(E)-Methyl 3-(3,4-dihy­droxy­phen­yl)acrylate

Li Wang; Fa-Yan Meng; Cui-Wu Lin; Hai-Yan Chen; Xuan Luo

doi:10.1107/S1600536810054504

. 2011 Jan 12;67(Pt 2):o354. doi: 10.1107/S1600536810054504

(E)-Methyl 3-(3,4-dihydroxyphenyl)acrylate

Li Wang ^a, Fa-Yan Meng ^a, Cui-Wu Lin ^a,^*, Hai-Yan Chen ^a, Xuan Luo ^a

PMCID: PMC3051619 PMID: 21523034

Abstract

The benzene ring in the title compound, C₁₀H₁₀O₄, makes an angle of 4.4 (1)° with the C—C—C—O linker. The hydroxy groups are involved in both intra- and intermolecular O—H⋯O hydrogen bonds. The crystal packing is stabilized by O—H⋯O hydrogen-bonding interactions. The molecules of the caffeic acid ester form a dimeric structure in a head-to-head manner along the a axis through O—H⋯O hydrogen bonds. The dimers interact with one another through O—H⋯O hydrogen bonds, forming supermolecular chains. These chains are further extended through C—H⋯O hydrogen bonds as well as van der Waals interactions into the final three-dimensional architecture.

Related literature

For properties of caffeic acids and their esters, see: Altug et al. (2008 ▶); Ates et al. (2006 ▶); Atik et al. (2006 ▶); Chun et al. (2008 ▶); Huang et al. (2010 ▶); Hwang et al. (2001 ▶); Padinchare et al. (2001 ▶). For a polymorphic form of the title compound, see: Chen et al. (1979 ▶).

Experimental

Crystal data

C₁₀H₁₀O₄
M _r = 194.18
Triclinic,
a = 5.129 (5) Å
b = 9.969 (8) Å
c = 10.586 (9) Å
α = 117.627 (7)°
β = 97.924 (11)°
γ = 94.322 (11)°
V = 468.9 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 296 K
0.33 × 0.24 × 0.18 mm

Data collection

Multiwire proportional diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.966, T _max = 0.981
2494 measured reflections
1619 independent reflections
1337 reflections with I > 2σ(I)
R _int = 0.013

Refinement

R[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 0.120
S = 1.05
1619 reflections
128 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.13 e Å⁻³

Data collection: SMART (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; 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 datablocks I, global. DOI: 10.1107/S1600536810054504/bg2376sup1.cif

e-67-0o354-sup1.cif^{(15.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810054504/bg2376Isup2.hkl

e-67-0o354-Isup2.hkl^{(79.8KB, 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
O4—H4A⋯O3	0.82	2.28	2.723 (2)	114
O4—H4A⋯O3ⁱ	0.82	2.15	2.835 (2)	141
O3—H3A⋯O2ⁱⁱ	0.82	1.95	2.764 (2)	175
C10—H10A⋯O2ⁱⁱ	0.93	2.56	3.260 (4)	132

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

Acknowledgments

This work was supported by a grant from the National Natural Science Foundation of China (20962002, 20662001) and the National Undergraduates Innovating Experimentation Project (091059314).

supplementary crystallographic information

Comment

Some naturally occurring caffeic acids and their esters attract much attention in biology and medicine (Hwang et al., 2001; Altug et al., 2008). These compounds show antiviral, antibacterial, vasoactive, antiatherogenic, antiproliferative, antioxidant and antiinflammatory properties (Atik et al., 2006; Padinchare et al., 2001; Ates et al., 2006). Our previous research found that the phenolic acids compounds including caffeic acid, chlorogenic acid, ferulic acid, vanillic acid, syringic acid and protocatechuic acid from Blumea riparia DC have a significant role at antiplatelet activity (Huang et al.., 2010). This prompted us to synthesize a series of caffeic acid esters and amides to investigate their properties. In this paper, we report a polymorph of C₁₀H₁₀O₄ (Chen et al.., 1979).

In the title compound (Fig. 1), all values of the geometric parameters are normal. The benzene ring is planar within experimental error and it makes an angle of 4.4 (1)° to the linker (C2–C3–C4–O2). Hydroxy groups contribute to intermolecular O—H···O hydrogen bonds. In the case of caffeic esters, the presence of an ethylenic spacer allows the formation of a conjugated system, strongly stabilized through π-electron delocalization (Chun et al., 2008).

The bond C3=C4 is a trans-double bond. The crystal packing is stabilized by intramolecular (Table 1, entries 1 and 2) and intermolecular hydrogen-bonding interactions (Table 1, remaining entries). The molecules of the caffeic acid ester form a dimeric structure through O—H···O hydrogen bonds along the a axis in a head-to-head manner (Table 1, third entry) . The dimer interacts with another dimmer through O—H···O hydrogen bonds (Table 1, fourth entry) to form one-dimensional supermolecule chains. These one-dimensional supermolecule chains are further extended through C—H···O hydrogen bonds (Table 1, fifth entry) as well as van der Waals interactions into the final 3-D architecture (Fig.2).

Experimental

Commercial caffeic acid (1.79 g, 10 mmol) was dissolved in tetrahydrofuran solution(16 ml), followed by methanol (16 ml) and the addition of concentrated hydrochloric acid (8 ml). The mixture was stirred at 60 °C for 60 minutes, followed by the addition of water and extracted with ethyl acetate. The organic layer was washed with sodium bicarbonate and water, dried over magnesium sulfate, and concentrated to give a solid residue. The residue was recrystallized from petroleum ether to give the title compound as a colourless crystal (1.64 g, yield: 84%)