Patent GB-518586-A (GB)
Title: Phenolic sugar alcohols
IPC: C07C39/11
Filed: 1938-08-27
Abstract: 518,586. Hydroxyaryl derivatives of carbohydrates;synthetic resins ; dyes ; cellulose derivatives ; explosives. NIEDERL, J. B.- Aug. 27, 1938, No. 25243. Convention date, Aug. 28, 1937. [Classes 2 (ii) and 2 (iii)] Compounds containing a hydroxyaryl group and a polyhydroxyalkyl group are obtained by treating a mono- or poly-saccharide with a monohydric phenolic compound at a temperature not exceeding 70‹C. in the presence of a strong acid condensing agent, the proportion of phenolic compound being one molecule per molecule of monosaccharide taken as such or producible by hydrolysis. Specified saccharides are d-glucose, d-mannose, d-galactose, d-arabinose, d-erythrose, glyceric aldehyde, and d-fructose. Specified phenolic compounds are (a) phenol and its homologues, such as cresols, xylenols, thymol, carvacrol, and butyl-, amyl-, hexyl-, heptyl-, and octyl phenols, (b) monohydric phenols containing a substituent such as an aldehyde, ketone, hydroxyalkyl, carboxylic or ether or ester group, such as salicyl aldehyde, p-hydroxyacetophenone, salicyclic acid, alkyl salicylates, guaiacol and vanillin, and (c) polynuclear monohydroxy phenolic compounds such as oc and #-naphthols, hydroxyanthracenes and phenanthrols. The condensing agent may be a mineral acid or a salt of strongly acid reaction, and a solvent may be present. The preferred solvent is glacial acetic acid, and when this is used partly acetylated products may be obtained ; these may be deacetylated by treatment with boiling water- or dilute alkali. The products are soluble in water and have bactericidal and germicidal properties. They may be converted into sodium salts by treatment in alcoholic solution with sodium ethylate, and yield water-soluble bromine derivatives when brominated by the usual methods. The products also couple with aromatic diazo compounds to yield dyestuffs, and may be converted by nitration into explosives containing both nitro and nitric ester groups. The conversion of the products into phenolic aldehydes, ketones and acids by oxidation, and the esterification and etherification of the products, are also mentioned. In the examples, (1) 1-hydroxyphenyl-sorbitol is prepared by interaction of phenol with d-glucose in glacial acetic acid, whilst dry hydrogen chloride is passed in ; its coupling with diazotized p-nitraniline, nitration with concentrated nitric acid at steam bath temperature, conversion into the sodium salt with sodium ethylate, acetylation with acetic anhydride and brominations are described ; (2) m-cresol is condensed with d-galactose ; (3) thymol is reacted with dglucose ; (4) #-naphthol is condensed with d-glucose ; (5) phenol is heated with d-fructose, giving 2-hydroxyphenyl-sorbitol whose sodium salt, nitration and bromination products are mentioned. The Specification as open to inspection under Sect. 91 also describes the use of polyhydric phenols and of cellulose and cellulosic derivatives. It also includes examples of the condensation of d-glucose with resorcinol and with acetyl-salicylic acid ; the resorcinol may be replaced by catechol, hydroquinone, orcinol, pyrogallol or phloroglucinol. It further states that all the phenolic sugar alcohol products may be oxidized to phenolic-polyhydroxylic acids which are useful in the tanning industry, or may be combined with formaldehyde in alkaline media to give resinous condensation products. This subject-matter does not appear in the Specification as accepted.