2,3:4,5-Di-O-isopropyl­idenefructos-1-yl p-toluene­sulfonate

Shiyong Huo; Yueqing Li; Chaoyan Liang; Jihong Liu; Weijie Zhao

doi:10.1107/S1600536810044582

. 2010 Nov 6;66(Pt 12):o3097. doi: 10.1107/S1600536810044582

2,3:4,5-Di-O-isopropylidenefructos-1-yl p-toluenesulfonate

Shiyong Huo ^a, Yueqing Li ^a, Chaoyan Liang ^a, Jihong Liu ^a, Weijie Zhao ^a,^*

PMCID: PMC3011573 PMID: 21589404

Abstract

The title compound, C₁₉H₂₆O₈S, has been synthesized from 2,3:4,5-di-O-isopropylidene-β-d-fructopyranose. The absolute configuration of the fused ring is confirmed by anomalous dispersion effects in the diffraction measurement. The six-membered β-fructopyranose ring has a twist-boat conformation with the two five-membered rings trans to each other. In the crystal, intermolecular non-classical C—H⋯O hydrogen bonds link the molecules into a three-dimensional network.

Related literature

For details of the synthesis of the title compound and its analogues, see: Hirst et al. (1953 ▶); Reitz et al. (1989 ▶); Dekany et al. (2007 ▶). For a related structure, see: Lis & Weichsel (1987 ▶).

Experimental

Crystal data

C₁₉H₂₆O₈S
M _r = 414.47
Monoclinic,
a = 13.870 (5) Å
b = 10.153 (4) Å
c = 15.715 (6) Å
β = 106.831 (4)°
V = 2118.2 (14) Å³
Z = 4
Mo Kα radiation
μ = 0.19 mm⁻¹
T = 273 K
0.43 × 0.36 × 0.27 mm

Data collection

Bruker SMART APEX CCD diffractometer
10503 measured reflections
6948 independent reflections
6040 reflections with I > 2σ(I)
R _int = 0.018

Refinement

R[F ² > 2σ(F ²)] = 0.034
wR(F ²) = 0.088
S = 1.04
6948 reflections
506 parameters
13 restraints
H-atom parameters constrained
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.19 e Å⁻³
Absolute structure: Flack (1983 ▶), 3010 Friedel pairs
Flack parameter: −0.02 (5)

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT-Plus (Bruker, 2001 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810044582/rk2243sup1.cif

e-66-o3097-sup1.cif^{(30.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810044582/rk2243Isup2.hkl

e-66-o3097-Isup2.hkl^{(340KB, 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
C3—H3A⋯O13ⁱ	0.98	2.70	3.358 (3)	125
C4—H4A⋯C17ⁱ	0.98	2.83	3.657 (5)	142
C21—H21A⋯O3ⁱⁱ	0.98	2.58	3.456 (3)	149
C23—H23A⋯O16ⁱⁱ	0.98	2.62	3.466 (3)	145
C23—H23A⋯C33ⁱⁱ	0.98	2.89	3.738 (4)	145
C37—H37A⋯O8	0.93	2.61	3.341 (4)	136

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

Acknowledgments

We thank Dr Yang Li for his help during the refinement.

supplementary crystallographic information

Comment

As we know, p-toluenesulfonyl group has been extensively approved as a good substituent group for a long time. A series of derivatives can be synthesized by the substituent reaction of the title compound (Reitz et al., 1989; Dekany et al., 2007). Furthermore, in our study we found that it also can easily react with pyrrole which will be one effective approach to synthesize the corresponding novel N-carbohydrate-derived pyrrole compound. The molecular and crystal structure is helpful to confirm the absolute configuration of the fused ring in the derivatives of the title compound.

In the title compound, as shown at Fig. 1, the pyranose ring adopts a twist boat conformation. This conformation is the result of distortion introduced by the fusion of one six- and two five-membered rings. All bond lengths and angles of this part are normal and comparable with those reported for the related structure (Lis & Weichsel, 1987). In the crystal, weak C—H···O non-classical H bonds (Table 1) link the molecules into a three-dimensional network.

Experimental

The title compound was prepared according to literature (Reitz et al., 1989). The product (1 g) was dissolved in ethyl ether (25 ml) and hexane (25 ml). Single crystals suitable for X-ray diffraction experiment were obtained from the solution by cooling at 255 K for three days.

The molecule is characterized by NMR (Fig. 2). ¹H NMR (CDCl₃, 400 MHz): δ 7.79 (2H, d, J = 8.2 Hz, H-11, H-11'), 7.34 (2H, d, J = 8.2 Hz, H-12, H-12'), 4.56 (1H, dd, J = 7.9 Hz, J = 2.5 Hz, H-4), 4.30 (1H, d, J = 2.5 Hz, H-5), 4.20 (1H, d, J = 7.9 Hz, H-3), 4.07 (1H, d, J = 10.3 Hz, H-1a), 4.01 (1H, d, J = 10.3 Hz, H-1b), 3.86 (1H, d, J = 12.8 Hz, H-6a), 3.80(1H, d, J = 12.8 Hz, H-6b), 2.44 (3H, s, H-14), 1.50, 1.36, 1.31 (3H, 6H, 3H, CH₃-7, CH₃-7', CH₃-8, CH₃-8').

¹³C NMR(CDCl₃, 100 MHz): δ 144.97 (C-10), 132.51(C-13), 129.84 (C-12, C-12'), 128.14 (C-11, C-11'), 109.18, 109.04 (C-9, C-9'), 100.67 (C-2), 70.59 (C-3), 69.90 (C-4, C-5), 69.04 (C-1), 61.26 (C-6), 26.44, 25.72, 25.17, 23.99 (CH₃-7, CH₃-7', CH₃-8, CH₃-8'), 21.62 (C-14).

HRMS(ES⁺): m/z [M+Na]⁺ calcd. for C₁₉H₂₆O₈SNa: 437.1246; found: 437.1261.