Patent GB-1019512-A (GB)
Title: Process for carrying out reactions involving sugars and their derivatives with reagents therefor
IPC: C07D307/46
Filed: 1962-08-07
Abstract: Reactions of sugars, e.g. polymerization with Friedel Crafts' catalysts and ammonium persulphate; and condensations involving prior formation of 5-hydroxymethyl furfural or malondialdehyde, are effected by dissolving the sugar by heating to 50-200 DEG  C. in a substantially anhydrous, water miscible, high boiling monohydric alcohol containing the grouping <FORM:1019512/C3/1> and reacting the solution with the reagent at 0-200 DEG  C.  The reaction mixtures must contain less than 5% by wt. of water.  The solvents include glycol derivatives, e.g. ethylene and diethylene glycol mono-ethers and esters, furfuryl and tetrahydrofurfuryl alcohols, and 2-hydroxy-methyl tetrahydropyrens.  In examples: (8) sucrose is polymerized with AlCl3 or BF3; (9), (10) phenol is reacted with Na in the solvent, a mixture of sucrose and paraformaldehyde added, the reaction product acidified, and the precipitate ether extracted to obtain a resin.ALSO:Reactions of sugars and their derivatives with reagents are effected by dissolving them by heating to 50-200 DEG  C. in a substantially anhydrous, water-miscible, high boiling monohydric alcohol containing the grouping <FORM:1019512/C2/1> and reacting the solution with the reagent at 0-200 DEG  C.  The reaction mixtures must contain less than 5% by weight of water. The solvents include glycol derivatives, e.g. ethylene and diethylene glycol mono-ethers and esters, furfuryl and tetrahydrofurfuryl alcohols, and 2-hydroxymethyl tetrahydropyrans.  Reactions referred to include reductions, reductive ammonolysis, hydrogenolysis, mercaptal and other sulphur compound formation, oxidations, reactions with amines, reactions of dialdehydes derived by periodate oxidation of sugars, e.g. alkaline condensation with paraffinic -CHNO2 compounds, carbonate formation, acetone-acetaldehyde reactions, periodate oxidations, dehydration reactions, e.g. formation of 5-hydroxymethyl furfural and anhydrosugars, polymerizations, e.g. with Friedel-Crafts catalysts or ammonium persulphate, condensations involving prior formation of 5-hydroxymethyl furfural or malondialdehyde, production of ethers of the solvent and 5-hydroxymethyl furfural, 2,5-dihydroxymethyl furan or tetrahydrofuran, and N-glycoside formation.  Examples describe (1) glucose reduction in glycol monomethyl ether to sorbitol hemihydrate; (2) mercaptal formation from glucose and n-butyl mercaptan; (3) oxidation of glucose with bromine in diethylene glycol monomethyl ether to d - and g -lactones of D-gluconic acid and free acid; (4) condensation of D-hydroxymethyl - D1 - methoxy diglycolic aldehyde with nitromethane; (5) production of the starting material of (4) from a -methyl-D-glucopyranoside and periodic acid; (6) dehydration of fructose to 5-hydroxymethylfurfural using mineral acid, sodium bisulphate or acid form resin.  Organic acids, kestose, insulin, sorbose or sucrose may be used; (7) erythritol in tetrahydrofurfuryl alcohol and benzene is refluxed with acid catalyst to give 3,4-dihydroxy tetrahydrofuran; (8) sucrose is polymerized with AlCl3 or BF3; (9), (10) formation of a resin from sucrose, phenol, and formaldehyde; (11), (12) formation of ethers of the solvent; diethylene glycol monomethyl ether or tetrahydro-furfuryl alcohol, and 5-hydroxymethylfurfural by dehydrating fructose; (13) reduction of ethers of this type to the corresponding 2,5-dihydroxymethylfuran ethers; (14) N-glycoside formation from dodecylamine and glucose.ALSO:Products for staining and finishing wood are obtained by polymerizing sucrose with AlCl3 or BF3 in diethylene glycol monomethyl ether or by condensing sucrose with phenol and formaldehyde in tetrahydrofurfuryl alcohol and dissolving the resinous product in a glycol ether or ethyl acetate.