4-Formyl­phenyl 2,3,4,6-tetra-O-acetyl-β-d-glucopyran­oside

Thorsten Heidelberg; Rusnah Syahila Duali Hussen; Nasrul Zamani Mohd Rodzi; Seik Weng Ng; Edward R T Tiekink

doi:10.1107/S1600536811008099

. 2011 Mar 9;67(Pt 4):o825. doi: 10.1107/S1600536811008099

4-Formylphenyl 2,3,4,6-tetra-O-acetyl-β-d-glucopyranoside

Thorsten Heidelberg ^a,^‡, Rusnah Syahila Duali Hussen ^a, Nasrul Zamani Mohd Rodzi ^a, Seik Weng Ng ^a, Edward R T Tiekink ^a,^*

PMCID: PMC3099765 PMID: 21754109

Abstract

The pyranoside ring in the title compound, C₂₁H₂₄O₁₁, has a chair conformation with the substituted benzene ring occupying an equatorial position. The crystal packing is dominated by C—H⋯O interactions that lead to the formation of supramolecular layers in the ab plane.

Related literature

For synthesis, see: Bao et al. (2004 ▶); Hongu et al. (1999 ▶); Patil & Ravindranathan Kartha (2008 ▶). For the natural anti-oxidant glucosylated resveratrol, see: La Torre et al. (2004 ▶). For the biological activity of related structures, see: Wen et al. (2008 ▶); Yan et al. (2009 ▶). For the structure of the isomeric allopyranoside and galactose derivatives, see: Ye et al. (2009 ▶); Hussen et al. (2011 ▶). For conformational analysis, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C₂₁H₂₄O₁₁
M _r = 452.40
Triclinic,
a = 5.7868 (2) Å
b = 8.9166 (3) Å
c = 11.4716 (3) Å
α = 102.473 (3)°
β = 93.481 (2)°
γ = 102.780 (3)°
V = 559.96 (3) Å³
Z = 1
Cu Kα radiation
μ = 0.94 mm⁻¹
T = 100 K
0.30 × 0.30 × 0.20 mm

Data collection

Agilent Supernova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent Technologies, 2010 ▶) T _min = 0.919, T _max = 1.000
7392 measured reflections
4097 independent reflections
4087 reflections with I > 2σ(I)
R _int = 0.021

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.115
S = 1.07
4097 reflections
293 parameters
3 restraints
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.17 e Å⁻³
Absolute structure: Flack (1983 ▶), 1855 Friedel pairs
Flack parameter: -0.02(12)

Data collection: CrysAlis PRO (Agilent Technologies, 2010 ▶); 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: ORTEP-3 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811008099/ez2235sup1.cif

e-67-0o825-sup1.cif^{(22.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811008099/ez2235Isup2.hkl

e-67-0o825-Isup2.hkl^{(200.8KB, 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
C1—H1⋯O5ⁱ	1.00	2.51	3.356 (2)	143
C3—H3⋯O5ⁱ	1.00	2.35	3.207 (2)	143
C6—H6A⋯O9ⁱⁱ	0.99	2.40	3.324 (2)	155
C8—H8C⋯O11ⁱⁱⁱ	0.98	2.54	3.475 (3)	160

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

Acknowledgments

This study was supported by the University of Malaya under research grant No. FS306/2007 C. The authors are also grateful to the University of Malaya for support of the crystallographic facility.

supplementary crystallographic information

Comment

The title compound, 4-formyl-phenyl 2,3,4,6-tetra-O-acetyl-β-D-glucopyranoside, a known species (Bao et al., 2004, Hongu et al., 1999; Patil et al.; 2008), which has been used for the preparation of potential pharmaceutically active compounds (Wen et al., 2008; Yan et al., 2009) was prepared as a precursor for the synthesis of glucosylated resveratrol, an interesting natural antioxidant (La Torre et al., 2004). The present analysis complements the recent report of the isomeric galactose derivative, see: Hussen et al. (2011).

The structure determination, Fig. 1, confirms the relative stereochemistry as well as the absolute structure, i.e. R, R, S, R and S for C1–C5, respectively. The pyranoside ring has a chair conformation as seen in the puckering parameters (Cremer & Pople, 1975): puckering amplitude (Q) = 0.6016 (18) Å, θ = 172.53 (16) °, and φ = 178.0 (14) °. Around the ring, all substituents are equatorial.

The crystal packing is dominated by C–H···O interactions, Table 1, involving carbonyl atoms as acceptors and methine-, methylene methyl-H as the donors. The carbonyl-O5 atom is bifurcated, spanning two methine-H atoms of a neighbouring molecule to form a supramolecular chain along the a axis. Altogether, the C–H···O interactions lead to the formation of supramolecular layers that stack along the c axis, Fig. 2.

The present report complements the structures reported recently for the isomeric allopyranoside (Ye et al., 2009) and galactose (Duali Hussen et al., 2011) derivatives.

Experimental

2,3,4,6-Tetra-O-acetyl-α-D-gluctopyranosyl bromide (4.0 g) and 4-hydroxybenzaldehyde (3.0 g) were dissolved in chloroform (30 ml) and the mixture treated with a solution of aqueous solution (15 ml) of sodium carbonate (2.7 g) and tetrabutylammonium bromide (0.7 g). The mixture was heated to reflux under vigorous stirring overnight, after which ethyl acetate was added and the organic layer was washed three times with sodium hydroxide solution (1 N) to remove remaining phenols. After drying the solution over magnesium sulfate and evaporation of the solvent, the target product (2.0 g, 45%) was obtained by crystallization from ethanol. Better crystals were obtained from 2-propanol.

¹H NMR (400 MHz, CDCl₃): δ 9.92 (s; CHO), 7.85 & 7.09 (AB syst; aromatic 4H), 5.34–5.26 & 5.24–5.14 (2 m, 2 x 2H; H1–H4), 4.27 (dd; H6a), 4.16 (dd; H6b), 3.92 (ddd; H5), 2.05–2.03 (3 s, 12H; Ac); ³J_4,5 = 10.0 Hz, ³J_5,6a = 5.0 Hz, ³J_{5,6 b} = 2.5 Hz and ²J₆ = 12.0 Hz.