3-Mesityl-2-oxo-1-oxaspiro­[4.4]non-3-en-4-yl 2-(4-chloro­phen­yl)-3-methyl­butyrate

Chuan-Ming Yu; Yong Zhou; Jing-Li Cheng; Jin-Hao Zhao

doi:10.1107/S1600536808043043

. 2008 Dec 20;65(Pt 1):o183. doi: 10.1107/S1600536808043043

3-Mesityl-2-oxo-1-oxaspiro[4.4]non-3-en-4-yl 2-(4-chlorophenyl)-3-methylbutyrate

Chuan-Ming Yu ^a, Yong Zhou ^a, Jing-Li Cheng ^b, Jin-Hao Zhao ^b,^*

PMCID: PMC2968092 PMID: 21581638

Abstract

In the title compound, C₂₈H₃₁ClO₄, the five-membered cyclopentyl ring displays an envelope conformation with the atom at the flap position 0.519 (3) Å out of the mean plane formed by the other four atoms. The furan ring makes dihedral angles of 72.9 (1) and 82.4 (1)°, respectively, with the trimethyl- and chlorophenyl rings. The dihedral angle between the two benzene rings is 15.3 (1)°. In the crystal, molecules are linked through intermolecular C—H⋯Cl hydrogen bonds, forming a chain running along the b axis.

Related literature

For related compounds, see: Holmstead et al. (1978 ▶); Bayer Aktiengesellschaft (1995 ▶).

Experimental

Crystal data

C₂₈H₃₁ClO₄
M _r = 467.00
Monoclinic,
a = 13.9224 (11) Å
b = 14.2735 (12) Å
c = 14.3209 (11) Å
β = 113.9567 (17)°
V = 2600.7 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.18 mm⁻¹
T = 296 (1) K
0.40 × 0.37 × 0.27 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T _min = 0.927, T _max = 0.953
25138 measured reflections
5906 independent reflections
2647 reflections with F ² > 2σ(F ²)
R _int = 0.054

Refinement

R[F ² > 2σ(F ²)] = 0.046
wR(F ²) = 0.101
S = 1.00
5906 reflections
299 parameters
H-atom parameters constrained
Δρ_max = 0.54 e Å⁻³
Δρ_min = −0.54 e Å⁻³

Data collection: PROCESS-AUTO (Rigaku, 1998 ▶); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ▶) and Larson (1970 ▶); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: CrystalStructure.

Supplementary Material

Crystal structure: contains datablocks General, I. DOI: 10.1107/S1600536808043043/is2366sup1.cif

e-65-0o183-sup1.cif^{(23.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808043043/is2366Isup2.hkl

e-65-0o183-Isup2.hkl^{(289.1KB, 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
C17—H173⋯Cl1ⁱ	0.96	2.80	3.624 (5)	144

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors thank the Natural Science Foundation of Zhejiang Province, China, for financial support (2008 C21029)

supplementary crystallographic information

Comment

2-(4-Chlorophenyl)-3-methylbutanoyl chloride is an intermediate in the synthesis of fenvalerate, an excellent insecticide (Holmstead et al., 1978). 4-Hydroxyl-3-(2,4,6-trimethylphenyl)-1-oxaspiro[4,4]non-3-en-2-one is the key intermediate in preparing highly efficient acaricide-Spiromesifen developed by Bayer company (BAYER Aktiengesellschaft, 1995). As part of our continuing interest in the new acaricide design and synthesis, We have isolated the product, (I), of the condensation reaction of 2-(4-chlorophenyl)-3-methylbutanoyl chloride and 4-hydroxyl-3-(2,4,6-trimethylphenyl)-1-oxaspiro[4,4]non-3-en-2-one as colorless crystals suitable for X-ray analysis.

The molecular structure of (I) is shown in Fig. 1. The molecule contains two six-membered rings and two five-membered rings. The dihedral angles between the (C9—C14) and (C23—C28) rings, the (C9—C14) and furan rings, and the (C23—C28) and furan rings, are 15.3 (1), 72.9 (1) and 82.4 (1)°, respectively. The cyclopentyl ring displays an envelope conformation with C3 atom at the flap position 0.519 (3) Å out of the mean plane formed by the other four atoms. The title molecules are linked through intermolecular hydrogen bond of C17—H173···Cl1, forming chains running along the b axis. As expected, C1—C8, C7—O2 and C18—O4 are typically double bonds with bond distances of 1.327 (2), 1.207 (2) and 1.189 (3) Å. The bond distance of C7—C8 is 1.480 (2) Å, suggesting that carbonyl group on C7 has formed conjugate system with double bond on C8 and C1.

Experimental

4-Hydroxyl-3-(2,4,6-trimethylphenyl)-1-oxaspiro[4,4]non-3-en-2-one (2.72 g, 10 mmol), 4-dimethylaminopyridine (0.58 g), triethylamine (1.31 g) and chloroform (100 ml) were added to a 250 ml round flask. Then the mixture was stirred and cooled to 273–278 K. Within 30 min 2-(4-chlorophenyl)-3-methylbutanoyl chloride (3.47 g) was added dropwise to the solution. The mixture was stirred at room temperature for 3 h and then 1% aqueous HCl was added. The organic layer was washed to neutral with water and dried over Na₂SO₄. After filtered and concentrated, the organic residue was purified by silica gel column chromatography, eluted with ethyl acetate–petroleum ether (1:30, v/v) to give a white solid (yield 79%, 3.69 g), which was then recrystallized from ethyl acetate/ethanol (1:1, v/v) to give colourless blocks.