UNIT (9) CARBOXYLIC ACIDS, ESTERS, AMINES, AND AMIDES

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1 UNIT (9) CARBXYLIC ACIDS, ESTERS, AMINES, AND AMIDES 9.1 Carboxylic Acids The functional group in carboxylic acids is called the carboxyl group. A carboxyl group is a carbonyl group (C = ) with a hydroxyl group (-H) attached to the carbonyl carbon atom. Representation of a carboxyl group C H or CH or C 2 H Carboxylic acid: R C H (R = H, or aliphatic or aromatic hydrocarbon) 9.2 Naming Carboxylic Acids The names of carboxylic acids end in -oic acid, indicating the presence of the carboxyl group, ie: propanoic acid, butanoic acid, pentanoic acid, etc. When naming carboxylic acids, the e is dropped from the alkane containing the carboxyl group and replaced with -oic acid. The chain is numbered from the carboxylic acid group which is always located on the first carbon. The location of the functional group is not included in the name. Examples: CH 3 - CH CH 3 - CH 2 - CH CH 3 - CH 2 - CH 2 - CH ethanoic acid propanoic acid butanoic acid CH 3 CH 3 - CH - CH 2 - CH methylbutanoic acid CH benzoic acid Some members of this class are widely known by their common names. Common names of acids you should know: HCH Formic acid CH 3 CH Acetic acid A solution of acetic acid and water is known as vinegar. 9-1

2 Worked Example 9-1 Give the IUPAC name for each of the following compounds: Br a) (CH 3 ) 3 C-CH b) CH 3 - CH - CH 2 - CH CH c) d) H N 2 Solution a) 2,2-dimethylpropanoic acid b) 3-bromobutanoic acid c) 4-nitrobenzoic acid d) 3,4-dimethylhexanoic acid Practice 9-1 Name each of the following acids: a) CH 3 CH 2 CF 2 CH 2 CH b) CH 3 - CH 2 - CH - CH H c) e) H H CH NH 2 CH 3 - CH - CH d) f) CH CH 3 H Answer a) 3,3-difluoropentanoic acid b) 2-hydroxybutanoic acid c) 3,4-dihydroxybenzoic acid d) 3-methylbenzoic acid e) 2-aminopropanoic acid f) 2-ethylhexanoic acid 9-2

3 9.3 Acidity of Carboxylic Acids Carboxylic acids are weak acids. When a carboxylic acid is placed in water, the following equilibrium is established. RCH H 2 RC - H 3 carboxylic acid carboxylate ion Carboxylate ions are named by dropping the ic ending from the name of the parent acid and replacing it with ate. CH H 2 H 3 3 CH CH 3 C - acetic acid acetate ion Neutralization of Carboxylic Acids (reaction of acids with bases) Carboxylic acids undergo neutralization reactions with strong bases as you have seen in unit 6.in a manner similar to that of inorganic acids. Neutralization of carboxylic acids produce a carboxylic acid salt and water. CH 3 CH NaH CH 3 C - Na H 2 acetic acid *sodium acetate carboxylic acid carboxylic acid salt *Note that carboxylic acid salts are named similarly to other ionic compounds (unit 4). The cation is named first, followed by the name of the anion. Worked Example 9-2 Complete the following reaction and name the carboxylic acid salt formed. CH KH Solution The protons of the acid are removed by the H - of the base to produce water. The cation of the base, in this case K, forms the salt of the carboxylic acid. CH C - K H KH 2 benzoic acid potassium benzoate 9-3

4 Practice 9-2 Complete the following reaction and name the carboxylic acid salt formed. Answer CH 3 - CH 2 - CH NaH CH 3 - CH 2 - CH NaH CH 3 - CH 2 - C - Na H 2 sodium propanoate 9.4 Esters Esters are derivative of carboxylic acids in which the H group on the carboxyl has been replaced with an R group. R - C - H carboxylic acid R- C - R ester Esterification (Preparation of Esters) The process of esterification involves the reaction of a carboxylic acid with an alcohol in the presence of an acid catalyst. Water is also a product in this reaction. The generalized reaction can be shown as: R-C-H carboxylic acid R'-H alcohol [H 2 S 4 ] R-C-R' ester H 2 When ethanol is added to acetic acid and a drop of sulfuric acid (symbolized as H ), the following equilibrium will result: CH 3 - C - H CH 3 -CH 2 -H [H ] CH 3 - C - - CH 2 -CH 3 H 2 9-4

5 Worked Example 9-3 What carboxylic acid and alcohol are required to produce the following ester? Solution CH 3 - CH 2 - C - - CH 2 -CH 2 -CH 2 -CH 3 Separate the molecule by drawing a line down through the oxygen in the carbon chain. Add an H on both sides of your line to create the carboxylic acid on the carbonyl side and the alcohol on the alkyl side. CH 3 - CH 2 - C - H H - CH 2 -CH 2 -CH 2 -CH 3 carboxylic acid alcohol (propanoic acid) (1-butanol) Worked Example 9-4 Complete the following esterification reaction: [H ] CH 3 -C-H CH 3 -H Solution Each ester has an acid part and an alcohol part. The acid part is the carboxylic acid minus the H group. The alcohol part is an alcohol molecule, minus the H atom of the H group. The H of the acid and the H of the alcohol form H 2 molecule. removal of H and H produces the ester CH 3 -C-H [H ] CH 3 -H CH 3 -C-CH 3 H 2 9-5

6 Practice 9-3 Complete the following esterification reaction: [H ] CH H 3 - CH 2 -H Answer removal of H and H produces the ester H CH 3 - CH 2 -H [H ] - CH 2 - CH 3 H Naming Esters Ester names consist of two words. Use the alkyl portion of the alcohol name first. The -ic acid ending of the name of the carboxylic acid is replaced with ate and follows the first name. Examples: CH 3 CH 2 CCH 3 Methyl propanoate CH 3 CCH 2 CH 2 CH 2 CH 3 Butyl acetate Worked Example 9-5 Name each of the following esters: a) CH 3 CH 2 CCH 2 CH 3 b) CCH 3 c) CH 3 CH 2 C d) C Solution a) ethyl propanoate b) methyl benzoate c) cyclopentyl propanoate d) cyclobutyl benzoate 9-6

7 Practice 9-4 Write the name for each of the following esters. a) CH 3 (CH 2 ) 5 CH 2 CCH 3 b) C CH CH 3 c) CH 2 CH 3 d) CH 3 CH 2 C CH 3 CH 2 CH 2 CH 3 Answer a) methyl octanate b) isopropyl benzoate c) ethyl butanoate e) propyl propanoate 9.6 The Hydrolysis of Esters Hydrolysis is a reaction in which an organic molecule reacting with water splits into two parts, each of which has fewer carbons than the original organic molecule. Esters hydrolysis is a very slow reaction. The reaction is considerably more rapid under either acidic or basic conditions. Ester hydrolysis under acidic condition (acid hydrolysis) is the reverse of acid-catalyzed ester formation. Ester hydrolysis under basic condition (base hydrolysis) produces the metal carboxylate salt instead of the carboxylic acid. I) Acid Hydrolysis of Esters Acid hydrolysis of esters requires the presence of a strong acid catalyst such as sulfuric acid. This reaction requires. The generalized hydrolysis can be shown as: H, R - C - - R' H 2 R - C - H R' - H Ester Acid Alcohol (This hydrolysis is the reverse of esterification.) 9-7

8 Worked Example 9-6 Complete the following reactions: CH 3 -C-CH 3 H 2 H -C-CH 2 CH 3 H 2 H Solution To write the hydrolysis product, under acidic condition, separate the compound at the ester bond, producing the parent carboxylic acid and alcohol. CH 3 -C-CH 3 H 2 -C-CH 2 CH 3 H 2 H H CH 3 -C-H -C-H CH 3 -H CH 3 CH 2 -H II) Base Hydrolysis of Esters Base hydrolysis of esters is called saponification and it is used to manufacture soaps from animal fats and vegetable oils. The generalized hydrolysis can be shown as: H 2 R - C - - R' NaH R - C - - Na R' - H Ester Carboxylate Alcohol salt Notice that this reaction is not an equilibrium reaction (see arrow). The formation of salt drives the equilibrium to the right, making the reaction irreversible. 9-8

9 Worked Example 9-7 Complete the following saponification (base hydrolysis) reactions: CH 3 - C - CH 2 CH 3 -C-CH 3 NaH NaH H 2 H 2 Solution The hydrolysis of ester, under the basic condition, produces the carboxylic acid salt and an alcohol CH 3 - C - CH 2 CH 3 NaH H 2 CH 3 - C - - Na CH 3 CH 2 - H ethyl acetate -C-CH 3 NaH H 2 sodium acetate -C- - Na CH 3 - H methyl benzoate sodium benzoate 9-9

10 Practice 9-5 Complete the following reactions: CH 3 CH 2 -C-CH 2 CH 3 CH 3 CH 2 -C-CH 2 CH 3 H 2 NaH H H 2 Answer CH 3 CH 2 -C-CH 2 CH 3 H 2 H CH 3 CH 2 -C-H CH 3 CH 2 H CH 3 CH 2 -C-CH 2 CH 3 NaH H 2 CH 3 CH 2 -C- - Na CH 3 CH 2 H 9.7 Amines The three most common elements in organic compounds are carbon, hydrogen, and oxygen. Amines contain nitrogen and are commonly found in a wide variety of biomolecules and important pharmaceutical compounds. For this reason, nitrogen ranks fourth on the list of common elements found in organic compounds. Amines are considered organic derivatives of ammonia (NH 3 ) in which one or more hydrogen atoms are replaced by an alkyl or aromatic group. Amines are classified as primary, secondary, or tertiary, depending on the number of organic groups directly attached to the nitrogen atom. H H R R H - N - H R - N - H R - N - H R - N - R Ammonia primary secondary tertiary amine amine amine 9-10

11 9.8 Naming Amines Common names are often used to name simple amines. If two or three alkyl groups are present, they are listed alphabetically along with the suffix amine. The name is written as one word. Aromatic amines are usually named based on aniline. Examples: CH 3 CH 3 - NH 2 CH 3 CH 2 - NH 2 CH 3 CH 2 - NH - CH 3 CH3 - N - CH 3 methylamine ethylamine ethylmethylamine trimethylamine NH 2 aniline NH 2 Cl 3-chloroaniline Worked Example 9-8 Name each of the following: a) CH 3 CH 2 CH 2 CH 2 CH 2 - NH 2 b) CH 3 CH 2 CH 2 CH 2 - NH-CH 2 CH 2 CH 2 CH 3 c) Solution CH 3 CHCH 3 CH 3 CH 2 CH 2 - N - CH 3 d) N(CH 3 ) 2 a) pentylamine (This amine has one alkyl group (pentyl) attached to the nitrogen atom.) b) dibutylamine (This amine has two identical alkyl groups (butyl) attached to the nitrogen atom.) c) isopropylmethylpropylamine (This amine has three alkyl groups (isopropyl, methyl, and propyl) attached to the nitrogen atom.) d) cyclohexyldimethylamine (This amine has three alkyl groups (a cyclohexyl and two methyl group) attached to the nitrogen atom.) 9-11

12 Practice 9-6 Name each of the following: NH 2 a) NH 2 b) Br Br c) CH 3 (CH 2 ) 5 -NH-CH 2 CH 3 d) N Answer a) cyclopentylamine b) 3,4-dibromoaniline c) ethylhexylamine d) diethylmethylamine 9.9 Basicity of Amines Recall (unit 6) that ammonia is also a weak base and accepts H from water to produce ammonium ion (NH 4 ) and hydroxide ion (H - ): NH 3 H 2 NH 4 H - ammonia ammonium ion Because the amines are derivatives of ammonia, they react in a similar ways. General reaction R-NH 2 H 2 RNH 3 H - Specific reaction CH 3 - NH 2 H 2 CH 3 - NH 3 H - Methylamine methylammonium ion Just as amines accept H from water, they can accept H from acids and form salts. For example, when methylamine reacts with HCl, the acid-base reaction produces methylammonium chloride. CH 3 NH 2 HCl CH 3 NH 3 Cl - methylamine acid methylammonium chloride 9-12

13 9.10 Amides The functional group of an amide is a carbonyl group (C = ) linked to a nitrogen atom (N). Amides are classified as primary, secondary, and tertiary amides. R - C - N - H R - C - N - R' R - C - N - R' H H R'' primary secondary tertiary R, R, and R could be aliphatic or aromatic Naming Amides Naming Primary Amides The ending of the name of the carboxylic acid is changed from ic acid (common) or oic acid (IUPAC) to amide. Examples CH 3 CH 2 CNH 2 CH 3 CH 2 CH 2 CNH 2 NH 2 Propanamide butanamide hexanamide Naming Secondary and Tertiary Amides The names of groups attached to nitrogen are placed first, using an N-prefix for each group. CH 3 CH 3 CH 3 - CH 2 - C - N - H CH 3 - CH 2 - C - N - CH 3 N-methylpropanamide N,N-dimethylpropanamide CH 3 CH 3 - CH 2 - C - N - CH 2 -CH 3 N-ethyl-N-methylpropanamide 9-13

14 Worked Example 9-9 Name each of the following amides: C - NH 2 a) CH 3 - CH 2 - CH 2 - CH 2 - C -NH 2 b) c) CH 3 - C - NH 2 d) H - C - NH 2 Solution a) pentanamide b) benzamide c) acetamide (ethanamide) d) formamide (methanamide) Practice 9-7 Name each of the following amides: H a) CH 3 - C - N b) C - NH - CH 2 -CH 3 c) CH 3 - CH 2 - CH 3 - CH 2 - C - NH Answer a) N-cyclohexylacetamide b) N-ethylbenzamide c) N-isopropylpentanamide 9-14

15 9.12 Hydrolysis of Amides Amides are very stable in water. Hydrolysis requires the ing of the amide in the presence of strong acid or base. Acidic hydrolysis gives a carboxylic acid and an amine salt. In aqueous base, the products of hydrolysis are a carboxylic acid salt and ammonia or an amine. General Reactions: Acid Hydrolysis of Amides R - C - NH - R' H 2 HCl R - C - H R' - NH 3 Cl - Base Hydrolysis of Amides R - C - NH - R' NaH R - C - - Na R' - NH 2 Example of Acid Hydrolysis of Amide: CH 3 - C - NH 2 H 2 HCl CH 3 -C-H NH 4 Cl acetamide water hydrochloric acid acetic acid ammonium chloride Example of Base Hydrolysis of Amide: CH 3 - C - NH 2 acetamide NaH CH 3 - C - - Na sodium hydroxide sodium acetate NH 3 ammonia 9-15

16 Worked Example 9-10 Draw the structures of the products in each of the following hydrolysis reactions. C - NH 2 NaH Answer CH 3 - CH 2 - C - NH - CH 3 H 2 HCl C NH 2 C - Na NaH NH 3 CH 3 - CH 2 - C - NH - CH 3 H 2 HCl CH 3 - CH 2 - C - H CH 3 -NH 3 Cl

17 Practice 9-8 Draw the structures of the products in each of the following hydrolysis reactions. C - NH 2 H 2 HCl Answer CH 3 - CH 2 - C - NH - CH 3 NaH C NH 2 C H H 2 HCl NH 4 Cl - CH 3 - CH 2 - C - NH - CH 3 NaH CH 3 - CH 2 - C - - Na CH 3 -NH

18 Homework Problems 9.1 Give the name for each of the following: CH a. Cl Cl b. H c. CH 3 CH 3 - CH -CH 2 - CH d. ( CH 3 CH 2 ) 3 CCH 9.2 Draw the structural formula for each of the following compounds: a. sodium hexanoate b. potassium acetate c. zinc benzoate d. calcium propanoate 9.3 Complete the following reactions: a. CH 3 -C-H CH 3 CH 2 CH 2 H [H ] b. (CH 3 ) 3 CCH 2 CH 2 CH (CH 3 ) 2 CHH [H ] c. CH CH 3 CH 2 H [H ] d. CH 3 (CH 2 ) 2 CH H [H ] 9-18

19 9.4 Draw a structural formula for each of the following esters: a. cyclohexyl propanoate b. methyl formate c. ethyl benzoate d. isopropyl acetate e. butyl butanoate f. propyl pentanoate 9.5 Assign names to each of the following amines: a. NH 2 b. c. CH 3 - NH - CH 2 - CH 3 (CH 3 CH 2 ) 3 N d. NH - CH 3 e. f. CH 3 CH 2 CH 2 - NH 2 N 9.6 Complete the following equations: a. CH 3 CH 2 NH 2 HCl NH 2 b. HCl c. CH 3 CH 2 NH-CH 3 HBr d. N(CH 3 ) 2 HBr 9.7 Draw the structures of 4 isomers of amides of formula C 5 H 11 N. 9-19