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WO2013030264A1 - Procédé pour modifier des glucides - Google Patents

Procédé pour modifier des glucides Download PDF

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Publication number
WO2013030264A1
WO2013030264A1 PCT/EP2012/066843 EP2012066843W WO2013030264A1 WO 2013030264 A1 WO2013030264 A1 WO 2013030264A1 EP 2012066843 W EP2012066843 W EP 2012066843W WO 2013030264 A1 WO2013030264 A1 WO 2013030264A1
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Prior art keywords
oxidant
process according
starch
oxidation
polysaccharide
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PCT/EP2012/066843
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English (en)
Inventor
Kevin Andre Jurgen HUVAERE
Jean-Baptiste Francine Georges JOOS
Koen Jeanne Alfons Van Aken
Philippe Elisabeth Marie Joseph WILLEMS
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Ecosynth Bvba
Orineo Bvba
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Publication of WO2013030264A1 publication Critical patent/WO2013030264A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
    • C08B15/02—Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B31/00—Preparation of derivatives of starch
    • C08B31/18—Oxidised starch
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
    • C08B37/0018—Pullulan, i.e. (alpha-1,4)(alpha-1,6)-D-glucan; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
    • C08B37/0021—Dextran, i.e. (alpha-1,4)-D-glucan; Derivatives thereof, e.g. Sephadex, i.e. crosslinked dextran
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
    • C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
    • C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0051—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Fructofuranans, e.g. beta-2,6-D-fructofuranan, i.e. levan; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0051—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Fructofuranans, e.g. beta-2,6-D-fructofuranan, i.e. levan; Derivatives thereof
    • C08B37/0054—Inulin, i.e. beta-2,1-D-fructofuranan; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/006—Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
    • C08B37/0087—Glucomannans or galactomannans; Tara or tara gum, i.e. D-mannose and D-galactose units, e.g. from Cesalpinia spinosa; Tamarind gum, i.e. D-galactose, D-glucose and D-xylose units, e.g. from Tamarindus indica; Gum Arabic, i.e. L-arabinose, L-rhamnose, D-galactose and D-glucuronic acid units, e.g. from Acacia Senegal or Acacia Seyal; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/006—Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
    • C08B37/0087—Glucomannans or galactomannans; Tara or tara gum, i.e. D-mannose and D-galactose units, e.g. from Cesalpinia spinosa; Tamarind gum, i.e. D-galactose, D-glucose and D-xylose units, e.g. from Tamarindus indica; Gum Arabic, i.e. L-arabinose, L-rhamnose, D-galactose and D-glucuronic acid units, e.g. from Acacia Senegal or Acacia Seyal; Derivatives thereof
    • C08B37/0096—Guar, guar gum, guar flour, guaran, i.e. (beta-1,4) linked D-mannose units in the main chain branched with D-galactose units in (alpha-1,6), e.g. from Cyamopsis Tetragonolobus; Derivatives thereof

Definitions

  • the present invention is related to a procedure to convert polysaccharides to an oxidized derivative, in particular an oxidized derivative in which the two adjacent secondary alcohol functions are converted to a dialdehyde with cleavage of the connective carbon- carbon bond. More particular, the invention relates to a procedure to convert starch using a hypervalent iodoarene derivative as the oxidant to convert starch into an oxidized derivative wherein the hydroxyl groups at the C 6 position and the C 2 -C 3 position are oxidized.
  • the present invention relates to a method to convert starch using a hypervalent iodoarene derivative such as bisacetoxyiodobenzene as the oxidant into dialdehyde starch (DAS) as the reaction product.
  • the procedure also comprises a method to regenerate the spent oxidant.
  • Oxidation is an important process to modify chemical and physical properties of polysaccharides in view of their use as functional biobased and biocompatible materials.
  • a controlled oxidation reaction leads to formation of aldehyde functions.
  • the resulting compounds have interesting properties as such or the electrophilic character of the aldehyde functionalities may be exploited in the process of further derivatization.
  • Oxidation to dialdehyde polysaccharides such as dialdehyde starch is particularly interesting, as these compounds are used for a variety of applications, including among others as cross-linking agent to improve wet strength of paper, as tanning agent in leather industry, and as component of biodegradable materials, cosmetics, coatings, glues and the like.
  • oxidation of polysaccharides using oxidants like oxygen or air, hydrogen peroxide, percarboxylic acids, anorganic oxoacids and derived salts, metals, hypochlorite or chlorite, and others.
  • oxidants are unselective and their reactivity is directed toward both primary and secondary hydroxyl functions.
  • primary hydroxyl functions are located at the C 6 -atom of the anhydroglucose unit of starch ( Figure 1) and oxidation gives an aldehyde function, which, depending on the oxidant used, can be further oxidized to a carboxylic group.
  • Secondary hydroxyls are bond to atoms C 2 and C 3 , thus forming a vicinal diol function (-CHOH-CHOH-), also known as a 1,2- dihydroxyethylene group. Oxidation of these secondary hydroxyls can give a-hydroxyketones and diketones or can induce cleavage of the diol with formation of a dialdehyde group or a dicarboxyl group upon further oxidation.
  • a general method in the art to produce oxidized polysaccharides with selective aldehyde formation uses periodate as oxidizing agent (See for example, Wongsagon et a I, Starch/die Starke, 57:166-172 (2005); McGuire and Mumbleretter, Starch/die Starke, 23:42-45 (1971)).
  • Periodic acid and derived salts are oxidants that selectively oxidize the vicinal diol function with cleavage of the C 2 -C 3 bond to form aldehyde moieties that are not further oxidized to carboxyl functions. If applied to starch, dialdehyde starch is obtained ( Figure 2).
  • High pH favors oxidation of iodate due to pH dependency of the redox potential of the periodate/iodate couple (1.6 V at low pH; 0.7 V at high pH). Moreover, at basic pH, the regenerated periodate precipitates and can be separated by filtration, washed, and reused.
  • the present invention is directed to a novel oxidation method in which an organoiodine compound instead of inorganic periodate is used as selective oxidant.
  • the novel method does not suffer from above-mentioned problems related to periodate regeneration.
  • the selective oxidant used in the method is an organoidine compound and more particularly, the compound is a hypervalent iodoarene derivative.
  • the present invention provides a method to produce oxidized polysaccharides such as for example C 6 /C 2 -C 3 oxidized starch or, more particular, dialdehyde starch efficiently and selectively with the possibility to regenerate spent oxidant.
  • the reaction can be carried out in water or in water mixed with an organic solvent and does not suffer from excessive salt formation.
  • the invention allows preparation of dialdehyde starch end product which is free from salts or contaminations from contact with leaching electrodes or toxic metals.
  • the present invention allows production in a batch process in which the spent oxidant is separated, regenerated to its hypervalent state, and re-used in a successive batch operation.
  • the oxidant can be immobilized on solid phase with the aqueous solution containing polysaccharides being sent through the solid phase reactor. After reaction, the spent oxidant is quantitatively recovered and regenerated.
  • a reactor consists for example of two (or multiple) reactor beds (or tubes) with oxidant immobilized on solid phase, thereby alternating the oxidation phase with a regeneration phase in the second reactor bed (or tube).
  • Figure 1 Schematic representation of an anhydroglucose unit of starch
  • Figure 2 Prior art process to produce oxidized polysaccharides with selective aldehyde formation uses periodate as oxidizing agent. If applied to starch, dialdehyde starch is obtained.
  • Figure 3 Schematic representation of starch showing the [alpha]-l,4-glycosidic bonds, and the [alpha]-l,6-glycosidic bonds as found in amylopectin, resulting in an overall branched structure.
  • FIG. 4 Schematic representation of the process of the present invention using hypervalent iodoarene derivative as oxidant instead, in this example (bisacetoxy)iodobenzene (BAIB).
  • BAIB bisacetoxyiodobenzene
  • Figure 5 Schematic representation of the immobilization of the oxidant to a solid report, using either a linker molecule or directly to a hypervalent iodopolystyrene resin.
  • Figure 6 Schematic representation of a batch process (A) using the process of the present invention or of continuous process (B).
  • Figure 7 FT-IR spectra of the solids were recorded on a Bruker Alpha diamond crystal ATR FT-IR spectrometer, (a) spectrum obtained for oxidized starch using the method of the present invention with clear occurrence of the peak around 1723 cm 1 (indicated by an arrow) characteristic for the presence of an aldehyde group, (b) spectrum for dried unoxidized starch lacking the aforementioned peak around 1723 cm “1 , (c) spectrum obtained for DAS 50% dialdehyde obtained with 0.5 equivalents of Nal0 4 - showing the upcoming aldehyde peak (indicated by arrow) at around 1723 cm "1 , (d) spectrum obtained for DAS 100% dialdehyde obtained with 1.0 equivalents of Nal0 4 - showing the same spectrum as using the method of the present invention ( Figure 7 (a)) with the aldehyde peak at around 1723 cm 1 (indicated by arrow).
  • Figure 8 In order to determine the degree of oxidation the oxidized starch is reduced and depolymerized as schematically shown and providing both unoxidized glucose units and dialdehyde (oxidized glucose) units that are detected as glucose and erythritol respectively.
  • Figure 9 LC-MS spectra of the glucose units and the erythritol units obtained in the reduction reaction to determine the degree of oxidation of the oxidized starch.
  • the present invention provides a method to produce oxidized polysaccharides. More particularly, the invention provides a method to oxidize polysaccharides with selective aldehyde formation, such as dialdehyde starch efficiently and selectively with the possibility to regenerate spent oxidant.
  • the aldehyde groups on the polysaccharide backbone are electrophiles that are targeted in subsequent derivatization steps or they act as reactive sites in cross-linking reactions.
  • the oxidation of polysaccharides to give ring opening of the monomeric carbohydrate units and oxidation of the vicinal diol group to a dialdehyde is known, but the use of a hypervalent organoiodine compound as oxidant for this conversion is novel to the field.
  • Starch and starch derivatives are preferred substrates for oxidation due to their availability, their acceptance in pharmaceutical formulations, and their biocompatibility.
  • Starch depending on its origin, consists of amylose and amylopectin in various ratios, polymeric molecules which are chemically built from connecting glucose units via [alpha]- 1,4-glycosidic bonds.
  • Amylopectin also contains [alpha]-l,6-glycosidic bonds, giving a branched structure when compared to the linear amylose ( Figure 3).
  • starch feed can originate from from wheat, barley, potato, rice, cassava, maize, tapioca, sorghum, orache, pea, other relevant sources or genetically modified variations thereof.
  • the method is equally applicable to other compounds in the starch group (including beside starch, amylopectin, and amylose, also hydrosylates such as maltodextrins or other derivatives thereof) as well as it is applicable to cellulose (which differs from amylose in its [beta]-l,4-glycosidic bonds) and other beta-glucans, galactomannans, fructans, xylans and the like, and alkylated, acetylated, carboxyalkylated, hydroxyalkylated, and other possible derivatives of mentioned polysaccharides that contain a vicinal diol group.
  • the present invention comprises another method to selectivity cleave a vicinal diol in polysaccharides with formation of dialdehydes or corresponding carboxylic groups, and to selectively convert the free hydroxyl groups such as for example found at the C 6 position of the anhydroglucose unit in [alpha]-l,4-glucans into the corresponding aldehyde or carboxylic group.
  • the method uses a hypervalent iodoarene derivative as oxidant, preferably, a compound wherein the oxidation state of the hypervalent iodine is +111 or +V as for example in (bisacetoxy)iodobenzene (BAIB; Figure 4) and iodoxybenzene, respectively.
  • a hypervalent iodoarene derivative as oxidant, wherein the oxidation state of the hypervalent iodine is +111, the oxidation of the polysaccharide results in a selective cleavage of the vicinal diols with the formation of the corresponding dialdehyde polysaccharide. It is accordingly an object of the present invention to provide the use of a hypervalent iodoarene derivative, characterized in that the oxidation state of the hypervalent iodine is +111, for cleaving a vicinal diol in a polysaccharide; for the production of a dialdehyde polysaccharide.
  • the invention provides the use of a hypervalent iodoarene derivative, characterized in that the oxidation state of the hypervalent iodine is +111, for cleaving vicinal diols in starch; for the production of dialdehyde starch (DAS).
  • DAS dialdehyde starch
  • the present invention provides the use of hypervalent iodoarene derivative, characterized in that the oxidation state of the hypervalent iodine is +V, to oxidize polysaccharides; for the production of C 6 /C 2 -C 3 oxidized starch.
  • hypervalent refers to the iodine element exceeding the octet rule, i.e. it has more than eight electrons in its valence shell.
  • the use of hypervalent iodoarene species in the present invention comprises hypervalent iodoarenes with acetoxy ligands but equally applies to hypervalent iodoarene species with other suitable ligands including, but not limited to, hydroxyl, methoxy, ethoxy, acetoxy, trifluoroacetoxy, propionate, formate, carbonate, mesylate, and triflate ligands and other oxygen-bound ligands, halides, carbon- bound ligands, nitrogen-bound ligands and the like, as well as it does apply to hypervalent iodoarenes in the absence of ligands.
  • iodoarenes all structures that comprise a iodine-substituted benzene moiety, such as, but not limited to, iodobenzene, iodonapthalene, iodobenzoic acids, iodobenzenesulfonic acids, and the like.
  • iodoarenes is also meant iodine-substituted heteroaromatic compounds, such as, but not limited, iodopyridine, iodopyrrole, iodothiophene, and the like.
  • the oxidation mechanism is based on substituting substrate hydroxyls for incipient ligands, followed by reductive elimination with formation of oxidized substrate and spent oxidant (iodobenzene; IB) ( Figure 4). Solubility of BAIB in aqueous solutions is obtained by slightly heating, the resulting iodobenzene is however insoluble in water. It can thus be separated from the aqueous phase and subsequently be regenerated.
  • reactions are carried out in water or in water mixed with an organic co- solvent.
  • reactions can be carried out using ionic liquids or supercritical fluids.
  • the pH of the aqueous solution can be acidic or basic, but should not be lower or higher than the pH at which degradation of starch or oxidant occurs.
  • the reaction is carried out in aqueous solution at neutral pH.
  • the mixture containing water and starch can be cooked for a specific time (depending on the starch nature) prior to reaction.
  • the resulting solution/suspension is then cooled to the temperature at which conversion from starch to dialdehyde starch occurs: this is between 0°C and 100°C, preferably between 20°C and 60°C and more preferably between 40°C and 50°C.
  • the reaction can be carried out under ambient or inert atmosphere at a pressure between 0.01 atm and 10 atm.
  • the reaction is preferably carried out under ambient atmosphere at 1 atm pressure.
  • dialdehyde starch is selectively obtained.
  • the invention allows preparation of dialdehyde starch in varying degrees of oxidation.
  • degree of oxidation is meant % of the C 2 -C 3 vicinal diol which is cleaved with formation of a dialdehyde moiety.
  • the reaction typically continues up to a degree of oxidation between 1% and 100%, preferably to a degree of oxidation between 5% and 50%, and most preferably to a degree of oxidation between 15% and 35%.
  • Factors influencing the degree of oxidation include reaction time, as well as the ratio and/or concentration of the reagents, i.e. of oxidant to vicinal diol.
  • a ratio of oxidant/vicinal diol of up to 0.3 will give almost quantitative conversion to dialdehydes to obtain up to and about 30% degree of oxidation.
  • the degree of oxidation is lower than the amount of oxidant used.
  • the present invention is further characterized in that the processes are performed with a ratio of oxidant to vicinal diol of up to 0.3 or more; in particular from up to about 0.3 until up to about 1.0; more in particular from up to about 0.3 until up to about 0.5; even more in particular up to about 0.3.
  • the regeneration of spent oxidant is understood as the oxidation of a iodoarene compound, which contains a iodine atom in oxidation state +1 and which in the method is referred to as the spent oxidant form, to a hypervalent iodoarene with iodine oxidation state +111 or +V with suitable ligands attached.
  • a hypervalent iodoarene with iodine oxidation state +111 or +V with suitable ligands attached In the absence of suitable ligands, iodosobenzene, another hypervalent iodoarene with iodine oxidation state +111 is formed.
  • the regeneration step is preferably carried out separated from the starch reaction mixture as to prevent further oxidation of aldehydes to carboxyl groups.
  • a catalytic amount of the hypervalent iodoarene oxidant can be used in the preparation of oxidized starch, using a terminal oxidant for in situ regeneration, i.e. within the starch reaction mixture, of the catalytic amount of hypervalent iodoarene.
  • a terminal oxidant for in situ regeneration i.e. within the starch reaction mixture, of the catalytic amount of hypervalent iodoarene.
  • in situ regeneration is preferably carried out by a suitable terminal oxidant that does not affect aldehyde functions.
  • the present invention comprises the use of oxidants, such as oxygen, ozone, chlorine, percarboxylic acids, anorganic oxoacids and derived salts, metals, hypochlorite, and others for the regeneration of the hypervalent iodoarenes, in particular for formation of hypervalent iodoarenes with iodine in the oxidation state +111 or +V and with suitable ligands as was mentioned before; more in particular using peracetic acid as oxidant.
  • oxidants such as oxygen, ozone, chlorine, percarboxylic acids, anorganic oxoacids and derived salts, metals, hypochlorite, and others for the regeneration of the hypervalent iodoarenes, in particular for formation of hypervalent iodoarenes with iodine in the oxidation state +111 or +V and with suitable ligands as was mentioned before; more in particular using peracetic acid as oxidant.
  • regeneration involves oxidation of a iodoarene, more particularly of iodobenzene, using acetic anhydride, acetic acid (or a derivative) in combination with an oxidant, preferably with hydrogen peroxide, to generate BAIB with only water and acetic acid as waste products.
  • the hypervalent iodoarene oxidant is immobilized on solid support material such as, but not limited to, a polymer compound. The solid support allows quantitative recovery of the spent oxidant from the reaction mixture. Beside free from salts and free from contamination from contact with leaching electrodes and toxic metals, starch end products prepared by the present invention are also free from residual oxidant.
  • the hypervalent iodoarene is attached to the solid phase, such as for example polystyrene, silica, or another type of suitable support, through a linker technique known to those skilled in the art ( Figure 5). More preferably, the iodine atom can be attached directly on the surface of beads made of aromatic polymers, for example as in iodopolystyrene ( Figure 5).
  • the present invention allows production of dialdehyde starch in a batch process or in a continuous process.
  • the spent oxidant iodobenzene or derivative
  • the aqueous reaction mixture from which the dialdehyde starch can be obtained for example by spray drying
  • Figure 6, A its density
  • the spent oxidant is then regenerated to its hypervalent form and re-used in a successive batch operation.
  • the oxidant is immobilized on solid phase.
  • the aqueous solution containing starch is sent through the solid phase reactor, after which the spent oxidant is quantitatively recovered and regenerated.
  • the reactor consists of two (or multiple) reactor beds or columns with oxidant immobilized on solid phase ( Figure 6, B). Continuity is obtained by alternating the oxidation phase with a regeneration phase in the second reactor bed or column.
  • wheat starch is used to start from.
  • a typical procedure for the preparation of dialdehyde starch is as described in Example 1.
  • Example 1 Oxidation of starch in aqueous medium using BAIB as oxidant
  • dialdehyde starch 1 g wheat starch (containing 10-11% water) was added to 30 mL of distilled water. The resulting suspension was heated to 70°C for 30 min and the resulting pale suspension was then left cooling to 50°C. At that point, the hypervalent iodoarene BAI B (1.9 g; 1.05 equivalents of starch vicinal diol groups) was added and readily dissolved, giving a slightly yellow color to the suspension. The mixture was kept at 50°C overnight, which turned the reaction mixture into a clear solution with small drops of iodobenzene dispersed on the bottom of the flask.
  • the mixture is extracted with diethylether to recover the iodobenzene.
  • Addition of 2 volumes of acetone to the aqueous layer led to flocculation of the dissolved or suspended starch product, allowing filtration on a glass-sintered filter.
  • the isolate was a white, pastelike gel that turned into white to colorless flakes upon further washing with acetone.
  • the product was dried under vacuum prior to detailed characterization. DAS was recovered in 68% yield weight based.
  • the FT-I R spectra are indicative of the changes occurring in starch after oxidation.
  • the appearance of a peak around 1723 cm 1 in the oxidized starch is characteristic for the presence of an aldehyde group. Intensity of the peak is however poor and particularly for low degrees of oxidation (for example for 25% degree of oxidation), observation of the aldehyde is difficult.
  • the major modification in the starch backbone i.e.
  • Example 2 The same procedure as described in Example 1 is used, with the exception that an organic cosolvent is used to assist solubilization of the oxidant. Yields and degree of oxidation of dialdehyde starch are given in Table 1. Overall, the presence of ethanol gave the highest yield of oxidized starch, but the degree of oxidation was lower compared to the products obtained with methanol or without the addition of a cosolvent.
  • Example 3 Oxidation of starch in aqueous medium using 0.15 equivalents BAIB as oxidant 3 g wheat starch (containing 10-11% water) is added to 50 ml water. The mixture is heated to 40°C. At that point, the hypervalent iodoarene (bisacetoxy)iodobenzene (0.81 g; 0.15 equivalents of starch vicinal diol groups) was added giving a slightly yellow color to the suspension. The temperature was raised to 50°C and stirred for 23 hours at that temperature. The reaction mixture turned into a milky solution with small drops of iodobenzene dispersed on the bottom of the flask.
  • BAIB hypervalent iodoarene
  • the mixture is extracted with diethylether to recover the iodobenzene.
  • Addition of 2 volumes of acetone to the aqueous layer led to flocculation of the dissolved or suspended starch product.
  • the mixture was centrifuged (4700 rpm, 10°C) for 20 min followed by filtration on a glass-sintered filter. The isolate turned into white to colorless flakes upon further washing with acetone.
  • the product was dried under vacuum prior to detailed characterization. DAS was recovered in 99% yield weight based.
  • the degree of oxidation was determined by titration via the quantitative alkali consumption method (Hookter et al, Analytical Chemistry 27:1930-1931 (1955)) as described in example 1 and the degree of oxidation amounted to 13.7%.
  • a 25 mg sample of the oxidized starch is first reduced by adding 1ml of an aqueous solution of sodium borohydride (0.8 M) and sodium hydroxide (0.1 M). The mixture is stirred for 22 hours at room temperature. Next 60 ⁇ of sulfuric acid is added and the mixture is stirred for 8h at 95°C. The obtained mixture is subsequently diluted and analyzed via LC-MS where the unoxidized glucose units of the polysaccharide are detected as glucose and the dialdehyde units are detected as erythritol ( Figure 8 and Figure 9). The ratio glucose/erythritol is a measure for the degree of oxidation.
  • Example 5 Oxidation of maltodextrin in aqueous medium using BAIB as oxidant
  • peracetic acid solution was prepared by reacting acetic acid with hydrogen peroxide in presence of a catalytic amount of strong acid as sulfuric acid and stirred for 17h at 30°C.
  • Example 7 Oxidation of starch in aqueous medium using polystyrene supported (bisacetoxy)iodobenzene
  • iodopolystyrene was prepared from polystyrene and l2/l2O5/50%H 2 SO 4 as described in literature (Tohma et al, Tetrahedron letters, 2001, 42, 6899-6902) and subsequently oxidized to polystyrene supported (bisacetoxy)iodobenzene with acetic anhydride and hydrogen peroxide as described in example 5.
  • Recovered iodopolystyrene from example 4 was suspended in acetic anhydride and cooled at 0°C. A 30% aqueous hydrogen peroxide solution was added dropwise. The reaction was stirred for 30 hours at room temperature. Diethylether was added to the reaction and the precipitated polymer was recovered by filtration and washed with diethylether.

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Abstract

La présente invention porte sur un procédé pour convertir des polysaccharides en un dérivé oxydé, en particulier un dérivé oxydé dans lequel les deux fonctions alcool secondaire adjacentes sont converties en un dialdéhyde avec clivage de la liaison carbone-carbone de jonction. Plus particulièrement, l'invention porte sur un procédé pour convertir de l'amidon à l'aide d'un dérivé d'iodoarène de valence très élevée servant d'oxydant pour convertir l'amidon en un dérivé oxydé dans lequel les groupes hydroxyle en position C6 et en position C2-C3 sont oxydés. Dans encore un autre mode de réalisation la présente invention porte sur un procédé pour convertir de l'amidon à l'aide d'un dérivé d'iodoarène de valence très élevée, tel que le bisacétoxyiodobenzène, servant d'oxydant en amidon dialdéhyde (DAS) en tant que produit réactionnel. Le procédé comprend également un procédé pour régénérer l'oxydant usé.
PCT/EP2012/066843 2011-08-31 2012-08-30 Procédé pour modifier des glucides WO2013030264A1 (fr)

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GB1330123A (en) * 1969-08-20 1973-09-12 Unilever Ltd Process for oxidising polysaccharides
JPH06115904A (ja) 1992-10-05 1994-04-26 Mitsui Toatsu Chem Inc 過ヨウ素酸カリウムの製造方法
US5747658A (en) 1993-11-04 1998-05-05 Instituut Voor Agrotechnologisch Onderzoek (Ato-Dlo) Method for the oxidation of carbohydrates
WO1998027118A1 (fr) 1996-12-16 1998-06-25 Coöperatieve Verkoop- En Productievereniging Van Aardappelmeel En Derivaten Avebe B.A. Procede d'oxydation d'amidon a l'aide de periodate
WO2000075070A1 (fr) 1999-06-07 2000-12-14 Sca Hygiene Products Zeist B.V. Procede de regeneration d'acide periodique
US20020072599A1 (en) * 2000-12-13 2002-06-13 Arie Besemer Recovery process for spent periodate
US20050002893A1 (en) 2001-10-24 2005-01-06 Helmut Goldmann Composition consisting of a polymer containing amino groups and an aldehyde containing at least three aldehyde groups
US20060078536A1 (en) 2004-10-07 2006-04-13 Kodokian George K Polysaccharide-based polymer tissue adhesive for medical use
WO2008133847A1 (fr) 2007-04-24 2008-11-06 E.I. Du Pont De Nemours And Company Procédé de fabrication d'un polysaccharide dialdéhyde ayant une pureté élevée
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US3376285A (en) * 1964-10-12 1968-04-02 Dow Chemical Co Dissolution of cellulose ethers
GB1330123A (en) * 1969-08-20 1973-09-12 Unilever Ltd Process for oxidising polysaccharides
JPH06115904A (ja) 1992-10-05 1994-04-26 Mitsui Toatsu Chem Inc 過ヨウ素酸カリウムの製造方法
US5747658A (en) 1993-11-04 1998-05-05 Instituut Voor Agrotechnologisch Onderzoek (Ato-Dlo) Method for the oxidation of carbohydrates
WO1998027118A1 (fr) 1996-12-16 1998-06-25 Coöperatieve Verkoop- En Productievereniging Van Aardappelmeel En Derivaten Avebe B.A. Procede d'oxydation d'amidon a l'aide de periodate
WO2000075070A1 (fr) 1999-06-07 2000-12-14 Sca Hygiene Products Zeist B.V. Procede de regeneration d'acide periodique
US20020072599A1 (en) * 2000-12-13 2002-06-13 Arie Besemer Recovery process for spent periodate
US6620928B2 (en) 2000-12-13 2003-09-16 Sca Hygiene Products Zeist B.V. Recovery process for spent periodate
JP4202002B2 (ja) 2001-05-10 2008-12-24 独立行政法人科学技術振興機構 高降伏応力Ｚｒ系非晶質合金
US20050002893A1 (en) 2001-10-24 2005-01-06 Helmut Goldmann Composition consisting of a polymer containing amino groups and an aldehyde containing at least three aldehyde groups
US20060078536A1 (en) 2004-10-07 2006-04-13 Kodokian George K Polysaccharide-based polymer tissue adhesive for medical use
WO2008133847A1 (fr) 2007-04-24 2008-11-06 E.I. Du Pont De Nemours And Company Procédé de fabrication d'un polysaccharide dialdéhyde ayant une pureté élevée

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