Diethyl 1-benzyl-2,2-dioxo-4-phenyl-3,4,6,7,8,8a-hexa­hydro-1H-pyrrolo­[2,1-c][1,4]thia­zine-1,3-dicarboxyl­ate

A Chitradevi; S Athimoolam; S Asath Bahadur; S Indumathi; S Perumal

doi:10.1107/S1600536811031047

. 2011 Aug 6;67(Pt 9):o2268. doi: 10.1107/S1600536811031047

Diethyl 1-benzyl-2,2-dioxo-4-phenyl-3,4,6,7,8,8a-hexahydro-1H-pyrrolo[2,1-c][1,4]thiazine-1,3-dicarboxylate

A Chitradevi ^a, S Athimoolam ^b,^*, S Asath Bahadur ^c, S Indumathi ^d, S Perumal ^d

PMCID: PMC3200855 PMID: 22058923

Abstract

In the title compound, C₂₆H₃₁NO₆S, the five-membered pyrrolidine ring adopts an envelope conformation and the six-membered thiazine ring is in a distorted chair conformation. The crystal packing is stabilized through an intermolecular C—H⋯O interaction, generating inversion-related R ₂ ²(10) ring motifs.

Related literature

For the biological and pharmacological importance of thiazine compounds, see: Moriyama et al. (2004 ▶); Koketsu et al. (2002 ▶). For the biological and pharmacological properties of compounds containing the pyrrolidine sub-structure, see: Hemming & Patel (2004 ▶); Kueh et al. (2003 ▶). For biological properties of compounds containing the pyrrolothiazine scaffold, see: Armenise et al. (1991 ▶, 1998 ▶). For ring puckering analysis, see: Cremer & Pople (1975 ▶). For hydrogen-bonding interactions, see: Desiraju & Steiner (1999 ▶). For graph-set analysis, see: Etter et al. (1990 ▶).

Experimental

Crystal data

C₂₆H₃₁NO₆S
M _r = 485.58
Monoclinic,
a = 13.5232 (9) Å
b = 16.8402 (12) Å
c = 12.1789 (9) Å
β = 116.568 (1)°
V = 2480.7 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.17 mm⁻¹
T = 293 K
0.22 × 0.18 × 0.15 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
23528 measured reflections
4360 independent reflections
3885 reflections with I > 2σ(I)
R _int = 0.023

Refinement

R[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 0.112
S = 1.05
4360 reflections
328 parameters
H-atom parameters constrained
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Data collection: SMART (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); 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 ▶); software used to prepare material for publication: SHELXTL/PC (Sheldrick, 2008 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811031047/su2277sup1.cif

e-67-o2268-sup1.cif^{(27.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811031047/su2277Isup2.hkl

e-67-o2268-Isup2.hkl^{(209.3KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811031047/su2277Isup3.cml

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
C5—H5⋯O11ⁱ	0.98	2.51	3.447 (2)	159

Open in a new tab

Symmetry code: (i) Inline graphic .

Acknowledgments

AC and SAB sincerely thank the Vice-Chancellor and Management of Kalasalingam University, Anand Nagar, Krishnan Koil, for their support and encouragement.

supplementary crystallographic information

Comment

Thiazines occupy a unique place in medicinal chemistry since they show diverse biological properties, such as antifungal, anti-inflammatory, anti-HIV, anti-psoriatic, sedative, neuroleptic, antitussive and anti-tubercular (Moriyama et al., 2004; Koketsu et al., 2002). In addition, compounds with a pyrrolidine sub-structure exhibit anti-tumour, analgesic, antidepressant, antihistaminic, anti-asthmatic and anti-Parkinson activities (Hemming & Patel, 2004; Kueh et al., 2003). Compounds containing the pyrrolothiazine scaffold have also been shown to exhibit anti-inflammatory, anti-fungal and anti-microbial activities (Armenise et al., 1998; Armenise et al., 1991).

The molecular structure of the title molecule is illustrated in Fig. 1. The five-membered pyrrolidine ring has an envelope conformation [puckering parameters: Q(2) = 0.412 (2) Å, φ(2) = 152.9 (3)°; Cremer & Pople, 1975], with atom C6 at the flap. The six-membered thazine ring adopts a slightly distorted chair conformation [Puckering parameters: Q(2) = 0.1011 (19) Å, φ(2) = 101.2 (9) ° and Q(3) = 0.6610 (17) Å]. The dihedral angle between the phenyl rings is 54.3 (1)°. The planes of the carboxylate groups (CO₂) are oriented with a dihedral angle of 22.5 (3)°.

In the crystal molecules are linked via intermolecular C—H···O interactions (Desiraju & Steiner, 1999). This interaction makes a R₂²(10) ring motif centered about an inversion center (Table 1, Fig. 2; Etter et al., 1990).

Experimental

A mixture of ethyl 2-[(2-ethoxy-2-oxoethyl)sulfonyl]acetate (1.6 mmol), benzaldehyde (3.2 mmol) and pyrrolidine (1.6 mmol) was dissolved in ethanol (10 ml), heated until the solution turned yellow and stirred at room temperature for 2–5 days. After completion of the reaction, the crude product was purified using flash column chromatography on silica gel (230–400 mesh) with petroleum ether and ethyl acetate mixture (95:5 v/v) as an eluent. Crystals, suitable for X-ray diffraction analysis, were obtained by recrystallization from ethanol.