(E)-3-(8-Benz­yloxy-2,3-dihydro-1,4-benzodioxin-6-yl)-1-[2-hy­droxy-4,6-bis­(meth­oxy­meth­oxy)phen­yl]prop-2-en-1-one

Yu Zhang; Yi-Nan Zhang; Ming-Ming Liu; Kum-Chol Ryu; De-Yong Ye

doi:10.1107/S160053681100924X

. 2011 Mar 19;67(Pt 4):o912–o913. doi: 10.1107/S160053681100924X

(E)-3-(8-Benzyloxy-2,3-dihydro-1,4-benzodioxin-6-yl)-1-[2-hydroxy-4,6-bis(methoxymethoxy)phenyl]prop-2-en-1-one

Yu Zhang ^a, Yi-Nan Zhang ^a, Ming-Ming Liu ^a, Kum-Chol Ryu ^b, De-Yong Ye ^a,^*

PMCID: PMC3100013 PMID: 21754185

Abstract

In the title molecule, C₂₈H₂₈O₉, the phenol and the benzene rings adjacent to the α,β-unsaturated ketone unit are inclined at 9.15 (13)° to each other. The terminal phenyl ring is oriented with respect to the phenol ring at a dihedral angle of 85.88 (13)°. In the crystal, the methylene C atoms of the dihydrodioxine ring are disordered over two sites with an occupancy ratio of 0.463 (18):0.537 (18), and both disordered components of the dihydrodioxine ring adopt twisted-chair conformations. An intramolecular O—H⋯O hydrogen bond and weak intermolecular C—H⋯O hydrogen bonds are present in the crystal structure.

Related literature

For background to 1,3-diaryl-2-propen-1-one, see: Carlo et al. (1999 ▶); Dimmock et al. (1999 ▶); Go et al. (2005 ▶); Nowakowska (2007 ▶); Yarishkin et al. (2008 ▶). For related structures, see: Özbey et al. (1997 ▶); Gao & Ng (2006 ▶); Loghmani-Khouzani et al. (2009 ▶); Rizvi et al. (2010 ▶). For the synthesis, see: Lin et al. (2007 ▶).

Experimental

Crystal data

C₂₈H₂₈O₉
M _r = 508.50
Triclinic,
a = 8.149 (4) Å
b = 11.744 (5) Å
c = 14.439 (7) Å
α = 72.752 (5)°
β = 84.269 (5)°
γ = 70.601 (5)°
V = 1244.7 (10) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 294 K
0.35 × 0.25 × 0.18 mm

Data collection

Bruker CCD 1000 area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.965, T _max = 0.982
5687 measured reflections
4774 independent reflections
3239 reflections with I > 2σ(I)
R _int = 0.026

Refinement

R[F ² > 2σ(F ²)] = 0.061
wR(F ²) = 0.195
S = 1.02
4774 reflections
353 parameters
H-atom parameters constrained
Δρ_max = 0.60 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681100924X/xu5171sup1.cif

e-67-0o912-sup1.cif^{(23KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053681100924X/xu5171Isup2.hkl

e-67-0o912-Isup2.hkl^{(233.8KB, hkl)}

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
O9—H9C⋯O4	0.82	1.71	2.448 (2)	149
C6—H6A⋯O9ⁱ	0.93	2.57	3.426 (3)	154
C21—H21A⋯O8ⁱⁱ	0.93	2.53	3.453 (3)	169

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

Acknowledgments

The authors greatly appreciate financial support from the Open Grant of the Institute of Bioscience, Fudan University, China.

supplementary crystallographic information

Comment

1,3-Diaryl-2-propen-1-ones, commonly known as chalcones are a kind of aromatic ketones that form the central core for a variety of important biological compounds, showing anti-bacterial, anti-fungal, anti-malarial, anti-viral, anti-inflammatory, anti-oxidant and anti-tumor properties, which have been reviewed by Carlo et al. (1999), Dimmock et al. (1999), Go et al. (2005) and Nowakowska (2007). Some even demonstrated the ability to block voltage-dependent potassium channels (Yarishkin et al., 2008). Chalcones can also be converted into flavonoids in several classical synthetic steps, consolidating its significance in synthetic chemistry.

The title compound, i.e. (E)-3-(8-(benzyloxy)-2,3-dihydrobenzo[b][1,4]dioxin-6-yl) -1-(2-hydroxy-4,6-bis(methoxymethyl)phenyl)prop-2-en-1-one, is first prepared aiming to find out potential anti-virus candidates. It is obtained from a dihydrobenzo[b][1,4]dioxine aldehyde derivative and an acetophenone derivative by a classical aldol condensation in the presence of potassium hydroxide as a catalyst (Lin et al., 2007). We now report here the synthesis and crystal structure, as part of our investigations in revealing the relationship between the structure and the anti-virus activity. A series of chalcones related to the title compound is also under investigation for their biological activities in our laboratory.

The title molecule is presented in Fig. 1. The least-square planes of the benzene and phenol rings defined by atoms C3—C8 and C19—C24, respectively, are inclined at 9.15 (13)° with respect to each other. The dihedral angle between the benzyloxy group and the benzene plane is 85.90 (7)°. Both the major and minor conformers of the disordered dioxane ring adopt twist-chair conformations [φ = 193.86 (8)°, θ = 77.63 (16)° (for ring C1—C2—O2—C3—C4—O1), and φ = 184.02 (10)°, θ = 95.1 (2)° (for ring C1'-C2'-O2—C3—C4—O1)], having total puckering amplitudes, Q_T, of 0.2538 (8) Å and 0.1675 (10) Å, respectively. The crystal structure is stabilized by a strong intramolecular O—H···O hydrogen bond, and further consolidated by the weak intermolecular hydrogen-bonding interactions of the type C—H···O, and Van der Waals forces (Table 1).

Experimental

1-[2-Hydroxy-4,6-bis-(methoxymethyl)-phenyl]-ethanone (1.8 g, 7.0 mmol) and 8-(benzyloxy)-2,3-dihydro-benzo[b][1,4]dioxine-6-carbaldehyde (1.9 g, 7.0 mmol) were dissolved in 95% EtOH, KOH/H₂O solution (3M). The reaction mixture was stirred at room temperature overnight, evaporated under reduced pressure, and further extracted by ethyl acetate. The extract layer was chromatographed on silica gel to afford the title compound (3.2 g, yield 90%) as an orange solid. Single crystals suitable for X-ray analysis were obtained by slow evaporation of an ethyl acetate and petroleum ether solution.