(E)-1-[2-Hy­droxy-4,6-bis­(meth­oxy­meth­oxy)phen­yl]-3-[3-meth­oxy-4-(meth­oxy­meth­oxy)phen­yl]prop-2-en-1-one

Liu-Shuan Chang; Chen-Yang Li; Yan-Mei Zhao; Fang Xu; Zheng-Yi Gu

doi:10.1107/S1600536811041213

. 2011 Oct 12;67(Pt 11):o2931. doi: 10.1107/S1600536811041213

(E)-1-[2-Hydroxy-4,6-bis(methoxymethoxy)phenyl]-3-[3-methoxy-4-(methoxymethoxy)phenyl]prop-2-en-1-one

Liu-Shuan Chang ^a, Chen-Yang Li ^b, Yan-Mei Zhao ^a, Fang Xu ^b, Zheng-Yi Gu ^b,^*

PMCID: PMC3247344 PMID: 22219962

Abstract

The title compound, C₂₂H₂₆O₉, crystallizes with two independent molecules in the asymmetric unit in which the dihedral angles between the two benzene rings are 21.4 (2) and 5.1 (2)°. An intramolecular O—H⋯O hydrogen bond occurs in each molecule. Intermolecular C—H⋯O hydrogen bonds stabilize the crystal structure.

Related literature

For the biological activity of flavonoids, see: Jung et al. (2006 ▶); Ong & Khoo (1996 ▶); Vessal et al. (2003 ▶); Sousa et al. (2004 ▶). For bond-length data, see: Allen et al. (1987 ▶); Chu et al. (2004 ▶); Zhang et al. (2011 ▶). For the preparation, see: Duan et al. (2006 ▶).

Experimental

Crystal data

C₂₂H₂₆O₉
M _r = 434.43
Monoclinic,
a = 12.008 (3) Å
b = 13.016 (4) Å
c = 13.663 (4) Å
β = 97.154 (4)°
V = 2119.0 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 113 K
0.24 × 0.22 × 0.18 mm

Data collection

Rigaku Saturn CCD area-detector diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2009) ▶ T _min = 0.975, T _max = 0.981
22288 measured reflections
5259 independent reflections
4715 reflections with I > 2σ(I)
R _int = 0.045

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.076
S = 1.03
5259 reflections
569 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Data collection: CrystalClear-SM Expert (Rigaku/MSC, 2009) ▶; cell refinement: CrystalClear-SM Expert ▶; data reduction: CrystalClear-SM Expert ▶; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811041213/hg5103sup1.cif

e-67-o2931-sup1.cif^{(34.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811041213/hg5103Isup2.hkl

e-67-o2931-Isup2.hkl^{(257.5KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811041213/hg5103Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O5—H5⋯O6	0.84	1.75	2.506 (2)	148
O14—H14⋯O15	0.84	1.72	2.475 (2)	148
C8—H8C⋯O8ⁱ	0.98	2.57	3.312 (3)	132
C9—H9A⋯O5ⁱⁱ	0.99	2.52	3.444 (3)	155

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Symmetry codes: (i) Inline graphic ; (ii) .

supplementary crystallographic information

Comment

Several flavonoids, such as Hesperidin and naringin(Jung et al., 2006), myricetin (Ong & Khoo, 1996), quercetin (Vessal et al., 2003), Kaempferol-3,7-O-(r)-dirhamnoside (Sousa et al., 2004), have been reported to treat diabetes. We synthesized a series of 5,7-dihydroxy flavonoids. The vitro antidiabetic activity experiment showed that most of the flavonoids showed a remarkable in vitro anti-diabetic activity. The title compound, (E)-1-(2-hydroxy-4,6-bis(methoxymethoxy)phenyl)-3- (3-methoxy-4-(methoxymethoxy)phenyl)prop-2-en-1-one was prepared as an intermediate.

In title compound, C₂₂H₂₆O₉, crystallizes with two independent molecules in the asymmetric unit. All bond lengths and angles in the molecular are normal (Allen et al., 1987) and in a good agreement with those reported previously (Chu et al., 2004; Zhang et al., 2011). The dihedral angle between two phenyl ring (C1—C6 and C14—C19; C23—C28 and C36—C41) are 21.4 (2)° and 5.1 (2) °, respectively. The C—H···O intermolecular hydrogen bonds stabilized the crystal structure (Table 1).

Experimental

A round-bottomed flask was charged with 1.52 g (10 mmol) of 4-hydroxy-3-methoxybenzaldehyde, 9.66 g (70 mmol) of K₂CO₃, 805 mg (10 mmol) of chloromethyl methyl ether (MOMCl) and 30 ml of anhydrous acetone, and the mixture was stirred at room temperature for four hours. The reaction mixture was filtered, and evaporated to afford 3-methoxy-4-(methoxymethoxy)benzaldehyde. Dropwise chloromethyl methyl ether (4.83 g, 6 mmol) was added to a mixture of 2,4,6-trihydroxyacetophenone (503.0 mg, 3 mmol) and K₂CO₃ (2.89 g, 21 mmol) in anhydrous acetone (30 ml). The mixture was heated at reflux for 1.5 h, filtered, and evaporated to afford 2-hydroxy-4,6-dimethoxymethoxyacetophenone. Then 3-methoxy-4-(methoxymethoxy)benzaldehyde (589 mg, 3.0 mmol) in 60% NaOH aqua (8 ml) and MeOH (15 ml) was added and stirred for 24 h. The resulting mixture was poured into cold 2 M HCl (40 ml), and then extracted with three 20-ml portions of EtOAc. The organic layer was washed with water and saturated brine, dried over MgSO4, and evaporated to afford the title compound via recrystallization from EtOH (Duan et al., 2006). Single crystals suitable for X-ray diffraction were obtained from slow evaporation of a solution of the pure title compound in ethanol at room temperature.