(S)-N-Phenyl-tert-butane­sulfinamide

Xiaofei Sun; Xiaoping Zhang; Binbin Zhang; Wenguo Wang; Qingle Zeng

doi:10.1107/S1600536812020673

. 2012 May 16;68(Pt 6):o1728. doi: 10.1107/S1600536812020673

(S)-N-Phenyl-tert-butanesulfinamide

Xiaofei Sun ^a, Xiaoping Zhang ^a, Binbin Zhang ^a, Wenguo Wang ^b, Qingle Zeng ^a,^*

PMCID: PMC3379318 PMID: 22719516

Abstract

The asymmetric unit of the title compound, C₁₀H₁₅NOS, contains two independent molecules with similar conformations. In the crystal, molecules are linked in a head-to-tail fashion by N—H⋯O hydrogen bonds into chains running along the b axis. The absolute configuration was assigned on the basis of known chirality of the parent compound.

Related literature

For the structures of related N-alkyl and N-aryl alkanesulfinamides, see: Datta et al. (2008 ▶, 2009a ▶,b ▶, 2010 ▶); Sun et al. (2012a ▶,b ▶) Zhang et al. (2012 ▶); Sato et al. (1975 ▶); Schuckmann et al. (1978 ▶); Ferreira et al. (2005 ▶).

Experimental

Crystal data

C₁₀H₁₅NOS
M _r = 197.29
Orthorhombic,
a = 9.3596 (4) Å
b = 10.4702 (4) Å
c = 22.7438 (10) Å
V = 2228.82 (17) Å³
Z = 8
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 293 K
0.38 × 0.32 × 0.30 mm

Data collection

Aglenet Xcalibur Eos diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ▶) T _min = 0.987, T _max = 1.000
6065 measured reflections
3993 independent reflections
2503 reflections with I > 2σ(I)
R _int = 0.025

Refinement

R[F ² > 2σ(F ²)] = 0.054
wR(F ²) = 0.090
S = 0.98
3993 reflections
249 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.26 e Å⁻³
Absolute structure: Flack (1983 ▶), 1390 Friedel pairs
Flack parameter: −0.09 (9)

Data collection: CrysAlis PRO (Agilent, 2011 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: OLEX2 (Dolomanov et al., 2009 ▶); software used to prepare material for publication: OLEX2.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812020673/rz2751sup1.cif

e-68-o1728-sup1.cif^{(20KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812020673/rz2751Isup2.hkl

e-68-o1728-Isup2.hkl^{(195.7KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812020673/rz2751Isup3.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
N1—H1⋯O2ⁱ	0.80 (3)	2.17 (3)	2.937 (4)	161 (3)
N2—H2⋯O1ⁱⁱ	0.83 (2)	2.11 (2)	2.914 (4)	166 (3)

Open in a new tab

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

Acknowledgments

We thank the Ministry of Human Resources and Social Security of China, the Science and Technology Bureau of Sichuan (grant No. 2011HH0016), the Open Fund of the State Key Laboratory of Geohazard Prevention and Geoenvironment Protection and the Cultivating Programme for Excellent Innovation Teams of Chengdu University of Technology (No. HY0084) for financial support.

supplementary crystallographic information

Comment

In recent years, sulfonamide moieties have played an increasingly important role in organic chemistry, particularly due to their use as chiral auxiliaries or precursors for the synthesis of a broad family of pharmaceutical agents. As a contribution to this research field, the X-ray crystallographic study of the title compound (Fig. 1) is reported herein. A number of related (R)—N-(3-methoxyphenyl) tert-butanesulfinamides, (R)—N-(4-biphenyl) tert-butanesulfinamide, N-aryl alkanesulfinamides and N-alkyl alkanesulfinamides have been reported recently (Datta et al., 2008, 2009a, 2009b, 2010; Sun et al., 2012a, 2012b Zhang et al., 2012; Sato et al., 1975; Schuckmann et al., 1978; Ferreira et al., 2005).

In the title compound, the value of the N-C(aryl) bond (N1—C1 = 1.403 (4) Å; N2—C11 = 1.403 (4) Å) is considerably shorter than those typically found in N-alkylsulfinamides (1.470–1.530 Å; Sato et al., 1975; Schuckmann et al., 1978; Ferreira et al., 2005), suggesting a significant delocalization of electrons over the nitrogen atom and the benzene ring. In the crystal structure, the molecules are linked into chains parallel to the b axis by intermolecular N—H···O hydrogen bonds (Fig. 2; Table 1).

Experimental

A oven-dried ground test tube, which was equipped with a magnetic stir bar and fitted with a rubber septum, was charged with (S)-tert-butanesulfinamide (0.121 g, 1.0 mmol), Pd₂(dba)3 (0.018 g, 0.02 mmol), tBu-XPhos (0.0212 g, 0.05 mmol) and NaOH (0.08 g, 2 mmol). The vessel was evacuated and backfilled with argon (this process was repeated a total of 3 times) and then phenyl bromide (1.3 mmol), toluene (10 ml) and degassed water (0.3 ml) were added via syringe. The solution was stirred at 90° for 20 h. The reaction mixture was then cooled to room temperature, quenched by water, and extracted with ethyl acetate (2 × 20 ml). The organic layer was combined, dried over anhydrous sodium sulfate and filtrated. The filterate was condensed under vacuum. The residual was purified with silica gel column chromatography with a solution of petroleum ether/ethyl acetate (5:1 v/v) as an eluent to give a white solid (0.167 g, yield 86%). A test tube containing the eluate (petroleum ether/ethyl acetate (5:1 v/v) was covered with a piece of filter paper and placed motionless at room temperature (about 20°), until a single-crystal was cultured in the bottom of the test tube. M.p.: 383–386 K. [α]D²¹ = +179 (c 3/4, ethyl acetate). Spectroscopic analysis: ¹H NMR (300 MHz, CDCl₃), δ (p.p.m.): 7.25–7.24 (m, 2H), 7.01 (t, J = 6.3 Hz, 3H), 5.41 (d, J = 11.1 Hz, 1H), 1.33 (s, 9H). ¹³C NMR (75 MHz, CDCl₃), δ (p.p.m.): 142.1, 129.1, 122.4, 117.9, 56.3, 22.3. IR (KBr), ν (cm^-1): 3452, 3145, 2961, 2889, 1598, 1495, 1412, 1363, 1287, 1236, 1053, 887, 751. ESI-MS (negative mode), m/z = 196 [M—H]^-.