4-(5-Hy­droxy­meth­yl-2-meth­oxy­phen­oxy)benzoic acid

Yanyan Niu; Bo Wu

doi:10.1107/S1600536811012190

. 2011 Apr 7;67(Pt 5):o1069. doi: 10.1107/S1600536811012190

4-(5-Hydroxymethyl-2-methoxyphenoxy)benzoic acid

Yanyan Niu ^a, Bo Wu ^a,^*

PMCID: PMC3089302 PMID: 21754394

Abstract

The title compound, C₁₅H₁₄O₅, crystallizes with two independent molecules in the asymmetric unit in which the benzene rings are inclined at dihedral angles of 79.4 (1) and 84.2 (1)°. In the crystal, intermolecular O—H⋯O hydrogen bonds link the molecules into double chains propagating in [001].

Related literature

For the bioactivity of diphenyl ether derivatives, see: Asakawa (2001 ▶); Hua et al. (2009 ▶); Kini et al.(2009 ▶). For background to Ullman coupling, see: Bringmann et al. (1990 ▶).

Experimental

Crystal data

C₁₅H₁₄O₅
M _r = 274.26
Triclinic,
a = 10.5420 (15) Å
b = 10.6153 (15) Å
c = 12.8070 (18) Å
α = 78.024 (2)°
β = 75.184 (2)°
γ = 88.451 (2)°
V = 1354.9 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 273 K
0.13 × 0.12 × 0.10 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ▶) T _min = 0.987, T _max = 0.990
5794 measured reflections
3874 independent reflections
3154 reflections with I > 2σ(I)
R _int = 0.015
θ_max = 23.3°

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.141
S = 1.02
3874 reflections
365 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); 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/S1600536811012190/cv5067sup1.cif

e-67-o1069-sup1.cif^{(24.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811012190/cv5067Isup2.hkl

e-67-o1069-Isup2.hkl^{(189.9KB, 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—H9⋯O1	0.82	1.80	2.620 (2)	175
O4—H4⋯O6	0.82	1.84	2.652 (2)	1670
O6—H6⋯O10ⁱ	0.82	2.01	2.791 (3)	159
O1—H1⋯O5ⁱⁱ	0.82	1.89	2.706 (2)	172

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

Acknowledgments

Financial support from the Department of Science and Technology of Shandong Province is gratefully acknowledged.

supplementary crystallographic information

Comment

The diphenyl ether analogs existing in many natural products exhibit various bioactivities, such as antitubercular (Kini et al., 2009), antibacterial (Hua et al., 2009), and cytotoxic (Asakawa, 2001) activities. Most of the diphenyl ethers were synthesized by Ullman coupling (Bringmann et al., 1990), using Cu complexes as catalysts. Herewith we present the title compound (I) - a new derivative of diphenyl ether.

The asymmetric unit of (I) contains two independent molecules (Fig. 1). In the independent molecules, two benzene rings form the dihedral angles of 79.4 (1) and 84.2 (1)°, respectively. In the crystal structure, O—H···O hydrogen bonds (Table 1) link the molecules into doubled chains propagated in [001].

Experimental

(3-Bromo-4-methoxyphenyl)methanol (5.00 g, 23.04 mmol), and methyl 4-hydroxybenzoate (3.50 g, 23.04 mmol), potassium carbonate (3.17 g, 46.08 mmol), and cupric oxide (0.18 g, 2.25 mmol) in pyridine (20 ml) were added in flask and the mixture was stirred under reflux for 12 h. The pyridine was distilled in vacuo and the residue was extracted with CH₂Cl₂(3*30 ml). The solution was concentrated and the residue was purified by flash column chromatograph on Al₂O₃, The yield of the coupling product was 4.35 g (65%) as white solid. The coupling products was hydrolyzed with 20% NaOH aq and then acidified to pH=6.0 with 1M HCl. The final product was extracted with CH₂Cl₂ (3*20 ml) and obtained the white solid by vacuum distillation. (4.11 g, 99%). The colourless crystals suitable for an X-ray diffraction experiment were obtained by cystal growth from ethanol.