Methyl 5-(2-bromo­acet­yl)-2-propoxybenzoate

Jiang Ke; Xu Guan-Hong; Li Fei

doi:10.1107/S1600536808016814

. 2008 Jun 7;64(Pt 7):o1242. doi: 10.1107/S1600536808016814

Methyl 5-(2-bromoacetyl)-2-propoxybenzoate

Jiang Ke ^a, Xu Guan-Hong ^a, Li Fei ^a,^*

PMCID: PMC2961638 PMID: 21202877

Abstract

The title compound, C₁₃H₁₅BrO₄, was synthesized from methyl 5-acetyl-2-hydroxybenzoate. With the exception of the ester group and some H atoms, the molecule is planar, the average deviation from planarity being 0.086 (5) Å. The dihedral angle between the phenyl ring and the ester group is 41.6 (3)°. Adjacent molecules are interconnected by C—H⋯O bonds, generating a layered structure.

Related literature

For related literature, see: Grisar et al. (1981 ▶); Gronnow et al. (2005 ▶); Watanabe et al. (1984 ▶).

Experimental

Crystal data

C₁₃H₁₅BrO₄
M _r = 315.16
Monoclinic,
a = 16.292 (3) Å
b = 10.534 (2) Å
c = 7.8160 (16) Å
β = 92.42 (3)°
V = 1340.2 (5) Å³
Z = 4
Mo Kα radiation
μ = 3.07 mm⁻¹
T = 293 (2) K
0.30 × 0.10 × 0.09 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: ψ scan(North et al., 1986 ▶) T _min = 0.459, T _max = 0.770
5055 measured reflections
2418 independent reflections
1255 reflections with I > 2σ(I)
R _int = 0.038
3 standard reflections every 200 reflections intensity decay: none

Refinement

R[F ² > 2σ(F ²)] = 0.067
wR(F ²) = 0.163
S = 1.01
2418 reflections
163 parameters
H-atom parameters constrained
Δρ_max = 0.58 e Å⁻³
Δρ_min = −0.57 e Å⁻³

Data collection: CAD-4 Software (Enraf–Nonius, 1989 ▶); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995 ▶); 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/S1600536808016814/kp2172sup1.cif

e-64-o1242-sup1.cif^{(15.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808016814/kp2172Isup2.hkl

e-64-o1242-Isup2.hkl^{(118.8KB, 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
C1—H1A⋯O1ⁱ	0.97	2.35	3.148 (9)	139
C8—H8A⋯O1ⁱ	0.93	2.59	3.500 (7)	165
C9—H9A⋯O2ⁱⁱ	0.96	2.61	3.534 (8)	162
C9—H9C⋯O3ⁱⁱⁱ	0.96	2.59	3.501 (8)	158
C13—H13A⋯O2^iv	0.97	2.59	3.484 (7)	154

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

Acknowledgments

We acknowledge staff of the Shanghai Institute of Materia Medica for their active cooperation in this work. We also thank the Instrument Analysis and Research Center of Nanjing University for the structural characterization.

supplementary crystallographic information

Comment

Methyl 5-acetyl-2-hydroxybenzoate is a common chemical intermediate, which can be easily obtained (Gronnow et al., 2005). It is widely used for the design and synthesis of biological compounds. Biological activities, such as antiulcer (Watanabe et al., 1984) and antihypertensive (Grisar et al., 1981) effects of methyl 5-acetyl-2-hydroxybenzoate derivatives have been reported. In our research, the title compound, (I) (Fig. 1) is an important intermediate used to synthesize variety of compounds, which might have an inhibitive effect on PDE5. Considerable attention has been devoted to the biological activities of methyl 5-acetyl-2-hydroxybenzoate derivatives, however, the crystal structure of the title compound has not been reported, yet. In this work, we present the crystal structure of the title compound.

The molecule is planar with the average deviation from the planarity of 0.086 (5) Å. However, the ester group is out of this plane. The dihedral angle between the phenyl and the ester group is 41.65°.

Packing analysis of the crystal structure shows that molecules are intercontacted by weak C—H···O interactions generating a layered structure (Table 1, Fig. 2).

Experimental

Methyl 5-acetyl-2-propoxybenzoate was obtained by the alkylation of methyl 5-acetyl-2-hydroxybenzoate. To a mixture of methyl 5-acetyl-2-propoxybenzoate (1 mmol), aluminium trichloride (0.15 mmol) and dichlormethane (15 mL), bromine (1.1 mmol) was added dropwise during 15 min at 273 K. The mixture was stirred at room temperature for 10 h. The resulting mixture was washed by aqueous solution of sodium thiosulfate, saturated salt solution, dried by anhydrous sodium sulfate, then the solvent was distilled off. Single crystals suitable for X-ray analysis (m.p. 379 K) were obtained by slow evaporation of solvent mixture of dichlormethane and methanol at room temperature.