(±)-Ethyl 6-(6-meth­oxy-2-naphth­yl)-4-(4-methyl­phen­yl)-2-oxocyclo­hex-3-ene-1-carboxyl­ate

Hongqi Li; A N Mayekar; B Narayana; H S Yathirajan; William T A Harrison

doi:10.1107/S1600536809016341

. 2009 May 7;65(Pt 6):o1186. doi: 10.1107/S1600536809016341

(±)-Ethyl 6-(6-methoxy-2-naphthyl)-4-(4-methylphenyl)-2-oxocyclohex-3-ene-1-carboxylate

Hongqi Li ^a,^*, A N Mayekar ^b, B Narayana ^c, H S Yathirajan ^b, William T A Harrison ^d

PMCID: PMC2969816 PMID: 21583059

Abstract

In the title compound, C₂₇H₂₆O₄, the dihedral angle between the naphthalene ring system and the benzene ring is 73.10 (5)°. In the crystal, a weak C—H⋯O interaction occurs. Two C—H groups of the cyclohexene ring are disordered over two sets of sites in a 0.796 (5):0.204 (5) ratio, which corresponds to partial overlap of the two enantiomeric molecules.

Related literature

For related structures, see: Fischer et al. (2007a ▶,b ▶, 2008 ▶).

Experimental

Crystal data

C₂₇H₂₆O₄
M _r = 414.48
Monoclinic,
a = 18.8013 (10) Å
b = 11.3604 (6) Å
c = 10.2356 (6) Å
β = 93.430 (2)°
V = 2182.3 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 296 K
0.44 × 0.38 × 0.22 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: none
26105 measured reflections
4269 independent reflections
3385 reflections with I > 2σ(I)
R _int = 0.024

Refinement

R[F ² > 2σ(F ²)] = 0.050
wR(F ²) = 0.147
S = 1.08
4269 reflections
292 parameters
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Data collection: SMART (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2006 ▶); 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.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809016341/dn2449sup1.cif

e-65-o1186-sup1.cif^{(26.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809016341/dn2449Isup2.hkl

e-65-o1186-Isup2.hkl^{(209.2KB, 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
C26—H26A⋯O3ⁱ	0.97	2.42	3.332 (4)	157

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Symmetry code: (i) Inline graphic .

Acknowledgments

ANM thanks the University of Mysore for research facilities.

supplementary crystallographic information

Comment

The crystal structures of (8RS,9SR)-ethyl 4-(3-bromothien-2-yl)- 6-(2-furyl)-2-oxocyclohex-3-ene-1-carboxylate, (7RS,8SR)-ethyl 6-(1,3-benzodioxol-5-yl)-3-(3-bromo-2-thienyl)-2-oxocyclohex-3- ene-1-carboxylate and ethyl 4-(3-bromo-2-thienyl)-2-oxo-6- phenylcyclohex-3-ene-1-carboxylate have been reported (Fischer et al., 2007a,b, 2008). As part of our ongoing studies of cyclohexene carboxylates, we now describe the crystal structure of the title compound, (I) (Fig. 1).

The dihedral angle between the mean planes of the naphthalene (C14–C23) and benzene (C2–C7) rings is 73.10 (5)°. Atom C24 is almost coplanar with its attached benzene ring [displacement = 0.029 (3) Å]. The cyclohexene ring shows a distorted half-chair conformation, with atoms C8, C9, C10 and C13 almost coplanar (r.m.s. deviation = 0.009 Å) and C11 and C12 displaced by 0.209 (4) and -0.549 (4) Å, respectively. C11 and C12 are disordered over two sites in a 0.796 (5):0.204 (5) ratio and the minor disorder components show displacements from C8/C9/C10/C13 in the opposite sense: C11A = -0.72 (1) Å; C12A = 0.21 (1)%A. C11 and C12 are stereogenic centres: in the major disorder component, they have S and R conformations respectively. In the minor component, C11A and C12A have R and S conformations, respectively, thus the disorder corresponds to partial overlap of enantiomeric molecules. However, a fully racemic mixture is generated by crystal symmetry.

In the crystal, a weak C—H···O interaction occurs (Table 1), leading to chains of molecules propagating in [001]. There are no aromatic π···π stacking interactions in the title compound, the shortest intermolecular aromatic ring centroid–centroid separation being greater than 5.3 Å.

Experimental

Ethyl acetoacetate (0.65 g, 5 mmol) and (2E)-3-(6-methoxynaphthalen-2-yl)-1-(4-methylphenyl)prop-2- en-1-one (1.51 g, 5 mmol) were refluxed for 6 hr in 10–15 ml of ethanol in the presence of 0.8 ml of 10% NaOH. The reaction mixture was cooled to room temperature and the reaction mass was filtered and recrystallized using acetonitrile to yield colourless blocks of (I) (m.p. 431–433 K). Analysis: found (calculated): C%, 78.15 (78.24); H%, 6.27 (6.32).