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

Andreas Fischer; H S Yathirajan; B V Ashalatha; B Narayana; B K Sarojini

doi:10.1107/S1600536808002717

. 2008 Feb 6;64(Pt 3):o560. doi: 10.1107/S1600536808002717

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

Andreas Fischer ^a,^*, H S Yathirajan ^b, B V Ashalatha ^c, B Narayana ^c, B K Sarojini ^d

PMCID: PMC2960782 PMID: 21201903

Abstract

The title compound, C₁₉H₁₇BrO₃S, crystallizes with two molecules in the asymmetric unit. The methyl group of one molecule is disordered approximately equally over two positions. The dihedral angles between the thiophene and phenyl groups are 68.5 (2) and 67.5 (2)° in the two molecules.

Related literature

For related structures, see Fischer et al. (2007a ▶,b ▶). For related literature, see: House (1972 ▶); Tabba et al. (1995 ▶); Dimmock et al. (1999 ▶).

Experimental

Crystal data

C₁₉H₁₇BrO₃S
M _r = 405.31
Triclinic,
a = 8.8925 (8) Å
b = 11.713 (2) Å
c = 16.853 (2) Å
α = 94.317 (11)°
β = 98.436 (10)°
γ = 90.235 (13)°
V = 1731.3 (4) Å³
Z = 4
Mo Kα radiation
μ = 2.50 mm⁻¹
T = 130 K
0.30 × 0.17 × 0.05 mm

Data collection

Bruker Nonius KappaCCD diffractometer
Absorption correction: numerical (HABITUS; Herrendorf & Bärnighausen, 1997 ▶) T _min = 0.638, T _max = 0.843
40436 measured reflections
7898 independent reflections
6074 reflections with I > 2σ(I)
R _int = 0.073

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.089
S = 1.04
7898 reflections
438 parameters
H-atom parameters constrained
Δρ_max = 0.84 e Å⁻³
Δρ_min = −0.54 e Å⁻³

Data collection: COLLECT (Nonius, 1999 ▶); cell refinement: DIRAX (Duisenberg, 1992 ▶); data reduction: EVALCCD (Duisenberg et al., 2003 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2007 ▶); software used to prepare material for publication: publCIF (Westrip, 2008 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808002717/pv2059sup1.cif

e-64-0o560-sup1.cif^{(24.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808002717/pv2059Isup2.hkl

e-64-0o560-Isup2.hkl^{(386.4KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The Swedish research council (VR) is acknowledged for providing funding for the single-crystal diffractometer.

supplementary crystallographic information

Comment

Chalcones and the corresponding heterocyclic analogs are valuable intermediates in organic synthesis and exhibit a multitude of biological activities (Dimmock et al., 1999). An important feature of chalcones and their heteroanalogs is the ability to act as activated unsaturated systems in conjugated addition reactions of carbanions in the presence of basic catalysts (House, 1972). This type of reaction may be exploited with the goal of obtaining highly functionalized cyclohexene derivatives (Tabba et al., 1995). In view of the importance of these derivatives and continuing our efforts in this field (Fischer et al., 2007a; 2007b), a new derivative, the title compound, (I), has been prepared and its crystal structure is reported in this paper.

The structure of (I) contains two molecules in an asymmetric unit (Figs. 1 and 2). A methyl C-atom of methoxy group in the molecule 1, presented in Fig. 1 is disordered over two sites C19 and C19'. The geometry in the two molecules is unexceptional. The crystal packing is stabilized by van der Waals forces. The dihedral angles between the thiophene groups and phenyl groups in the two molecules are 68.5 (2) and 67.5 (2)°.

Experimental

(2E)-1-(3-Bromo-2-thienyl)-3-phenylprop-2-en-1-one (1.5 g, 5 mmol) and ethyl acetoacetate (0.65 g, 5 mmol) were refluxed for 2 hr in 10–15 ml e thanol in the presence of 0.8 ml 10% NaOH. The reaction mixture was cooled to room temperature and the reaction mass was filtered and recrystallized using methanol. Crystals were grown from acetone (m.p. 399–400 K).