Ethyl 4-chloro-2′-fluoro-3-hy­droxy-5-methyl­biphenyl-2-carboxyl­ate

Muhammad Adeel; Peter Langer; Alexander Villinger

doi:10.1107/S160053681103217X

. 2011 Aug 17;67(Pt 9):o2336. doi: 10.1107/S160053681103217X

Ethyl 4-chloro-2′-fluoro-3-hydroxy-5-methylbiphenyl-2-carboxylate

Muhammad Adeel ^a,^*, Peter Langer ^b,^c, Alexander Villinger ^b

PMCID: PMC3200854 PMID: 22058957

Abstract

In the title compound, C₁₆H₁₄ClFO₃, the dihedral angle between the mean planes of the two benzene rings is 71.50 (5)°. Due to an intramolecular O—H⋯O hydrogen bond between the hydroxy group and the carbonyl O atom of the ethyl ester group, the ethyl ester group lies within the ring plane. The crystal structure is consolidated by intermolecular C—H⋯O and C—H⋯F interactions.

Related literature

For a related structure, see: Adeel et al. (2009 ▶). For synthetic procedures and the pharmacological relevance of 3-chlorosalicylates, see: Wolf et al. (2009 ▶).

Experimental

Crystal data

C₁₆H₁₄ClFO₃
M _r = 308.73
Triclinic,
a = 8.212 (4) Å
b = 9.780 (3) Å
c = 10.156 (3) Å
α = 71.18 (3)°
β = 76.41 (2)°
γ = 71.34 (2)°
V = 723.5 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.28 mm⁻¹
T = 173 K
0.31 × 0.18 × 0.08 mm

Data collection

Bruker APEXII KappaCCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ▶) T _min = 0.918, T _max = 0.978
12813 measured reflections
3773 independent reflections
2902 reflections with I > 2σ(I)
R _int = 0.028

Refinement

R[F ² > 2σ(F ²)] = 0.047
wR(F ²) = 0.139
S = 1.07
3773 reflections
195 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.87 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Data collection: APEX2 (Bruker, 2003 ▶); cell refinement: SAINT (Bruker, 2003 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S160053681103217X/pv2433sup1.cif

e-67-o2336-sup1.cif^{(18.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681103217X/pv2433Isup2.hkl

e-67-o2336-Isup2.hkl^{(181.2KB, hkl)}

Supplementary material file. DOI: 10.1107/S160053681103217X/pv2433Isup3.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
C7—H7C⋯O1ⁱ	0.98	2.59	3.473 (3)	150
C9—H9A⋯Fⁱⁱ	0.99	2.40	3.320 (3)	155
O1—H1⋯O2	0.82 (3)	1.77 (3)	2.521 (2)	153 (3)

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

Acknowledgments

Financial support from the Higher Education Commission of Pakistan (HEC) under the resource grant programme is gratefully acknowledged.

supplementary crystallographic information

Comment

Functionalized chloroarenes are of considerable pharmacological relevance. 3-Chlorosalicylates and related compounds are employed as pharmacological agents (Wolf et al., 2009).

In the title compound (Fig. 1), the dihedral angle between the mean planes of the two benzene rings is 71.50 (5)°. The ethyllester group lies within the ring plane due to an intramolecular hydrogen bond between the hydroxyl group and the carbonyl O atom of the ehtyllester group, O1—H1···O2. The crystal structure is consolidated by weak C7—H7C···O1 and C9—H9A···F intermolecular interactions.

Experimental

Experimental: The title compound was prepared according to a previously published procedure (Wolf et al. 2009). To a CH₂Cl₂ (6 ml) solution of 1-(2-fluoro-phenyl)-3-trimethylsilanyloxy-but-2-en-1-one (720 mg, 2.8 mmol) and 4-chloro-1-ethoxy-1,3-bis-trimethylsilanyloxy-buta-1,3-diene (970 mg, 3.1 mmol) was added TiCl₄ (0.34 ml, 3.1 mmol) at 195 K under argon atmosphere. The solution was allowed to warm to ambient temperature within 20 hrs. To the solution was added a saturated solution of NaHCO₃ (15 mL). The organic and the aqueous layers were separated and the latter was extracted with diethyl ether (3 × 20 ml). The filtrate was concentrated in vacuo and the residue was purified by chromatography (silica gel, EtOAc / n-heptane = 1:4). The title compound was isolated as a colorless crystalline solid. Yield: 390 mg, 45%. Mp. = 352 K. Crystallization from a saturated dichloromethane/methanol (9:1) solution at ambient temperature gave colorless crystals.