Hydrophobic Effect Driven Esterification of Sucrose in Aqueous MediumFootnote¹

1. Presented at the XVIII International Carbohydrate Symposium, Milan, Italy, July 21-26, 1996.

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• A typical experiment consisted in adding neat octanoyl chloride (8.78 mmol, 1.5 mL) using an automatic syringe (0.1 mL/min flow rate) to a stirred 60% w/w sucrose aqueous solution (sucrose: 88 mmol, 30g, water: 20g) adjusted to pH 10 with 10N NaOH (pH-stat or manually). Reactions were monitored by TLC using a 56:20:20:4 mixture of dichloromethane, methanol, acetone and water as the eluent. After neutralization by adding 0.5N hydrochloric acid, water was added in order to get a less viscous solution, and the crude sucrose esters could be extracted with 1—butanol (2 or 3x 30 mL). After evaporation of the solvent, flash chromatography (same solvent as for TLC) allowed isolation first of the more substituted esters, then the diesters, and finally the monoesters. The average substitution degree was determined by comparing integration for the alkyl chain and sugar regions in 1H NMR spectra (d6-DMSO). Monoesters could be further purified by semi-preparative HPLC (nucleosil NH2, 0.5″ Ø, 93/7 MeCN/water, 7 mL/min, RI detection) and identified by 1H and 13C NMR spectroscopy. Sucrose reference data (D2O, 50.32 Mhz) δ 104.1 (C-2'), 92.6 (C-1), 81.8 (C-5'), 76.8 (C-3'), 74.4 (C-4'), 73.0 (C-3), 72.8 (C-5), 71.5 (C-2), 69.7 (C-4), 62.8 (C-1'), 61.8 (C-6'), 60.5 (C-6); 2-O-octanoyl sucrose: 176.5 (C=O), 104.4 (C-2'), 90.1 (C-1), 81.9 (C-5'), 75.9 (C-3'), 74.3 (C-4'), 73.0 (C-2), 72.8 (C-5), 70.8 (C-3), 69.7 (C-4), 62.8 (C-1'), 61.5 (C-6'), 60.5 (C-6), 34.2, 31.5, 28.7, 28.6, 24.6, 22.5, 13.9 (alk); 3-O-octanoyl sucrose: 176.8 (C=O), 104.3 (C-2'), 92.6 (C-1), 81.9 (C-5'), 76.9 (C-3'), 75.4 (C-3), 74.5 (C-4'), 72.8 (C-5), 69.9 (C-2), 68.0 (C-4), 62.8 (C-1'), 61.8 (C-6'), 60.5 (C-6), 34.6, 31.7, 28.9, 28.8, 25.0, 22.6, 14.0 (alk); 3'-O-octanoyl sucrose: 176.4 (C=O), 103.7 (C-2'), 92.0 (C-1), 82.3 (C-5'), 77.5 (C-3'), 73.4 (C-4'), 72.8 (C-3), 72.6 (C-5), 71.4 (C-2), 69.5 (C-4), 63.3 (C-1'), 62.2 (C-6'), 60.5 (C-6), 34.2, 31.4, 28.6, 28.4, 24.8, 22.4, 13.8 (alk); 4'-O-octanoyl sucrose: 175.8 (C=O), 104.6 (C-2'), 92.7 (C-1), 80.1 (C-5'), 76.4 (C-4'), 75.1 (C-3'), 73.0 (C-3), 72.9 (C-5), 71.5 (C-2), 69.5 (C-4), 62.7 (C-1'), 61.6 (C-6'), 60.4 (C-6), 34.2, 31.3, 28.5, 28.4, 24.7, 22.4, 13.8 (alk). Esterification position was determined through shift effects analysis
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