1. 1 Announcements & Agenda (04/02/07) Pop Quiz Right Now! Quiz on Wednesday (Chirality & Ch 13) Will hand HW practice in lab Today Esters (13.3) Esters (13.3) Amines (13.4) Amines (13.4) Amides (13.5) Amides (13.5)

2. 2 Last Time: Drawing Fischer Projections

3. 3 Last Time: Carboxylic Acids Carboxylic acids are weak acids.are weak acids. ionize in water to produce carboxylate ions and hydronium ions.ionize in water to produce carboxylate ions and hydronium ions. O O O O ║ ║ ║ ║ CH 3 − C − OH + H 2 O CH 3 − C − O – + H 3 O + ~1% Also: Neutralization Reactions! Esterification!

4. 4 Ester Products Aspirin is used to relieve pain and reduce inflammation.is used to relieve pain and reduce inflammation. is an ester of salicylic acid and acetic acid.is an ester of salicylic acid and acetic acid. Oil of wintergreen is used to soothe sore muscles.is used to soothe sore muscles. is an ester of salicylic acid and methanol.is an ester of salicylic acid and methanol.

5. 5 Naming Esters The name of an ester contains the names of the alkyl group from the alcohol.the alkyl group from the alcohol. the carbon chain from the acid with –ate ending.the carbon chain from the acid with –ate ending. methyl ethanoate (acetate) methyl ethanoate (acetate) O O   CH 3 — O—C —CH 3 CH 3 — O—C —CH 3 IUPAC: methyl ethanoate common: methyl acetate -oate: means ester present

6. 6 Esters in Plants Esters give flowers and fruits their pleasant fragrances and flavors.

7. 7 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 Acid Hydrolysis of Esters

8. 8 is the reaction of an ester with a strong base.is the reaction of an ester with a strong base. produces the salt of the carboxylic acid and an alcohol.produces the salt of the carboxylic acid and an alcohol. O || || CH 3 —C—O—CH 2 —CH 3 + NaOH CH 3 —C—O—CH 2 —CH 3 + NaOH O  CH 3 —C—O – Na + + HO—CH 2 —CH 3  CH 3 —C—O – Na + + HO—CH 2 —CH 3 salt of carboxylic acid alcohol salt of carboxylic acid alcohol Base Hydrolysis (Saponification)

9. 9 Last Time: Base Hydrolysis of Triglycerides Make Soaps

10. 10 Carboxylic acids with lots of carbons are fatty acids (usually even #, 10, 12, 14, 16, 18) Sodium salts of fatty acids are soaps.

11. 11 Cleaning Action of Soap A soap contains a nonpolar end that dissolves in nonpolar fats and oils, and a polar end that dissolves in water.contains a nonpolar end that dissolves in nonpolar fats and oils, and a polar end that dissolves in water. forms groups of soap molecules called micelles that dissolve in water and are washed away.forms groups of soap molecules called micelles that dissolve in water and are washed away.

12. 12 Write the organic products when methyl acetate reacts with A. water and an acid catalyst. O   CH 3 —C—OH + HO—CH 3 CH 3 —C—OH + HO—CH 3 B. KOH. O O   CH 3 —C—O – K + + HO—CH 3 CH 3 —C—O – K + + HO—CH 3 Learning Check

13. 13 13.4 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. H CH 3 CH 3 H CH 3 CH 3 | | | | | | CH 3 —N—H CH 3 —N—H CH 3 —N—CH 3 CH 3 —N—H CH 3 —N—H CH 3 —N—CH 3 1° 2° 3° 1° 2° 3° Quaternary (4°) amines also possible (4 C groups attached to nitrogen atom)

14. 14 Naming Amines (No need to memorize) Simple amines are named as alkylamines.Simple amines are named as alkylamines. Names of alkyl groups bonded to the N atom listed in alphabetical order in front of amine.Names of alkyl groups bonded to the N atom listed in alphabetical order in front of amine. CH 3 —CH 2 —NH 2 ethylamine CH 3 —NH—CH 3 dimethylamine CH 3 —NH—CH 3 dimethylamine CH 3 CH 3 | CH 3 —N—CH 2 —CH 3 ethyldimethylamine

15. 15 Hydrogen Bonding for Amines N-H bond provides hydrogen bonding in 1°and 2° amines, but not in 3° amines.N-H bond provides hydrogen bonding in 1°and 2° amines, but not in 3° amines. is not as polar as the O-H bonds in alcohols.is not as polar as the O-H bonds in alcohols. H-bonding not as good  H-bonding not as good 

16. 16 Solubility in Water Amines with 1-5 carbon atoms are soluble in water.Amines with 1-5 carbon atoms are soluble in water. Form hydrogen bonds with the polar O-H bond in water.Form hydrogen bonds with the polar O-H bond in water.

17. 17 Like ammonia, amines are weak bases in water. NH 3 + H 2 O NH 4 + + OH – NH 3 + H 2 O NH 4 + + OH – ammonium hydroxide ammonium hydroxide CH 3 —NH 2 + H 2 O CH 3 —NH 3 + + OH – CH 3 —NH 2 + H 2 O CH 3 —NH 3 + + OH – methylammonium hydroxide methylammonium hydroxide Amines React as Bases

18. 18 An amine salt forms when an amine is neutralized by acid.forms when an amine is neutralized by acid. CH 3 —NH 2 + HCl CH 3 —NH 3 + Cl – methylamine Neutralization forms Amine Salts methylammonium chloride

19. 19 OK so far??? 1.Yes 2.No 3.Kinda… 12345

20. 20 Properties of Amine Salts solids at room temperature.solids at room temperature. soluble in water and body fluids.soluble in water and body fluids. the form used for drugs.the form used for drugs. DON’T STINK!DON’T STINK!

21. 21 Alkaloids physiologically active nitrogen-containing compounds.physiologically active nitrogen-containing compounds. obtained from plants.obtained from plants. used as anesthetics, antidepressants, and in stimulants such as caffeine.used as anesthetics, antidepressants, and in stimulants such as caffeine. often addictive.often addictive.

22. 22 Cocaine sold illegally as the amine salt.sold illegally as the amine salt. reacted with NaOH to produce the free amine form known as “crack.”reacted with NaOH to produce the free amine form known as “crack.”

23. 23 Caffeine is a stimulant of the central nervous systemis a stimulant of the central nervous system Caffeine and Nicotine Nicotine increases adrenaline level in blood N CH 3

24. 24 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.

25. 25 In amides, an amino group(–NH 2 ) replaces the –OH group of carboxylic acids.In amides, an amino group(–NH 2 ) replaces the –OH group of carboxylic acids. O O O O || || || || CH 3 —C—OH CH 3 —C—NH 2 CH 3 —C—OH CH 3 —C—NH 2 Amides 13.5

26. 26 Preparation of Amides 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

27. 27 Some Amides in Health and Medicine

28. 28 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.

29. 29 Hydrogen Bonding of Amides O || || CH 3 —C—N—H CH 3 —C—N—H | HHydrogen bonding occurs HHydrogen bonding occurs between primary amides. O O || || CH 3 —C—N—H CH 3 —C—N—H | H

30. 30 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

31. 31 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