Carboxylic Acids and Esters

Nomenclature Physical Properties Sources Reactions Carboxylic Acid Derivatives

General structure
Carboxylic acid functional R group ! ! !
O C OH
R C Z

R-COOH
O

Carboxylic acid derivatives where Z = could be a lot of things!

Carboxylic derivatives
O R C Cl

Acid nomenclature
O C

Acid Chloride

O R C
R

Ester
O R'

Find the longest carbon chain that contains the

Amide NH2
O

O * R C *

O O C R'

COOH group. Drop the -e from the end of the hydrocarbon name and substitute -oic acid. substituents. Number 1 carbon is acid carbon. Name and number other substituents.

Acyl group

Acid anhydride

Number and name any branches or other

R groups can be replace with Ar.

Examples
C C C

Examples
CH3CH2CH2CH(CH3)CH2COOH Parent compound=6carbons, hexane Drop-e and add -oicacid hexanoic acid Carboxylic carbon is #1 Name remaining substituents 3-methylhexanoic acid

OH

1. Longest chain containing carbonyl is 3. propane 2. The -e ending is replaced with -oic acid. propanoic acid

Examples
Br H3C CH C H2 O C OH
Cl CH CH3

More examples
Cl CH C H2 O C OH

trans-2-butenoic acid

3-bromobutanoic acid

3,4-dichloropentanoic acid
H3C CH2 CH H3C CH2 C OH O

methoxyethanoic acid

HOOC

Cl

hexanedioic acid p-chlorobenzoic acid or 4-chlorobenzoic acid 2-ethylbutanoic acid

Some common names

Common Formic Acetic Butyric Capric Lauric Steric IUPAC methanoic ethanoic butanoic decanoic dodecanoic octadecanoic Formula
HCOOH CH3COOH CH3(CH2)2COOH CH3(CH2)8COOH CH3(CH2)10COOH CH3(CH2)16COOH

Aromatic carboxylic acids

Commonly named as derivatives of benzene We also rely on a wide range of common names.
benzoic acid p-bromobenzoic acid

O
Br

OH

OH

Aromatic carboxylic acids

O OH
O OH O OH

Acid halides
-OH of acid is replaced with a F, Cl, Br or I. Name like with acid but use -oyl halide.
O O C Cl Cl

CH3

m-toluic acid

phthalic acid

H3CH2CH2C

Examples of aromatic common names.

butanoyl chloride

benzoyl chloride

Nomenclature examples
Cl CH H3C C Br
H2 C H2 C O

Esters
-OH of acid is replaced with -OR group.

2-chloropropanoyl bromide

Name R group like a side chain (with a space). Then name acid portion with -oate ending
O H3C C O H2 C
O

H3C

CH CH3

C Cl

C H2

CH3

H3C

C H2

H2 C

CH3

3-methylpentanoyl chloride

propyl ethanoate

ethyl propanoate

Esters
O H3C C H2 C O H2 C

This part is treated like a branch with a -yl ending.

CH3

Esters
propyl butanoate
H2 C O C H2 C O H2 C

propyl

H3C

CH2

CH3

Look for this carbon It is the number one carbon on the original acid - it is given the -oate ending.

From

H3C

H2 C

O C H2 C OH

(butanoic acid)

so you would use butanoate.

Nomenclature examples
O H3C C C H2 O H2 C H C CH3 CH3

Acid anhydrides
Formed from the combination of two acids and the loss of water.

2-methylpropyl propanoate 2
H3C

O C OH

H+ heat

O H3C C O

O C CH3

+H2O

O H3C H2 C C H2 C H2 C O

2 ethanoic acids cyclopropyl butanoate

ethanoic anhydride

Acid anhydrides
Nomenclature Simple example: both halves are from the same acid. Name by changing acid ending to anhydride.
O H3C C H2 C O O C C H2 CH3
O C O O C

Properties
Acids Very polar with high boiling points Exhibit hydrogen bonding
O R C OH O HO C R

propanoic anhydride

benzoic anhydride

Can dissociate - acid character R - COOH R - COO- + H+

Properties
Derivatives ! Acid chlorides ! Noxious, irritating, slightly polar ! React violently with water ! Esters ! Slightly polar, pleasant odor ! Low MW species are water soluble

Sources of carboxylic acids

Natural Sources ! Formic acid - ants ! Low MW acids - tart and citrus fruit. Fatty acids - found in fats, milk, plant oil
O HO HO C O C C CH2 O OH
O OH H

CH2 C OH
H3C

C C OH

! Acid anhydrides ! Not as polar as acids ! May decompose in water

citric acid

lactic acid

Sources of carboxylic acids

Industrial ! Oxidation of ethanol or ethanal
H3CH2C OH
oxidi zing agen

Laboratory sources
Produced by oxidation of aldehydes
O R C H

Oxidizing agent

O R C OH

ethanol
O H3CC H

O H3CC OH

primary alcohols
R H2 C OH

oxidizing

agent

[O]

O R C H

[O]

O R C OH

ethanoic acid

ethanal

1o alcohol

aldehyde

carboxylic acid

Reactions of carboxylic acids

All are weak acids. ! Dissociation in water.
R C O OH

Carboxylate ion

+ H2O

R C + H O+ 3 O-

O R C OH
R C

O
+ H+

Carboxylate ion

Reactions of carboxylic acids

Reaction with a strong base ! Salt formation.
H3C C O

Reactions of carboxylic acids

Soap formation ! Produced from long-chain acids
O H 2C O C O HC O C O H 2C O C R R R
MOH

OH acetic acid sodium (weak acid) hydroxide (strong base)

+ NaOH

O sodium acetate (salt) (weak base)

H3C C Na+ + H2O -

H 2C HC H 2C

OH OH OH

C O

O- M +

water

H2O, heat

C O

O- M +

O- M +

M = Na+ or K+

How soap works

Reactions of carboxylic acids

Formation of derivatives ! Acid chlorides

-OOC

-OOC COO
-

-OOC

Nonpolar tail dissolves in oil.

-

H3C C

O OH

PCl3

H3C C

O Cl

COO -OOC

COO -OOC COO

-

COO

Polar heads are attracted to the water.

ethanoic acid (acetic acid)

ethanoyl chloride

Reactions of carboxylic acids

Formation of Esters
H3CC O OH

Reactions of carboxylic acids

Hydrolysis of acid anhydrides

+ CH3CH2OH

H3CC

OCH2CH3

+ H2O

ethyl ethanoate
H3CH2CC O OH

O C

O C

+ H2O
heat

+ CH3-OH

H3CH2CC

methyl propanoate

OCH3

+ H2O

O 2R C OH

Some significant examples

Analgesics - pain killers Antipyetics - fever reducers
O C OH O C O CH3

More examples, pheromones

H N OH

H3C

C O

Pheromones - chemicals secreted by animal and insects that alter the behavior of other members of the same species.
O || CH3CH2CH=CH(CH2)9CH2OCCH3

Acetylsalicylc acid (Aspirin)

Acetaminophen (Tylenol)

H N O

tetracecenyl acetate (european corn borer sex pheromone)

CH3 O | || CH3CHCH2CH2OCCH3

CH3 CH2

CH3

Phenacetin (APC tablets)

isoamyl acetate (honey bee alarm)

Smelly stuff
O || CH3CH2CH2COCH3 O || CH3CH2CH2COSCH3

methylbutanoate Apples
O || CH3CH2CH2COCH2CH3

methylthiobutanoate Strawberries
O || CH3CH2CH2CO(CH2)4CH3

ethylbutanoate Pineapples

pentylbutanoate Apricots