Ethyl 6-(4-chloro­phen­yl)-4-(4-methoxy­phen­yl)-2-oxocyclo­hex-3-ene-1-carboxyl­ate

Hoong-Kun Fun; Samuel Robinson Jebas; K S Girish; Balakrishna Kalluraya

doi:10.1107/S1600536809016237

. 2009 May 7;65(Pt 6):o1235. doi: 10.1107/S1600536809016237

Ethyl 6-(4-chlorophenyl)-4-(4-methoxyphenyl)-2-oxocyclohex-3-ene-1-carboxylate

Hoong-Kun Fun ^a,^*,^‡, Samuel Robinson Jebas ^a,^§, K S Girish ^b, Balakrishna Kalluraya ^b

PMCID: PMC2969664 PMID: 21583102

Abstract

In the title compound, C₂₂H₂₁ClO₄, the cyclohex-3-ene unit adopts an envelope conformation in both independent molecules comprising the asymmetric unit. The two benzene rings are inclined to each other at a dihedral angle of 82.03 (5)° [86.37 (5)°]. In the crystal, the molecules interact via C—H⋯O, C—H⋯Cl and C—H⋯π interactions.

Related literature

For the biological activity of cyclohexenones, see: Hamon et al. (1996 ▶); Honda (2002 ▶); Keil et al. (1996 ▶). For green chemistry, see: Hoel & Nielsen (1999 ▶); Larhed et al. (1999 ▶). For ring puckering analysis, see: Cremer & Pople (1975 ▶). For stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C₂₂H₂₁ClO₄
M _r = 384.84
Monoclinic,
a = 11.9729 (3) Å
b = 8.1713 (2) Å
c = 39.2033 (8) Å
β = 98.990 (1)°
V = 3788.31 (15) Å³
Z = 8
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 100 K
0.57 × 0.40 × 0.17 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.882, T _max = 0.962
60118 measured reflections
14422 independent reflections
10971 reflections with I > 2σ(I)
R _int = 0.043

Refinement

R[F ² > 2σ(F ²)] = 0.072
wR(F ²) = 0.180
S = 1.16
14422 reflections
473 parameters
H-atom parameters constrained
Δρ_max = 1.03 e Å⁻³
Δρ_min = −0.96 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, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809016237/tk2440sup1.cif

e-65-o1235-sup1.cif^{(33.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809016237/tk2440Isup2.hkl

e-65-o1235-Isup2.hkl^{(690.8KB, 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
C11A—H11A⋯O1Bⁱ	0.98	2.53	3.492 (2)	167
C11B—H11B⋯O1Aⁱⁱ	0.98	2.53	3.501 (2)	170
C12A—H12B⋯O2B	0.97	2.51	3.450 (2)	162
C12B—H12C⋯O2Aⁱⁱⁱ	0.97	2.56	3.441 (2)	151
C15B—H15B⋯O4B^iv	0.93	2.59	3.485 (3)	163
C20B—H20D⋯Cl1A^iv	0.97	2.83	3.585 (2)	136
C22A—H22A⋯Cg1ⁱⁱ	0.97	2.83	3.666 (2)	146

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

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 also thanks Universiti Sains Malaysia for the Research University Golden Goose grant No. 1001/PFIZIK/811012.

supplementary crystallographic information

Comment

Cyclohexenones are important intermediates in the synthesis of a wide variety of biologically active simple, condensed and bridged heterocycles. These cyclohexenones are also found to possess various types of biological activity, e.g. herbicidal (Keil et al., 1996), in vitro inhibition of human platelet cylooxygenase (Hamon et al., 1996), as an HMG-CoA reductase inhibitor (Honda, 2002), and displays anti-obesity properties (Honda, 2002). Today green chemistry plays an important role in chemical research. The large number of publications clearly indicates the development of this area of chemistry (Hoel & Nielsen, 1999; Larhed et al., 1999).

The asymmetric unit of (I) (Fig. 1) comprises of two crystallographically independent molecules (A & B) with almost similar geometries. The cyclohex-3-ene unit in both the molecules adopt an envelope conformation with puckering parameters Q = 0.5107 (18) Å, θ = 124.6 (2)° and φ = 47.7 (2)° for molecule A, and Q = 0.50 (18) Å, θ = 56.0 (2)° and φ = 231.5 (2)° for molecule B (Cremer & Pople, 1975). The two benzene rings are inclined to each other forming dihedral angles of 66.82 (6)° (C1A—C6A:C13A—C18A) in molecule A and 73.68 (5)° (C1B—C6B: C13B—C18B) in molecule B.

Globally, the crystal packing comprises layers stabilized by C—H···O and C—H···Cl contacts (Fig. 2) together with C—H···π interactions (Table 1).

Experimental

1-(p-Methoxyphenyl)-3-(p-chlorophenyl)-2-propene-1-one (0.01 mol), potassium carbonate (0.04 mol), ethyl acetoacetate (0.02 mol) were ground in a mortar using a pestle for uniform mixing. The paste formed was transferred to a 50 mL beaker and placed in a microwave oven operating at 160 W for 5 mins. The product (I) was poured into cold water, filtered, dried and recrystallized from ethanol-dioxane mixture; m. pt. = 411 - 412 K.