Derivatives of d-glucose diethylmercaptal and an attempted synthesis of 5-methyglucose
Degree GrantorUniversity of Canterbury
Degree NameMaster of Science
Kilimi (1866) first showed that an aldehyde group was present in glucose, by forming the cyanhydrin, which on hydrolysis and reduction gave n-heptoic acid. Glucose was later represented by the straight chain, “Fischer Projection Formula” and this was in general use until 1926, when Haworth proposed the pyranose ring structure for sugars. [Diagram] A ring formula was given to the isomeric methyglucosides, by Fischer. (These derivatives were obtained by the reaction of glucose with 0.5% methyl alcoholic hydrogen chloride at 80%.) Fischer did not extend the ring formula to glucose itself and he wrongly assumed that the ring was a (1,4) or butylene oxide ring. By a consideration of the phenomenon of mutarotation, later workers were able to show that sugars themselves had ring structures. A study of the oxidation products of tetramethylglucose showed that normal glucose had a (1:5) ring. This pyranose ring was represented by a hexagonal formula and X-ray evidence in support of it has been obtained.