Reactions of Starch Dialdehyde

Mercaptolysis of starch dialdehyde occurs upon reaction with thiolacetic acid.525 It is possible that acetalation and crosslinking are involved in making a size consisting of starch dialdehyde, starch, and boric acid.526 

Sodium hydrogensulfite reacts with starch dialdehyde in a 1 1 ratio.527,528 Despite the fact that aldehydes react with hydrogensulfites, these compounds are described as adducts. Sodium sulfite degrades starch dialdehyde and the glyoxal liberated forms tetrahydrobenzoquinone.529 

Etherification of starch dialdehyde is possible. The reaction of starch dialdehyde with propylene oxide and other etherification reactions were described.530 Esterification of starch dialdehyde with carboxylic anhydrides stabilizes the viscosity and adhesiveness of starch dialdehyde.531 This adhesive is additionally blended with urea. 

Esterification of starch dialdehyde with chlorosulfonic acid in formamide gave a sulfate ester that could be transformed into an amide and methyl ester.532-536 The classical method of sulfonation, namely, by the action of sulfur trioxide in pyridine, is also applicable.537,538 Hemiacetals of starch dialdehyde result upon treatment with suitable alcohols in the presence of an acidic catalyst. In acetic media amides condensed with the carbonyl groups. Acetylation of starch dialdehyde with acetic anhydride is an obvious reaction. Esters with hexanedioic (adipic) acid were also prepared.537 Starch dialdehyde undergoes etherification with monochloroacetic acid in an alkaline medium.538 

Starch dialdehyde also reacts with carbanions. For instance, reaction with nitromethane produces a nitro compound that after reduction with iron(II) hydroxide in ammonia afforded an animated product.539 Molded articles from starch dialdehyde and elemental sulfur were also patented.540 

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Reactions of Starch Dialdehyde and Other Starch Derivatives. 285... 

Starch dialdehyde condenses readily with amino amides2624 and diamines,2625 and forms oximes with hydroxylamine.2626 The reaction of starch dialdehyde with isoniazid, 4 -formacelanilide thiosemicarbazone, 4 - amin o b e n z a I de h y de thiosemicarbazone or thiosemicarbazone, produced the corresponding condensation products.613-615 617 2627-2629 Hydrazones were readily formed when hydrazine and its derivatives were blended with starch dialdehyde and acidified with acetic acid2543,2630 or simply on heating the reaction mixture.2631 Condensation of starch... 

Reaction of starch dialdehyde with urea gave a condensation product.442,2633 Carboxyamides,2624 including acrylamide,524,585 were also allowed to react with starch dialdehyde. Condensation can occur between starch dialdehyde and macromolecules containing amido groups, for instance, epichlorohydrin-crosslinked polyamide resin,598 ammonia-diethylamine-epichlorohydrin copolymer,588 dicyanamide-formaldehyde resins,565,566 quaternary alkylam-monium compounds,596,610,611 amino acids,2634,2635 protein,626,2636-2639 and aminoalkylated starch.2515 The reactions are favored by low pH. The guanidino moieties of proteins entered the condensation the most readily. 

Starch derivatives may also undergo hydrolysis and degradation under alkaline conditions. The hydrolysis of the nitriles, amides, and esters resulting from the reaction of starch with corresponding vinyl monomers is obvious. Considerable attention has been paid to the alkaline degradation of starch dialdehyde. It de-polymerized readily supposedly as a result of -elimination at C-5, although such a questionable -elimination should not be facile).70... 

Starch was oxidized by Jackson and Hudson,who used periodic acid at room temperature. Considerable study has recently been made of the oxidation of starch on a commercial basis, using electrolytically regenerated periodic acid. The reaction is carried out under what are normally drastic conditions for a periodate oxidation, namely pH 1.2-1.4 and 100°F, apparently without occurrence of any over-oxidation. Oxystarch is known commercially as dialdehyde starch. ... 

Amidooximation of cyanoethylated starch is relevant here. The reaction of (cyanoethyl)starch with hydroxylamine at pH 7.1 and a temperature of 90 °C for 90 min produced a material used to chelate Fe(III) and A1 cations.2640 By reacting starch dialdehyde with acrylonitrile and hydrazine in alkaline solution, followed by adjusting the pH to 5-6 a glue was prepared.2641... 

The absorbance of the red quinonamine dye formed in the reaction of phenol and 4-amino-l,5-dimethyl-2-phenyl-3-pyrazolone (4-aminoantipyrine) with periodate ions has been used in the estimation of periodate consumption in the oxidation of starch and other carbohydrates. The evaluation of the use of pyridine as a solvent in the oxidation of water-insoluble carbohydrates by periodate has been reported. The three types of dialdehydes produced by this oxidation were converted to the TMS ethers of the dithioacetals and measured by g.l.c. Oxidation proceeded in a normal Malapradian fashion but more slowly than it does in water. 

Vicinal alcohol groupings in polysaccharides can be oxidized by periodate to cleave the carbon-carbon bond and produce two aldehyde groups. Starch is the principal polysaccharide that has been oxidized to produce dialdehyde starch (reaction 7.22) [15]. The degree of oxidation can be controlled by the amount of... 

The periodate oxidation leads to dialdehyde starches by specific action on C2 and C3 of the AGU. Continuous production is run in a series of stirred tanks in a heterogeneous system of a neutral starch slurry and sodium periodate. During reaction, the reagent is reduced to iodic acid, which is separated, reoxidized in an electrolytic cell and recycled to the process. The dialdehyde starch (DAS) is washed and dried in the usual manner,... 

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