2-Methyl-3-(5-methyl-2-thien­yl)-5-phenyl­perhydro­pyrrolo[3,4-d]isoxazole-4,6-dione

Mustafa Odabaşoğlu; Hamdi Özkan; Yılmaz Yıldırır; Orhan Büyükgüngör

doi:10.1107/S1600536809009209

. 2009 Mar 25;65(Pt 4):o862–o863. doi: 10.1107/S1600536809009209

2-Methyl-3-(5-methyl-2-thienyl)-5-phenylperhydropyrrolo[3,4-d]isoxazole-4,6-dione

Mustafa Odabaşoğlu ^a, Hamdi Özkan ^b, Yılmaz Yıldırır ^c, Orhan Büyükgüngör ^d,^*

PMCID: PMC2968779 PMID: 21582577

Abstract

In the molecule of the title compound, C₁₇H₁₆N₂O₃S, the phenyl ring is oriented with respect to the thiophene and succinimide rings at dihedral angles of 88.08 (3) and 57.81 (3)°, respectively; the dihedral angle between the thiophene and succinimide rings is 35.69 (3)°. The isoxazole ring adopts an envelope conformation with the N atom at the flap position. In the crystal structure, intermolecular C—H⋯O hydrogen bonds link the molecules into infinite chains along the b axis. Weak C—H⋯π interactions may further stabilize the structure.

Related literature

For nitrones as versatile synthetic intermediates in organic synthesis, see: Black et al. (1975 ▶); Banerji & Sahu (1986 ▶); Torsell (1988 ▶); Banerji & Basu (1992 ▶). For nitrones as a convenient class of compounds for the syntheses of ultimate carcinogens, see: Mallesha, Ravikumar, Mantelingu et al. (2001 ▶); Mallesha, Ravikumar & Rangappa (2001 ▶). For the 1,3-dipolar cycloaddition reaction of nitrones with alkenes in the preparation of isoxazolidines, see: Tufariello (1984 ▶). For isoxazolidines in the synthesis of β-lactams, see: Padwa et al. (1981 ▶, 1984 ▶). For the use of β-lactams to treat bacterial infections, see: Ochiai et al. (1967 ▶); as natural products, see: Baldwin & Aube (1987 ▶); as versatile synthetic intermediates, see: Padwa (1984 ▶). For the preparation of C-(5-Methyl-2-thienyl)-N-methylnitrone used in the synthesis, see: Heaney et al. (2001 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₁₇H₁₆N₂O₃S
M _r = 328.38
Monoclinic,
a = 12.6558 (5) Å
b = 8.5738 (3) Å
c = 19.3824 (8) Å
β = 128.654 (3)°
V = 1642.42 (13) Å³
Z = 4
Mo Kα radiation
μ = 0.21 mm⁻¹
T = 296 K
0.73 × 0.52 × 0.26 mm

Data collection

STOE IPDS 2 diffractometer
Absorption correction: integration (X-RED32; Stoe & Cie, 2002 ▶) T _min = 0.685, T _max = 0.946
19464 measured reflections
3401 independent reflections
2872 reflections with I > 2σ(I)
R _int = 0.028

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.098
S = 1.05
3401 reflections
222 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2002 ▶); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809009209/hk2634sup1.cif

e-65-0o862-sup1.cif^{(20.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809009209/hk2634Isup2.hkl

e-65-0o862-Isup2.hkl^{(163.5KB, hkl)}

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
C8—H18⋯O2ⁱ	0.94 (2)	2.41 (2)	3.103 (2)	130
C2—H2⋯Cg1ⁱⁱ	0.93	2.99	3.83 (2)	152 (1)

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Symmetry codes: (i) Inline graphic ; (ii) . Cg1 is the centroid of the S1/C13–C16 ring.

Acknowledgments

The authors acknowledge the Faculty of Arts and Sciences, Ondokuz Mayıs University, Turkey, for use of the Stoe IPDS 2 diffractometer (purchased under grant No. F.279 of the University Research Fund).

supplementary crystallographic information

Comment

1,3-Dipolar cycloaddition reaction of nitrones to olefins is of synthetic interest. In the present work, isoxazolidines have been synthesized in high yield via intermolecular cycloaddition of N-arylnitrone with monosubstituted olefins and are employed for biological evaluation. Nitrones are versatile synthetic intermediates in organic synthesis (Black et al., 1975; Banerji & Sahu, 1986; Torsell, 1988; Banerji & Basu, 1992). Recently, they reported that nitrones are a convenient class of compounds for the syntheses of ultimate carcinogens (Mallesha, Ravikumar, Mantelingu et al., 2001); Mallesha, Ravikumar & Rangappa, 2001), which are biologically interesting molecules. The 1,3-dipolar cycloaddition reaction of nitrones with alkenes is an important method for preparing isoxazolidines in a regioselective and stereoselective manner (Tufariello, 1984). These isoxazolidines are used in the syntheses of β-lactams (Padwa et al., 1981; Padwa et al., 1984) which are of value in the treatment of bacterial infections (Ochiai et al., 1967), occur as natural products (Baldwin & Aube, 1987), serve as versatile synthetic intermediates (Padwa, 1984), and are biologically interesting compounds (Ochiai et al., 1967). In view of the interest shown in these compounds, we report herein the crystal structure of the title compound.

In the molecule of the title compound (Fig. 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges. Rings A (C1-C6), B (N1/C7-C10) and D (S1/C13-C16) are, of course, planar, and they are oriented at dihedral angles of A/B = 57.81 (3), A/D = 88.08 (3) and B/D = 35.69 (3) °. Ring C (O3/N2/C8/C9/C11) adopts envelope conformation with N2 atom displaced by 0.736 (3) Å from the plane of the other ring atoms.

In the crystal structure, intermolecular C-H···O hydrogen bonds (Table 1) link the molecules (Fig. 2) into infinite chains along the b-axis, in which they may be effective in the stabilization of the structure. The weak C—H···π interaction (Table 1) may further stabilize the structure.

Experimental

C-(5-Methyl-2-thienyl)-N-methylnitrone was prepared from 5-methylthiophene-2 -carbaldehyde, N-methyl-hydroxylamine hydrochloride and sodium carbonate in CH₂Cl₂ (Scheme 2) according to the literature method (Heaney et al., 2001). For the preparation of the title compound, C-(5-methyl-2-thienyl)-N -methylnitrone (471 mg, 3 mmol) and N-phenylmaleimide (570 mg, 3.3 mmol) were dissolved in benzene (50 ml). The reaction mixture was refluxed for 12 h, and monitored by TLC (Scheme 2). After evaporation of the solvent, the reaction mixture was separated by column chromatography, using mixtures of petroleum ether and ethyl acetate (1:2) as the eluant. The trans-isomer, was recrystallized from CHCl₃/n-hexane (1:3) in 2 d (m.p. 425-428 K).