(R)-[(R)-3-Benzyl-2-oxooxazolidin-4-yl][4-(methyl­sulfon­yl)phen­yl]methyl acetate

Feng Li; Ming-Zhong Zhao; Chun-Hua Jin; Jian-Wei Zou

doi:10.1107/S1600536814009106

. 2014 Apr 26;70(Pt 5):o606. doi: 10.1107/S1600536814009106

(R)-[(R)-3-Benzyl-2-oxooxazolidin-4-yl][4-(methylsulfonyl)phenyl]methyl acetate

Feng Li ^a, Ming-Zhong Zhao ^b, Chun-Hua Jin ^a,^*, Jian-Wei Zou ^a

PMCID: PMC4011233 PMID: 24860399

Abstract

The structure of the title compound, C₂₀H₂₁NO₆S, is of interest with respect to its antibacterial properties. The oxazolidine ring makes dihedral angles of 79.63 (14) and 56.16 (12)° with the phenyl and benzene rings, respectively, while the phenyl and benzene rings make a dihedral angle of 64.37 (13)°. In the crystal, non-classical C—H⋯O hydrogen bonds link adjacent molecules along the c axis.

Related literature

For the original synthesis of the title compound, see: Li et al. (2011 ▶). For inversion of the configuration of the sulfonyloxy moiety, see: Shi et al. (2010 ▶). For background to the anti-bacterial properties of thiamphenicol-like compounds, see: Nagabhushan (1980 ▶, 1981 ▶); Jommi et al. (1985 ▶).

Experimental

Crystal data

C₂₀H₂₁NO₆S
M _r = 403.44
Monoclinic,
a = 5.837 (3) Å
b = 21.021 (10) Å
c = 7.884 (4) Å
β = 100.256 (7)°
V = 952.0 (7) Å³
Z = 2
Mo Kα radiation
μ = 0.21 mm⁻¹
T = 296 K
0.30 × 0.25 × 0.16 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T _min = 0.940, T _max = 0.968
6495 measured reflections
3658 independent reflections
3254 reflections with I > 2σ(I)
R _int = 0.022

Refinement

R[F ² > 2σ(F ²)] = 0.035
wR(F ²) = 0.091
S = 1.02
3658 reflections
255 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.17 e Å⁻³
Absolute structure: Flack (1983 ▶), 1356 Friedel pairs
Absolute structure parameter: −0.06 (6)

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814009106/hg5390sup1.cif

e-70-0o606-sup1.cif^{(21.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814009106/hg5390Isup2.hkl

e-70-0o606-Isup2.hkl^{(179.3KB, hkl)}

Click here for additional data file.^{(4.7KB, cdx)}

Supporting information file. DOI: 10.1107/S1600536814009106/hg5390Isup3.cdx

Click here for additional data file.^{(7.5KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814009106/hg5390Isup4.cml

CCDC reference: 998863

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C7—H7A⋯O4ⁱ	0.97	2.52	3.373 (3)	147
C10—H10⋯O6ⁱ	0.98	2.54	3.384 (3)	144
C13—H13C⋯O1ⁱⁱ	0.96	2.55	3.305 (3)	135

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

Acknowledgments

The authors thank Professor Xiang-shan Wang for his help and advice in the solution of the crystal structure.

supplementary crystallographic information

1. Comment

During the study on the synthesis of florfenicol, a class of antibiotics with pronounced broad-spectrum antibacterial activity, (Nagabhushan, 1980 & Jommi et al., 1985). the title compound was produced and is a key intermediate in the synthetic route to florfenicol (Li et al., 2011). The title compound was synthesized through the nucleophilic substitution reaction of (S)-((R)-3-benzyl-2-oxooxazolidin-4-yl)(4-(methylsulfonyl) phenyl)methylmethane sulfonate. Here we report the crystal structure of the title compound.

Fig. 1 shows the molecular structure of the title compound. The enantiomer was selected on the basis of the configuration of the starting material. All chiral carbon atoms (C10 and C11) are R-configuration. Only one molecule is included in the asymmetrical unit of this compound (Fig. 1). All the bond lengths and relevant angles are in the typical ranges. Although there is no –NH or –OH group available in the structure to form strong hydrogen bonds, the C atoms are involved in the formation of non-classical inter-molecular C—H···O hydrogen bonds (Fig 2).

2. Experimental

The literature procedure according to Li et al. (2011) was followed. A solution of 1,8-diazabicyclo[5.4.0]undec-7-ene (700 mg, 4.56 mmol) and glacial acetic acid (550 mg, 9.11 mmol) in anhydrous toluene (5 mL) was stirred for 1.5 h at room temperature. (S)-((R)-3-benzyl-2-oxooxazolidin-4-yl)(4-(methylsulfonyl)phenyl)methylmethanesulfonate was added and the reaction mixture was heated to 363 K for 8 h. The resulting mixture was cooled to r.t., diluted with CH₂Cl₂ (40 mL) and washed with 2M aq. HCl (30 mL), 10% aq. K₂CO₃ (30 mL), and brine (30 mL) successively. The organic phase was dried over Na₂SO₄, concentrated in vacuo. The residue was purified by flash chromatography to afford the title compound 850 mg (92%) as a white solid. Suitable crystals for X-ray experiments were obtained by slow evaporation from an AcOEt/CHCl₃ solution at room temperature.

2.1. Refinement

Hydrogen atoms bonded to the carbon atoms were placed in calculated positions and refined as riding mode, with C—H = 0.93Å (methane) or 0.96Å (methyl) and U_iso(H) = 1.2U_eq (C_methane) or U_iso(H) = 1.5U_eq (C_methyl).