2,5-Dihexyl­thio­phene 1,1-dioxide

Johannes Van Tonder; Mukut Gohain; Nagarajan Loganathan; Barend C B Bezuidenhoudt

doi:10.1107/S1600536812046867

. 2012 Nov 24;68(Pt 12):o3437. doi: 10.1107/S1600536812046867

2,5-Dihexylthiophene 1,1-dioxide

Johannes Van Tonder ^a, Mukut Gohain ^a, Nagarajan Loganathan ^a,^*, Barend C B Bezuidenhoudt ^a

PMCID: PMC3589018 PMID: 23476254

Abstract

In the title molecule, C₁₆H₂₈O₂S, the two n-hexyl groups are in all-trans conformations. Their C atoms are situated close to the plane of the thiophene ring with a maximum deviation of 0.718 (6) Å for one of the terminal methyl groups. In the crystal, a short C—H⋯O contact is observed between thiophene 1,1-dioxide groups.

Related literature

For the preparation of the title compound, see: Barbarella et al. (1998 ▶). For a review on thiophene-1,1-dioxide derivatives and their applications, see: Nakayama et al. (1999 ▶). For the biological activity of sulfone compounds, see: Naesens et al. (2006 ▶); Kim et al. (2008 ▶); Sagardoy et al. (2010 ▶). graphic file with name e-68-o3437-scheme1.jpg

Experimental

Crystal data

C₁₆H₂₈O₂S
M _r = 284.44
Monoclinic,
a = 5.8249 (11) Å
b = 11.248 (2) Å
c = 27.207 (6) Å
β = 91.770 (8)°
V = 1781.7 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.18 mm⁻¹
T = 293 K
1.00 × 0.30 × 0.10 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker 2008 ▶) T _min = 0.841, T _max = 0.982
18944 measured reflections
3149 independent reflections
2207 reflections with I > 2σ(I)
R _int = 0.072

Refinement

R[F ² > 2σ(F ²)] = 0.062
wR(F ²) = 0.167
S = 1.07
3149 reflections
174 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT-Plus (Bruker, 2008 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶) and WinGX (Farrugia 2012) ▶; program(s) used to refine structure: SHELXTL; molecular graphics: DIAMOND (Brandenburg & Putz, 2005 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Click here for additional data file.^{(22.6KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812046867/gk2532sup1.cif

e-68-o3437-sup1.cif^{(22.6KB, cif)}

Click here for additional data file.^{(154.5KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812046867/gk2532Isup2.hkl

e-68-o3437-Isup2.hkl^{(154.5KB, hkl)}

Click here for additional data file.^{(6.1KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536812046867/gk2532Isup3.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
C3—H3⋯O2ⁱ	0.93	2.54	3.186 (3)	126

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Symmetry code: (i) Inline graphic .

Acknowledgments

The University of the Free State and Sasol Ltd are gratefully acknowledged for the financial support. Special thanks to Professor Andreas Roodt.

supplementary crystallographic information

Comment

Tetrahydrothiophene 1,1-dioxide otherwise known as sulfolane, is an important industrial solvent used in the purification of natural gas, particularly for the extraction of aromatic hydrocarbon from the other hydrocarbon mixtures. Thiophene 1,1-dioxide is an important intermediate in the synthesis of various class of organic compounds. This class of compound is also known for their bioapplications (Nakayama et al., 1999; Naesens et al., 2006; Kim et al., 2008; Sagardoy et al., 2010). For example, some of them have been found to be effective inhibitors of hepatitis C virus polymerase (Kim et al., 2008).

The title compound, 2,5-dihexyl-thiophene-1,1-dioxide, was synthesized by the procedure of Barbarella et al. (1998).

Experimental

A mixture of 2,5-dihexylthiophene (0.500 g; 2.0 mmol) and NaHCO₃ (0.667 g; 7.9 mmol; 4.0 eq) was taken in dichloromethane(30 ml) at 0 °C and allowed to stir vigorously for a few minutes. To which a freshly recrystallized (from dichloromethane) solid of m-chloroperbenzoic acid (1.411 g; 8.2 mmol; 4.1 eq.) was added in portion over 60 min. After 16hrs of stirring, the precipitate was removed by filtration and successively washed with dichloromethane (2 x 5 ml). The collective filtrate was then evaporated to dryness. Crystals of title compound were obtained as white needles from n-pentane. Yield: 0.304 g; 53.9%. ¹H NMR (600 MHz, CDCl3) δ 6.28 – 6.24 (2H, m, H-3,4), 2.46 (4H, t, J = 7.7 Hz, H-1'), 1.68 – 1.61 (4H, m, H-2'), 1.41 – 1.34 (4H, m, H-3'), 1.33 – 1.26 (8H, m, H-4',5'), 0.91 – 0.86 (6H, m, H-6'). 13 C NMR (151 MHz, CDCl3) δ 144.08 (C-2,5), 121.80 (C-3,4), 31.51 (C-4',5'), 28.91 (C-3'), 26.67 (C-2'), 24.41 (C-1'), 22.63 (C-4',5'), 14.16 (C-6'). EI—MS m/z: 284.10 (35.47%; M+), 165.10 (78.57), 95.10 (100.00), 81.05 (83.06).