1 Announcements & Agenda (04/04/07) Will start with quiz today Review session 3pm (same place) Today Amides (13.5) Amides (13.5) Sugars! Section Sugars! Section Carbohydrates Carbohydrates Monosaccharides Monosaccharides Cyclic Monosaccharides (?) Cyclic Monosaccharides (?)

2 an ester reacts with water to produce a carboxylic acid and an alcohol.an ester reacts with water to produce a carboxylic acid and an alcohol. an acid catalyst is required.an acid catalyst is required. O  H +  H + H—C—O—CH 2 —CH 3 + H 2 O O   H—C—OH + H—O—CH 2 —CH 3 Last Time: Hydrolysis of Esters Base Hydroylsis forms an alcohol plus the salt of a carboxylic acid!

3 What acid and alcohol make the following ester? Ethanol (2C) and acetic acid (2C) 2.Propanol (3C) & acetic acid (2C) 3.Ethanol (2C) & propionic acid (3C) 4.Methanol (1C) & propionic acid (3C)

4 Last Time: Base Hydrolysis of Triglycerides Make Soaps

5 Last Time: Amines (Derivatives of NH 3 ) Typically 3 kinds: primary (1°) amines: 1 carbon group is bonded to Nprimary (1°) amines: 1 carbon group is bonded to N secondary (2°) amines: 2 carbon groups bonded to Nsecondary (2°) amines: 2 carbon groups bonded to N tertiary (3°) amines: 3 carbon groups bonded to N.tertiary (3°) amines: 3 carbon groups bonded to N. Can H-bond like alcohols, although N is not as polar decent BPs & solubility in waterdecent BPs & solubility in water Act as weak bases: CH 3 —NH 2 + H 2 O CH 3 —NH OH – Useful properties of amine salts: solids at RT, very soluble in body fluids (ideal for drug molecules, and salts don’t stink solids at RT, very soluble in body fluids (ideal for drug molecules, and salts don’t stink

6 Last Time: Alkaloids physiologically active nitrogen-containing compounds.physiologically active nitrogen-containing compounds. often addictive.often addictive. N CH 3 nicotine

7 Morphine and Codeine alkaloids.alkaloids. obtained from the oriental poppy plant.obtained from the oriental poppy plant. used as painkillers.used as painkillers. modified to make heroin.modified to make heroin.

8 Chocolate Chocolate is found in cocoa beans

9 Last Time: Amides (13.5) made from… Amine + Carboxylic Acid Amides are produced by reacting a carboxylic acid with ammoniaby reacting a carboxylic acid with ammonia or an amine (1° or 2°). using heat.using heat. O O O O  Heat   Heat  CH 3 —C—OH + NH 3 CH 3 —C—NH 2 + H 2 O CH 3 —C—OH + NH 3 CH 3 —C—NH 2 + H 2 O O O O O  Heat   Heat  CH 3 —C—OH + CH 3 —NH 2 CH 3 —C—NH—CH 3 + H 2 O CH 3 —C—OH + CH 3 —NH 2 CH 3 —C—NH—CH 3 + H 2 O

10 Some Amides in Health and Medicine

11 Physical Properties of Amides SIMILAR TO AMINES… primary ( − NH 2 ) or secondary ( − NH − ) amides form hydrogen bonds.primary ( − NH 2 ) or secondary ( − NH − ) amides form hydrogen bonds. primary have higher mp’s than secondary.primary have higher mp’s than secondary. tertiary (no H on N) do not form hydrogen bonds & have lower melting points. tertiary (no H on N) do not form hydrogen bonds & have lower melting points. all form hydrogen bonds with water.all form hydrogen bonds with water. with 1-5 carbon atoms are soluble in water.with 1-5 carbon atoms are soluble in water.

12 Amides undergo Acid hydrolysis to produce a carboxylic acid and an ammonium salt.Acid hydrolysis to produce a carboxylic acid and an ammonium salt. Base hydrolysis to produce the salt of a carboxylic acid and an amine or ammonia.Base hydrolysis to produce the salt of a carboxylic acid and an amine or ammonia. REACTIONS LOOK SIMILAR TO THOSE OF ESTERS!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!REACTIONS LOOK SIMILAR TO THOSE OF ESTERS!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!! Hydrolysis of Amides IMPORTANT TO KNOW

13 acid hydrolysis acid hydrolysis O || || O CH 3 —C—OH + NH 4 + Cl – O CH 3 —C—OH + NH 4 + Cl – || HCl + H 2 O || HCl + H 2 O CH 3 —C—NH 2 NaOH O NaOH O || || CH 3 —C—O – Na + + NH 3 CH 3 —C—O – Na + + NH 3 base hydrolysis Hydrolysis Reactions

14 Ch 14 Carbohydrates a major source of energy from our dieta major source of energy from our diet composed of C, H, & Ocomposed of C, H, & O also known as saccharides, which means “sugars.”also known as saccharides, which means “sugars.”

15 Practice Problems (Ch 14) 14.05, 14.07, 14.09, 14.13, 14.15, 14.19, 14.21, 14.23, 14.25, 14.27, 14.29, 14.31, 14.33, 14.35, 14.37, 14.39, 14.41, 14.47, 14.49, 14.51, 14.53, 14.57, 14.59

16 Carbohydrates produced by photosynthesis in plantsproduced by photosynthesis in plants Example: glucose synthesized in plants from CO 2, H 2 O, and energy from the sun.Example: glucose synthesized in plants from CO 2, H 2 O, and energy from the sun. are oxidized in living cells to produce CO 2, H 2 O, and energy.are oxidized in living cells to produce CO 2, H 2 O, and energy.

17 Types of Carbohydrates Monosaccharides: simplest carbohydrates.Monosaccharides: simplest carbohydrates. Disaccharides: consist of two monosaccharides.Disaccharides: consist of two monosaccharides. Polysaccharides: contain many monosaccharides.Polysaccharides: contain many monosaccharides.

18 Monosaccharides typically 3-6 carbon atomstypically 3-6 carbon atoms have a C=O group (aldehyde or ketone)have a C=O group (aldehyde or ketone) aldoses aldoses ketoses ketoses several hydroxyl groupsseveral hydroxyl groups

19 Aldoses monosaccharides with an aldehyde group…monosaccharides with an aldehyde group… …and many hydroxyl groups.…and many hydroxyl groups. triose (3C atoms) tetrose (4C atoms) pentose (5C atoms) hexose (6C atoms) O ║ C─H aldose C─H aldose │ H─ C─OH H─ C─OH │ │ CH 2 OH CH 2 OH Erythose Erythose

20 Ketoses monosaccharides with a ketone group…monosaccharides with a ketone group… …and many hydroxyl groups.…and many hydroxyl groups. CH 2 OH CH 2 OH │ C=O ketose C=O ketose │ H─ C─OH H─ C─OH │ │ │ CH 2 OH CH 2 OH Fructose, a ketohexose

21 Fischer Projections also used to represent carbohydrates.also used to represent carbohydrates. places the most oxidized group at the top.places the most oxidized group at the top. shows chiral carbons as the intersection of vertical and horizontal lines.shows chiral carbons as the intersection of vertical and horizontal lines.

22 D & L Notations: Know This Now… In a Fischer projection, the −OH group on the chiral carbon farthest from the carbonyl group determines an L or D isomer.chiral carbon farthest from the carbonyl group determines an L or D isomer. left = L for the L-form.left = L for the L-form. right = D for the D-form. (MOST COMMON IN NATURE!)right = D for the D-form. (MOST COMMON IN NATURE!)

23 Learning Check Identify each as the D or L isomer. A.B. C. A.B. C. __-Ribose __- Threose __- Fructose L LD

24 D-Glucose found in fruits, corn syrup, and honeyfound in fruits, corn syrup, and honey an aldohexose with the formula C 6 H 12 O 6an aldohexose with the formula C 6 H 12 O 6 known as blood sugar in the bodyknown as blood sugar in the body the monosaccharide in polymers of starch, cellulose, and glycogenthe monosaccharide in polymers of starch, cellulose, and glycogen

25 Blood Glucose Level In the body, normal blood: [glucose] = mg/dL.normal blood: [glucose] = mg/dL. a glucose tolerance test measures blood glucose for several hours after ingesting glucose.a glucose tolerance test measures blood glucose for several hours after ingesting glucose.

26 D-Fructose is a ketohexose C 6 H 12 O 6is a ketohexose C 6 H 12 O 6 is the sweetest carbohydrateis the sweetest carbohydrate found in fruit juices and honeyfound in fruit juices and honey converts to glucose in the bodyconverts to glucose in the body

27 D-Galactose is an aldohexose C 6 H 12 O 6.is an aldohexose C 6 H 12 O 6. not found free in nature.not found free in nature. is obtained from lactose, a disaccharide.is obtained from lactose, a disaccharide. has a similar structure to glucose except for thehas a similar structure to glucose except for the –OH on C4 –OH on C4 Which C is C4???

28 Cyclic Structures (14.3) prevalent form of monosaccharides with 5 or 6 carbon atomsprevalent form of monosaccharides with 5 or 6 carbon atoms form when the hydroxyl group on C-5 reacts with the aldehyde group or ketone groupform when the hydroxyl group on C-5 reacts with the aldehyde group or ketone group Orgo-Chem reaction not previously mentioned: “C=O” + ROH → hemiacetal Orgo-Chem reaction not previously mentioned: “C=O” + ROH → hemiacetal

29 Drawing Cyclic Structures: Practice! Example: Glucose STEP 1 Number the carbon chain and turn clockwise to form a linear open chain

30 Cyclic Structure for Glucose STEP 2 Fold into a hexagon. Bond the C5 –O– to C1.Bond the C5 –O– to C1. Place the C6 group above the ring.Place the C6 group above the ring. Write the –OH groups on C2 & C4 below the ring (These are the C atoms that pointed down from Step 1).Write the –OH groups on C2 & C4 below the ring (These are the C atoms that pointed down from Step 1). Write the –OH group on C3 above the ring.Write the –OH group on C3 above the ring. Write a new –OH on C1.Write a new –OH on C

31 Cyclic Structure for Glucose  -D-Glucose  -D-Glucose  STEP 3 Write the new –OH on C1 down for the  form. up for the  form. 

32 Summary of the Formation of Cyclic Glucose

33 Mutarotation cyclic structures open and close.cyclic structures open and close.  -D-glucose converts to β-D-glucose & vice versa.  -D-glucose converts to β-D-glucose & vice versa. at any time, only a small amount of open chain forms.at any time, only a small amount of open chain forms.  -D-glucose D-glucose (open) β-D-glucose  -D-glucose D-glucose (open) β-D-glucose (36%) (trace) (64%) (36%) (trace) (64%) O H CH 2 OH OH O C H OH OH OH OH OH OH CH 2 OH O OH OH OH OH CH 2 OH O

34 D-fructose  -D-fructose α-D-fructose Cyclic Structure of Fructose is a ketohexose.is a ketohexose. reacts the -OH on C-5 with the C=O on C-2reacts the -OH on C-5 with the C=O on C-2