Oxidation of polysaccharides with nitroxyls

Abstract: A simplified process for oxidising starch and other polysaccharides in an aqueous solution or suspension using hypochlorite in the presence of a catalytic amount of a nitroxyl compound is described. The oxidation is process is bromide-free and is carried out at a pH between 7 and 9.3 and at a temperature between 15 and 25°C.

Description: The present invention relates to a process for oxidising starch and other polysaccharides in an aqueous medium using hypochlorite in the presence of a nitroxyl compound. WO 95/07303 discloses a process for oxidising polysaccharides including starch, using hypochlorite TEMPO (tetramethylpiperidine-N-oxyl) in the presence of a catalytic amount of bromide at a pH between 9 and 13 at a temperature between -5 and +10°C. This process results in selective oxidation of the hydroxymethyl group at the 6-position of the anhydroglucose units to a carboxyl group. In example IV of this document, the effect of bromide was studied and the results suggest that no complete reaction can be achieved in the absence of bromide. The TEMPO-mediated oxidation of starch is also described in DE-19746805. The reaction conditions according to this teaching are: use of about 7.5 minol TEMPO and about 110 mmol bromide per mol starch, room temperature and a pH between 7 and 9. WO 99/23240 discloses the oxidation of starch with TEMPO and oxygen using an enzyme (laccase). As a reference, chemical oxidation with TEMPO and hypochlorite and bromide at pH 10.8 at 0°C is described. The current teaching is to always use bromide as a co-catalyst in the TEMPO-mediated oxidation of carbohydrates, as the absence of bromide is thought to be detrimental to the yield and purity (chain degradation) of the polymeric product. However, the use of bromide is undesired because it is corrosive and is environmentally hazardous. It was surprisingly found according to the invention that starch and related polysaccharides can be oxidised with hypochlorite and TEMPO at near-neutral conditions in the absence of a bromide catalyst without any loss on selectivity for 6-oxidation or yield. The pH optimum was found to be lower (about pH 8-9) than with bromide catalysis (about pH 10). Also, no substantial depolymerisation was found around the pH optimum. The reaction rate at ambient temperatures is equal to that of the bromide catalysed reaction performed at about 2°C, which constitutes a practical advantage. Advantageously the results in terms of depolymerisation and other undesired side-reactions at ambient temperatures are about the same as the bromide process carried out at low temperatures, and is better than the bromide process carried at ambient temperatures. Thus the process of the invention is characterised in that this oxidation is carried out in the absence of a bromide (or other halide) catalyst, at a pH between 7 and 9.3 and at a temperature between 15 and 25°C. The preferred pH depends on the particular type of nitroxyls. For most nitroxyls such as unsubstituted TEMPO and 4-hydroxy-TEMPO, the preferred pH is between 8.0 and 9.5, especially between 8.3 and 9.0, whereas for 4-acetamido-TEMPO the preferred pH is between 7.5 and 8.2. Polysaccharides that can be oxidised using the process of the invention should contain a hydroxymethyl group, for example at the 6-position of the monosaccharide unit. Such polysaccharides include the starch-type polysaccharides (α-1,4-glucans), pullulan and other α-1,3-glucans, cellulose-type polysaccharides (β-1,4-glucans) and other β-glucans such as chitin, fructans, galacto- and gluco-mannans (guar and the like), xyloglucans, etc. The process of the invention is particularly concerned with the oxidation of starch and starch analogues and derivatives, such as gelatinised starch, hydrolysed starch, amylose, amylopectin, alkylated, hydroxyalkylated, carboxyalkylated, aminoalkylated, acylated starch etc. The only requirement is that at least a part of the 6-hydroxyl functions is still available as such. The degree of oxidation to be achieved with the process can be determined on the basis of the intended use, by choosing the appropriate amount of hypochlorite. Hypochlorite can be used as such or as a precursor, e.g. as molecular chlorine. At low degree of oxidation, a mixture of 6-aldehyde-starch and 6-carboxy-starch is obtained, while at high degrees of oxidation (e.g. more than 50%), 6-carboxy-starch is the predominant product. For complete oxidation to 6-carboxy starch, two moles of hypochlorite are required per mole of starch unit (i.e. anhydroglucose unit). If an aldehyde-free product is desired at partial oxidation, any aldehyde product can be either reduced to the alcohol, e.g. with borohydride, or oxidised to the carboxyl product, e.g. with sodium chlorite. The nitroxyl compound to be used can be any organic nitroxyl compounds lacking α-hydrogen atoms, such as 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO), 2,2,5,5-tetramethylpyrrolidine-N-oxyl (PROXYL), 4-hydroxy-TEMPO, 4-acetamido-TEMPO and other derivatives thereof It is preferred to use a relatively low amount of TEMPO, in particular between 3 and 7.2 mmol of nitroxyl compound per mole of starch unit. Example Potato starch (12.2 g; 10.0 g dry weight: 62 mmol) was gelatinised in demineralised water (450 ml) at 95 °C under mechanical stirring. The solution was then slowly cooled to 20 °C. TEMPO (4-8 mg per g of starch) was dissolved in the starch solution. A hypochlorite solution (concentration 2.0 mol/l) was added in portions of 2 ml. In total 86 mmoles were added, corresponding to a theoretical degree of oxidation of 70%. The pH was kept at 8.5 by addition of 0.5 M NaOH controlled by a pH-stat. After completion of the reaction, remaining carbonyl intermediates were reduced back to the alcohol by sodium borohydride (0.2 g). The oxidised material was precipitated in 2 volumes of ethanol, separated by filtration, rinsed with acetone and dried in a vacuum oven at 30 °C. The product was then redissolved in water, ion-exchanged (Dowex 50WX8-100 cation exchanger, Sigma) and freeze-fried, to remove salts and to convert carboxylates to the protonated form. 13 C NMR (D 2 O) δ (ppm): 99.2 (C-1), 73.2, 73.7, 74.0, 74.5 (C-2-5), 61.7 (C-6), 177.6 (C-6 oxidised). The isolated yield was over 90%, with a degree of oxidation of 65%. Size exclusion chromatography showed very little depolymerisation. The elution pattern was almost identical to the pattern resulting from oxidation using bromide at 2°C and it showed less decomposition compared to oxidation using bromide at 20°C.

Claims: A process for oxidising polysaccharides in an aqueous solution or suspension using hypochlorite in the presence of a catalytic amount of a nitroxyl compound, characterised in that the oxidation is carried out in the absence of a bromide catalyst, at a pH between 7 and 9.3 and at a temperature between 15 and 25°C. A process according to claim 1, in which between 3 and 7.2 mmol of nitroxyl compound is used per mole of monosaccharide unit of the polysaccharide. A process according to claim 1 or 2, in which the nitroxyl compound is TEMPO (tetramethylpiperidine-N-oxyl) or 4-hydroxy-TEMPO. A process according to claim 3, in which the oxidation is carried out at a pH between 8.3 and 9.0. A process according to claim 1 or 2, in which the nitroxyl compound 4-acetoxy-TEMPO. A process according to claim 5, in which the oxidation is carried out at a pH between 7.3 and 8.3. A process according to any one of claims 1-6, in which the polysaccharide is starch or a starch derivative.

Inventors: BESEMER ARIE CORNELIS, BRAGD PETTER, THORNTON JEFFREY WILSON, BESEMER, ARIE CORNELIS, BRAGD, PETTER, THORNTON, JEFFREY WILSON
Applicants: SCA HYGIENE PROD ZEIST BV, SCA HYGIENE PRODUCTS ZEIST B.V.
Application year: 2000
Main classification: C08B31
IPC codes: C08B15, C08B31