3-Mesityl-2-oxo-1-oxaspiro­[4.4]non-3-en-4-yl 4-chloro­benzoate

Ming-Hua Ji; Min Xia; Guo-Nian Zhu; Jin-Hao Zhao

doi:10.1107/S1600536809006503

. 2009 Mar 6;65(Pt 4):o705. doi: 10.1107/S1600536809006503

3-Mesityl-2-oxo-1-oxaspiro[4.4]non-3-en-4-yl 4-chlorobenzoate

Ming-Hua Ji ^a, Min Xia ^a, Guo-Nian Zhu ^b, Jin-Hao Zhao ^b,^*

PMCID: PMC2969026 PMID: 21582443

Abstract

The title compound, C₂₄H₂₃ClO₄, is a potent insecticide and miticide. The five-membered cyclopentane ring displays an envelope conformation with the atom at the flap position 0.611 (2) Å out of the mean plane formed by the other four atoms. The furan ring makes dihedral angles of 71.3 (2) and 81.9 (2)°, respectively, with the 2,4,6-trimethylphenyl and 4-chlorophenyl rings. The dihedral angle between the two benzene rings is 76.6 (1)°. In the crystal, molecules are linked through weak intermolecular C—H⋯O hydrogen bonds, forming chains running along the c axis.

Related literature

For a related insecticide, see: Bayer, (1995 ▶). For a related methylbutyrate structure, see: Yu et al. (2009 ▶). For the extinction correction, see: Larson (1970 ▶).

Experimental

Crystal data

C₂₄H₂₃ClO₄
M _r = 410.90
Monoclinic,
a = 6.4880 (2) Å
b = 22.9397 (8) Å
c = 14.6305 (6) Å
β = 91.533 (1)°
V = 2176.72 (14) Å³
Z = 4
Mo Kα radiation
μ = 0.20 mm⁻¹
T = 296 K
0.62 × 0.48 × 0.34 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T _min = 0.867, T _max = 0.934
33470 measured reflections
4926 independent reflections
3235 reflections with F ² > 2σ(F ²)
R _int = 0.030

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.092
S = 1.00
4926 reflections
263 parameters
H-atom parameters constrained
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Data collection: PROCESS-AUTO (Rigaku, 1998 ▶); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004 ▶); program(s) used to solve structure: SIR97 (Altomare et al., 1993 ▶); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: CrystalStructure.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809006503/si2154sup1.cif

e-65-0o705-sup1.cif^{(21.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809006503/si2154Isup2.hkl

e-65-0o705-Isup2.hkl^{(241.3KB, 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
C24—H242⋯O2ⁱ	0.97	2.57	3.475 (2)	155

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors are grateful for support from the National Natural Science Foundation of China (No. 30700532) and the Science and Technology Project of Zhejiang Province (No. 2008C02007-3, 2008C21029). They also thank Professor Jian-Ming Gu for help with the analysis of the crystal data.

supplementary crystallographic information

Comment

4-hydroxyl-3-(2,4,6-trimethylphenyl)-1-oxaspiro[4,4]non-3-en-2-one (HTPO) is a key intermediate of Spiromesifen, which is an efficient insecticide and miticide, developed by Bayer company (Bayer, 1995). As part of our continuing interest in the design and synthesis of the new insecticide and miticide, we have isolated the title compound (Fig. 1), by the condensation reaction of 4-chlorophenyl- acetylchloride and HTPO as colorless crystals. The molecule contains two six-membered rings and two five-membered rings. Atoms C1, C2, C12, C20, O1 and O2 are coplanar, the largest deviation being 0.011 (11) Å for O1. As expected, C2=C12, C1=O2 and C13=O4 are typical double bonds with bond distances of 1.317 (2), 1.202 (2) and 1.195 (3) Å suggests that C2, C12 and C13 atoms are sp² hybridized. The bond distance of C1—C2 is 1.475 (2) Å, suggesting that the carbonyl group on C1 has formed a conjugate system with double bond on C2 and C12. In the crystal, molecules are linked through weak intermolecular C—H···O hydrogen bonds (Table 1), forming chains running along the c axis (Fig. 2), in contrast to the related 3-mesityl-2-oxo-1-oxaspiro[4.4]non-3-en-4-yl 2-(chlorophenyl)-3-methyl- butyrate structure, where intermolecular C—H···Cl hydrogen bonds forming chains along the screw axis direction b (Yu et al. 2009).

Experimental

4-hydroxyl-3-(2,4,6-trimethylphenyl)-1-oxaspiro[4,4]non-3-en-2-one (0.272 g, 1 mmol) and triethylamine (0.152 g, 1.5 mmol) were dissolved in dry dichloromethane (15 ml) with stirring. 4-chlorophenylacetyl chloride (0.210 g, 1.2 mmol) was added dropwise to the mixture in a water bath. The mixture was stirred at 293–298 K for 5 h, and then 1% aqueous HCl was added. The organic layer was washed to neutral with water and dried via Na₂SO₄. After filtered and concentrated, the organic residue was purified by silica gel column chromatography, eluted with ethyl acetate-petroleum ether (1:3. v/v) to give a white solid (yield 81%, 0.334 g), which was then recrystallized from acetone/ethanol (1:2, v/v) to give colourless blocks.