(4S)-Benzyl 4-isopropyl-5-oxo-1,3-oxazolidine-3-carboxyl­ate

Wu, J.-B.; Lin, K.; Guo, J.-N.; Tang, G.; Zhao, Y.-F.

doi:10.1107/S1600536808004455

organic compounds

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ISSN: 2056-9890

Volume 64| Part 4| April 2008| Page o685

doi:10.1107/S1600536808004455

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(4S)-Benzyl 4-isopropyl-5-oxo-1,3-oxazolidine-3-carboxylate

Jian-Bin Wu,^a Kan Lin,^a Jian-Nan Guo,^a ^* Guo Tang ^a and Yu-Fen Zhao ^a

^aKey Laboratory for Chemical Biology of Fujian Province, Department of Chemistry, Xiamen University, Xiamen 361005, People's Republic of China
^*Correspondence e-mail: t12g21@xmu.edu.cn

(Received 25 January 2008; accepted 14 February 2008; online 12 March 2008)

In the crystal structure of the title compound, C₁₄H₁₇NO₄, obtained by the reaction of N-benzoxycarbonyl-L-valine, paraformaldehyde and 4-methylbenzenesulfonic acid, molecules are linked by C—H⋯O hydrogen bonds, generating linear chains parallel to the a axis. C—H⋯π interactions of stacked benzene rings also provide stability for the crystal structure.

Related literature

For related literature, see: Dorow & Gingrich (1999 ); Allen et al. (1987 ); Pavel et al. (1993 ); Reddy et al. (2000 ).

Experimental

Crystal data

C₁₄H₁₇NO₄
M_r = 263.29
Orthorhombic, P 2₁ 2₁ 2₁
a = 6.0528 (2) Å
b = 13.1581 (5) Å
c = 16.6778 (6) Å
V = 1328.28 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 153 (2) K
0.50 × 0.17 × 0.09 mm

Data collection

Bruker APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.953, T_max = 0.991
5718 measured reflections
1368 independent reflections
1100 reflections with I > 2σ(I)
R_int = 0.028

Refinement

R[F² > 2σ(F²)] = 0.028
wR(F²) = 0.062
S = 0.99
1368 reflections
172 parameters
H-atom parameters constrained
Δρ_max = 0.12 e Å⁻³
Δρ_min = −0.13 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg is the centroid of the C9–C14 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2A⋯O5ⁱ	0.97	2.32	3.258 (2)	163
C12—H12A⋯Cgⁱⁱ	0.93	3.37	3.963 (3)	124
Symmetry codes: (i) x-1, y, z; (ii) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, -z]$ .

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); 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 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808004455/cf2183sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808004455/cf2183Isup2.hkl

checkCIF report

Comment top

The title compound (I) belongs to a class of 5-oxazolidinone and has been used to synthesize dipeptides and a series of biologically active molecules (Dorow & Gingrich, 1999).

In the compound, the oxazolidine ring is formed by the reaction of N-benzoxycarbonyl-L-valine, paraformaldehyde, and 4-methylbenzenesulfonic acid. The phenyl and the oxazolidine rings make a dihedral angle of 49.7 (1) (Fig. 1). The absolute configuration (S) of the stereocentre C4 remains unchanged during the synthetic procedure. An X-ray crystal structure determination of the molecular structure of compound (I) was carried out to determine its conformation. The bond lengths are within normal ranges (Allen et al., 1987).

The packing is shown in Fig. 2. The occurrence of C—H···O hydrogen bond interactions lead to the formation of linear chains parallel to the a axis. The packing is further stabilized by C—H···π interactions of stacked benzene rings in the chains (Fig. 3), with typical geometry (Pavel et al., 1993).

Related literature top

For related literature, see: Dorow & Gingrich (1999); Allen et al. (1987); Pavel et al. (1993); Reddy et al. (2000).

Experimental top

The title compound was prepared by a method based on one described by Reddy et al. (2000). A mixture of N-benzoxycarbonyl-L-valine (7.53 g, 3 mmol), paraformaldehyde (1.8 g, 6 mmol) and 4-methylbenzenesulfonic acid (PTSA, 0.31 g, 1.8 mmol) in benzene (25 ml) was refluxed, using a Dean–Stark apparatus, for about 1 h. After cooling, the resulting mixture was washed with 0.3 M aqueous K₂CO₃ solution (30 ml) followed by saturated aqueous NaCl solution (30 ml). The organic layer was separated and dried with Mg₂SO₄, filtered and concentrated in vacuo to give the crude product as a white solid (5.12 g, 65%). Crystals suitable for X-ray diffraction were obtained from an ethanol solution.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); 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 (I) with the atom-labeling scheme, showing 50% probability displacement ellipsoids. H atoms are drawn as spheres of arbitrary radius.
	Fig. 2. The packing of the molecules, viewed down the a axis.
	Fig. 3. C—H···π interactions of (I). These and hydrogen bonds are shown as dashed lines. [Symmetry codes: (i) x - 1/2, -y + 1/2, -z; (ii) x + 1/2, -y + 1/2, -z.]

(4S)-Benzyl 4-isopropyl-5-oxo-1,3-oxazolidine-3-carboxylate top

Crystal data top

C₁₄H₁₇NO₄	F(000) = 560
M_r = 263.29	D_x = 1.317 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2839 reflections
a = 6.0528 (2) Å	θ = 2.9–32.6°
b = 13.1581 (5) Å	µ = 0.10 mm⁻¹
c = 16.6778 (6) Å	T = 153 K
V = 1328.28 (8) Å³	Needle, colourless
Z = 4	0.50 × 0.17 × 0.09 mm

Data collection top

Bruker APEX CCD diffractometer	1368 independent reflections
Radiation source: sealed tube	1100 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
Detector resolution: 16.1903 pixels mm^-1	θ_max = 25.0°, θ_min = 2.9°
ϕ and ω scans	h = −7→7
Absorption correction: multi-scan (SADABS; Bruker, 2001)	k = −14→15
T_min = 0.953, T_max = 0.991	l = −19→19
5718 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)] = 0.028	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.062	H-atom parameters constrained
S = 0.99	w = 1/[σ²(F_o²) + (0.0398P)²] where P = (F_o² + 2F_c²)/3
1368 reflections	(Δ/σ)_max < 0.001
172 parameters	Δρ_max = 0.12 e Å⁻³
0 restraints	Δρ_min = −0.13 e Å⁻³

Crystal data top

C₁₄H₁₇NO₄	V = 1328.28 (8) Å³
M_r = 263.29	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 6.0528 (2) Å	µ = 0.10 mm⁻¹
b = 13.1581 (5) Å	T = 153 K
c = 16.6778 (6) Å	0.50 × 0.17 × 0.09 mm

Data collection top

Bruker APEX CCD diffractometer	1368 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1100 reflections with I > 2σ(I)
T_min = 0.953, T_max = 0.991	R_int = 0.028
5718 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.028	0 restraints
wR(F²) = 0.062	H-atom parameters constrained
S = 0.99	Δρ_max = 0.12 e Å⁻³
1368 reflections	Δρ_min = −0.13 e Å⁻³
172 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

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	−0.4445 (2)	−0.27913 (11)	0.18553 (8)	0.0312 (3)
C2	−0.6151 (3)	−0.24832 (15)	0.13165 (12)	0.0315 (5)
H2A	−0.7493	−0.2318	0.1607	0.038*
H2B	−0.6473	−0.3017	0.0932	0.038*
N3	−0.5269 (3)	−0.15900 (11)	0.09160 (9)	0.0250 (4)
C4	−0.3046 (3)	−0.13532 (13)	0.11905 (11)	0.0242 (4)
H4A	−0.2008	−0.1412	0.0742	0.029*
O5	−0.1002 (2)	−0.23774 (11)	0.21593 (8)	0.0361 (4)
C5	−0.2637 (3)	−0.22044 (15)	0.17824 (11)	0.0261 (4)
O6	−0.7800 (2)	−0.17466 (10)	−0.00699 (9)	0.0348 (4)
C6	−0.6135 (3)	−0.13483 (15)	0.01957 (12)	0.0268 (5)
O7	−0.4976 (2)	−0.06146 (10)	−0.01706 (7)	0.0308 (3)
C8	−0.5807 (4)	−0.02766 (16)	−0.09484 (11)	0.0325 (5)
H8A	−0.6570	−0.0837	−0.1206	0.039*
H8B	−0.4566	−0.0089	−0.1286	0.039*
C9	−0.7346 (4)	0.06079 (15)	−0.08858 (11)	0.0287 (5)
C10	−0.9408 (4)	0.05173 (17)	−0.05121 (12)	0.0361 (5)
H10A	−0.9819	−0.0099	−0.0283	0.043*
C11	−1.0833 (4)	0.13326 (18)	−0.04812 (13)	0.0435 (6)
H11A	−1.2181	0.1269	−0.0218	0.052*
C12	−1.0276 (4)	0.22421 (19)	−0.08374 (14)	0.0482 (6)
H12A	−1.1247	0.2790	−0.0821	0.058*
C13	−0.8260 (4)	0.23316 (17)	−0.12188 (15)	0.0467 (6)
H13A	−0.7882	0.2941	−0.1466	0.056*
C14	−0.6801 (4)	0.15252 (15)	−0.12363 (12)	0.0365 (5)
H14A	−0.5438	0.1600	−0.1487	0.044*
C15	−0.2829 (3)	−0.02961 (14)	0.15749 (11)	0.0266 (5)
H15A	−0.3376	0.0202	0.1186	0.032*
C16	−0.4247 (4)	−0.02032 (17)	0.23247 (13)	0.0378 (5)
H16A	−0.4075	0.0464	0.2550	0.057*
H16B	−0.3791	−0.0703	0.2710	0.057*
H16C	−0.5769	−0.0312	0.2187	0.057*
C17	−0.0424 (3)	−0.00377 (16)	0.17484 (13)	0.0375 (5)
H17A	−0.0338	0.0625	0.1988	0.056*
H17B	0.0401	−0.0043	0.1257	0.056*
H17C	0.0182	−0.0532	0.2110	0.056*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0307 (8)	0.0288 (7)	0.0341 (7)	−0.0021 (7)	0.0004 (6)	0.0064 (6)
C2	0.0256 (11)	0.0325 (12)	0.0363 (11)	−0.0034 (10)	0.0005 (9)	0.0050 (10)
N3	0.0244 (9)	0.0243 (8)	0.0261 (9)	−0.0028 (7)	−0.0006 (7)	0.0013 (7)
C4	0.0224 (10)	0.0257 (10)	0.0244 (10)	−0.0005 (9)	0.0020 (8)	0.0008 (9)
O5	0.0331 (8)	0.0374 (8)	0.0378 (8)	0.0059 (7)	−0.0048 (7)	0.0036 (7)
C5	0.0274 (11)	0.0248 (10)	0.0261 (10)	0.0032 (9)	0.0033 (10)	−0.0028 (9)
O6	0.0328 (8)	0.0344 (8)	0.0372 (8)	−0.0060 (7)	−0.0088 (7)	−0.0012 (7)
C6	0.0267 (11)	0.0232 (11)	0.0304 (11)	0.0002 (10)	0.0014 (9)	−0.0039 (9)
O7	0.0325 (8)	0.0313 (7)	0.0286 (7)	−0.0057 (7)	−0.0029 (6)	0.0055 (6)
C8	0.0396 (12)	0.0346 (11)	0.0232 (10)	−0.0033 (10)	−0.0023 (9)	0.0027 (9)
C9	0.0375 (12)	0.0298 (11)	0.0187 (9)	−0.0039 (10)	−0.0045 (9)	0.0003 (9)
C10	0.0414 (13)	0.0358 (12)	0.0310 (11)	−0.0023 (11)	0.0010 (10)	0.0037 (10)
C11	0.0388 (13)	0.0509 (15)	0.0408 (13)	0.0027 (13)	−0.0022 (11)	−0.0038 (12)
C12	0.0554 (17)	0.0377 (14)	0.0514 (14)	0.0107 (13)	−0.0094 (13)	−0.0075 (12)
C13	0.0624 (16)	0.0283 (12)	0.0493 (13)	−0.0039 (12)	−0.0102 (13)	0.0045 (12)
C14	0.0430 (13)	0.0360 (12)	0.0305 (11)	−0.0070 (11)	−0.0022 (10)	0.0017 (11)
C15	0.0299 (11)	0.0212 (10)	0.0288 (10)	0.0002 (9)	−0.0049 (9)	0.0012 (8)
C16	0.0353 (12)	0.0364 (12)	0.0419 (12)	0.0045 (10)	0.0002 (10)	−0.0116 (10)
C17	0.0365 (13)	0.0365 (13)	0.0395 (12)	−0.0090 (11)	−0.0019 (10)	−0.0004 (10)

Geometric parameters (Å, º) top

O1—C5	1.345 (2)	C10—C11	1.378 (3)
O1—C2	1.428 (2)	C10—H10A	0.930
C2—N3	1.454 (2)	C11—C12	1.378 (4)
C2—H2A	0.970	C11—H11A	0.930
C2—H2B	0.970	C12—C13	1.381 (4)
N3—C6	1.349 (2)	C12—H12A	0.930
N3—C4	1.455 (2)	C13—C14	1.381 (3)
C4—C5	1.513 (3)	C13—H13A	0.930
C4—C15	1.537 (2)	C14—H14A	0.930
C4—H4A	0.980	C15—C16	1.522 (3)
O5—C5	1.194 (2)	C15—C17	1.523 (3)
O6—C6	1.219 (2)	C15—H15A	0.980
C6—O7	1.340 (2)	C16—H16A	0.960
O7—C8	1.461 (2)	C16—H16B	0.960
C8—C9	1.495 (3)	C16—H16C	0.960
C8—H8A	0.970	C17—H17A	0.960
C8—H8B	0.970	C17—H17B	0.960
C9—C14	1.381 (3)	C17—H17C	0.960
C9—C10	1.400 (3)

C5—O1—C2	111.63 (15)	C11—C10—H10A	119.7
O1—C2—N3	104.66 (15)	C9—C10—H10A	119.7
O1—C2—H2A	110.8	C10—C11—C12	120.5 (2)
N3—C2—H2A	110.8	C10—C11—H11A	119.8
O1—C2—H2B	110.8	C12—C11—H11A	119.8
N3—C2—H2B	110.8	C11—C12—C13	119.3 (2)
H2A—C2—H2B	108.9	C11—C12—H12A	120.4
C6—N3—C2	117.21 (16)	C13—C12—H12A	120.4
C6—N3—C4	126.09 (16)	C14—C13—C12	120.6 (2)
C2—N3—C4	111.61 (15)	C14—C13—H13A	119.7
N3—C4—C5	101.42 (15)	C12—C13—H13A	119.7
N3—C4—C15	113.81 (15)	C13—C14—C9	120.7 (2)
C5—C4—C15	112.56 (15)	C13—C14—H14A	119.7
N3—C4—H4A	109.6	C9—C14—H14A	119.7
C5—C4—H4A	109.6	C16—C15—C17	111.42 (17)
C15—C4—H4A	109.6	C16—C15—C4	111.55 (16)
O5—C5—O1	121.14 (18)	C17—C15—C4	111.28 (16)
O5—C5—C4	128.30 (19)	C16—C15—H15A	107.4
O1—C5—C4	110.55 (16)	C17—C15—H15A	107.4
O6—C6—O7	125.19 (18)	C4—C15—H15A	107.4
O6—C6—N3	122.92 (18)	C15—C16—H16A	109.5
O7—C6—N3	111.88 (17)	C15—C16—H16B	109.5
C6—O7—C8	116.37 (15)	H16A—C16—H16B	109.5
O7—C8—C9	112.93 (16)	C15—C16—H16C	109.5
O7—C8—H8A	109.0	H16A—C16—H16C	109.5
C9—C8—H8A	109.0	H16B—C16—H16C	109.5
O7—C8—H8B	109.0	C15—C17—H17A	109.5
C9—C8—H8B	109.0	C15—C17—H17B	109.5
H8A—C8—H8B	107.8	H17A—C17—H17B	109.5
C14—C9—C10	118.4 (2)	C15—C17—H17C	109.5
C14—C9—C8	120.14 (19)	H17A—C17—H17C	109.5
C10—C9—C8	121.37 (18)	H17B—C17—H17C	109.5
C11—C10—C9	120.6 (2)

C5—O1—C2—N3	−3.0 (2)	O6—C6—O7—C8	0.1 (3)
O1—C2—N3—C6	157.15 (15)	N3—C6—O7—C8	−178.52 (15)
O1—C2—N3—C4	0.8 (2)	C6—O7—C8—C9	92.1 (2)
C6—N3—C4—C5	−152.48 (17)	O7—C8—C9—C14	117.2 (2)
C2—N3—C4—C5	1.34 (19)	O7—C8—C9—C10	−66.2 (2)
C6—N3—C4—C15	86.4 (2)	C14—C9—C10—C11	−1.4 (3)
C2—N3—C4—C15	−119.80 (17)	C8—C9—C10—C11	−178.02 (19)
C2—O1—C5—O5	−176.54 (18)	C9—C10—C11—C12	1.8 (3)
C2—O1—C5—C4	4.0 (2)	C10—C11—C12—C13	−0.7 (4)
N3—C4—C5—O5	177.38 (19)	C11—C12—C13—C14	−0.8 (4)
C15—C4—C5—O5	−60.6 (3)	C12—C13—C14—C9	1.2 (3)
N3—C4—C5—O1	−3.20 (19)	C10—C9—C14—C13	−0.1 (3)
C15—C4—C5—O1	118.80 (17)	C8—C9—C14—C13	176.57 (19)
C2—N3—C6—O6	11.0 (3)	N3—C4—C15—C16	62.4 (2)
C4—N3—C6—O6	163.56 (17)	C5—C4—C15—C16	−52.3 (2)
C2—N3—C6—O7	−170.34 (15)	N3—C4—C15—C17	−172.49 (16)
C4—N3—C6—O7	−17.8 (2)	C5—C4—C15—C17	72.8 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2A···O5ⁱ	0.97	2.32	3.258 (2)	163
C12—H12A···Cgⁱⁱ	0.93	3.37	3.963 (3)	124

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

Experimental details

Crystal data
Chemical formula	C₁₄H₁₇NO₄
M_r	263.29
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	153
a, b, c (Å)	6.0528 (2), 13.1581 (5), 16.6778 (6)
V (Å³)	1328.28 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.50 × 0.17 × 0.09

Data collection
Diffractometer	Bruker APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.953, 0.991
No. of measured, independent and observed [I > 2σ(I)] reflections	5718, 1368, 1100
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.028, 0.062, 0.99
No. of reflections	1368
No. of parameters	172
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.12, −0.13

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), 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
C2—H2A···O5ⁱ	0.97	2.32	3.258 (2)	163.4
C12—H12A···Cgⁱⁱ	0.93	3.37	3.963 (3)	123.6

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

Acknowledgements

The authors acknowledge financial support from the Key Foundation of Science and Technology Project of Fujian Province, China (Key grant No. 2002H011).

References

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