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UNIT II CARBOHYDRATES II INTER-CONVERSION OF SUGARS Glucose to Fructose (Aldose to Ketose aldohexose to ketohexose)

Fructose to Glucose (Ketose to Aldose ketohexose to aldohexose)

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Ascending the Sugar Series (Kiliani Synthesis) (An aldose into the next higher aldose or a pentose into a hexose or an aldopentose into an aldohexose)

The conversion of a lower member in the carbohydrate series into the next higher member via the formation of the respective cyanohydrin is known as Kiliani synthesis. Descending the Sugar series (Wohls Method) (An aldose into the next lower aldose or a hexose into a pentose or an aldohexose into an aldopentose)

Disaccharides Disaccharides are sugars containing two molecules of monosaccharides. Disaccharides are formed by the condensation of two molecules of monosaccharides with the elimination of one molecule of water. Department of Chemistry Sri Sarada Niketan College of Arts & Science for Women Kanavaipudur.

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In disaccharides, monosaccharides are linked by the glycosidic bonds. e.g., Sucrose and Maltose. MALTOSE (C12H22O11) Maltose occurs in germinating seeds like cerals. Preparation From Starch When starch is hydrolysed with the enzyme present in yeast we get maltose. It may be obtained by partial hydrolysis of starch with dilute acid.

Physical Properties It is a white crystalline solid. It is sweet. It is optically active and is dextrorotatory. Chemical Properties 1. Hydrolysis On hydrolysis with dil.hydrochloric acid or with the enzyme maltase, it gives two molecules of glucose.

2. Oxidation It is oxidized by bromine water and we get maltobionic acid, C11H21O10.COOH. Department of Chemistry Sri Sarada Niketan College of Arts & Science for Women Kanavaipudur.

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It reduces Fehlings solution and Tollens reagent. Therefore it is a reducing sugar. 3. Acetylation It reacts with acetic anhydride giving an octa acetyl derivative. 4. Reactions of the carbonyl group Maltose forms an oxime with hydroxylamine and an osazone with phenylhydrazine. Uses It is used in the manufacture of malted milk and in the manufacture of baby foods. Structural elucidation of Maltose 1. Molecular formula of maltose is C12H22O11. 2. It undergoes mutarotation in aqueous solutions. Therefore it exists in - and -forms. 3. It reacts with excess phenyl hydrazine giving maltosazone. This shows that a carbonyl group present in it. 4. It is oxidized by bromine water to maltobionic acid which has the same number of carbon atoms as in maltose. Therefore the carbonyl group in maltose should be an aldehyde group. 5. On hydrolysis it gives two molecules of D(+)-glucose. This shows that two glucose molecules are linked through an oxygen atom. 6. It is a reducing sugar. It reduces Fehlings solution and Tollens reagent. This shows that atleast one aldehyde group of the two molecules of glucose present in free in maltose. 7. When maltose is oxidized with bromine water we get maltobionic acid. This is a monocarboxylic acid. When this acid is subjected to complete methylation with dimethyl sulphate and sodium hydroxide it gives an octa-o-methyl maltobionic acid. This on hydrolysis gives 2,3,5,6-tetra-o-methyl-c-gluconic acid (I) and 2,3,5,6-tetra methyl D-glucose (II).

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8. C4 in (I) and C1 in (II) have free hydroxyl groups on them. This suggests that these two parts are linked in maltose through these carbon atoms only. 9. Maltase hydrolyses maltose into two molecules of D(+)-glucose. Therefore the non-reducing half of maltose molecule is -in character. 10. Therefore maltose is 4--D-glucopyranosyl-1--D-glucopyranoside. Plane diagram of maltose

Perspective formula

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Sucrose (C12H22O11) Sucrose occurs in sugarcane and beet. Manufacture from Sugarcane 1. The sugarcane is cleaned and cut into bits. 2. They are crushed in crushers and the juice is extracted. 3. It is subjected to clarification by sulphonation and by carbonation. 4. Clarification is done to avoid fermentation of sucrose into glucose and fructose and for removing unwanted matter. 5. The clear juice is concentrated in a multiple effect evaporator. 6. The acidity of the solution is carefully maintained at a desired level in order to avoid loss of sucrose by inversion and destruction. 7. The clear syrupy juice thus got is boiled in a vacuum pan. Sugar crystals begin to form. 8. They are centrifuged out, dried and bagged. Physical properties It is a colourless crystalline substance. It is sweet and dextrorotatory. It does not show mutarotation. Chemical properties 1. Action of heat

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a) When heated with a small quantity of water, it melts and on cooling gives an amorphous glassy mass called barley sugar. b) When heated to about 200 0C, it loses water and gives a brown mass called caramel. Caramel is used in confectionary and colouring wine. c) When heated to very high temperature it carbonizes to give sugar charcoal. 2. Hydrolysis (Inversion of cane sugar) Sucrose when warmed with dil.mineral acids, it is hydrolysed to glucose and fructose.

i.

Cane sugar has a specific rotation of +66.50. On hydrolysis it is converted to glucose and fructose. Glucose has a specific rotation of +52.50 and fructose has a specific rotation of -920. During hydrolysis the specific rotation changes from a +ve value to a ve value. This change of dextro-rotatory sucrose into laevorotatory mixture of glucose and fructose is called inversion of cane sugar.

ii. iii. iv.

3. Oxidation When treated with conc.nitric acid, it is oxidized to oxalic acid.

4. Dehydration When treated with conc.sulphuric acid, it is dehydrated giving sugar charcoal. This is called charring of sugar. A smell of sulphur dioxide is noticed due to reduction of sulphuric acid.

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5. Fermentation i. ii. iii. When a solution of sucrose is fermented with yeast we get ethanol. The enzyme invertase in the yeast converts sucrose into a mixture of glucose and fructose. The enzyme zymase present in yeast converts glucose and fructose into ethanol and carbon dioxide.

6. Formation of sucrosates Sucrose reacts with metallic hydroxides giving sucrosates. For example, with calcium hydroxide it gives calcium sucrosate, (C 12H22O11.3CaO) 7. Acetylation Sucrose reacts with acetic anhydride giving an octaacetyl derivative. It does not reduce Tollens reagent and Fehlings solution. It does not give resins with sodium hydroxide. It does not give osazone with phenyl hydrazine. It does not exhibit mutarotation. Uses Sucrose is used Department of Chemistry Sri Sarada Niketan College of Arts & Science for Women Kanavaipudur.

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a) as a sweetening agent in sweets and drinks b) to preserve fruits c) for the preparation of oxalic acid in the laboratory. Tests a) When heated in a dry test tube, a characteristic smell of burnt sugar is noticed. b) On heating with conc.sulphuric acid, charring takes place and a smell of sulphur dioxide is noticed. c) It answers Molisches test. d) It answers Selivanoffs test. e) It answers Furfural test. Structural Elucidation of Sucrose 1. The molecular formula of sucrose is C12H22O11. 2. On hydrolysis it gives a mixture of glucose and fructose. It shows that a molecule of glucose and a molecule of fructose are linked through an oxygen atom in sucrose. 3. Sucrose is not a reducing sugar i.e., it does not reduce Tollens reagent and Fehlings solution. This shows that the aldehyde group of glucose is absent in sucrose. That is why sucrose is a non-reducing sugar whereas glucose is a reducing sugar. 4. Further it does not form an oxime or osazone. This shows that the ketonic group of fructose also is not present in sucrose. Sucrose does not undergo mutarotation. This also proves that neither the aldehyde group of glucose nor the ketonic group of fructose is free in sucrose. 5. Therefore both the monosaccharides must be linked through their respective reducing groups in sucrose. 6. On treatment with acetic anhydride it gives an octaacetyl derivative. It shows the presence of eight hydroxyl groups in sucrose.

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7. On complete methylation it gives an octamethyl derivative, this on hydrolysis gives 2,3,4,6tertamethyl--glucose (I) and 1,3,4,6-tetramethyl--fructose (II).

8. The above fact shows that C5 in (I) and (II) have no OH groups on them. This suggests that they must be involved in some ring formation in their molecules. 9. C1 in (I) and C2 in (II) have free hydroxyl groups on them. This suggests that the two parts are linked in sucrose through these carbon atoms only. 10. Maltase hydrolyses sucrose. Therefore one reducing part of sucrose is in character. 11. Kinetics of hydrolysis and optical rotation of sucrose have shown that glucose part is in character and fructose part is in character. 12. Therefore sucrose is 1--D-glucopyranosyl-2--D-fructofuranoside. Plane diagram of sucrose

Perspective formula of surose

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Polysaccharides Polysaccharides, which are also known as glycans composed of number of monosccharide units. They represent condensation products of several molecules of simple sugars or monosaccharides. Monosaccharides are linked together by glycosidic bonds in polysaccharides. They form linear chain or branched chain molecules. They contain only one type of monosaccharide units or many types of monosaccharide units. According to this nature polysaccharides are classified into two groups, 1. Homopolysaccharides 2. Heteropolysaccharides.Po Homopolysaccharides are composed of only one type of monosaccharides. On hydrolysis they yield only one type of monosaccharides Eg. starch, glycogen, cellulose etc. which yield only glucose on hydrolysis. Heteropolysaccharides are composed of a mixture of monosaccharides. On hydrolysis, they yield a mixture of monosaccharides. Eg. Hyaluronic acid, Heparin, Mucopolysaccharides. Starch It is a polysaccharide. It consists of a large number of molecules of glucose. Its molecular formula is (C6H10O5)n. It occurs in rice, potatoes, wheat, barley etc., Starch consists of two components namely amylose and amylopectin. Amylose 1. Starch consists of 10 20 % of amylose. It is soluble in water. Department of Chemistry Sri Sarada Niketan College of Arts & Science for Women Kanavaipudur.

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2. It gives blue colour with iodine. 3. It consists of several glucose units in the form of linear chains. 4. The glucose units are joined together with each other by an -glycosidic linkage between C1 of one glucose unit and C4 of the next glucose unit. 5. The molecular weight of amylose ranges from 10,000 to 50,000. 6. A single chain of amylose may contain about 60 to 300 D-glucose units. There is no cross link between the amylose chains.

Amylopectin 1. Starch consists of 80 90 % of amylopectin. It is sparingly soluble in water. 2. Its molecular weight is very high. 3. It consists of several glucose units linked together by -glycosidic linkage in the form of chains. 4. There is cross link between the chains and has branched structure. 5. Each chain consists of about 300 to 600 D-glucose units and the molecular weight ranges from 50,000 to 10,00,000.

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Manufacture The starch material from which starch is to be manufactured is washed with water. It is disintegrated mechanically. A paste like mass called pulp is obtained. It contains starch granules. This is contaminated with finely divided fibrous material. The mixture is washed with water and then sieved. The fibrous materials are thus separated. The filtrate is allowed to stand. The heavier starch granules settle down. The supernatant liquid is decanted. The residue is centrifuged and dried slowly and then packed. Physical Properties Starch is tasteless, odourless and white amorphous powder. It is insoluble in water. Chemical Properties 1. Action of Heat On heating to 200 260 0C starch changes into a gum like substance called dextrin. Dextrin is used in calico printing and as an adhesive. Starch chars at higher temperature. Department of Chemistry Sri Sarada Niketan College of Arts & Science for Women Kanavaipudur.

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2. Hydrolysis a) On hydrolysis with dilute mineral acids, starch is converted into dextrin and finally to glucose.

b) When starch is hydrolysed with malt extract it gives maltose. The malt extract contains the enzyme diastase, which converts starch into maltose.

3. With Iodine It gives a blue colour with iodine. The colour disappears on heating and reappears on cooling. 4. Formation of soluble starch Ordinary starch is heated with 10% HCl for 24 hours. It is converted into soluble starch. Uses 1. It is one of the most valuable constituents of food as rice, bread, cornflour, potato etc., 2. It is used in the manufacture of glucose, alcohol, dextrin and adhesives. 3. It is used in laundry as a stiffening agent. 4. It is used in calico printing. 5. Starch acetate, a derivative of starch is used for making sweets. 6. Nitro starch, another derivative of starch is used as an explosive for blasting. Cellulose Occurrence

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It occurs in the cell walls of plants and in certain animal tissues. It is the main structural material of trees and plants. Its main sources are cotton and wood. Preparation From wood 1. Wood shavings are successively treated with dilute alkali, dilute acid, water, alcohol and ether. 2. All other substances like lignin, resin and accompanying cellulose are removed by these treatments and cellulose is obtained as an amorphous mass. 3. It may be bleached with hypochlorites to give a white amorphous powder of cellulose. Structure 1. Cellulose is a straight chain polysaccharide composed of D-glucose units. 2. These units are joined by -glycosidic linkages between C1 of one glucose unit and C4 of the next glucose unit. 3. The number of D-glucose units in cellulose ranges from 300 2500.

Physical properties 1. It is an amorphous white solid insoluble in water. 2. Artificial silk (Rayon) Department of Chemistry Sri Sarada Niketan College of Arts & Science for Women Kanavaipudur.

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It is soluble in ammonical copper hydroxide solution. When acids, alcohols or salts are added to the solution it is precipitated. This property is made use of in the manufacture of rayon (artificial silk). 3. Mercerizing Cellulose on treatment with concentrated sodium hydroxide, becomes a gelatinous translucent (miuFiwaha; xspf;fjpu;fs; CLUTfpw) mass. Cotton goods treated in this way get a silky lustre. Such cotton is known as mercerized cotton. The process is called mercerizing. Chemical properties 1. Action of conc.H2SO4 Cellulose dissolves in cold conc.H2SO4. On dilution it is precipitated as amyloid. For example, when an ordinary paper is dipped in conc.H2SO4 for a few seconds and then washed with water, amyloid is precipitated on the surface of the paper and the surface of the paper becomes rough. Such a paper is called parchment paper. 2. Hydrolysis When it is boiled with dilute acids, it is hydrolysed to glucose. 3. Acetylation On treatment with acetic anhydride it forms triacetate. 4. Nitration On treatment with nitric acid, it gives nitro cellulose. 5. Formation of esters On treatment with acids like acetic acid, nitric acid etc., it gives esters. These esters are commercially important. Department of Chemistry Sri Sarada Niketan College of Arts & Science for Women Kanavaipudur.

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Uses 4. Cellulose forms the raw material for the textiles and paper industries. 5. Cellulose nitrate is called gun cotton. Gun cotton is used in the manufacture of explosives like blasting gelatin and cordite. 6. Lower cellulose nitrates are called pyroxylins. Pyroxylin is used to manufacture of collodion which is used in photography. 7. Pyroxylin is also used to manufacture celluloid which is used for making toys, photographic films etc., 8. Cellulose is used for the preparation of artificial silk like viscose rayon. Derivatives of Cellulose 1. Cellulose nitrate (Nitro cellulose) 1. The highest nitrate of cellulose is the trinitrate, (C 6H7N3O11)3 2. It contains 14.4% nitrogen. 3. The nitrates are prepared by the reaction of cellulose with a mixture of nitric acid and sulphuric acid. 4. Cellulose nitrate is known as Gun cotton. It is used in the manufacture of blasting explosive and smokeless powders. 5. The lower nitrates in the solid state are known as pyroxylin. Pyroxylin mixed with camphor as plasticizer is converted into celluloid. 2. Cellulose acetate 1. When acetylated with acetic anhydride in the presence of H2SO4 cellulose is converted into cellulose triacetate. 2. The triacetate is decomposed to diacetate by adding water. 3. The diacetate is washed, dried and dissolved in a mixture of organic solvents. From this solution fine threads of cellulose acetate are drawn. 3. Ethyl cellulose

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1. Cellulose may be treated with ethyl chloride in the presence of alkali to form ethyl cellulose. 2. It is used for making plastic, textiles and films. 4. As a cattle food 1. Grazing animals like cattle, goats have in their digestive system an enzyme called cellulase, which digests cellulose by hydrolyzing it into glucose. 2. So they can take grass, straw etc., directly as their food.

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