O-Ethyl S-{(S)-1-oxo-1-[(R)-2-oxo-4-phenyl­oxazolidin-3-yl]propan-2-yl} carbonodi­thio­ate

J Pablo García-Merinos; Heraclio López-Ruiz; Yliana López; Susana Rojas-Lima

doi:10.1107/S1600536814007636

. 2014 Apr 18;70(Pt 5):o584–o585. doi: 10.1107/S1600536814007636

O-Ethyl S-{(S)-1-oxo-1-[(R)-2-oxo-4-phenyloxazolidin-3-yl]propan-2-yl} carbonodithioate

J Pablo García-Merinos ^a,^b,^*, Heraclio López-Ruiz ^a, Yliana López ^b, Susana Rojas-Lima ^a

PMCID: PMC4011202 PMID: 24860384

Abstract

In the title compound, C₁₅H₁₇NO₄S₂, synthesized by addition of O-ethylxanthic acid potassium salt to a diastereomeric mixture of (4R)-3-(2-chloropropanoyl)-4-phenyloxazolidin-2-one, the oxazolidinone ring has a twist conformation on the C—C bond. The phenyl ring is inclined to the mean plane of the oxazolidinone ring by 76.4 (3)°. In the chain the methine H atom is involved in a C—H⋯S and a C—H⋯O intramolecular interaction. In the crystal, molecules are linked by C—H⋯π interactions, forming chains along [001]. The S configuration at the C atom to which the xanthate group is attached was determined by comparison to the known R configuration of the C atom to which the phenyl group is attached.

Related literature

For the use of chiral oxazolidinones auxiliaries in asymmetric synthesis, see: Evans (1982 ▶); Ager et al. (1997 ▶). For the oral activity of oxazolidinonas against multidrug-resistant Gram-positive bacteria, see: Müller & Schimz (1999 ▶). For our work on the synthesis of novel heterocyclic compounds, see for example: López-Ruiz et al. (2011 ▶). For the crystal structures of similar compounds, see: Bartczak et al. (2001 ▶); Kruszynski et al. (2001 ▶); Wouters et al. (1997 ▶). For the crystal structures of 3,4-disubstituted oxazolidinone derivatives, see: Marsh et al. (1992 ▶); Evain et al. (2002 ▶); Hwang et al. (2006 ▶). For standard bond lengths, see: Allen et al. (1987 ▶). For ring puckering analysis, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C₁₅H₁₇NO₄S₂
M _r = 339.42
Monoclinic,
a = 10.8558 (15) Å
b = 6.1867 (9) Å
c = 12.3057 (17) Å
β = 94.911 (4)°
V = 823.4 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.34 mm⁻¹
T = 293 K
0.2 × 0.17 × 0.16 mm

Data collection

Bruker SMART CCD diffractometer
10191 measured reflections
3223 independent reflections
1681 reflections with I > 2σ(I)
R _int = 0.152

Refinement

R[F ² > 2σ(F ²)] = 0.067
wR(F ²) = 0.191
S = 0.87
3223 reflections
201 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.35 e Å⁻³
Absolute structure: Flack (1983 ▶), 6968 Friedel pairs
Absolute structure parameter: 0.08 (18)

Data collection: SMART (Bruker, 1999 ▶); cell refinement: SAINT (Bruker, 1999 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶) and publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I. DOI: 10.1107/S1600536814007636/su2715sup1.cif

e-70-0o584-sup1.cif^{(19.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814007636/su2715Isup2.hkl

e-70-0o584-Isup2.hkl^{(154.9KB, hkl)}

Click here for additional data file.^{(5.9KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814007636/su2715Isup3.cml

CCDC reference: 995594

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

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

Cg is the centroid of the C10–C15 phenyl ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯S1	0.98	2.65	3.180 (9)	114
C4—H4⋯O3	0.98	2.34	2.895 (10)	115
C2—H2B⋯Cg ⁱ	0.97	2.90	3.807 (8)	156

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Symmetry code: (i) Inline graphic .

Acknowledgments

Financial support from CONACYT (project No. 183980) and CIC–UMSNH is gratefully acknowledged. JM is grateful to CONACYT for a scholarship (grant: 186053) to support his studies. YLC is grateful to CONACYT (project No. 183980) for providing a license to use the Cambridge Structural Database. We are indebted to Dr Rosa Santillan and Marco A. Leyva-Ramírez (CINVESTAV–IPN) for helpful discussions.

supplementary crystallographic information

1. Comment

Oxazolidinones and their derivatives show interesting chemical and biological activities. The use of chiral oxazolidinones auxiliaries in asymmetric synthesis has found wide application in a variety of stereoselective reactions over the last two decades (Evans, 1982; Ager et al., 1997). In addition oxazolidinonas represent a novel class of synthetic antimicrobial agents, the most promising feature of these compounds is their oral activity against multidrug-resistant Gram-positive bacteria which have created tremendous therapeutic problems in recent years (Müller et al., 1999). Based on this, and as part of our ongoing research program directed toward the synthesis of novel heterocyclic compounds (see for example: López-Ruiz et al., 2011) we report herein on the use of (R)-4-phenyloxazolidin-2-one for the synthesis of the title xanthate-oxazilidinone derivative, which has potential applications as a chiral auxiliary in asymmetric reactions.

The title compound was obtained by addition of O-Ethylxanthic acid potassium salt to a diastereomeric mixture of (4R)-3-(2-Chloropropanoyl)-4-phenyloxazolidin-2-one in acetone.

The absolute configuration of the newly created stereogenic carbon, C4, could be deduced from the relative configuration of carbon atom C9, see Fig. 1. The oxazolidinone ring has a twisted conformation on bond C9—C8 [puckering parameters (Cremer & Pople, 1975), φ = 313 (4)°] similar to the twisted conformation on bond C6—C8 for the axazolidinone ring in the 3-amino-2-oxazolidinone derivatives [φ = 53.6174° and φ = 54.0837°] (Bartczak et al., 2001; Kruszynski et al., 2001) and the same conformation was observed for unsubstituted 2-oxazolidinone (Wouters et al., 1997).

The bond angles around atom N1 in the oxazolidinone ring are in agreement with the observed tendencies for the bond angles in 3,4-disustituted oxazolidinone derivatives (Marsh et al., 1992; Evain et al., 2002; Hwang et al., 2006). The C9—N1, C7—N1 and C6—N1 bond distances, 1.483 (7), 1.382 (8) and 1.411 (8) Å, respectively, are slightly longer than the average values reported for Csp³—N(3) and Csp²—N(3) in γ-lactams [C*—N(—C*)—C=O (endo) = 1.462 and C*—N(—C*)—C=O = 1.347 Å respectively] (Allen et al., 1987).

The C7═O3 bond length 1.198 (8) Å is slightly shorter than a Csp²=O(1) in γ-lactams [C*—N(—C*)—C=O = 1.225 Å] and close to normal Csp²=O(1) in γ-lactones [C*—C(=O)—O—C* = 1.201 Å]. The C8—O4 bond, 1.449 (8) is slightly shorter than the Csp³—O(2) [C*—O—C(=O) = 1.464 Å] in γ-lactones while C7—O4 bond 1.343 (7) Å is close to normal Csp²=O(2) in γ-lactones [C*—C(═O)—O—C* = 1.350 Å]. Moreover the C4—S2 and C3=S1 bond distances are 1.811 (6) and 1.642 (7) Å respectively being slightly shorter than Csp³—S(2) and Csp²═S(1) [C—CH—S—C = 1.819 and (X)₂—C═S (X = C, N, O, S) = 1.671 Å, respectively].

In the crystal, molecules are linked via C-H···π interactions forming zigzag chains along [001]; (Table 1 and Fig. 2).

2. Experimental

For the preparation of the title compound, a solution of (4R)-4-phenyloxazolidin-2-one (10.70 mmol) in distilled THF (25 ml) was cooled to 195 K under a nitrogen atmosphere, and a solution of n-butyllithium in hexane (12.95 mmol) was added dropwise. After 2-chloropropanoyl chloride (10.79 mmol) was introduced dropwise and stirring was continued at 195 K for 6 h. Then the reaction mixture was diluted with saturated solution of NH₃SO₄ and extracted with dichloromethane (3 × 10 ml). The combined organic layers were washed with water and brine, dried over anhydrous Na₂SO₄ and concentrated under vacuum. Purification by chromatography column on silica gel (eluent: hexane/ethyl acetate 9:1) gave the diastereomeric mixture of (4R)-3- (2-Chloropropanoyl)-4-phenyloxazolidin-2-one in 98% yield. To a solution of this diastereomeric mixture (31.19 mmol) in acetone at 273 K was added the O-Ethylxanthic acid potassium salt (46.78 mmol) and the reaction was stirred at room temperature for 12 h. Then the reaction mixture was diluted with a saturated solution of NH₃SO₄ and extracted with dichloromethane (3 × 10 ml). The organic layer was dried over anhydrous Na₂SO₄ and concentrated under vacuum. Purification by chromatography column on silica gel (eluent: hexane/ethyl acetate 9:1) gave the diastereomeric mixture of (4R)-3-((2R)-(2-O-Ethyl carbonodithioate) propanoyl)-4-phenyloxazolidin-2-one in a 77% of yield. Block-like colourless crystals of the title compound were obtained by slow evaporation of an hexane/ethyl acetate (9:1) solution. Spectroscopic data for the title compound are available in the archived CIF.