The chemistry of glucosone

Abstract

Although the osones were first prepared by Emil Fischer sixty-five years ago and, in the intervening period, investigation of these compounds has not been neglected, there exists no modern comprehensive review of their chemistry and biochemistry. In consequence, Part I of this thesis is a full and critical survey of work published on the osones up to June 1953. Part II, a discussion of the methods and results of the author’s own research on the subject, is presented under the same arrangement of sub-titles as that used in Part I. The object of this research was to investigate the preparation and properties of the osones, in particular D-glucosone, and their derivatives by the application of both modern and classical methods of carbohydrate chemistry, with a view to establishing the structural features of these compounds. An attempt has been made to correlate the author;s own results with those of other workers and, at the same time, to develop lines of attack which have hitherto received no attention. Part III is a detailed report of the author’s experimental work. The material presented stands as a contribution to carbohydrate chemistry. That further investigation of the osones is justified may be realised from consideration of the following facts: no completely satisfactory methods for the preparation, characterisation, and estimation and no preparation of a crystalline derivative from which the ozone may be readily regenerated has been described; there is little definitive knowledge of ozone structure. In addition, the elucidation of the precise chemical structure of D-glucose and its behaviour in solution is essential for the complete understanding of the biological significance of the compound. 1. A critical and comprehensive review of the published work on the preparation, properties, structure, and biological significance of the osones is presented. 2. A full experimental investigation of the methods of preparation of osones is reported. By the introduction of modifications established methods have been adapted for the preparation of osones, possessing a high degree of purity, in higher yields than hitherto obtained; a number of new preparative procedures are described. 3. The physical properties of glucosone, including rotational behaviour, ultraviolet absorption spectrum, chromatographic analysis, and ionophoretic analysis of aqueous solutions, properties which have hitherto received little or no attention, have been studied; the results are discussed in relation to the structural features of the osone and to the detection and identification of glucosone when in admixture with other sugars or in biological material. 4. The effect of acids and of alkalis on glucosone has been investigated and the preparation and properties of a number of ozone derivatives with substituted hydrazines are described. Methods of estimation of glucosone in the presence of other sugars have been evolved. 5. The preparation, properties, and structures of isopropylidene derivatives of a number of osones are described. 1:2-2:3-5:6-Tri-o-isopropylidene d-and l-glucosone hydrate and 1:2-2:3-5:6-tri-o-isopropylidene l-gulosone hydrate were obtained, the first crystalline derivatives from which the corresponding osones may be readily regenerated. 6. The possible structures which may be assigned to d-glucosone on the available evidence are discussed.