(E)-Methyl 2-[(4-bromo-2-formyl­phen­oxy)meth­yl]-3-phenyl­acrylate

T Anuradha; G Sivakumar; P R Seshadri; M Bakthadoss

doi:10.1107/S1600536811047520

. 2011 Nov 16;67(Pt 12):o3322. doi: 10.1107/S1600536811047520

(E)-Methyl 2-[(4-bromo-2-formylphenoxy)methyl]-3-phenylacrylate

T Anuradha ^a, G Sivakumar ^b, P R Seshadri ^a,^*, M Bakthadoss ^b

PMCID: PMC3238972 PMID: 22199821

Abstract

The C=C double bond in the title compound, C₁₈H₁₅BrO₄, adopts an E configuration. The two rings are almost orthogonal to each other, making a dihedral angle of 82.8 (1)°. An intramolecular C—H⋯O hydrogen bond occurs. The crystal structure is stabilized by intermolecular C—H⋯O hydrogen bonds.

Related literature

For background to the synthesis, see: Bakthadoss et al. (2009 ▶). For related phenyl acrylate compounds, see: Wang & Kong (2006 ▶); Wang et al. (2011 ▶). For the biological properties of cinnamate, see: Sharma (2011 ▶).

Experimental

Crystal data

C₁₈H₁₅BrO₄
M _r = 375.21
Monoclinic,
a = 8.2798 (2) Å
b = 22.1975 (5) Å
c = 9.2537 (2) Å
β = 99.857 (2)°
V = 1675.64 (7) Å³
Z = 4
Mo Kα radiation
μ = 2.47 mm⁻¹
T = 293 K
0.20 × 0.20 × 0.20 mm

Data collection

Bruker SMART APEXII area–detector diffractometer
16035 measured reflections
4185 independent reflections
2619 reflections with I > 2σ(I)
R _int = 0.033

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.116
S = 0.99
4185 reflections
209 parameters
H-atom parameters constrained
Δρ_max = 0.68 e Å⁻³
Δρ_min = −0.53 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); 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 and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811047520/bt5689sup1.cif

e-67-o3322-sup1.cif^{(16.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811047520/bt5689Isup2.hkl

e-67-o3322-Isup2.hkl^{(200.9KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811047520/bt5689Isup3.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
C3—H3⋯O3	0.93	2.50	3.290 (3)	143
C2—H2⋯O1ⁱ	0.93	2.58	3.383 (4)	145
C13—H13⋯O1ⁱⁱ	0.93	2.55	3.291 (3)	137
C14—H14⋯O4ⁱⁱⁱ	0.93	2.39	3.302 (4)	167

Open in a new tab

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

Acknowledgments

BB thanks the TBI X-ray facility, CAS in Crystallography and Biophysics, University of Madras, India, for the data collection.

supplementary crystallographic information

Comment

The title compound is used as precursor to obtain the desired tetra cyclic chromenopyran pyrimidinedione compounds via a tandem Knoevenagel intra-molecular hetero-Diels-Alder reaction (Bakthadoss et al., 2009). Cinnamic acid and its derivatives including esters and carboxylic functional derivatives are used as important components in flavours, perfumes, synthetic indigo and pharmaceuticals. Cinnamate can act as optical filters or deactivate substrate molecules that have been excited by light for the protection polymers and organic substances. They are used as cosmetic grades and as sunscreen agents to reduce skin damage by blocking UV—A, B (Sharma, 2011). In view of this medicinal importance, the crystal structure determination of the title compound was carried out and the results are presented here.

The molecule adopts an E configuration about the C7 ═ C8 double bond. The dihedral angle between the best planes through the bromo-formylphenoxy group (C11—C18/O3/O4/Br) and phenylacrylate group (C1—C10/O1/O2) is 82.8 (1)°. The formyl group (C18/H18/04) is axial to the plane of the benzene ring to which it is attached as evidenced by the torsion angle C18—O4— C17— C12 of -7.9 (1)°.

From the bond length and bond angle analysis of the compound, the conformation of phenylacrylate group are comparable with corresponding values for the structure of ((E) – methyl 3-(3,4– dihydroxyphenyl)acrylate (Wang et al., 2011).

The crystal packing is stabilized by intramolecular and intermolecular C—H···O hydrogen bonding interaction (Table 1).

Experimental

A solution of 5-bromo-2-hydroxybenzaldehyde (1.0 mmol, 0.201 g) and potassium carbonate (2.0 mmol, 0.2293 g) in acetonitrile solvent (5 ml) was stirred for 15 minute at room temperature. To this solution, (Z)-methyl2-(bromomethyl)-3-phenylacrylate (1.2 mmol, 0.25 g) was added dropwise. After the completion of the reaction, as indicated by TLC, acetonitrile was evaporated. EtOAc (15 ml) and water (15 ml) were added to the crude mass. The organic layer was dried over anhydrous sodium sulfate. Removal of solvent led to the crude product, which was purified through pad of silica gel (100–200mesh) using ethylacetate and hexanes(1:9) as solvents. The pure title compound was obtained as a colourless solid (0.31 g, 83% yield). Recrystallization was carried out using ethylacetate as solvent.