trans-5,6-Diphenyl­perhydro­pyran-2,4-dione

Laura C de Souza; Dennis de O Imbroisi; Carlos A De Simone; Mariano A Pereira; Valéria R S Malta

doi:10.1107/S1600536809000087

. 2009 Jan 8;65(Pt 2):o250. doi: 10.1107/S1600536809000087

trans-5,6-Diphenylperhydropyran-2,4-dione

Laura C de Souza ^a, Dennis de O Imbroisi ^a, Carlos A De Simone ^a,^*, Mariano A Pereira ^a, Valéria R S Malta ^a

PMCID: PMC2968273 PMID: 21581866

Abstract

In the title compound, C₁₇H₁₄O₃, the pyran ring adopts a boat conformation and the dihedral angle between the aromatic ring planes is 59.1 (1)°. In the crystal structure intermolecular C—H⋯O hydrogen bonds and C—H⋯π interactions link the molecules.

Related literature

For general background, see: Yen & Chen (1995 ▶); Soler-Rivas et al. (2000 ▶). For related structures and biological activity, see: Brand-William et al. (1995 ▶); Sánchez-Moreno et al. (1998 ▶); Souza et al. (2004 ▶). For the synthesis, see: Souza (2008 ▶). For geometric analysis, see: Cremer & Pople (1975 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₁₇H₁₄O₃
M _r = 266.28
Monoclinic,
a = 8.9940 (2) Å
b = 8.2310 (4) Å
c = 18.9040 (8) Å
β = 101.412 (2)°
V = 1371.79 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 295 K
0.30 × 0.30 × 0.18 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: none
5298 measured reflections
3113 independent reflections
2459 reflections with I > 2σ(I)
R _int = 0.017

Refinement

R[F ² > 2σ(F ²)] = 0.050
wR(F ²) = 0.131
S = 1.05
3113 reflections
181 parameters
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Data collection: COLLECT (Nonius, 2000 ▶); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO (Otwinowski & Minor, 1997 ▶) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809000087/bq2110sup1.cif

e-65-0o250-sup1.cif^{(18.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809000087/bq2110Isup2.hkl

e-65-0o250-Isup2.hkl^{(149.6KB, 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
C6—H6⋯O2ⁱ	0.98	2.44	3.380 (2)	161
C17—H17⋯O3ⁱⁱ	0.93	2.46	3.351 (3)	160
C3—H3B⋯Cg1ⁱ	0.97	2.97	3.681 (2)	131
C5—H5⋯Cg2ⁱⁱⁱ	0.98	2.96	3.830 (2)	149

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) . Cg1 and Cg2 are the centroids of the C7–C12 and C13–C18 rings, respectively.

Acknowledgments

This work has received partial support from CNPq, CAPES, FAPEAL, IM-INOFAR and FINEP.

supplementary crystallographic information

Comment

The free radicals generated in bioorganic redoxi processes induce oxidative damage in various components of the cells (e.g., lipids, proteins and nucleic acids) and their play a significant role in the development of life-limiting chronic diseases such as cancer, hypertension, arteriosclerosis, rheumatism, cataracts and other (Yen & Chen, 1995; Soler-Rivas et al.,2000). The dihydropyran-2,4-diones exhibit structural features present bin many biologically active natural products possessing important pharmacological activities (Brand-William et al.,1995; Sánchez-Moreno et al.,1998). As part of our continuing studies aimed at ascertaining the biological activity of this class, the title compound was synthetized (Souza, 2008) and its antioxidant activity analyzed in vitro, by measuring the decrease in absorbance at 515 nm that occurred when the 2,2-diphenyl-1-picryl-hydrazyl radical (DPPH) was reduced by the antioxidant. The spectrophotometric assay was used to determine the radical scavenging activity (Souza et al.,2004).

The ORTEP-3 (Farrugia, 1997) representation of the title compound (5,6-DPDP) is showing in (Fig. 1). Bond lengths and angles are in good agreement with the expected values reported in the literature (Allen et al., 1987). The pirane ring adopts a boat conformation and the calculated puckering parameters are: q₂ = 0.624 (1) Å, q₃ = 0.121 (1) Å, Q_T = 0.636 (1) Å, θ = 79.0 (1)° and φ = 287.5 (1)° (Cremer & Pople, 1975). The dihedral angle between planes passing through atoms C7—C12 and C13—C18 of the aromatic rings is 59.1 (1) °. In the crystal packing, molecules interact through two intermolecular C–H···O hydrogen bonds and two C—H···.π interactions, Fig. 2 and Table 1.

Experimental

The trans-5, 6-diphenyltetradehydropyran-2,4-dione has showed similar antioxidant activity at the positive control, the synthetic antioxidant BHT (2,6-di-tert-butyl-4-methylphenol) used as food conserving. The reduction percentage after 60 minutes to a solution of 20 nM of sample were 88% to 5,6-DPDP and 82% to BHT (Souza, 2008).The 5,6-DPDP was synthesized in one pot by preparation of the dianion of the ethyl 3-oxo-4-phenylbutanoate (NaH, n-butillithium, THF, -10° C), and alkylation reaction with benzaldehyde followed by ester hydrolysis (NaOH, H₂O, 12 h, RT) and lactonization in acidic medium (HCl, H₂O, 2 h, 0°C). The compound was purified by silica gel chromatography and the crystals for x-ray diffraction studies were grown by slow evaporation from a CHCl₃ solution.