Ethyl 6-r-(2-chlorophenyl)-2-oxo-4-phenyl­cyclohex-3-ene-1-t-carboxylate

N Anuradha; A Thiruvalluvar; K Pandiarajan; C Yuvaraj

doi:10.1107/S1600536808043055

. 2008 Dec 20;65(Pt 1):o191. doi: 10.1107/S1600536808043055

Ethyl 6-r-(2-chlorophenyl)-2-oxo-4-phenylcyclohex-3-ene-1-t-carboxylate

N Anuradha ^a, A Thiruvalluvar ^a,^*, K Pandiarajan ^b, C Yuvaraj ^b

PMCID: PMC2968099 PMID: 21581646

Abstract

In the title molecule, C₂₁H₁₉ClO₃, the cyclohexene ring adopts an envelope conformation, with all substituents equatorial. The plane through its five coplanar atoms makes dihedral angles of 12.75 (14) and 74.16 (8)° with the phenyl and benzene rings, respectively. The dihedral angle between the latter two rings is 81.73 (12)°. Intermolecular C—H⋯O hydrogen bonds and intramolecular C—H⋯Cl contacts are found in the crystal structure; a weak C—H⋯π interaction is also present.

Related literature

For synthetic applications and biological activities, see: Cokcer et al. (1995 ▶); Friedrich et al. (2006 ▶); Pandey et al.(2004 ▶); Rebacz et al. (2007 ▶). For related crystal structures, see: Guzei (2004 ▶); Shishkina et al. (2002 ▶).

Experimental

Crystal data

C₂₁H₁₉ClO₃
M _r = 354.81
Triclinic,
a = 8.0115 (3) Å
b = 11.3525 (4) Å
c = 11.6386 (4) Å
α = 62.261 (2)°
β = 77.975 (2)°
γ = 75.297 (2)°
V = 901.16 (6) Å³
Z = 2
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 293 (2) K
0.25 × 0.20 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T _min = 0.945, T _max = 0.956
17066 measured reflections
3885 independent reflections
2825 reflections with I > 2σ(I)
R _int = 0.028

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.137
S = 1.05
3885 reflections
227 parameters
H-atom parameters constrained
Δρ_max = 0.53 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT-NT (Bruker, 2004 ▶); data reduction: SAINT-NT; 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: PLATON (Spek, 2003 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808043055/wn2298sup1.cif

e-65-0o191-sup1.cif^{(23.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808043055/wn2298Isup2.hkl

e-65-0o191-Isup2.hkl^{(186.6KB, 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
C17—H17A⋯Cg1ⁱ	0.97	2.89	3.538 (3)	125
C5—H5⋯Cl2	0.98	2.56	3.0843 (19)	114
C33—H33⋯O16ⁱⁱ	0.93	2.58	3.296 (3)	134
C56—H56⋯O16ⁱⁱⁱ	0.93	2.45	3.308 (3)	154

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) . Cg1 is the centroid of the C51–C56 ring.

Acknowledgments

AT thanks the UGC, India, for the award of a Minor Research Project [File No. MRP-2355/06(UGC-SERO), Link No. 2355, 10/01/2007].

supplementary crystallographic information

Comment

Cyclohex-2-enone derivatives exhibit antifungal (Friedrich et al., 2006) and anticancer (Rebacz et al., 2007) activities. Cyclohex-2-enones have also been used in organic synthesis (Cokcer et al., 1995; Pandey et al., 2004).

Guzei (2004) has reported a crystal structure determination of 4,4,6,6-tetraphenylcyclohex-2-en-1-one, wherein the cyclohexenone ring is in a half-chair conformation. Shishkina et al. (2002) have reported the molecular structures of chloro-, methoxy- and methoxyphenyl-substituted (1R)-arylidene-p-(4-menthen)-3-ones. The cyclohexenone ring in these compounds has a sofa conformation.

The present X-ray diffraction study was undertaken to determine how the conformation of the system is affected by the substitution of a phenyl group at position 4, chlorophenyl group at position 6 and ethoxycarbonyl group at position 1 of the cyclohexenone ring.

In the title molecule, C₂₁H₁₉ClO₃, (Fig. 1), the cyclohexene ring adopts an envelope conformation, with all substituents equatorial. The plane through the five coplanar atoms C1/C2/C3/C4/C6 makes dihedral angles of 12.75 (14)° and 74.16 (8)° with the phenyl and benzene rings, respectively. The dihedral angle between the phenyl and benzene rings is 81.73 (12)°. C33—H33···O16(1 + x, -1 + y, z) and C56—H56···O16(-x, 1 - y, -z) intermolecular hydrogen bonds and a C5—H5···Cl2 intramolecular contact are found in the crystal structure. Furthermore, a C17—H17A···π(-1 + x, y, z) interaction involving the benzene (C51—C56) ring is also found (Fig. 2, Table 1).

Experimental

A mixture of o-chlorobenzylideneacetophenone (3.65 g, 0.015 mol), ethyl acetoacetate (2 ml, 0.015 mol) and sodium ethoxide (1 g, 0.015 mol) in absolute alcohol (50 ml) was refluxed for 14 h. After cooling, the reaction mixture was neutralized with 0.1 N HCl. It was than extracted with diethyl ether (3x20 ml). The organic layer was dried over anhydrous sodium sulfate, filtered and the solvents removed by rotary vacuum evaporation. A solid mass was obtained which was recrystallized from ethanol. Yield 2.22 g (61%).