chapter 3
DESCRIPTION
Chapter 3. Carboxylic Acids. Carboxylic Acids. The functional group of carboxylic acids consists of a C=O with -OH bonded to the same carbon. Carboxyl group is usually written -COOH. Aliphatic acids have an alkyl group bonded to -COOH. Aromatic acids have an aryl group. - PowerPoint PPT PresentationTRANSCRIPT
Carboxylic Acids
Chapter 20 2
Carboxylic AcidsThe functional group of carboxylic acids
consists of a C=O with -OH bonded to the same carbon.
Carboxyl group is usually written -COOH.Aliphatic acids have an alkyl group bonded
to -COOH.Aromatic acids have an aryl group.Fatty acids are long-chain aliphatic acids.
=>
Carboxylic Acids Carboxylic acid, compounds of the type
RCOOH such as Acetic acid ( present in vinegar), Malonic acid and Benzoic Acid.
CH3COOHH2C
COOH
COOH
COOH
Acetic acid Malonic acid Benzoic acid
4
Common NamesMany aliphatic acids have historical names.Positions of substituents on the chain are
labeled with Greek letters.
1-Carboxylic Acid Nomenclature
CH3CH2CH2CHCOOH
BrCH3CHCH2COOH
CH3
bromovaleric acid -methylbutyric acid
isovaleric acid
COOH
COOH COOH COOH
CH3
CH3CH3
benzoic acid
o-toluic acid m-toluic acid p-toluic acid
special names
Chapter 20 6
IUPAC NamesRemove -e from alkane (or alkene) name,
add -oic acid.The carbon of the carboxyl group is #1.
CH3CH2CHC
Cl
OH
O
2-chlorobutanoic acid
PhC
HC
H
COOH
trans-3-phenyl-2-propenoic acid (cinnamic acid)
=>
parent chain = longest, continuous carbon chain that contains the carboxyl group alkane, drop –e, add –oic acid
HCOOH methanoic acid
CH3CO2H ethanoic acid
CH3CH2CO2H propanoic acid
CH3
CH3CHCOOH 2-methylpropanoic acid
BrCH3CH2CHCO2H 2-bromobutanoic acid
8
Dicarboxylic AcidsAliphatic diacids are usually called by their
common names (to be memorized).For IUPAC name, number the chain from the
end closest to a substituent.Two carboxyl groups on a benzene ring
indicate a phthalic acid.
HOOCCH2CHCH2CH2COOH
Br
3-bromohexanedioic acid -bromoadipic acid =>
dicarboxylic acids:
HOOC-COOH oxalic acid
HO2C-CH2-CO2H malonic acid
HO2C-CH2CH2-CO2H succinic acid
HO2C-CH2CH2CH2-CO2H glutaric acid
HOOC-(CH2)4-COOH adipic acid
HOOC-(CH2)5-COOH pimelic acid
CO2H
CO2H
CO2H
CO2H
CO2H
CO2Hphthalic acid isophthalic acid
terephthalic acid
CCOOHH
CCOOHH
CCOOHH
CHHOOC
maleic acid fumaric acid
Chapter 20 11
Naming Cyclic AcidsCycloalkanes bonded to -COOH are named as
cycloalkanecarboxylic acids.Aromatic acids are named as benzoic acids.
COOH
CH(CH3)2
2-isopropylcyclopentanecarboxylic acid
COOH
OH
o-hydroxybenzoic acid(salicylic acid)
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2-Physical properties1- Boiling pointIntermolecular forces, especially hydrogen
bonding, are stronger in carboxylic acids than in other compounds of similar shape and molecular weight.
Acetic acid exists as a hydrogen-bonded dimer in the gas phase. The hydroxyl group of each molecule is hydrogen-bonded to the carbonyl oxygen of the other.
2-2-Solubility in WaterSolubility in WaterCarboxylic acids are similar to alcohols in respect to their solubility in water
Form hydrogen bonds to water
HH33CCCC
OO HH OO
OOHHOO
HH
HH
HH
3-Acidity of carboxylic acidsMost carboxylic acids have a pKa close to 5.Carboxylic acids are weak acids but carboxylic
acids are far more acidic than alcohols.
The greater difference in ionization energy (∆ G) of ethanol and acetic acid reflects a greater stabilization of acetate ion relative to ethoxide ion.
Greater acidity of carboxylic acids is attributedstabilization of carboxylate ion by inductive effect of carbonyl group
And by resonance stabilization of carboxylate ion.
Salts of Carboxylic Acids
salts of carboxylic acids:
name of cation + name of acid: drop –ic acid, add –ate
CH3CO2Na sodium acetate or sodium ethanoate
CH3CH2CH2CO2NH4 ammonium butyrate
ammonium butanoate
(CH3CH2COO)2Mg magnesium propionate
magnesium propanoate
4-Substituent and acid strength Alkyl substituents have negligible
effect
Electronegative substituents increase acidity
Electronegative substituents withdraw electrons from carboxyl group; increase K for loss of H+
Effect of substituent decreases the acidity as number of bonds between X and carboxyl group increases.
COOH
OCH3
COOH COOH
NO2
COOH
NO2
COOH
NO2
p-methoxy benzoic acid m-nitro p-nitro o-nitro
pKa = 4.46 pKa = 4.19 pKa = 3.47 pKa = 3.41 pKa = 2.16
Ionization of Substituted Benzoic AcidsHybridization Effectsp2-hybridized carbon is more electron-withdrawing
than sp3, and sp is more electron-withdrawing than sp2
Effect is small unless X is electronegative; effect is largest for ortho substituent
5-Synthesis of carboxylic acids1- Oxidation of alkylbenzene
2- Oxidation of primary alcohols
3- Oxidation of aldehydes
4-Carboxylation of Grignard reagents
5- Hydroylsis of nitriles
6- Reactions of Carboxylic acids1- Formation of Acyl chlorides
2-Lithium aluminium hydride reduction
3-Esterification
Mechanism of Esterification
Intramolecular ester formation (Lactones)
4-α-Halogenation
This reaction of α- bormination of carboxylic acid is called Hell- Volhard- Zelinasky reaction
5- Decarboxylation of carboxylic acids