(E)-Methyl 2-chloro-4-dicyclo­hexyl­amino-4-oxobut-2-enoate

Cai-Mei Liu; Fu-Ling Xue; Jian-Hua Fu; Zhao-Yang Wang

doi:10.1107/S1600536811027760

. 2011 Jul 16;67(Pt 8):o2051. doi: 10.1107/S1600536811027760

(E)-Methyl 2-chloro-4-dicyclohexylamino-4-oxobut-2-enoate

Cai-Mei Liu ^a, Fu-Ling Xue ^a, Jian-Hua Fu ^a, Zhao-Yang Wang ^a,^*

PMCID: PMC3213498 PMID: 22091077

Abstract

In the title compound, C₁₇H₂₆ClNO₃, both cyclohexyl rings have chair conformations. In the crystal, molecules are linked by weak intermolecular C—H⋯O hydrogen bonds.

Related literature

For the synthesis, see: Song et al. (2009 ▶). For the biological activity of 2(5H)-furanones, see: Lattmann et al. (2005 ▶); Rowland et al. (2007 ▶); Kim et al. (2002 ▶). For chemical, pharmaceutical and agrochemical applications of 3,4-amino-2(5H)-furanones, see: Kimura et al. (2000 ▶); Tanoury et al. (2008 ▶). For related structures, see: Lattmann et al. (1999 ▶, 2006 ▶).

Experimental

Crystal data

C₁₇H₂₆ClNO₃
M _r = 327.84
Monoclinic,
a = 8.8291 (19) Å
b = 10.533 (2) Å
c = 19.139 (4) Å
β = 92.955 (3)°
V = 1777.5 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 298 K
0.32 × 0.22 × 0.20 mm

Data collection

Bruker APEXII area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.931, T _max = 0.956
8635 measured reflections
3886 independent reflections
2457 reflections with I > 2σ(I)
R _int = 0.051

Refinement

R[F ² > 2σ(F ²)] = 0.053
wR(F ²) = 0.160
S = 1.02
3886 reflections
201 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); data reduction: SAINT; 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 datablock(s) global, I. DOI: 10.1107/S1600536811027760/lx2191sup1.cif

e-67-o2051-sup1.cif^{(20.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811027760/lx2191Isup2.hkl

e-67-o2051-Isup2.hkl^{(185.7KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811027760/lx2191Isup3.cml

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—H17A⋯O1ⁱ	0.96	2.44	3.323 (4)	153
C9—H9⋯O2ⁱⁱ	0.93	2.50	3.389 (3)	160

Open in a new tab

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

Acknowledgments

This work was supported by the National Natural Science Foundation of China (grant No. 20772035) and the Natural Science Foundation of Guangdong Province, China (grant No. 5300082).

supplementary crystallographic information

Comment

Molecules possessing 2(5H)-furanone moiety are useful heterocyclic compounds due to their valuable biological activities such as antibacterial, anti-inflammatory and antitumor (Lattmann et al., 2005; Rowland et al., 2007; Kim et al., 2002). The 5-alkoxy-3,4-dihalo-2(5H)-furanones being a kind of synthons are widely used in tandem Michael addition-elimination reactions (Song et al., 2009). The 4-amino-2(5H)-furanones exhibit an antibiotic activity against MRSA (Lattmann et al., 1999; Lattmann et al., 2006). Therefore, we are interested in the tandem Michael addition-elimination reaction of the synthon 3,4-dichloro-5-methoxyfuran-2(5H)-one with secondary amines in the present of potassium fluoride. However, we obtained an unanticipated product, (E)-methyl 2-chloro-4-(dicyclohexylamino)-4-oxobut-2-enoate, instead of the expected compound 3-chloro-4-(dicyclohexylamino)-5-methoxyfuran-2(5H)-one (Lattmann et al., 1999). Herein, we report the crystal structure of the title compound.

In the title compound (Fig. 1), the both cyclohexyl rings are in the chair form. The molecular packing (Fig. 2) is stabilized by weak intermolecular C—H···O hydrogen bonds; the first one between the H atom of the vinyl group and the O atom of the ester group (Table 1; C9—H9···O2ⁱⁱ), and a methyl H atom and the O atom of the amide group (Table 1; C17—H17A···O1ⁱ).

Experimental

The precursor 3,4-dichloro-5-methoxyfuran-2(5H)-one was prepared according to the literature procedure (Song et al., 2009). The solution of dicyclohexylamine (2.736 g, 3.0 mL) in tetrahydrofuran (3.0 mL) was added to a stirred solution of 3,4-dichloro-5-methoxyfuran-(5H)-one (36.39 mg, 2.0 mmol) and potassium fluoride (34.85 mg, 6.0 mmol) in tetrahydrofuran (3.0 mL) under nitrogen atmosphere. After being stirred at room temperature for 24 h, the solvent was removed under reduced pressure. The residual solid was dissolved in dichloromethane and then the combined organic layer was concentrated under reduced pressure. The residue was purified by silica gel column chromatography with the gradient mixture of petroleum ether and ethyl acetate to give the title compound (yield 22.6%). Single crystals suitable for X-ray diffraction were prepared by slow evaporation of a solution of the title compound in (insert proper solvent) at room temperature.