1,2-Di-tert-butyl­ethane-1,2-diyl bis­(tert-butane­sulfinamide)

Xiaoxia Sun; Yu Hu; Congbin Fan; Weihong Xiao

doi:10.1107/S1600536808042360

. 2008 Dec 20;65(Pt 1):o172. doi: 10.1107/S1600536808042360

1,2-Di-tert-butylethane-1,2-diyl bis(tert-butanesulfinamide)

Xiaoxia Sun ^a,^*, Yu Hu ^b, Congbin Fan ^a, Weihong Xiao ^a

PMCID: PMC2968083 PMID: 21581629

Abstract

In the title compound, C₁₈H₄₀N₂O₂S₂, a vicinal diamine derivative, the crystal structure is stabilized by two intramolecular N—H⋯O hydrogen bonds. The distance between the two kernel chiral C atoms is 1.580 (2) Å.

Related literature

For details of the preparation, see: Sun et al. (2005 ▶). For background to vicinal diamines, see: Roland et al. (1999 ▶); Lucet et al. (1998 ▶). For related literature, see: Alexakis et al. (2000 ▶).

Experimental

Crystal data

C₁₈H₄₀N₂O₂S₂
M _r = 380.64
Monoclinic,
a = 13.053 (2) Å
b = 9.578 (1) Å
c = 18.279 (2) Å
β = 92.069 (8)°
V = 2283.6 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 287 (2) K
0.50 × 0.44 × 0.38 mm

Data collection

Bruker P4 diffractometer
Absorption correction: none
4904 measured reflections
4242 independent reflections
3039 reflections with I > 2σ(I)
R _int = 0.014
3 standard reflections every 97 reflections intensity decay: 4.6%

Refinement

R[F ² > 2σ(F ²)] = 0.036
wR(F ²) = 0.096
S = 1.00
4242 reflections
238 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Data collection: XSCANS (Siemens, 1994 ▶); cell refinement: XSCANS; data reduction: SHELXTL (Sheldrick, 2008 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808042360/jh2069sup1.cif

e-65-0o172-sup1.cif^{(22.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808042360/jh2069Isup2.hkl

e-65-0o172-Isup2.hkl^{(207.9KB, 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
N1—H1N⋯O2	0.850 (9)	2.204 (10)	3.023 (2)	161.9 (16)
N2—H2N⋯O1	0.837 (9)	2.210 (10)	3.013 (2)	161.0 (16)

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Acknowledgments

This work was supported by the Science Fund of the Education Office of Jiangxi, China ([2007]279).

supplementary crystallographic information

Comment

In recent years, enantiopure vicinal diamines 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 bidentate ligands (Lucet et al., 1998). Among all organic vicinal diamine compounds, ditertbutyl vicinal diamine are the most promising candidates for those application, mainly due to the great steric hindrance (Roland et al., 1999).

The X-ray crystallographic study confirms the molecular structure previously proposed on the basis of spectroscopic data (Fig. 1). The molecule adopts big steric hindrance with excellent diastereoselectivity and high enantioselectivity.The distance between the two kernel chiral C atoms is 1.580 (2) Å. The syn relative configuration of the newly formed stereocenters is expected according to the Cram rule (Alexakis et al., 2000).

Experimental

Compound (Ia) was prepared from Bis-[(R)- N-tert-Butanesulfinyl]ethanediimine (264 mg, 1.00 mmol). To a flask was added the Bis-[(R)- N-tert-Butanesulfinyl] ethanediimine in the specified solvent and the solution was then cooled to 195 K under a argon atmosphere. 2 mol/L t-BuLi in diethyl ether (2.0 ml) was added slowly to the solution and stirred for 3-5 h. The reaction mixture warmed to room temperature and stirred for a further 2 h. The mixture cooled to 273 K and quenched by the addition of a saturation solution of sodium sulfate. Organic phase separated and aqueous phase extracted with ethyl acetate. Combined organic layers were dried over magnesium sulfate, filtered and concentrated. The residue purified via flash chromatography to afford disulfinamide (Sun et al., 2005).

Finally the colorless crystals were obtained by slow vapour diffusion of diethyl ether. The titile compound was characterized by melting point, Rotation, IR, HRMS and NMR(m.p.134.7–135.4 K). ¹HNMR (300 MHz, CDCl₃, TMS): δ 1.03 (s, 18H,–6CH₃), 1.27 (s, 18H,–6CH₃), 3.16(d, 2H, J = 10.2 Hz, –2CH), 5.34(d, 2H, J = 10.4 Hz–2NH); ¹³C NMR (75 MHz, CDCl₃): δ 23.38, 28.40, 37.15, 56.94, 65.55; IR (KBr, cm^-1): 1040, 2869, 3192; a = -79.4 (c=0.94, CHCl3); HRMS for C₁₈H₄₀N₂O₂S₂Na (M+Na): calcd. 403.2423, found: 403.2412.