(3aR,4S,7R,7aS)-2-Phenyl-4-propyl-3a,4,7,7a-tetra­hydro-1H-4,7-epithio­iso­indole-1,3-dione 8-oxide

Aydın Demircan; Ertan Şahin; Gözde Beyazova; Muhsin Karaaslan; Tuncer Hökelek

doi:10.1107/S1600536811012876

. 2011 Apr 13;67(Pt 5):o1085–o1086. doi: 10.1107/S1600536811012876

(3aR,4S,7R,7aS)-2-Phenyl-4-propyl-3a,4,7,7a-tetrahydro-1H-4,7-epithioisoindole-1,3-dione 8-oxide

Aydın Demircan ^a, Ertan Şahin ^b, Gözde Beyazova ^a, Muhsin Karaaslan ^c, Tuncer Hökelek ^d,^*

PMCID: PMC3089067 PMID: 21754407

Abstract

In the tetrahydroisoindole moiety of the title compound, C₁₇H₁₇NO₃S, the six-membered ring assumes a boat configuration and the –S=O group bridges the prow and stern of the boat. The phenyl ring is oriented at a dihedral angle of 83.2 (1)° with respect to the pyrrole ring. In the crystal, intermolecular C—H⋯O hydrogen bonds link the molecules into a three-dimensional network. A weak C—H⋯π interaction involving the phenyl ring is also found. The crystal studied was an inversion twin.

Related literature

For background to the thiophenen system, see: Lert & Trindle (1971 ▶). For the conditions of cycloaddition reactions of thiophene, see: Al-Omran et al. (1996 ▶); Kuhn & Gollnick (1972 ▶); Kotsuki et al. (1978 ▶); Thiemann et al. (1995 ▶). For the biological activity of some thiophene 1,1-dioxide derivatives, see: Thiemann et al. (2009 ▶). For thiophene s-oxides with alkyl groups at positions 2,3,4 and 5, see: Rajappa (1984 ▶). For related structures, see: Arslan & Demircan (2007 ▶); Koşar et al. (2006 ▶).

Experimental

Crystal data

C₁₇H₁₇NO₃S
M _r = 315.39
Orthorhombic,
a = 7.7712 (3) Å
b = 10.8413 (3) Å
c = 18.9762 (4) Å
V = 1598.74 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.21 mm⁻¹
T = 294 K
0.30 × 0.25 × 0.20 mm

Data collection

Rigaku R-AXIS RAPID-S diffractometer
Absorption correction: multi-scan (Blessing, 1995 ▶) T _min = 0.807, T _max = 0.865
34450 measured reflections
3279 independent reflections
2686 reflections with I > 2σ(I)
R _int = 0.088

Refinement

R[F ² > 2σ(F ²)] = 0.047
wR(F ²) = 0.108
S = 1.08
3279 reflections
210 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.22 e Å⁻³
Absolute structure: Flack (1983 ▶), 1379 Friedel pairs
Flack parameter: 0.37 (9)

Data collection: CrystalClear (Rigaku/MSC, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; 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 ▶) and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811012876/xu5179sup1.cif

e-67-o1085-sup1.cif^{(20.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811012876/xu5179Isup2.hkl

e-67-o1085-Isup2.hkl^{(157.6KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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

Cg1 is the centroid of the C12–C17 phenyl ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5⋯O1ⁱ	0.95 (2)	2.51 (3)	3.326 (4)	144 (2)
C17—H17⋯O3ⁱⁱ	0.93	2.57	3.315 (3)	137
C7—H7⋯Cg1ⁱⁱⁱ	0.98	2.77	3.693 (3)	157

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

Acknowledgments

The authors are indebted to the Department of Chemistry, Atatürk University, Erzurum, Turkey, for use of the X-ray diffractometer purchased under grant No. 2003/219 of the University Research Fund. We thank The Scientific & Technological Research Council of Turkey (TUBITAK) for financial support of this work (PN: 107T831).

supplementary crystallographic information

Comment

Thiophene behaves as the least reactive diene among all aromatic five-membered heterocycles; the presence of 3d orbitals on sulfur contributes to the resonance stability of the thiophene system (Lert & Trindle, 1971). Cycloaddition reactions of thiophene also have limitations therefore its 4 + 2 cycloaddition can occur under following conditions; use of highly reactive dienophiles (Thiemann et al., 1995), enhance electron density on the thiophene by having substituent at position 2 or 5 (Al-Omran et al., 1996), high reaction temperature (Kuhn & Gollnick, 1972) or use of high pressure (Kotsuki et al., 1978). However, the number of publications dealing with the chemistry of thiophene dioxide based new materials, namely, semiconductor organic transistors and light diodes first designed about 13 years ago. New data on the biological activities of some thiophene 1,1-dioxide derivatives were observed in recent years (Thiemann et al., 2009).

Thiophene s-oxides are derivatives of thiophene, which belong to an important group of five-membered heterocyclic compounds having non-aromatic character. Thiophene s-oxides with alkyl groups at positions 2,3,4 and 5 have been the subject of extensive studies in recent past (Rajappa, 1984). Owing to the unique structure combined with high reactivity, they can be used to prepare various heterocyclic systems; therefore, these compounds are useful building blocks in synthetic organic chemistry. In continuation of our research program and following our previous interest in the sytheses of fused heterocyclic compounds using furan (Arslan & Demircan, 2007; Koşar et al., 2006), it has been found that mono alkylated thiophene at position 2 will lead to an excellent building block for the synthesis of the title compound.

The title compound contains two non-planar five- and six-membered rings, which has a pyrrole (C1/N2/C3/C3a/C7a) ring (B) on one side and a propyl moiety at position 4. It also contains a phenyl (C12-C17) ring (A) bonded to the pyrrole ring (B) at position 2. The angles C4-C5-C6 [111.4 (3)°] and C5-C6-C7 [111.1 (3)°] about the double bond have an average value of 111.3 (3)°. The dihedral angles between planes A, B, C (C3a/C4/C7a C7), D (C4-C7) and E (C4/S8/C7) are as follows: A/B = 83.2 (1)°, B/C = 61.9 (1)°, C/D = 60.6 (1)°, C/E = 58.8 (1)° and D/E = 60.7 (1)°.

In the crystal, intermolecular C—H···O hydrogen bonds link the molecules to form a three-dimensional network (Table 1 and Fig. 2). There also exist a weak C—H···π interaction involving the phenyl ring A (C12-C17) (Table 1).

Experimental

For the preparation of the title compound, BF₃.Et₂O (6.1 ml, 47.75 mmol) was added slowly to a solution of 2-propylthiophene (1.00 g, 7.90 mmol) and N-phenylmaleimide (2.06 g, 11.90 mmol) in dry dichloromethane (DCM) (40 ml) under an inert atmosphere at 253 K. The reaction mixture was stirred for 10 min at 253 K, and then a solution of meta chloroperbenzoic acid (m-CPBA) (2.05 g, 11.90 mmol) in dry DCM (40 ml) was added slowly. The reaction mixture was stirred for 2 h at 253 K, and then the suspension was poured into a mixture of aqueous NaHCO₃ solution (80 ml) and DCM (50 ml) and stirred at room temperature for 20 min. The organic phase was separated, and the aqueous phase was extracted with DCM (3 x 25 ml). The combined organic phase was washed with water and brine, and then dried over anhydrous MgSO₄. After removal of the solvent in vacuo, the residue was chromatographed on silica gel to give the title compound as colorless crystals.