CARBOXYLIC ACIDS

AND DERIVATIVES

High Yield Notes

 NOTES
CARBOXYLIC ACIDS
AND DERIVATIVES
INTRODUCTION
Organic compounds containing
-COOH group
Carb-cabonyl group
oxyl-hydoxyl group
Acidic in nature
Thus, overall called as carboxylic
acids.
General formula: CnH2nO2

Aliphatic Carboxylic Acids Aromatic Carboxylic Acids

R-COOH Ar-COOH
COOH
phthalic acid
Palmitic Acid (C15H31COOH) COOH

Stearic Acid (C17H35COOH)

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 NOTES NOMENCLATURE
Monocarboxylic Acids

IUPAC Name Common name

Carboxylic Acid
(alkanoic acid) (origin)

Methanoic Acid Formic acid (ant bite)

Ethanoic acid Acetic acid (vinegar)

Propanoic acid Propionic acid

Butanoic acid Butyric acid (butter)

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 NOTES Dicarboxylic Acids

IUPAC Name Common

Carboxylic Acid (alkanedioic name
acid) (origin) Here’s a Trick!

Ethanedioic Acid Oxalic acid Old

1,3-propanedioic
Malonic acid Maps
acid

hghg
1,4-butanedioic
Succinic acid Show
acid

1,5-Pentanedioic
Glutaric acid Great
acid

1,6-Hexanedioic
Adipic acid Adventures
acid

Polycarboxylic Acids

IUPAC Name Common Name

Carboxylic Acid
(alkanoic acid) (origin)

2-hydroxypropane-1,2,3-
Citric Acid
tricarboxylic acids

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 NOTES ACIDITY

Electron Position of Electron Number of Electron

Withdrawing Groups Withdrawing Group Withdrawing Groups

Presence of electron
withdrawing groups
More the number of
decreases electron The closer the electron
electron withdrawing
density on oxygen and as withdrawing group is to
groups present in
a result the resonance carbonyl group the more
compound more is the
structure gets stabilized is the acidic strength.
acidic strength.
hence increasing the
stability.

Carboxylic Acid Structure pKa

Ethanoic Acid 4.7

Propanoic Acid 4.9

Fluoroethanoic Acid 2.6

Chloroethanoic Acid 2.9

Dichloroethanoic Acid 1.3

Trichloroethanoic Acid 0.9

Nitroethanoic Acid 1.7

Acidic Strength
Carboxylic Acids > Phenol > Water > Alcohol

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 NOTES METHODS OF
PREPARATION
Oxidation

Primary K2Cr2O7
H2SO4.
.
Alcohols

K2Cr2O7
Aldehydes H2SO4.

Alkyl K2Cr2O7
Benzene H2SO4.

Hydrolysis

Alkane +
H or OH
-

HCl. R - C N + H2O . R - COOH + NH3

Nitriles CH3C N + 2 H2O + HCl CH3COOH + NH4Cl

NaOH R - COOR’ + NaOH

-
R - COO Na + R’ - OH
+
Esters HCl. - +
R - COO Na + HCl R - COOH + NaCl

Oxidative Cleavage

-
KMnO4 / OH
R - CH = CH - R + 4[O] 2 R - COOH
Alkenes KMnO4/OH.
Symmetrical Alkene Carboxylic Acid

-
KMnO4 / OH
H3C - CH = CH - CH 3+ 4[O] 2 CH3- COOH
2 - Butene
Ethanoic Acid

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 NOTES Carbonation

dry - + H
+ X
R - MgX + O = C = O ether [R - COOMgX] R - COOH + Mg
Grignard Dry ether H2O
OH
S- S- S+ S- Br
H2O/acid.
+
dry - +
reagent CH3- MgBr + O = C = O ether
[R - COOMgBr] H
H2O
CH3-COOH + Mg
OH

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 NOTES PHYSICAL PROPERTIES

Smell Solubility Melting Point Boiling Point

C1 to C3 colorless C1 to C3 very
and pungent soluble due to H They have high
Even no of C
smell. bond. BP Due to
atoms > odd no of
C4 to C6 As C increase Hydrogen bond.
C atoms.
colorless with solubility
unpleasant smell. decreases.

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 NOTES REACTIVITY OF
CARBOXYL GROUP
Due to Chemistry of both carbonyl and hydroxyl group.

Reactions

O O
R - C - O - SR’ R - C - O - Cl
R’
SH

2
Cl
SO
O O O
O
R’ R’NHR’’ R’COCl
R-C-O-N R-C-O-H R - C - O - C - R’
R’’
se R’O
Ba H
O O
-
R-C-O R - C - O - OR’

Reactions Involving
Hydrogen Atom

O O
H2O - +
R-C-O-H R-C-O H
Carboxylate Ion

Forms salt
With Bases CH3COOH + NaOH CH3COONa + H2O
and water.

With Carbonate Forms salt 2 CH3COOH + Na2CO3

-
2 CH3COO Na + CO2+ H2O
+

and and water - +

and CO2. CH3COOH + NaHCO3 CH3 COO Na + CO2 + H2 O
Bi-carbonates

Forms salt
With Metals and H2
2 CH
- +
2 CH3COOH + 2 Na 3 COO Na + + H 2
(gas).

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 NOTES Reactions Involving OH
Group
Attack by nucleophile.

Reagent Product Conditions Reaction

With Forms Pyridine is CH3COCl + POCl3+ HCl

CH3COOH + PCl5
PCL5 and Acid needed with
CH3COOH + SOCl2 CH3COCl + SO2 + HCl
SOCL2. Halides. SOCl2

With Forms Concentrated H2SO4

CH3COOH + C2H5OH CH3COOC2H5+ H2O
Alcohol. Esters. acid.

CH3COOH + NH3 CH3COONH4

With Forms
- - +
Ammonia Amides. CH3COO N H4
heat
CH 3CONH2+ H2O

With
Forms O O
another P2O5 and
Acid CH3COOH + HOOCCH3 P2 O5
CH3- C - O - C - CH3+ H2O
carboxyli Red Hot
Anhydride Acetic Anhydride

-c acid

Esters

Ester Flavor
Here’s how to remember this!
Amyl acetate Banana
Alligators In Bathroom
Isobutyl Formate Raspberry Esters:
Eat Apples, Oh!
Benzyl acetate Jasmine
Big Red Juicy
Ethyl Butyrate Pineapple Flavors:
Apples, Oh!
Amyl Butyrate Apricot
Octyl acetate Orange

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 NOTES Reactions Involving COOH
Group

Reduction Products Conditions Reaction

Partial LiAlH 4
Alcohols. LiAlH4 CH3COOH + 4[H] CH3CH2OH + H2O
Reduction.

Complete HI and red CH3COOH + 6 HI

P
CH3CH3+ 3 I2+ 2 H2O
Alkenes.
Reduction. phosphorus

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 NOTES ACETIC ACID
Ethanoic acid.
Also called vinegar when its in a
dilute solution (acetum means
vinegar).

Preparations

Laboratory Method Conditions Product

Oxidation of ethyl
K2Cr2O7 / H2SO4 Acetic Acid
alcohol or acetaldehyde.

Hydrolysis of methyl
H2O / HCl Acetic Acid
cyanide.

Manufacture
Conditions Product
Method

O
From Acetylene. 20% H2SO4 1% HgSO4 80 C Ethanal

Now add V2O5 to

V2O5 Acetic Acid
Ethanal.

Commercial Method
Conditions Product
(fermentation)

Ethyl alcohol K2Cr2O7 / H2SO4 Acetic Acid

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 NOTES Physical Properties

Colorless liquid.
B.P 118°,C.
Has vinegar odor.
Sour in taste.
Freezes at 17C (glacial acetic
acid).

Uses

Used as coagulant for latex.

Used in manufacture of
plastic(poly vinyl acetate) or
rayon(cellulose acetate) and silk.
Medicine as local irritant.
Used as solvent.
Used for pickle.

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 NOTES AMINO ACIDS
I - isoleucine
Like - leucine
Lemons - lysine
Make - methionine
A - arginine
Very - valine
Tasty - threonine
Homemade - histidine
General Structure of Amino Acids Pie - phenylalanine
Tomorrow - tryptophan
All naturally occurring are alpha
amino acids (20):
10 essential amino acids.
10 non essential amino acids.

Acidic Amino Acids Basic Amino Acids Neutral Amino Acids

Giraffes - Glycine
Acidic Grape. LH hormone.
Always - Alanine
Aspartic acid. Lysine.
Visit - Valine
Glutamic acid. Histidine.
Parks - Proline

Preparations

R - CH2COOH + Br2 R - CHCOOH + HBr

By reaction of
Br
alpha bromo acids R - CHCOOH + 2 NH3 . R - CHCOOH + NH4Br
with Ammonia Br NH2
R - CHO + HCN + NH 3 R - CH - CN + H2O
NH2
- amino nitdl upon acidic hydrolysis yields an - amino acid:
Strecker’s synthesis.
R - CH - CN H3O
+
R - CH - COOH
NH2 NH2

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 NOTES Reactions

With alcohol
in presence of Forms ester
strong acid.

With nitrous
Forms N2 gas
acid (HNO2).

Test
Ninhydrin test: If amino acids are
present an intensely colored
blue violet product is formed.

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