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

Ye, J.; Liu, Y.-N.; Cheng, Y.

doi:10.1107/S1600536812017576

organic compounds

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Volume 68| Part 5| May 2012| Page o1537

doi:10.1107/S1600536812017576

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

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

^aCollege of Chemistry and Chemical Engineering, China West Normal University, Nanchong 637002, People's Republic of China
^*Correspondence e-mail: yejia407169849@163.com

(Received 7 April 2012; accepted 20 April 2012; online 25 April 2012)

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, P 2₁ /n
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 $[Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ) 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[F² > 2σ(F²)] = 0.042
wR(F²) = 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

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
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ ; (ii) x, y+1, z; (iii) -x+2, -y, -z+2.

Data collection: CrysAlis PRO (Oxford Diffraction, 2009 $[Oxford Diffraction (2009). CrysAlis PRO. Oxford Diffraction Ltd, Yarnton, England.]$ ); 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812017576/su2406sup1.cif

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

Supporting information file. DOI: 10.1107/S1600536812017576/su2406Isup3.cml

checkCIF report

Comment top

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).

Related literature top

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 top

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.

Computing details top

Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); 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 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title molecule, with the atom numbering. Displacement ellipsoids are drawn at the 30% probability level.

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

Crystal data top

C₁₁H₁₃NO₄	F(000) = 472
M_r = 223.22	D_x = 1.327 Mg m⁻³
Monoclinic, P2₁/n	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2yn	Cell parameters from 7888 reflections
a = 11.8322 (3) Å	θ = 3.8–71.9°
b = 6.0853 (1) Å	µ = 0.85 mm⁻¹
c = 15.8570 (3) Å	T = 291 K
β = 101.864 (2)°	Block, colourless
V = 1117.35 (4) Å³	0.40 × 0.36 × 0.30 mm
Z = 4

Data collection top

Oxford Gemini S Ultra diffractometer	2165 independent reflections
Radiation source: Enhance Ultra (Cu) X-ray Source	1921 reflections with I > 2σ(I)
Mirror monochromator	R_int = 0.034
Detector resolution: 15.9149 pixels mm^-1	θ_max = 72.1°, θ_min = 5.7°
ω scans	h = −14→13
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	k = −6→7
T_min = 0.726, T_max = 0.784	l = −19→18
10901 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.097	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ²(F_o²) + (0.0323P)² + 0.2933P] where P = (F_o² + 2F_c²)/3
2165 reflections	(Δ/σ)_max < 0.001
151 parameters	Δρ_max = 0.20 e Å⁻³
0 restraints	Δρ_min = −0.12 e Å⁻³

Crystal data top

C₁₁H₁₃NO₄	V = 1117.35 (4) Å³
M_r = 223.22	Z = 4
Monoclinic, P2₁/n	Cu Kα radiation
a = 11.8322 (3) Å	µ = 0.85 mm⁻¹
b = 6.0853 (1) Å	T = 291 K
c = 15.8570 (3) Å	0.40 × 0.36 × 0.30 mm
β = 101.864 (2)°

Data collection top

Oxford Gemini S Ultra diffractometer	2165 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	1921 reflections with I > 2σ(I)
T_min = 0.726, T_max = 0.784	R_int = 0.034
10901 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.097	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.20 e Å⁻³
2165 reflections	Δρ_min = −0.12 e Å⁻³
151 parameters

Special details top

Experimental. Absorption correction: (CrysAlisPro; Oxford Diffraction, 2009) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell esds are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.79693 (8)	0.06822 (15)	0.78232 (6)	0.0518 (3)
O2	0.82481 (9)	−0.20986 (16)	0.88556 (6)	0.0604 (4)
O3	1.04065 (10)	−0.0305 (2)	0.89858 (10)	0.0901 (5)
O4	0.96722 (8)	0.30583 (16)	0.89779 (7)	0.0641 (4)
N1	0.67179 (10)	0.0582 (2)	0.76513 (8)	0.0535 (4)
C1	0.3265 (2)	−0.1664 (6)	0.87113 (15)	0.1076 (12)
C2	0.4303 (2)	−0.2651 (4)	0.90278 (16)	0.1061 (10)
C3	0.53265 (17)	−0.1617 (3)	0.89530 (14)	0.0857 (7)
C4	0.53083 (13)	0.0405 (3)	0.85666 (10)	0.0629 (5)
C5	0.42474 (15)	0.1361 (4)	0.82446 (13)	0.0843 (7)
C6	0.32309 (17)	0.0312 (5)	0.83205 (16)	0.1066 (10)
C7	0.63963 (12)	0.1531 (2)	0.84333 (10)	0.0577 (5)
C8	0.74876 (13)	0.1335 (3)	0.91548 (10)	0.0613 (5)
C9	0.83371 (12)	0.0138 (2)	0.87205 (9)	0.0522 (4)
C10	0.96003 (12)	0.0898 (2)	0.89183 (9)	0.0553 (5)
C11	1.08082 (14)	0.4029 (3)	0.90958 (12)	0.0719 (6)
H1	0.25820	−0.23540	0.87650	0.1290*
H2	0.43250	−0.40170	0.92940	0.1270*
H3	0.60300	−0.23020	0.91670	0.1030*
H4	0.6564 (13)	−0.088 (3)	0.7630 (10)	0.062 (4)*
H5	0.42140	0.27220	0.79740	0.1010*
H6	0.25230	0.09750	0.81010	0.1280*
H7	0.62260	0.30950	0.83270	0.0690*
H8A	0.77780	0.27740	0.93560	0.0740*
H8B	0.73310	0.04990	0.96390	0.0740*
H9	0.84150	−0.27740	0.84510	0.0900*
H11A	1.07520	0.55870	0.91730	0.1080*
H11B	1.11280	0.37440	0.85970	0.1080*
H11C	1.12990	0.34020	0.95950	0.1080*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0502 (5)	0.0495 (6)	0.0538 (5)	−0.0012 (4)	0.0064 (4)	0.0012 (4)
O2	0.0731 (7)	0.0478 (6)	0.0577 (6)	−0.0060 (5)	0.0076 (5)	0.0027 (4)
O3	0.0607 (7)	0.0555 (7)	0.1493 (12)	0.0081 (6)	0.0105 (7)	−0.0051 (7)
O4	0.0539 (6)	0.0465 (6)	0.0867 (8)	−0.0031 (4)	0.0023 (5)	0.0018 (5)
N1	0.0496 (6)	0.0472 (7)	0.0608 (7)	−0.0018 (5)	0.0049 (5)	−0.0032 (5)
C1	0.0765 (14)	0.163 (3)	0.0888 (15)	−0.0423 (16)	0.0295 (11)	−0.0271 (16)
C2	0.1073 (18)	0.1077 (18)	0.1067 (16)	−0.0414 (14)	0.0303 (13)	0.0013 (13)
C3	0.0734 (11)	0.0809 (13)	0.1028 (14)	−0.0142 (10)	0.0179 (10)	0.0070 (11)
C4	0.0565 (8)	0.0657 (10)	0.0669 (9)	−0.0030 (7)	0.0136 (7)	−0.0112 (8)
C5	0.0627 (10)	0.0975 (14)	0.0922 (13)	0.0080 (10)	0.0149 (9)	−0.0081 (11)
C6	0.0572 (11)	0.153 (2)	0.1111 (18)	−0.0031 (13)	0.0211 (11)	−0.0198 (17)
C7	0.0593 (8)	0.0481 (8)	0.0653 (9)	0.0006 (6)	0.0120 (7)	−0.0059 (6)
C8	0.0593 (8)	0.0635 (9)	0.0605 (8)	−0.0063 (7)	0.0110 (7)	−0.0115 (7)
C9	0.0564 (8)	0.0463 (7)	0.0511 (7)	−0.0023 (6)	0.0046 (6)	−0.0007 (6)
C10	0.0566 (8)	0.0474 (8)	0.0588 (8)	0.0015 (6)	0.0044 (6)	0.0008 (6)
C11	0.0593 (9)	0.0615 (10)	0.0893 (12)	−0.0118 (8)	0.0026 (8)	0.0030 (8)

Geometric parameters (Å, º) top

O1—N1	1.4507 (16)	C5—C6	1.389 (3)
O1—C9	1.4384 (17)	C7—C8	1.544 (2)
O2—C9	1.3852 (16)	C8—C9	1.517 (2)
O3—C10	1.1897 (18)	C9—C10	1.534 (2)
O4—C10	1.3195 (16)	C1—H1	0.9300
O4—C11	1.445 (2)	C2—H2	0.9300
O2—H9	0.8200	C3—H3	0.9300
N1—C7	1.4866 (19)	C5—H5	0.9300
N1—H4	0.907 (18)	C6—H6	0.9300
C1—C2	1.367 (4)	C7—H7	0.9800
C1—C6	1.350 (5)	C8—H8A	0.9700
C2—C3	1.391 (3)	C8—H8B	0.9700
C3—C4	1.373 (3)	C11—H11A	0.9600
C4—C7	1.511 (2)	C11—H11B	0.9600
C4—C5	1.383 (3)	C11—H11C	0.9600

N1—O1—C9	105.41 (10)	O4—C10—C9	111.15 (11)
C10—O4—C11	117.46 (12)	C2—C1—H1	120.00
C9—O2—H9	109.00	C6—C1—H1	120.00
O1—N1—C7	104.68 (10)	C1—C2—H2	120.00
C7—N1—H4	109.2 (10)	C3—C2—H2	120.00
O1—N1—H4	103.7 (10)	C2—C3—H3	120.00
C2—C1—C6	120.0 (2)	C4—C3—H3	120.00
C1—C2—C3	120.2 (2)	C4—C5—H5	120.00
C2—C3—C4	120.62 (19)	C6—C5—H5	120.00
C3—C4—C5	118.15 (17)	C1—C6—H6	120.00
C3—C4—C7	122.23 (15)	C5—C6—H6	120.00
C5—C4—C7	119.50 (16)	N1—C7—H7	108.00
C4—C5—C6	120.8 (2)	C4—C7—H7	108.00
C1—C6—C5	120.3 (2)	C8—C7—H7	108.00
C4—C7—C8	117.92 (13)	C7—C8—H8A	111.00
N1—C7—C8	105.64 (11)	C7—C8—H8B	111.00
N1—C7—C4	108.18 (12)	C9—C8—H8A	111.00
C7—C8—C9	103.42 (12)	C9—C8—H8B	111.00
O1—C9—O2	111.23 (10)	H8A—C8—H8B	109.00
O1—C9—C8	104.16 (11)	O4—C11—H11A	109.00
C8—C9—C10	118.11 (12)	O4—C11—H11B	109.00
O1—C9—C10	102.52 (11)	O4—C11—H11C	109.00
O2—C9—C8	108.85 (12)	H11A—C11—H11B	109.00
O2—C9—C10	111.50 (11)	H11A—C11—H11C	109.00
O3—C10—O4	124.61 (14)	H11B—C11—H11C	109.00
O3—C10—C9	124.22 (12)

C9—O1—N1—C7	38.90 (12)	C3—C4—C7—C8	−38.7 (2)
N1—O1—C9—O2	76.12 (13)	C5—C4—C7—N1	−94.88 (18)
N1—O1—C9—C8	−40.98 (12)	C5—C4—C7—C8	145.43 (16)
N1—O1—C9—C10	−164.61 (9)	C4—C5—C6—C1	0.0 (4)
C11—O4—C10—O3	2.8 (2)	N1—C7—C8—C9	−3.24 (15)
C11—O4—C10—C9	−175.29 (12)	C4—C7—C8—C9	117.76 (14)
O1—N1—C7—C4	−148.04 (11)	C7—C8—C9—O1	26.43 (14)
O1—N1—C7—C8	−20.90 (13)	C7—C8—C9—O2	−92.30 (13)
C6—C1—C2—C3	0.4 (4)	C7—C8—C9—C10	139.28 (12)
C2—C1—C6—C5	−0.6 (4)	O1—C9—C10—O3	−103.08 (16)
C1—C2—C3—C4	0.4 (3)	O1—C9—C10—O4	75.06 (13)
C2—C3—C4—C5	−1.0 (3)	O2—C9—C10—O3	16.0 (2)
C2—C3—C4—C7	−176.90 (18)	O2—C9—C10—O4	−165.86 (11)
C3—C4—C5—C6	0.8 (3)	C8—C9—C10—O3	143.17 (16)
C7—C4—C5—C6	176.83 (19)	C8—C9—C10—O4	−38.69 (17)
C3—C4—C7—N1	81.02 (19)

Hydrogen-bond geometry (Å, º) top

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

Symmetry codes: (i) −x+3/2, y−1/2, −z+3/2; (ii) x, y+1, z; (iii) −x+2, −y, −z+2.

Experimental details

Crystal data
Chemical formula	C₁₁H₁₃NO₄
M_r	223.22
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	291
a, b, c (Å)	11.8322 (3), 6.0853 (1), 15.8570 (3)
β (°)	101.864 (2)
V (Å³)	1117.35 (4)
Z	4
Radiation type	Cu Kα
µ (mm⁻¹)	0.85
Crystal size (mm)	0.40 × 0.36 × 0.30

Data collection
Diffractometer	Oxford Gemini S Ultra diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)
T_min, T_max	0.726, 0.784
No. of measured, independent and observed [I > 2σ(I)] reflections	10901, 2165, 1921
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.097, 1.05
No. of reflections	2165
No. of parameters	151
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.12

Computer programs: CrysAlis PRO (Oxford Diffraction, 2009), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

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

Symmetry codes: (i) −x+3/2, y−1/2, −z+3/2; (ii) x, y+1, z; (iii) −x+2, −y, −z+2.

Acknowledgements

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

References

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