六与高中九十五学年度第一学期认辅.pptVIP

25.17Carbohydrate Structure Determination Carbohydrate Structure Determination Spectroscopy X-Ray Crystallography Chemical Tests once used extensively; now superceded by spectroscopic methods and x-ray crystallography reactions of carbohydrates can involve either open-chain form, furanose, or pyranose form 25.18Reduction of Carbohydrates Reduction of Carbohydrates Carbonyl group of open-chain form is reduced to an alcohol. Product is called an alditol. Alditol lacks a carbonyl group so cannot cyclize to a hemiacetal. Reduction of D-Galactose 25.19Oxidation of Carbohydrates Benedicts Reagent Benedicts reagent is a solution of the citrate complex of CuSO4 in water. It is used as a test for reducing sugars. Cu2+ is a weak oxidizing agent. A reducing sugar is one which has an aldehyde function, or is in equilibrium with one that does. A positive test is the formation of a red precipitate of Cu2O. Examples of Reducing Sugars Aldoses: because they have an aldehyde function in their open-chain form. Ketoses: because enolization establishes an equilibrium with an aldose. Examples of Reducing Sugars Disaccharides that have a free hemiacetal function. Examples of Reducing Sugars Disaccharides that have a free hemiacetal function. Glycosides are not reducing sugars Oxidation of Reducing Sugars The compounds formed on oxidation of reducing sugars are called aldonic acids. Aldonic acids exist as lactones when 5- or 6-membered rings can form. A standard method for preparing aldonic acids uses Br2 as the oxidizing agent. Oxidation of D-Xylose Oxidation of D-Xylose Nitric Acid Oxidation Nitric acid oxidizes both the aldehyde function and the terminal CH2OH of an aldose to CO2H. The products of such oxidations are called aldaric acids. Nitric Acid Oxidation Uronic Acids Uronic acids contain both an aldehyde and a terminal CO2H function. 25.20Cyanohydrin Formation and Carbohydrate Chain Extension Extending the Carbohydrate Chain Carbohydrate chains can be extended by us