Ethyl 4-(4-bromo­phen­yl)-6-(4-ethoxy­phen­yl)-2-oxocyclo­hex-3-enecarboxyl­ate

Amir Badshah; Aurangzeb Hasan; Cecilia R Barbarín

doi:10.1107/S1600536809003523

. 2009 Feb 6;65(Pt 3):o467. doi: 10.1107/S1600536809003523

Ethyl 4-(4-bromophenyl)-6-(4-ethoxyphenyl)-2-oxocyclohex-3-enecarboxylate

Amir Badshah ^a, Aurangzeb Hasan ^a,^*, Cecilia R Barbarín ^b

PMCID: PMC2968510 PMID: 21582138

Abstract

The title compound, C₂₃H₂₃BrO₄, is an intermediate in the synthesis of fused heterocycles. In the title molecule, the cyclohexene ring has a distorted half-chair conformation. The bromophenyl ring and the mean plane of the cyclohexene ring form a dihedral angle of 13.8 (3)°, whereas the benzene and cyclohexene rings are approximately perpendicular [88.44 (17)°]. There are only weak C—H⋯O and C—H⋯π intermolecular interactions.

Related literature

For applications of cyclohexenones, see: Eddington et al. (2000 ▶); Li & Strobel (2001 ▶); Luu et al. (2000 ▶); Padmavathi et al. (2000 ▶, 2001 ▶).

Experimental

Crystal data

C₂₃H₂₃BrO₄
M _r = 443.32
Monoclinic,
a = 12.792 (4) Å
b = 14.537 (4) Å
c = 12.114 (4) Å
β = 113.88 (2)°
V = 2059.8 (11) Å³
Z = 4
Mo Kα radiation
μ = 2.02 mm⁻¹
T = 298 (2) K
0.50 × 0.50 × 0.08 mm

Data collection

Bruker P4 diffractometer
Absorption correction: gaussian (XSCANS; Bruker, 1999 ▶) T _min = 0.246, T _max = 0.941
7765 measured reflections
3630 independent reflections
2088 reflections with I > 2σ(I)
R _int = 0.054
3 standard reflections every 97 reflections intensity decay: 6.4%

Refinement

R[F ² > 2σ(F ²)] = 0.059
wR(F ²) = 0.175
S = 1.01
3630 reflections
254 parameters
H-atom parameters constrained
Δρ_max = 0.44 e Å⁻³
Δρ_min = −0.41 e Å⁻³

Data collection: XSCANS (Bruker, 1999 ▶); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXTL-Plus (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL-Plus; molecular graphics: SHELXTL-Plus and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXTL-Plus.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809003523/gk2184sup1.cif

e-65-0o467-sup1.cif^{(21.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809003523/gk2184Isup2.hkl

e-65-0o467-Isup2.hkl^{(178KB, 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
C5—H5A⋯O1ⁱ	0.93	2.42	3.163 (6)	137
C8—H8A⋯O2ⁱⁱ	0.97	2.59	3.244 (6)	125
C15—H15B⋯O2	0.96	2.58	3.062 (13)	111
C23—H23A⋯Cgⁱⁱⁱ	0.96	2.90	3.741 (6)	147

Open in a new tab

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

Acknowledgments

AB is grateful to the Higher Education Commission of Pakistan for a PhD scholarship.

supplementary crystallographic information

Comment

Cyclohexenones are either prepared from natural sources or entirely via synthetic routes. The reason for their preparation is a variety of medical effects. The molecules provide anticonvulsant, antimalarial, antiinflamatory and cardiovascular effects (Eddington et al., 2000). Cyclohexenones are also important intermediates for many biologically active compounds (Padmavathi et al., 2001; Padmavathi et al., 2000). A series of novel compounds have been synthesized, known as cyclohexenoic long chain fatty alcohols, which are used in the treatment of neurological disorders (Luu et al., 2000). A number of their derivatives have fungicidal and antitumor activities (Li & Strobel, 2001).

In the title compound, C₂₃H₂₃BrO₄ (Scheme 1, Fig. 1), the two rings, i.e. bromophenyl [C1-C6] and the cyclohexene [C7-C12], are slightly twisted' with the dihedral angle of 13.8 (3)°. Cyclohexene [C7- C12], is approximately perpendicular to the benzene ring [C16-C21] [88.44 (17)°]. The title molecule has two asymmetric carbon atoms C9 and C12 that are in RS and SR configurations, respectively. The comformation of the cyclohexene ring is distorted half chair [Θ = 50.6 (10) and Φ = 138.9 (13)°, compared with the ideal values of Θ = 50.0 and Φ = 150.0°].

As indicated by intermolecular contacts. there are only weak intermolecular interactions X—H···O and C—H···π (Table 1). The crystal packing is shown in Fig. 2.

Experimental

Ethyl 4-(4-bromophenyl)-6-(4-ethoxyphenyl)-2-oxocyclhex-3-enecarboxylate was synthesized by refluxing ethyl acetoacetate (0.39 g, 0.40 ml, 3 mmol) with 1-(4-bromophenyl)-3-(4-ethoxyphenyl) prop-2-ene-1-one (3 mmol, 0.990 g) for 2 h in 10–15 ml of ethanol in presence of 0.5 ml 10% NaOH. The reaction mixture was then poured while having been stirred intensively into 200 ml of ice-cold water. The mixture was kept at room temperature until the reaction product separated as a solid, which was filtered off and recrystallized from ethanol (yield 65%, m.p. 400 K).