Methyl 5-hy­droxy-3-phenyl-1,2-oxazolidine-5-carboxyl­ate

Jia Ye; Ya-Nan Liu; Yu Cheng

doi:10.1107/S1600536812017576

. 2012 Apr 25;68(Pt 5):o1537. doi: 10.1107/S1600536812017576

Methyl 5-hydroxy-3-phenyl-1,2-oxazolidine-5-carboxylate

Jia Ye ^a,^*, Ya-Nan Liu ^a, Yu Cheng ^a

PMCID: PMC3344639 PMID: 22590401

Abstract

In the title compound, C₁₁H₁₃NO₄, the isoxazolidine ring has an envelope conformation with the O atom as the flap. In the crystal, molecules are liked via N—H⋯O and bifurcated O—H⋯(O,N) hydrogen bonds forming chains propagating along [010]. There are also C—H⋯O interactions present.

Related literature

For the use of isoxazolidine-containing compounds as building blocks in synthesis, see: Carrillo et al. (2006 ▶); Lv et al. (2010 ▶); Ibrahem et al. (2007 ▶); Sharma et al. (1999 ▶). For information on conjugation additions to α,β-unsaturated ketones, see: Wu et al. (2006 ▶). For standard bond-lengths see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₁₁H₁₃NO₄
M _r = 223.22
Monoclinic,
a = 11.8322 (3) Å
b = 6.0853 (1) Å
c = 15.8570 (3) Å
β = 101.864 (2)°
V = 1117.35 (4) Å³
Z = 4
Cu Kα radiation
μ = 0.85 mm⁻¹
T = 291 K
0.40 × 0.36 × 0.30 mm

Data collection

Oxford Gemini S Ultra diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009 ▶) T _min = 0.726, T _max = 0.784
10901 measured reflections
2165 independent reflections
1921 reflections with I > 2σ(I)
R _int = 0.034

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.097
S = 1.05
2165 reflections
151 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.12 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812017576/su2406sup1.cif

e-68-o1537-sup1.cif^{(17KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812017576/su2406Isup2.hkl

e-68-o1537-Isup2.hkl^{(104.3KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812017576/su2406Isup3.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
N1—H4⋯O1ⁱ	0.907 (18)	2.315 (18)	3.1158 (15)	147.0 (13)
O2—H9⋯O1ⁱ	0.82	2.51	3.0673 (13)	127
O2—H9⋯N1ⁱ	0.82	1.99	2.7826 (16)	162
C11—H11A⋯O3ⁱⁱ	0.96	2.54	3.480 (2)	166
C11—H11C⋯O2ⁱⁱⁱ	0.96	2.53	3.419 (2)	154

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

Acknowledgments

The authors thank the Testing Centre of Sichuan University for the diffraction measurements and China West Normal University for suport.

supplementary crystallographic information

Comment

Isoxazolidines are interesting heterocyclic compounds that may be regarded as unusual constrained β-amino acids or as furanose mimetics, and have been exploited as analogues of natural products (Lv et al., 2010). Isoxazolidines are also applied in the synthesis of oligopeptides in the absence of coupling reagents (Carrillo et al., 2006) and used as building blocks in organic synthesis (Ibrahem et al., 2007; Sharma et al., 1999).

Nitrogen containing nucleophiles such as hydroxylamines and hydrazoic acid are widely employed in conjugation additions to α,β-unsaturated ketones (Wu et al., 2006). The title compound is a Michael addition product from the transformation of hydroxylamine to an α,β-unsaturated ketone ester. We report herein on the crystal structure of the title compound.

The molecular structure of the title molecule is shown in Fig. 1. The bond lengths (Allen et al., 1987) and angles are normal. The isoxazolidine ring possesses an envelope conformation with atom O1 as the flap.

In the crystal, molecules are linked via N—H···O and bifurcated O—H···O,N hydrogen bonds to form chains along the b axis (Table 1). These chains are linked via C-H···O interactions (Table 1).

Experimental

To the solution of (E)-methyl 2-oxo-4-phenylbut-3-enoate (0.019 g, 0.1 mmol) and hydroxylamine hydrochloride (0.07 g, 0.1 mmol) in dichloromethane (1 mL) was added triethylamine (0.012 g, 0.12mmol) at room temperature. The reaction mixture was stirred for 24 h at 273 K. The solvent was then removed under reduced pressure, and the residue was purified through column chromatography (petroleum ether: ethyl acetate = 3:1(V/V)). Single crystals, suitable for X-ray diffraction, were obtained by slow evaporation of an ethyl acetate solution at room temperature for 2 d.