela Universitaria, Bucaramanga, Colombia
Juan Manuel Urbina
Affiliation:
Laboratorio de Química Orgánica y Biomolecular (LQOBio), Escuela de Química, Facultad de Ciencias, Universidad Industrial de Santander, A.A. 678, Carrera 27, Calle 9 Ciudadela Universitaria, Bucaramanga, Colombia
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Abstract

The 4-benzyloxy-1-oxaspiro-[4.6]-undec-3-en-2-one (C17H20O3) was prepared through a domino reaction from benzyl α-hydroxycycloheptanecarboxylate and the cumulated ylide Ph3P=C=C=O by: (i) addition and (ii) intramolecular Wittig Olefination reaction. The reaction was carried out using anhydrous toluene as solvent under an argon atmosphere in a Schlenk flask. Molecular characterization was performed by Fourier transform infrared spectroscopy, gas chromatography-mass spectrometry, (1H,13C – mono and bidimensional) nuclear magnetic resonance spectroscopy; crystallographic characterization was completed by X-ray diffraction of polycrystalline samples (XRPD). The title compound crystallized in a monoclinical system and unit-cell parameters are reported [a = 13.207(3) Å, b = 5.972(1) Å, c = 19.719(4) Å, β = 105.67(2)°, unit-cell volume V = 1497.5 (4) Å3, Z = 4]. All of the measured lines were indexed with the P21/n (No. 14) space group.

Keywords

O-Bencyl tetronateX-ray powder diffraction dataspiro tetronic acid
Type
New Diffraction Data
Information
Powder Diffraction , Volume 28 , Issue 4 , December 2013 , pp. 315 - 320
Copyright
Copyright © International Centre for Diffraction Data 2013 

I. INTRODUCTION

There are many studies related to the synthesis of compounds structurally related to conjugated systems derived from the 4-hydroxyfuran-2[5H]-one core; many of these derivatives have shown several activities in different biological reactions and they are usually employed as precursors of substances of high relevance in the battle against many diseases. Most of the methodologies reported for its preparation are generally limited by the instability of the substances employed and the difficulty of obtaining the desired structure (Tejedor, Reference Tejedor and García-Tellado2004).

Until now, one of the best methodologies used to obtain butenolides (furan-2[5H]-ones) is Wittig Olefination; using the cumulated ylide Ph3P=C=C=O as a Wittig reagent and different α-hydroxyesters, it is possible to achieve the synthesis of several analogs of substances that have shown biological activity (antitumor and anticancer among the most important); the use of Ph3P=C=C=O also allows us to obtain molecules with spiroatoms that usually are not easy to access by the conventional reaction methods (Schobert, Reference Schobert2007).

In this work, the preparation of 4-benzyloxy-1-oxaspiro-[4.6]-undec-3-en-2-one (2) using Ph3P=C=C=O and the corresponding benzyl α-hydroxycycloheptanecarboxylate (1) is presented (Figure 1), reporting molecular characterization [Fourier transform infrared spectroscopy, gas chromatography-mass spectrometry (GC-MS), 1H, nuclear magnetic resonance spectroscopy on carbons (13C NMR), and X-ray powder diffraction (XRPD)] data. Crystallographic information by X-ray diffraction about this type of derivatives has been little explored. This compound has been obtained in an easy and fast way and owing to its similarity with the analogs already reported is expected to be of biological interest.

Figure 1. Synthesis of 4-benzyloxy-1-oxaspiro-[4.6]-undec-3-en-2-one (2).

II. EXPERIMENTAL

A. Synthesis

In a 250-ml round bottom Schlenk flask, 2.18 g (7.21 mmol) of keteneylidenetriphenylphosphorane (Ph3P=C=C=O) were loaded under argon atmosphere; 150 ml of anhydrous toluene were added and the mixture was magnetically stirred. Approximately 0.87 g (3.5 mmol) of benzyl 1-hydroxycycloheptanecarboxylate (1) (previously dried under vacuum for 1 h) were added. The reaction mixture was refluxed for 72 h, after completion of the reaction indicated by thin layer chromatography (TLC). Toluene was removed under vacuum using a rotary evaporator. To remove the phosphine oxide formed during the reaction, the residue was initially dissolved in dichlorometane (DCM) and filtered over silica gel (60–120 mesh). Then, the residual crude product was purified by column chromatography using silica gel (60–120 mesh) and hexane–ethyl acetate (5:1) as eluents to afford the pure O-benzyltetronate (2) (yield 70%). R f = 0.4 (SiO2, hexane:ethyl acetate, 5:2).

4-O-(bencyloxy)-1-oxaspiro[4.6]undec-3-en-2-one ( 2 ): White solid, m.p. 95 °C. IR [KBr, ν (cm−1)] = 3472 (w), 3119 (w), 2924 (m), 2862 (w), 1747 (vs), 1624 (vs), 1460 (w), 1033 (m) [ν(C–O)], 812 (m), 736 (w), 700 (m). 1H NMR (400 MHz, CDCl3), δ (ppm): 7.42 (2H, d, J*, Hortho), 7.40 (2H, td, J*, Hmeta), 7.36 (1H, t, J*, Hpara), 5.05 (2H, s, ϕ–CH2–), 4.95 (1H, s, H–C=), 1.50–2.03 (12H, m, cycloheptane ring) [* J not resolved, appear as broad signal]. 13C-NMR (100 Hz, CDCl3), δ (ppm): 185.99 (C = O), 172.27 (4-C), 134.34 (C ipso), 128.96 (2C, Cmeta), 128.89 (C para), 127.60 (2C,C ortho), 87.39 (5-C spiro), 87.22 (H–C = ), 74.18 (ϕ–CH2 –), 36.94 (2C, a-C), 29.24 (2C, b-C), 22.67 (2C, c-C). GC-MS (EI) m/z (%): 272 (1, M + ), 254 (2, M + –H2O), 228 (1, M + –CO2), 181 (2, M + –C7H7), 127 (1, M + –CO–C8H5O), 91 (100, M +–C10H13O3), 95 (10, M +–C10H9O3,), and 56 (4, M +–C13H12O3). Anal. Calcd for C17H20O3 (272 g mol−1): C, 74.97; H, 7.40.

B. Powder data collection

The title compound was ground and sieved to a grain size <38 μm. The compound was mounted on a zero-background specimen holder. The diffraction pattern was collected at room temperature (298 K) in the range from 2 to 70° 2θ with a step size of 0.015 26° 2θ and a count time of 0.4 s per step, using an D8 ADVANCE BRUKER with geometry DaVinci diffractometer operating in Bragg–Brentano geometry quipped with a Cu-target X-ray tube (40 kV and 30 mA), a nickel filter and a one-dimensional LynxEye detector. A fixed antiscatter slit of 8 mm, receiving slit of 1 mm, soller slits of 2.5°, and a detector slit of 0.6 mm were used.

PowderX program (Dong, Reference Dong1999) was used to remove the background (Sonnerveld and Visser, Reference Sonnerveld 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 is given in Table I. Indexing of the experimental XRPD pattern was performed using the DICVOL06 program (Boultif and Louër, Reference Boultif and Louër2006) with an absolute error of 0.03° 2θ. The title compound crystallized in a monoclinical system with space group P21/n (No. 14) estimated by the CHEKCELL program (Laugier and Bochu, Reference Laugier and Bochu2002), which was compatible with the systematic absences and with the crystal density (1.211 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. X-ray powder diffraction pattern of 4-benzyloxy-1-oxaspiro-[4.6]-undec-3-en-2-one.

Table I. X-ray powder diffraction data of 4-benzyloxy-1-oxaspiro-[4.6]-undec-3-en-2-one. CuKα1 radiation (λ = 1.5406 Å).

Table II. Crystal-structure data for 4-benzyloxy-1-oxaspiro-[4.6]-undec-3-en-2-one.

ACKNOWLEDGEMENTS

This work was supported by internal grant 5165 (VIE-UIS). The authors express their acknowledgement to Universidad Industrial de Santander-UIS and Parque Tecnológico Guatiguará-PTG (Bucaramanga-Colombia) for data collection. José H. Quintana Mendoza thanks COLCIENCIAS and Universidad Industrial de Santander for his scholarship (Programa Jóvenes Investigadores e Innovadores, año 2012).

References

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Figure 0

Figure 1. Synthesis of 4-benzyloxy-1-oxaspiro-[4.6]-undec-3-en-2-one (2).

Figure 1

Figure 2. X-ray powder diffraction pattern of 4-benzyloxy-1-oxaspiro-[4.6]-undec-3-en-2-one.

Figure 2

Table I. X-ray powder diffraction data of 4-benzyloxy-1-oxaspiro-[4.6]-undec-3-en-2-one. CuKα1 radiation (λ = 1.5406 Å).

Figure 3

Table II. Crystal-structure data for 4-benzyloxy-1-oxaspiro-[4.6]-undec-3-en-2-one.