Ethyl 4-(4-methoxy­phen­yl)-2-oxo-6-phenyl­cyclo­hex-3-ene-1-carboxyl­ate

Hoong-Kun Fun; Samuel Robinson Jebas; Jyothi N Rao; B Kalluraya

doi:10.1107/S1600536808039093

. 2008 Nov 26;64(Pt 12):o2448. doi: 10.1107/S1600536808039093

Ethyl 4-(4-methoxyphenyl)-2-oxo-6-phenylcyclohex-3-ene-1-carboxylate

Hoong-Kun Fun ^a,^*, Samuel Robinson Jebas ^a,^‡, Jyothi N Rao ^b, B Kalluraya ^b

PMCID: PMC2960071 PMID: 21581416

Abstract

The asymmetric unit of the title compound, C₂₂H₂₂O₄, consists of two independent molecules (A and B) which differ significantly in the orientations of ethyl carboxylate groups. The phenyl ring in molecule B is disordered over two orientations with occupancies of 0.55 (2) and 0.45 (2). The cyclohexenone ring of both molecules adopts an envelope conformation. The dihedral angle between the two aromatic rings is 81.12 (7)° in molecule A and 70.8 (3)° in molecule B [57.5 (4)° in the minor disorder component]. The crystal structure is stabilized by weak intermolecular C—H⋯O hydrogen bonds and C—H⋯π interactions.

Related literature

For general background, see: Kalluraya & Rai (2003 ▶); Kalluraya & Rahiman (2003 ▶). For bond-length data, see: Allen et al. (1987 ▶). For ring puckering analysis, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C₂₂H₂₂O₄
M _r = 350.40
Triclinic,
a = 9.6095 (2) Å
b = 12.5386 (3) Å
c = 15.9704 (3) Å
α = 75.916 (1)°
β = 78.879 (1)°
γ = 88.413 (1)°
V = 1831.00 (7) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 100.0 (1) K
0.50 × 0.28 × 0.24 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.958, T _max = 0.980
57259 measured reflections
13169 independent reflections
9552 reflections with I > 2σ(I)
R _int = 0.032

Refinement

R[F ² > 2σ(F ²)] = 0.058
wR(F ²) = 0.169
S = 1.02
13169 reflections
528 parameters
144 restraints
H-atom parameters constrained
Δρ_max = 0.92 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808039093/ci2722sup1.cif

e-64-o2448-sup1.cif^{(35.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808039093/ci2722Isup2.hkl

e-64-o2448-Isup2.hkl^{(643.8KB, 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
C3A—H3AA⋯O2Bⁱ	1.00	2.57	3.4093 (18)	142
C5A—H5AA⋯O4Bⁱⁱ	0.95	2.55	3.3630 (17)	143
C8A—H8AA⋯O4Bⁱⁱ	0.95	2.31	3.2446 (18)	166
C14B—H14B⋯O2Aⁱ	0.95	2.58	3.500 (5)	163
C16A—H16A⋯O2Bⁱⁱⁱ	0.95	2.47	3.2789 (18)	143
C17B—H17B⋯O3A^iv	0.95	2.47	3.116 (9)	125
C21B—H21D⋯Cg1^v	0.98	2.85	3.811 (2)	167
C22B—H22D⋯Cg2^vi	0.98	2.87	3.644 (4)	137

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) ; (vi) . Cg1 and Cg2 are the centroids of the C13A–C18A and C13B–C18B rings, respectively.

Acknowledgments

HKF and SRJ thank the Malaysian Government and Universiti Sains Malaysia for the Science Fund grant No. 305/PFIZIK/613312. SRJ thanks Universiti Sains Malaysia for a post–doctoral research fellowship. HKF thanks Universiti Sains Malaysia for the Research University Golden Goose Grant No. 1001/PFIZIK/811012.

supplementary crystallographic information

Comment

Cyclohexenone is an organic compound which is a versatile intermediate used in the synthesis of a variety of chemical products such as pharmaceuticals and fragrances. The Robinson annulation is an organic reaction used to create a cyclic six-membered, β-unsaturated ketones. Different methods including solvent-free synthesis of these compounds have been reported (Kalluraya & Rai, 2003). Cyclohexenone and their derivatives are known for anti-inflammatory and analegesic activities (Kalluraya & Rahiman, 2003).

The asymmetric unit of the title compound consists of two independent molecules (Fig. 1). Bond lengths in the molecules (Fig. 1) are found to have normal values (Allen et al., 1987). The two independent molecules differ significantly in the orientations of ethyl carboxylate groups [C4A—C3A—C19A—O1A = 63.32 (14)° and C4B—C3B—C19B—O1B = 105.25 (13)°]. The phenyl ring in molecule B is disordered over two orientations. The cyclohexenone ring in both molecules adopts an envelope conformation, with puckering parameters Q = 0.494 (1) Å, θ = 52.1 (2)° and φ = 67.4 (2)° for molecule A, and Q = 0.429 (2) Å, θ = 130.1 (2)° and φ = 250.4 (3)° in molecule B (Cremer & Pople, 1975). The dihedral angle between the two aromatic rings is 81.12 (7)° in molecule A and 70.8 (3)° in molecule B [57.5 (4)° in the minor disorder component].

The crystal structure is stabilized by intermolecular weak C—H···O hydrogen bonds (Table 1) and C—H···π interactions (Fig 2).

Experimental

To a solution of 1-phenyl-3-anisyl-prop-2-en-1-one (0.01 mol) in dry acetone (25 ml), dry potassium carbonate (0.04 mol) and ethyl acetoacetate (0.02 mol) in dry acetone (25 ml) were added. The mixture was stirred at room temperature for overnight and was filtered. The solvent from the filtrate on evaporation gave a solid which was recrystallized from a mixture of ethanol-dioxane.