3-Acetyl-4-hydroxy­phenyl acrylate

V Azeezaa; G Usha; Sundari Bhaskaran; A Anthonysamy; S Balasubramanian

doi:10.1107/S1600536809032176

. 2009 Aug 29;65(Pt 9):o2271. doi: 10.1107/S1600536809032176

3-Acetyl-4-hydroxyphenyl acrylate

V Azeezaa ^a, G Usha ^a,^*, Sundari Bhaskaran ^a, A Anthonysamy ^b, S Balasubramanian ^b

PMCID: PMC2969962 PMID: 21577666

Abstract

In the title compound, C₁₂H₁₂O₄, the hydroxy O and the C and O atoms of the acetyl group are almost coplanar [maximum deviation = 0.0356 (1) Å] with the benzene ring. The dihedral angle between the benzene ring and the plane through the non-H atoms of the methacryloyloxy group is 86.1 (1)°. In the crystal structure, molecules are linked by two C—H⋯O hydrogen bonds, forming dimers with graph-set descriptor R ₂ ²(16). A strong intramolecular O—H⋯O hydrogen bond is also observed.

Related literature

For reference bond-length data, see: Allen et al. (1987 ▶). For graph-set notation, see Bernstein et al. (1995 ▶). For the biological properties of acetophenone derivatives, see Favier et al. (1998 ▶); Sala et al. (2001 ▶); Suksamrarn et al. (1997 ▶). Acetophenones are useful synthons for the preparation of a wide variety of polyphenolic compounds such as chalcones and flavones, see Parmar et al. (1996 ▶).

Experimental

Crystal data

C₁₂H₁₂O₄
M _r = 220.22
Monoclinic,
a = 8.8335 (3) Å
b = 11.9320 (3) Å
c = 11.3295 (3) Å
β = 111.277 (2)°
V = 1112.75 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 293 K
0.25 × 0.17 × 0.17 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T _min = 0.976, T _max = 0.983
14184 measured reflections
3437 independent reflections
2080 reflections with I > 2σ(I)
R _int = 0.026

Refinement

R[F ² > 2σ(F ²)] = 0.048
wR(F ²) = 0.161
S = 1.05
3437 reflections
155 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT and XPREP (Bruker, 2004 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809032176/wn2339sup1.cif

e-65-o2271-sup1.cif^{(16.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809032176/wn2339Isup2.hkl

e-65-o2271-Isup2.hkl^{(165.2KB, 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
O2—H2⋯O1	0.82	1.82	2.546 (2)	146
C5—H5A⋯O1ⁱ	0.93	2.57	3.483 (2)	166
C11—H11B⋯O4ⁱ	0.96	2.57	3.336 (2)	137

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors thank Professor D. Velmurugan, Centre for Advanced Study in Crystallography and Biophysics, University of Madras, for providing the computer facilities.

supplementary crystallographic information

Comment

Acetophenones are useful synthons for the preparation of a wide variety of polyphenolic compounds such as chalcones and flavones (Parmar et al., 1996). Acetophenone derivatives have shown many interesting biological properties such as anti-inflammatory (Sala et al., 2001; Favier et al., 1998), cytotoxic and choleretic (Suksamrarn et al., 1997) activities. Acetophenone is also used as a solvent for cellulose ethers and esters for the production of alcohol-soluble resins. 2-Hydroxy-4- methoxybenzophenone is used on an industrial scale as an ultraviolet absorber in cosmetics and plastics. 2-Hydroxyl-4,6-dimethoxyacetophenone was isolated from the leaves of the peperomia glabella family. Peperomia glabella is an epiphyte used in Venezuelan folk medicine as an anti-asthmatic.

The bond lengths C7—C8, C9—C10 and C10—C11 [1.495 (1), 1.476 (2) and 1.479 (1) Å] are comparable with standard values (Allen et al., 1987). The carbonyl group bond length C7—O1 [1.235 (2) Å] is longer than C9—O4 [1.185 (2) Å]. This may be a result of O1 being involved in intramolecular and intermolecular hydrogen bonds; this would tend to lengthen the C7—O1 bond.

O2, C7, O1 and C8 are coplanar with the benzene ring. The angle between the benzene ring and the plane through O3, C9, O4, C10, C11 and C12 is 86.1 (1)° (Fig. 1).

The molecular structure of the compound is stabilized by a weak intramolecular O—H···O hydrogen bond and the crystal packing is stabilized by intermolecular C—H···O hydrogen bonds. The molecule at (x, y, z) is linked to the symmetry-related molecule at (-1/2 + x, 1/2 - y, -1/2 + z), forming a dimer with graph set descriptor R₂²(16) (Bernstein et al., 1995). Propagation of these dimer units generates an infinite molecular chain along the crystallographic c axis. Fig. 2 shows the crystal packing of the compound, viewed approximately down the a axis.

Experimental

2,5-Dihydroxyacetophenone (26.31 mmol, 4.0 g), K₂CO₃ (31.55 mmol, 4.36 g) and 150 ml of dry acetone were taken up in a 250 ml round bottomed flask and the temperature was maintained at 0 °C. A solution of methacryloyl chloride (26.80 mmol, 2.8 ml) in 20 ml of dry acetone was then added dropwise to the mixture, with constant stirring for 30 min. After the addition was complete the reaction mixture was stirred for another 6 h. The salt formed during the reaction was filtered and the filtrate was washed with water and dried over anhydrous MgSO₄. The filtrate was concentrated under reduced pressure and the crude product was purified by column chromatography (silica) using a hexane/ethyl acetate mixture (90:10). The product was collected and recrystallized from chloroform to give a crystalline white solid. Yield: 4.5 g (77%); Mp: 65–66 °C.