4-Tosyl-1-oxa-4-aza­spiro­[4.5]deca-6,9-dien-8-one

Ping Yin; Wen-Wen Zhang; Hai-Bin Yin; Ling He; Wen-Cai Huang

doi:10.1107/S1600536809001524

. 2009 Feb 28;65(Pt 3):o649. doi: 10.1107/S1600536809001524

4-Tosyl-1-oxa-4-azaspiro[4.5]deca-6,9-dien-8-one

Ping Yin ^a, Wen-Wen Zhang ^a, Hai-Bin Yin ^b, Ling He ^a, Wen-Cai Huang ^c,^*

PMCID: PMC2968445 PMID: 21582297

Abstract

In the molecule of the title compound, C₁₅H₁₅NO₄S, the two six-membered rings are almost parallel to each other [dihedral angle = 1.87 (9)°] and perpendicular to the mean plane through the five-membered ring [dihedral angles of 89.98 (10) and 89.04 (10)°]. The crystal structure is stabilized by intermolecular C—H⋯O hydrogen-bonding interactions.

Related literature

For general background to the catalytic oxidation of phenol derivatives using transition metal complexes, see: Bernini et al. (2006 ▶); Cheung et al. (2005 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C₁₅H₁₅NO₄S
M _r = 305.34
Monoclinic,
a = 11.882 (3) Å
b = 14.973 (6) Å
c = 8.369 (5) Å
β = 107.00 (3)°
V = 1423.9 (11) Å³
Z = 4
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 294 K
0.30 × 0.25 × 0.20 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
Absorption correction: none
2996 measured reflections
2625 independent reflections
1526 reflections with I > 2σ(I)
R _int = 0.008
3 standard reflections every 300 reflections intensity decay: 1.6%

Refinement

R[F ² > 2σ(F ²)] = 0.046
wR(F ²) = 0.119
S = 1.02
2625 reflections
192 parameters
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Data collection: DIFRAC (Gabe & White, 1993 ▶); cell refinement: DIFRAC; data reduction: NRCVAX (Gabe et al., 1989 ▶); 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: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809001524/rz2288sup1.cif

e-65-0o649-sup1.cif^{(16.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809001524/rz2288Isup2.hkl

e-65-0o649-Isup2.hkl^{(131.5KB, 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
C2—H2⋯O4ⁱ	0.93	2.48	3.211 (4)	134
C15—H15B⋯O2ⁱⁱ	0.96	2.57	3.520 (5)	171

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

Acknowledgments

This work was financially supported by the Industry–Academia–Research Combination Project of the Ministry of Education of China and Guangdong Province (No.2007B090400016)

supplementary crystallographic information

Comment

In the course of our studies aimed to prepare a substituted quinone from the corresponding aromatic ether by catalytic oxidation using transition metal complexes (Cheung et al., 2005; Bernini et al.,2006), the title compound was unexpectedly obtained in about 70% yield. In the molecule of the title compound (Fig. 1) the C1–C6 and C9–C14 six-membered rings are almost parallel to each other(dihedral angle 1.87 (9)°) and perpendicular to the mean plane through the O1/N1/C1/C7/C8 ring, forming dihedral angles of 89.98 (10) and 89.04 (10)°, respectively. The five-membered ring adopts an envelope conformation, with puckering parameters Q2 = 0.269 (3) Å and φ2 =104.4 (6)° ((Cremer & Pople, 1975). The crystal structure (Fig. 2) is enforced by intermolecular C—H···O hydrogen bonds (Table 1).

Experimental

A solution of 2-phenoxyethyl-p-toluenesulfon amide (1 mmol) and indobenzene diacetate (1.5 mmol) in dichloromethane was charged in a reaction flask and 4 A molecular sieves was added. Then, the mixture was stirred at 303 K under a nitrogen atmosphere for 4 h. After cooling to room temperature, the resulting mixture was filtered and the solvent was removed under vacuo. The residue was purified by flash column chromatography on silica gel with petroleum ether/ethyl acetate (5:1 v/v) as the eluent. Colorless crystals suitable for X-ray analysis were obtained by slow evaporation in a cyclohexane/ether solution (5:1 v/v) at room temperature.