3,4-Dicyano­phenyl 2,3,4,6-tetra-O-acetyl-α-d-glucopyran­oside

Yuejing Bin; Fuqun Zhao; Fushi Zhang; Ru-Ji Wang

doi:10.1107/S1600536807049860

. 2007 Dec 6;64(Pt 1):o63. doi: 10.1107/S1600536807049860

3,4-Dicyanophenyl 2,3,4,6-tetra-O-acetyl-α-d-glucopyranoside

Yuejing Bin ^a, Fuqun Zhao ^a, Fushi Zhang ^a,^*, Ru-Ji Wang ^b

PMCID: PMC2915021 PMID: 21200940

Abstract

The title compound, C₂₂H₂₂N₂O₁₀, was prepared by the glycosidation method through nitrite displacement on substituted nitrophthalonitrile. The molecule contains a benzene ring, two nitrile groups and an acetyl-protected d-glucose fragment which adopts a chair conformation. The absolute configuration was determined by the use of d-glucose as starting material. All substituents of the protected sugar are in equatorial positions, with the exclusive presence of the α-anomer. The crystal packing is stabilized by C—H⋯O and C—H⋯N hydrogen-bonding interactions.

Related literature

For related literature, see: Alvarez-Mico et al. (2006 ▶, 2007 ▶); Burkhardt et al. (2007 ▶); Ribeiro et al. (2006 ▶); Huang et al. (2005 ▶); Dinçer et al. (2004 ▶); Berven et al. (1990 ▶); Ocak et al. (2004 ▶).

Experimental

Crystal data

C₂₂H₂₂N₂O₁₀
M _r = 474.42
Orthorhombic,
a = 8.175 (2) Å
b = 10.2076 (10) Å
c = 29.562 (6) Å
V = 2466.9 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 295 (2) K
0.6 × 0.5 × 0.1 mm

Data collection

Bruker P4 diffractometer
Absorption correction: none
5277 measured reflections
2639 independent reflections
1348 reflections with I > 2σ(I)
R _int = 0.056
3 standard reflections every 97 reflections intensity decay: none

Refinement

R[F ² > 2σ(F ²)] = 0.059
wR(F ²) = 0.112
S = 1.06
2639 reflections
307 parameters
H-atom parameters constrained
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Data collection: XSCANS (Bruker, 1996 ▶); cell refinement: XSCANS; data reduction: XSCANS; program(s) used to solve structure: SHELXTL (Bruker, 1997 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807049860/rz2165sup1.cif

e-64-00o63-sup1.cif^{(20.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807049860/rz2165Isup2.hkl

e-64-00o63-Isup2.hkl^{(129.6KB, 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
C5—H5A⋯O2	0.93	2.57	3.016 (7)	110
C11—H11A⋯O6	0.98	2.27	2.675 (6)	103
C12—H12A⋯O8	0.98	2.30	2.713 (8)	104
C13—H13A⋯O1	0.98	2.40	2.800 (6)	104
C20—H20A⋯O10	0.97	2.23	2.617 (7)	102
C5—H5A⋯O6ⁱ	0.93	2.41	3.224 (8)	146
C9—H9A⋯O6ⁱ	0.98	2.46	3.346 (7)	151
C10—H10A⋯O10ⁱⁱ	0.98	2.40	3.283 (7)	149
C15—H15C⋯N1ⁱⁱⁱ	0.96	2.58	3.465 (9)	153

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

Acknowledgments

This work was supported financially by the National Science Fund of China (grant Nos. 20333080 and 20572059) and the National Basic Research Program of China (grant No. 2007CB808000).

supplementary crystallographic information

Comment

Phthalocyanine has been used in applications based upon their close structural relationship of the phthalocyanines with porphyrin complexes. However, a serious limitation of phthalocyanine is their insolubility. Phthalocyanine compounds are made soluble in a variety of solvents by appropriate peripheral substitution. The synthesis routes of amphiprotic glucose-appended phthalocyanines include the preparation of dicyanophenyl glucopyranoside as precursor and further macrocyclization forming phthalocyanine-glucoconjugates. These glucose-appended phthalocyanines are highly soluble and self-assemble in water (Ribeiro et al., 2006). Aggregation of these phthalocyanine compounds in solution and in the solid state significantly affects the optical properties of such solutions and films. The crystal structure of phthalocyanine is difficult to attain. The structure of the precursors could provide some clues to elucidate the self-assembly of phthalocyanine-glucocongates. The precursor of the phthalocyanine-glucoconjugates is the title compound, 3,4-dicyanophenyl 2,3,4,6-tetra-O-acetyl-α-D-glucopyranoside, which was prepared by the glycosidation method through nitrite displacement on substituted nitrophthalonitrile. The main products were exclusively the thermodynamically favored α-anomers obtained by reversible SNAr reactions in polar aprotic solvents like Me₂SO or DMF in the presence of a base (Berven et al., 1990). We report here the crystal structure of the title compound.

In the title compound (Fig. 1) the 2,3,4,6-tetra-O-acetyl-D-glucopyranoside ring mean plane is oriented exactly perpendicular to that of the phthalocyanine ring. The four acetyl groups with atoms are in equatorial positions (Burkhardt et al., 2007). The crystal structure reveals a ⁴C₁ chair conformation for the sugar ring, with the 3,4-dicyanophenyl substituent at C9 in the vertical position, corresponding to the exclusive presence of the α-anomer of the saccharide, in agreement with the ¹H NMR results (Alvarez-Mico et al., 2006, 2007). The C1≡N1 (1.132 (8) Å) and C2≡N2 (1.130 (8) Å) bond distances are consistent with a triple bond character, and are in good agreement with the literature values (Dinçer et al., 2004; Ocak et al., 2004; Huang et al., 2005).

The crystal structure (Fig. 2) is stabilized by intra- and intermolecular C—H···O and C—H···N hydrogen bonding interactions (Table 1).

Experimental

A suspension of anhydrous D-glucose (25 g, 0.15 mol) and anhydrous sodium acetate (12.5 g, 0.15 mol) in 100 mL (1.1 mol) of acetic anhydride was slowly heated to reflux temperature in a round-bottomed flask. Then the heater was removed and the reaction left to reflux. Once the colour of the solution changed from colourless to yellow, the solution was poured onto l liter of crushed ice and stirred for 2 h. The solid product was filtered off, washed with water and recrystallized from ethanol to yield colourless crystals of 1,2,3,4,6-penta-O-acetyl-D-glucopyran (27 g; yield 50%; m. p. 135° C). To a solution of ethylenediamine (1.2 g, 20 mmol) in DMF (10 ml), glacial acetic acid (1.2 g, 20 mmol) was added dropwise, then 1,2,3,4,6-penta-O-acetyl-D-glucopyran (7.8 g, 20 mmol) was added and the mixture stirred at RT for 5 h. Water (100 ml) was added and the mixture extracted with acetic ester. The organic phase was subsequently washed with 2 N HCl, saturated NaHCO₃ solution and concentrated in vacuo. The compound obtained (5.0 g, 14.4 mmol) and 4-nitrophthalodinitrile (1.8 g, 10.4 mmol) were dissolved in DMF (15 ml), the new roasted anhydrous potassium carbonate (4 g) was added to the solution as three batches in 1 h, and stirred at R. T. for 48 h. The mixture was poured into ice water, and the precipitated product was filtered off, washed with water and recrystallized from toluene to give the title compound (2.4 g; yield 50%; m. p. 159–160° C; m/z 497.23 [M+Na]⁺).