12.

Aldehydes, Ketones and Carboxylic Acids

Marks without option: 06 Marks with option: 08
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Aldehydes, ketones and carboxylic acids are organic compounds containing carbonyl group, hence
they are known as carbonyl compounds.

ALDEHYDES AND KETONES:- Aldehydes are the first oxidation products of primary alcohols. The
functional group in aldehydes is formyl or aldehyde group (‒CHO). This is group is always present at
the terminal carbon of the chain.

Classification of aldehydes:-

(a)Aliphatic aldehydes:- The aldehydes in which formyl (‒CHO) group is attached to a sp3 hybridized
carbon atom i.e. saturated carbon atom are called as aliphatic aldehydes. Exception: Formaldehyde is
classified as aliphatic aldehyde though ‒CHO group is not attached to any carbon atom. For example;
O O
O O

H C H H3C C H H3C CH2 C H R C H

Formaldehyde Acetaldehyde Propionaldehyde General Formula

(b)Aromatic aldehydes:- The aldehydes in which formyl (‒CHO) group is attached to carbon atom of
aromatic ring are called as aromatic aldehydes. For examples;
O O O
C H C H C H
OH

NO 2

Benzaldehyde Salicylaldehyde p-nitrobenzaldehyde

Ketones are the first oxidation products of secondary alcohols. The functional group in is keto or
oxo group ( C=O). The keto group is not located at the terminal carbon of the chain.

Classification of ketones :- Ketones are classified as aliphatic ketones and aromatic ketones.

(a) Aliphatic ketones :- The ketones in which keto ( C=O) group is attached to two alkyl groups are
called as aliphatic ketones. On the basis of types of alkyl groups bonded to carbonyl carbon, these are
further classified as simple and mixed ketones.

(i)Simple or Symmetrical ketones:- The ketones in which both alkyl groups bonded to carbonyl carbon
are identical (R=R’) are called simple or symmetrical ketones.

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 O O

H3C C CH3 H5C2 C C2H5

Acetone Diethyl ketone

(ii)Mixed of unsymmetrical ketones:- The ketones in which two alkyl groups bonded to carbonyl
carbon are different (R ≠ R’) are called mixed or unsymmetrical ketones.
O O

H3C C CH2 CH3 H7 C3 C C 2 H5

Ethyl methyl ketone Ethyl n-propyl ketone

(b) Aromatic ketones :- The ketones in which keto ( C=O) group is attached to two aryl groups or one
aryl and one alkyl group are called as aromatic ketones. For example,
O O

C C
CH3

Benzophenone (Diphenyl ketone) Acetophenone (Methyl phenyl ketone)

(IUPAC Name) (Common Name) (IUPAC Name) (Common Name)

Nomenclature:- A] Common Names:-

Aldehydes:-The common names of most of aldehydes are derived from common names of corresponding
carboxylic acids replacing ending ‘-ic acid’ with aldehyde. The positions of substituent in the carbon chain
are indicated by Greek letters α, β, ϒ, δ etc. α carbon is the one which is directly linked to aldehyde group.

Ketones:-The common names of symmetrical ketones are obtained as dialkyl ketone. The common
names of unsymmetrical ketones are obtained by entering the names of two alkyl of aryl groups in
alphabetical order followed by the word ‘ketone’. Locations of the substituents are given by Greek
letters. A ketone in which the carbonyl group is attached to a benzene ring is named as a phenone. Alkyl
phenyl ketone is usually named by adding acyl group as prefix to phenone.

B] IUPAC System:-

Aldehydes:-IUPAC names of aliphatic aldehydes are derived from names of corresponding alkanes by
replacing ending ‘e’ with ‘al’. (Alkane to Alkanal). The longest continuous carbon chain containing ‘‒
CHO’ group is selected and is always numbered as one. The suffix ‘dial’ is added to appropriate alkane
names when compound contains two aldehyde groups; the ending ‘e’ is retained is such case.

When aldehyde group is attached to a ring, the suffix carbaldehyde is added after the name of
cycloalkane. The numbering should start from carbon containing aldehyde group. IUPAC name of
benzaldehyde is benzenecarbaldehyde; however common name benzaldehyde is accepted by IUPAC.
Other aromatic aldehydes are named as substituted benzaldehyde.

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 O CHO
O O O
CH3
H C HC CH2 C H H3C C CH2 C H COOH

2-methylbutanedial 3-Oxobutanal 2-formylbenzoic acid

Ketones :-In IUPAC system, ketones are named as ‘alkanones’. The longest continuous chain containing
keto group is selected as parent chain and name is derived by replacing ending ‘e’ from alkane with ‘one’.
Numbers to the carbon atoms in the chain are given from that end which is nearer to keto group. In cyclic
ketones, carbonyl carbon is numbered as one. In polyfunctional compounds the presence of aldehyde
group is indicated by prefix formyl and a keto group by oxo with a number.

Common and IUPAC names of some aldehydes and ketones:-

Sr. No. Compound Common Name IUPAC Name

Aldehydes
1. H CHO Formaldehyde Methanal
2. H 3C CHO Acetaldehyde Ethanal
3. H3C CH2 CHO Propionaldehyde Propanal
4. H3C CH2 CH2 CHO n-butyraldehyde Butanal
5. CH3 Isobutyraldehyde 2-methylpropanal
(α-methyl propionaldehyde)
H3C CH CHO
6. H2C CH CHO Acrolein/Acrylaldehyde Porp-2-enal
7. H3C CH CH CHO Crotonaldehyde But-2-enal
8. CHO Oxaldehyde (Glyoxal) Ethane-di-al
CHO
9. CHO
Benzaldehyde Benzaldehyde
(Benzenecarbaldehyde)
10. CHO Phthaldehyde Benzene-1,2 dicarbaldehyde
CHO

11. CHO Salicylaldehyde 2-hydroxybenzaldehyde.

OH

12. CHO o-tolualdehyde 2-methyl benzaldehyde

CH3

13. CHO
Cyclohexane aldehyde Cyclohexanecarbaldehyde

Ketones
1. H3C CO CH3 Acetone/ Dimethyl ketone Propanone
2. H3C CO CH2 CH3 Ethyl methyl ketone Butanone
3. H3C CO CH2 CH2 CH3 Methyl n-propyl ketone Pentan-2-one
4. H3C CH2 CO CH2 CH3 Diethyl ketone Pentan-3-one

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5. Br α-bromo ethyl n-propyl ketone 2-bromohexan-3-one
H3C CH CO CH2 C2H5
6. CH3 O Mesityl oxide 4-Methylpent-3-en-2-one
H3C C CH C CH3 Isobutenyl methyl ketone
7. O O ‒‒‒‒ Hexane-2,4-di-one
H3C C CH2 C CH2 CH3
9. O
Cl
‒‒‒‒ 2- chloro-4-
methylcyclohexanone

CH3

Methods of preparation:-

I] By Oxidation of Alcohols:- Oxidation of primary and secondary alcohols leads to the formation of
aldehydes and ketones as well as carboxylic acids. The –OH group of 10 and 20 alcohols form carbonyl
group by removal of two hydrogen atoms; one from –O–H group and other from α-carbon atom. 30
alcohols do not undergo oxidation.

(i)Oxidation of primary alcohol:- Primary alcohols on oxidation using strong oxidizing agents like
K2Cr2O7, KMnO4, HNO3 etc. first gives as aldehyde which on further oxidation gives carboxylic acid.
Aldehydes are more easily oxidized than alcohols. The best reagent for obtaining only aldehydes
from primary alcohols is pyridiniumchlorochormate(PCC). PCC is a mild oxidizing agent that oxidizes
primary alcohols to aldehydes only.
O
PCC
R CH2 OH + (O) R C H + H2O

Alcohol (10) Aldehyde

(ii) Oxidation of secondary alcohol:- Secondary alcohols on oxidation with chromic anhydride (CrO3)
gives ketone. The ketone formed does not undergo further oxidation. Secondary alcohols can be
oxidized to ketones by PCC.

OH O
CrO3
R CH R' + (O) R C R' + H2O
Alcohol (20) Ketone

(iii) Heating with copper (Dehydrogenation):- Vapours of primary and secondary alcohols are passed
over heated copper at 573K to give aldehyde and ketone respectively. Tertiary alcohols undergo
dehydration.
O
Cu
(1) H3C CH2 OH
573 K
H3C C H + H2

Ethanol Ethanal

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 OH O
Cu
(2) H3C CH CH3
573 K
H3C C CH3 + H2

Propan-2-ol Acetone
CH3 CH3
Cu
(3) H2C C CH3
573 K
H2C C CH3 + H2O
H OH
2-methyl propene
t-butyl alcohol

II]From unsaturated hydrocarbons:-

a)By ozonolysis of alkenes:- When a steam of ozonide oxygen is passed through solution of alkene, it
gives unstable ozonide. Ozonides on reduction with zinc dust and water gives aldehyde or ketone or
mixture of both.

O
Zn/H2O
H2C CH2 + O3 H2C CH2 2 H-CHO + ZnO
O O

Ethene Ethylene ozonide Formaldehyde
O
H3C Zn/H2O
H3C CH CH2 + O3 HC CH2 CH3-CHO + H-CHO + ZnO
O O 
Propene Propylene ozonide Acetaldehyde Formaldehyde

b)By hydration of alkynes:- Alkynes on passing through 40% H2SO4 in presence of 1% mercuric
sulphate, aldehydes or ketones are formed.
H
40%H2SO4 Tautomerism
HC CH + H-OH H2C CH O H H3C C O

III] From acyl chlorides (Acid chlorides):- Aldehydes and ketones both can be prepared from acyl
chlorides by following different methods.

(i) Preparation of aldehyde from acyl chloride :- An acyl chloride is hydrogenated over catalyst,
palladium poisoned by barium sulphate to give an aldehyde. This reaction is called as Rosenmund
Reduction.

O O
Pd-BaSO4
R C Cl + H2 R C H + HCl

Acyl chloride Aldehyde

(ii) Preparation of ketone (aliphatic and aromatic) from acyl chloride :-Ketones are obtained from
acyl chloride by reaction with dialkyl cadmium(R2-Cd). Grignard reagent reacts with cadmium chloride to
give dialkylcadmium.

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 2 R-Mg-X + CdCl 2 R2Cd + 2 Mg(X)Cl

2 R-COCl + R 2Cd 2 R-CO-R + CdCl 2

Acyl chloride Ketone

For example,

2 CH3COCl + (CH3)2Cd 2 CH3-CO-CH3 + CdCl2

2 C6H5-COCl + (CH 3)2Cd 2 C6H5-CO-CH 3 + CdCl 2

(ii) Preparation of aromatic ketones from acyl chloride:- Friedel-Crafts acylation:- When benzene
or its derivative is treated acyl chloride in presence of anhydrous aluminium chloride, it gives
corresponding ketone. The reaction is known as Friedel-Crafts acylation.
O

O C CH3
Anhydrous AlCl3
+ H3C C Cl

+ HCl

Benzene Acetyl chloride Acetophenone

II]From nitriles :-Aldehydes and ketones both can be obtained from nitriles by different methods as
follows,

(i)Nitriles are reduced to corresponding imine hydrochloride by stannous chloride in presence of dil. HCl
which on acid hydrolysis give corresponding aldehyde. This reaction is called as Stephen Reaction.
H
SnCl2 H+/H2O
R C N + 2 (H) Dil.HCl
R CH NHHCl R C O + NH 4Cl

Alkane nitrile Imine hydrochloride Aldehyde

H
SnCl2 H+/H2O
H3C C N + 2 (H) Dil.HCl
H3C CH NHHCl H3C C O + NH 4Cl

Acetonitrile Imine hydrochloride Acetaldehyde

H
SnCl2 H+/H2O
H 5C 6 C N + 2 (H) Dil.HCl
H 5C 6 CH NHHCl H 5C 6 C O + NH 4Cl

Benzonitrile Imine hydrochloride Benzaldehyde

(ii)Nitriles are selectively reduced by di-isobutyl aluminium hydride(DIBAl-H) to imines followed by

acid hydrolysis gives aldehyde. The advantage of this method is that double or triple bond is present in
the same molecule is not reduced.

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 i)DIBAl-H
H3C CH CH CH2 C N H3C CH CH CH2 CHO
ii)H+/H2O

Pent-3-en-nitrile Pent-3-enal

III] Preparation of ketones from nitriles:- A nitrile reacts with Grignard reagent in presence of dry
ether to give an imine complex which on acid hydrolysis gives a ketone. Nitrile and Grignard reagent
should be taken in equimolar mixture.
CH3 O Cl
Dry ether H-OH
H3C C N + CH 3-Mg-Cl H3C C N-Mg-Cl
H+
H3C C CH3 + Mg
OH
Ethanenitrile Methyl Magnesium chloride Imine complex Acetone

O
N MgBr
C N MgBr C C
H + OH
+ Dry Ether
+ Mg
H2O
Br
Benzonitrile Phenyl Magnesium Bromide Imine complex Benzophenone

IV]From aromatic hydrocarbons:- Aromatic aldehydes and ketones can be prepared from aromatic
hydrocarbons by following different methods.

i)Oxidation of methyl benzene (toluene)/Etard reaction :- Chromyl chloride converts methyl group in
toluene to a chromium complex which on acid hydrolysis gives corresponding aldehyde. This reaction is
called Etard reaction.
CH3 CH(OCrOHCl 2)2 CHO
CS2 H+/H2O
+ 2 CrO2Cl 2

Toluene Chromium Complex Benzaldehyde

ii)Toluene and its derivatives on treatment with chromium oxide in acetic anhydride gives a diacetate
derivative which on acid hydrolysis produces corresponding aldehyde.
CH3 CH(OCOCH 3) 2 CHO
273-278K H 3O +
+ (CH 3CO) 2O
CrO3


Toluene Diacetate derivatives Benzaldehyde

iii)Chlorination of side chain followed by hydrolysis: Commercial method for preparation of

benzaldehyde:- Side chain chlorination of toluene gives benzal chloride which on acid hydrolysis at 373K
gives benzaldehyde.

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 CH3 CHCl2 CHO
Cl2/hv H+ / H2O


Toluene Benzal chloride Benzaldehyde

V] Gattermann-Koch Formylation:-When benzene or its derivative is treated under high pressure with
carbon monoxide and HCl in presence of catalyst anhydrous aluminium chloride and cuprous chloride, it
gives benzaldehyde or substituted benzene.
CHO
CO,HCl
Anhydrous AlCl3

Benzene Benzaldehyde

VI] Preparation of aromatic ketones from hydrocarbons/Fridel-Crafts acylation reaction:- When

benzene or its derivative is treated acyl chloride in presence of anhydrous aluminium chloride, it gives
corresponding ketone. The reaction is known as Friedel-Crafts acylation.
O

O C CH3
Anhydrous AlCl3
+ H3C C Cl

+ HCl

Benzene Acetyl chloride Acetophenone

VII] From esters (Aldehydes only):- Aliphatic or aromatic esters are partially reduced to aldehydes
with DIBAl-H. Reaction is carried out at 1950C to avoid further reduction of aldehyde to alcohol.

O O
i)DIBAl-H in toluene
R C OR' R C H
ii)H+/H2O

Ester Aldehyde

Physical Properties:-

1) Nature of intermolecular forces :- The carbonyl group in aldehydes and ketones is a polar co-valent
bond. Thus these compounds contain dipole-dipole forces of attraction.

2) Physical State :- Formaldehyde is a gaseous substance and has irritating odour. Acetaldehyde is
extremely volatile, colourless liquid. Higher aldehydes have pleasant odour. Acetone is a colourless
liquids and has pleasant odour. Most of the higher ketones have bland odours.

3)Boiling Point :- The boiling points of aldehydes and ketones increases with increase in number of
carbon atoms.

4) Solubility :- The carbonyl oxygen can involve in hydrogen bonding with water molecule. As a result
the lower aldehydes and ketones are water soluble. As the molecular mass increases, the proportion of
hydrocarbon part of molecule increases hence the solubility in water decreases.

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Polarity of carbonyl group :- The polarity of carbonyl group originates
from higher electronegativity of oxygen than the carbonyl carbon as well as
the resonance effect. The carbonyl carbon has positive polarity, thus it is
electron deficient. As a result, this carbon atom is electrophilic and
susceptible to attack by nucleophile.

Reactivity of aldehydes and ketones:- Reactivity of aldehydes and

ketones is due to polarity of carbonyl group which results in electrophilicity
of carbon. In general, aldehydes are more reactive than ketones toward
nucleophilic attack. This reactivity can e explained on the basis of following
two effects.

1] Influence of electronic effects:- Alkyl groups have electron donating inductive (+I) effect. A ketone
has two electron donating alkyl groups bonded to carbonyl carbon. These two alkyl groups decreases the
positive polarity and electrophilicity. In contrast, aldehydes have only one electron donating group
bonded to carbonyl group. This makes aldehydes more electrophilic than ketones.

2] Steric effects: - Two bulky alkyl groups in ketone produces steric hindrance to nucleophilic attack.
Nucleophile can attack on carbonyl carbon in aldehydes easily because it has only one alkyl group which
is less crowded and sterically less hindered. Hence aldehydes are more easily attacked by nucleophiles
than ketones.

Chemical porperties of aldehydes and ketones:-

a)Laboratory test for aldehydes:- Aldehydes are easily oxidized to carboxylic acids and therefore act as
reducing agent towards mild oxidizing agents. Oxidation of ketones is difficult as it involves breaking of
C-C bond. On the basis of this difference, aldehydes and ketones are distinguished. Aldehydes acts as
reducing agents as they reduce (i) Fehling solution, (ii) Tollens regent and (iii)Schiff reagent.

(i)Fehling solution :- It is a tartaric acid complex of cupric ions. When an aldehyde is boiled with Fehling
solution, the deep blue color of solution disappears and red precipitate of cuprous oxide is formed. The
aldehyde ion gets oxidized to acetate ion and Cu2+ is reduced to red colored cuprous oxide. α-hydroxy
ketones also gives this test positive.
–
H O

R C O + 2 Cu 2+ + 5 OH
-
R C O + Cu 2O + 3 H 2O

Aldehyde Fehling solution Carboxylate ion Red ppt

(ii)Tollens regent/ Silver mirror test:- It is a silver ammonical complex. When an aldehyde is warmed
with ammoniocal silver nitrate, a bright silver mirror is produced or grayish black precipitate is obtained.
The aldehyde ion gets oxidized to acetate ion and silver ion is reduced to silver metal.
–
H O

R C O + 2 [Ag(NH 3)2]+ + 3 OH - R C O + 2 Ag + 2 H 2O + 4 NH 3
Aldehyde Tollens reagent Carboxylate ion Silver mirror
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(iii)Schiff reagent:- Schiff reagent is a colorless solution, when treated with alcoholic solution of
aldehyde, pink or red or magenta color is restored. This confirms the presence of aldehyde group.

Laboratory Test for Ketonic Group:- a) Sodium nitroprusside test : When a freshly prepared sodium
nitroprusside solution is added to a ketone, mixture is shaken well and basified by adding sodium
hydroxide solution drop by drop, red colour appears in the solution, which indicates the presence of
ketonic ( >C=O) group.

CH3-CO-CH3 + OH― CH3-CO-CH2― + [Fe(CN)5NO]2― [Fe(CN)5NO (CH3-CO-CH2―)]3―

b)Addition reactions of aldehydes and ketones with nucleophile:-The C=O in aldehydes and ketones
is polar and hence they undergo addition reactions. A nucleophile gets attached to positively polarized
carbonyl carbon atom in aldehydes and ketones.

i)Addition of hydrogen cyanide:- Aldehydes and ketones add hydrogen cyanide (weak acid) to give
corresponding cyanohydrins. The reaction is reversible, hence a small amount of an acid or base is used.
For example,
H H
OH-
H3C C O + H-CN H3C C OH

CN

Acetaldehyde Acetaldehyde cyanohydrin

CH3 CH3
OH-
H3C C O + H-CN H3C C OH

CN
Acetone Acetone cyanohydrin

ii)Addition of sodium bisulphite(NaHSO3):- Aldehydes and ketones when treated with saturated
aqueous solution of sodium bisulphite gives addition product hydroxy sulphonic acid. This reaction is
used for separation and purification of aldehydes and ketones.

H H

H3C C O + NaHSO 3 H3C C OH

SO3Na

Acetaldehyde Acetaldehyde sodium bisulphite adduct

CH3 CH3

H3C C O + NaHSO 3 H3C C OH

SO3Na
Acetone Acetone sodium bisulphite adduct

iii)Addition of Alcohols:- Aldehydes reacts with one molecule of anhydrous monohydric alcohol in
presence of dry HCl to give an alkoxyalcohol known as hemiacetal. This hemiacetal further reacts with
one more molecule of anhydrous monohydric alcohol to give a germinal dialkoxy compound known as
acetal by elimination of water molecule.
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 O OH
H+ R R OR
H+
R C H + R-OH C + R-OH C + H2O
H OR H OR

Aldehyde Hemiacetal (Unstable) Acetal (Stable)

O OH
H+ H3C OC 2H 5
H+ H3C
H3C C H + C 2H 5-OH C + C 2H 5-OH C + H2O
H OC 2H 5 H OC 2H 5

Acetaldehyde Hemiacetal (Unstable) 1,1-diethoxyethane (Stable)

Similarly ketones react with alcohol in presence of acid catalyst to form hemiketal and ketal.
Ketones reacts with 1,2 or 1,3- diols in presence of dry HCl to give five or six membered cyclic ketals.

R HO CH2 H+ R O CH2
C O + HO CH2
C + H2O
R R O CH2

Ketone Ethane-1,2-diol cyclic ketal

The reaction can be reversed by treating the cyclic ketal with aqueous HCl solution to regenerate
the ketone.

iv) Addition of Grignard reagent:- An aldehyde or ketone undergoes nucleophilic addition of Grignard
regent in presence of dry ether to form a complex which on acid hydrolysis gives an alcohol.

1. Methanal reacts with methyl magnesium iodide in presence of dry ether to give a complex which on
acid hydrolysis gives ethanol.

H H I
Dry ether H-OH
H C O + CH3-Mg-I H3C C O-Mg-I
H+
H3C CH2 OH + Mg
H OH

Formaldehyde Mg Complex Ethanol

2. Ethanal reacts with methyl magnesium iodide in presence of dry ether to give a complex which on acid
hydrolysis gives propan-2-ol.

H CH3 CH3 I
Dry ether H-OH
H3C C O + CH3-Mg-I H3C C O-Mg-I
H+
H3C CH OH + Mg
H OH

Ethanal Complex Propan-2-ol

3. Propanone reacts with methyl magnesium iodide in presence of dry ether to give a complex which on
acid hydrolysis gives 2-methylpropan-2-ol.

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 CH3 CH3 CH3 I
Dry ether H-OH
H3C C O + CH3-Mg-I H3C C O-Mg-I
H+
H3C C OH + Mg
CH3 OH
CH3

Propanone Complex 2-methylpropan-2-ol

v) Addition of ammonia derivatives :- A number of ammonia derivatives of H2N-Z type adds to

aldehydes and ketones to give addition elimination reaction to form products containing C = N bonds
(imines) where Z is –R, -Ar, -OH, -NH2, -NHC6H5 etc. A substituted imine is called as a Schiff base. These
imines are used for characterization of aldehydes and ketones. (For aldehydes R’ = H and for ketones R’ ≠
H ).

R H+ R
C O + H2 N R C N R + H2 O
R' R'
Primary amine Substituted imine (Schiff Base)

R H+ R
C O + H2 N OH C N OH + H2 O
R' R'
Hydroxyl amine Oxime

R H+ R
C O + H2N NH2 C N NH2 + H2O
R' R'
Hydrazine Hydrazone

R H+ R
C O + H2N NH C6H5 C N NH C 6 H 5 + H2 O
R' R'
Phenyl hydrazine Phenyl hydrazone
NO2 NO2
R H+ R
C O + H2N NH C N NH
+ H2O
R' R'
NO2 NO2
2,4-Dinitrophenylhydrazine 2,4-Dinitrophenylhydrazone

R H+ R
C O + H2N NH CONH2 C N NH CONH2 + H2O
R' R'
Semicarbazide Semicarbazone

All the aldehydes and ketones give the products with high molecular mass and are crystalline.
Therefore useful in characterization of aldehydes and ketones.

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d) Haloform reaction:- This reaction is given by acetaldehyde, all methyl ketones and all alcohols
containing CH3‒(CH-OH)- group. A ketone having α-methyl group or alcohol is oxidized by sodium
hypohalite to give sodium salt of carboxylic acid and haloform. Sodium salt of acid formed contains one
carbon atom less than the substrate. The methyl group is converted to haloform. Methyl ketones are
characterized by this reaction.

Acetone is oxidized by sodium hypoiodite to give sodium salt of acetic acid and yellow precipitate
of iodoform. Sodium hypoiodite prepared in situ by action of NaOH on I2.

O O
NaOH / I2
H3C C CH3 + 3 NaOI 
H3C C O Na
- +
+ CHI 3 + 2 NaOH
Acetone Sodium hypoiodite Sodium acetate Iodoform

E] Aldol Condensation:- The α-hydrogen atom of aldehyde or ketone is acidic in nature. In presence of
dilute base (like NaOH, KOH or Na2CO3),two molecules of aldehydes containing at least one α-hydrogen
atom undergo a reaction to give β-hydroxy aldehyde(aldol). The reaction is called aldol condensation
reaction.

Aldol suggests that two functional groups aldehyde and alcohol in product. Formation of aldol is
an addition reaction and aldol formed having α-hydrogens on subsequent heating undergoes dehydration
to form α-β unsaturated aldehyde. This reaction results in formation a new C-C bond. For example,

H H H H H H H H
dil. NaOH H+
H3C C O + H2C C O H3C C C C O

H3C C C C O + H2O

H OH H
Acetaldehyde Acetaldehyde 3-hydroxy butanal but-2-enal
(β-hydroxy aldehyde) (α-β unsaturated aldehyde)

The overall reaction is an aldol condensation reaction. It is a nucleophilic addition elimination

reaction. Ketones containing at least one α-hydrogen atom also undergo aldol condensation reaction and
give α-β unsaturated ketone. For example,

CH3 CH3 CH3 CH3 CH3 CH3

dil. NaOH H+
H3C C O + H2C C O H3C C CH C O

H3C C CH C O + H2O

H OH H

Propanone Propanone 4-methyl-4-methylpentan-2-one 4-methylpent-3-ene-2-one

(β-hydroxy ketone) (α-β unsaturated ketone)

Crossed Aldol Condensation:- An aldol condensation between two different carbonyl compounds is
called crossed or mixed aldol condensation. If both carbonyl compounds contain α hydrogen atom, a
mixture of four different aldols are formed. In reaction between an aldehyde and ketone, α carbon of
ketone is attached to carbonyl carbon of aldehyde.

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For example, a mixture of ethanal and propanal on reaction with dilute alkali followed by heating gives a
mixture of four products as follows,

Self
H3C CH CH CHO + H3C CH2 CH C CHO

i)Dil.NaOH CH3
H3C CHO + H3C CH2 CHO
ii) 
Crossed
H3C CH C CHO + H3C CH2 CH CH CHO
CH3

F]Cannizzaro reaction:- In presence of concentrated or alcoholic alkali, aldehydes which do not have α
hydrogen atom undergo self oxidation and reduction(disproportionation) to give a mixture of alcohol and
a salt of carboxylic acid. This reaction is known as Cannizzaro reaction. In this reaction one aldehyde
molecule is reduced to alcohol and at the same time second molecule is oxidized to salt of carboxylic acid.
H H H O
H C O + H C O + NaOH H C OH + H C O Na
- +

H
Formaldehyde (50%) Methanol sodium formate
H H O
C O C O CH2 OH - +
C OK
+ + KOH
+
Benzaldehyde (50%) Benzyl alcohol potassium benzoate

Crossed Cannizzaro Reaction:- Two different aldehydes, not having α-hydrogen atoms undergo
disproportionation in presence concentrated alkali. If one of the aldehyde is formaldehyde, it is oxidized
to formate and other aldehyde is reduced to alcohol. Sodium formate on acidification converted into
formic acid. E.g.

C O CH2 OH
H O
(i) NaOH
+ H C O
(ii)H+/H2O
+ H C OH

Benzaldehyde Formaldehyde Benzyl alcohol Sodium formate

G] Oxidation and reduction reactions of aldehydes and ketones :-

(i) Oxidation of aldehydes and ketones :- Aldehydes are oxidized to corresponding carboxylic acids by
oxidizing agents such as dil. HNO3, alkaline KMnO4, acidified K2Cr2O7 etc.

P B Patil Science Academy, Mudal Nipani. 14 Martand S. S. 9021355181

 O O
K2Cr2O7
R C H R C OH
Dil. H2SO4
Aldehyde Carboxylic acid

Ketones resists oxidation due to strong CO‒C bond, but they are oxidized by strong oxidizing
agents such as CrO3, alkaline KMnO4 or hot concentrated HNO3 to a mixture of carboxylic acids having
less number of carbon atoms than in starting ketone. This oxidation of ketones is accompanied by
breaking of C‒C bond.

O O
CrO3
H3C C CH3 + 4 [O] H3C C OH + CO 2 + H2O

O O
CrO3
H3C C C 2H 5 + 3 [O] 2 CH 3 C OH

(ii) Clemmensen and Wolff Kishner reduction (Deoxygenation) :- Aldehydes and ketones when
heated with zinc amalgam and conc. HCl gives alkanes. In this reaction, carbonyl group is converted into –
CH2. This reaction is known as Clemmensens reduction.

H H
Zn-Hg/conc.HCl
C O + 4 (H) CH2 + H2O
H  H

O
Zn-Hg/conc.HCl
H3C C CH3 + 4 (H) H3C CH2 CH3 + H2O


Zn-Hg/conc.HCl
H3C CH2 CHO + 4 (H) H3C CH2 CH3 + H2O


Aldehydes and ketones when heated with hydrazine and followed by heating with KOH or NaOH
in solvents like ethylene glycol give alkanes. This reduction is known as Wolff-Kishner reduction.

H H2N-NH2 H KOH / 
C O C N NH2 -CH2 + N2
H -H2O H Ethylene glycol

H5C2 H2N-NH2 H5C2 KOH / 

C O C N NH2 H3C CH2 CH3 + N2
H -H2O H Ethylene glycol

H 5C 2 CH2 C 2H 5
H2N-NH2 H 5C 2 KOH / 
C O C N NH2 + N2
-H2O Ethylene glycol

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 Wolff Kishner reduction reaction is used to synthesize straight chain alkyl substituted benzene
which is not possible by Friedel Crafts alkylation reaction.

H] Electrophilic Substitution Reaction:- Aromatic aldehydes or ketones undergo electrophilic

substitution in aromatic ring. Carbonyl group is deactivating and meta-directing group.
H H

C O C O
Conc. H2SO4
+ HO NO 2 + H2O

H NO 2

Benzaldehyde m-nitro benzaldehyde

Carboxylic Acids:- Carboxylic acids are the organic compounds containing one or more carboxyl group
in their molecules. Their functional group is –COOH i.e. carboxyl group. It is the combination of carbonyl
group and hydroxyl group.

Classification of carboxylic acids :- Carboxylic acids are classified as aliphatic and aromatic carboxylic
acids.

a)Aliphatic carboxylic acids : The organic compounds in which carboxyl group is attached to an alkyl
group are called as aliphatic carboxylic acids or fatty acids. They have general formula as CnH2n+1COOH or
CnH2nO2.Formic acid (H-COOH) is an exception. It is an aliphatic carboxylic acid. For example,

O O
O
H 5C 2 C OH R C OH
H3C C OH
Acetic acid Propionic acid General Formula
Depending upon number of carboxyl groups, carboxylic acids may be classfied as mono, di, tri and
polycarboxylic acids.
O
O
O H2C C OH
C OH
H3C C OH
HO C COOH
C OH
O H2C C OH

O
Acetic acid Oxalic acid Citric acid
(Monocarboxylic acid) (Dicarboxylic acid) (Tricarboxylic acid)

b)Aliphatic carboxylic acids : These are the compounds in which one or more carboxyl groups are
attached directly to the aromatic ring. For example,

P B Patil Science Academy, Mudal Nipani. 16 Martand S. S. 9021355181

 O O O
C C
OH C
OH OH

OH
C OCOCH 3

Benzoic acid Phthalic acid Acetyl salicylic acid (Aspirin)

Nomenclature of acids:-

A]Common System:- The common names of some carboxylic acids are derived from their source. In
branched carboxylic acids, positions of substituents are indicated by Greek numerals as α, β, ϒ, δ adjacent
to –COOH group.

B]IUPAC Names:- in this system, longest continuous carbon chain containing –COOH group is selected.
The carboxyl carbon is always numbered as one. The name of the carboxylic acid is derived from parent
alkane by replacing ‘e’ with ‘oic acid’. The positions of substituents is indicated by proper numbers.

For acids containing more than one carboxyl group, the ending ‘e’ is retained. The number of
carboxyl group is indicated by prefixes di, tri, tetra etc. Aromatic carboxylic acids are generally named as
derivatives of parent benzoic acid.
COOH
CHO

CH3 COOH

OH

4-hydroxy-3-methyl benzoic acid 2-formylbenzoic acid

Sr. No. Fatty acid Common Name IUPAC Name

1. H-COOH Formic acid Methanoic acid
2. CH3-COOH Acetic acid Ethanoic acid
3. CH3-CH2-COOH Pripionic acid Propanoic acid
4. CH3-CH2-CH2-COOH n-butyric acid Butanoic acid
5. CH3 Isobutyric acid 2-methyl propanoic acid
H3C CH COOH (α-methylpropionic acid)
6. H2C CH COOH Acrylic acid Prop-2-enoic acid
7. HOOC-COOH Oxalic acid Ethane-di-oic acid
8. HOOC-(CH2)4-COOH Adipic acid Hexane-di-oic acid.
9. O Benzoic acid Benzoic acid
C (Benzene carboxylic acid)
OH

10. O
o-Toluic acid 2-methylbenzoic acid
C
OH

CH3

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11. O
Salicylic acid 2-hydroxy benzoic acid
C
OH

OH

12. COOH
Phthalic acid Benzene1,2 dicarboxylic acid.

COOH
13. COOH
Cyclohexylcarboxylic acid Cyclohexanecarboxylic acid

Methods Of Preparation:-

i)From nitriles and amides(by hydrolysis):- Alkyl or aryl nitriles on acid hydrolysis gives
corresponding amides. Amides on further acid hydrolysis gives corresponding carboxylic acid. Hydrolysis
is carried out by using dilute mineral acid (like HCl or H2SO4).

O O
OH H-OH
R C N + H-OH
R C NH
R C NH2
Dil.HCl R C OH + NH3

Nitrile Amide Carboxylic acid

O

R C N + 2 H2O + HCl R C OH + NH 4Cl

ii)From acyl chlorides and acid anhydrides(By hydrolysis):-Acid chlorides react with water to yield
carboxylic acids. The reaction is carried out in presence of a base pyridine or NaOH and is useful in the
preparation of aliphatic as well as aromatic acids.

O O
R C Cl + H2O R C OH + HCl

Acyl chloride Carboxylic acid

Acid anhydrides react with water to give carboxylic acid.

O O O
R C O C R + H2O 2 R C OH
Acid anhydride Acetic acid

iii)From esters [a] By acid hydrolysis:- When ester is heated with dilute mineral acid like H2SO4 or HCl
gives carboxylic acids and alcohol.

O O
dil. H2SO4
R C O-R' + H2O R C OH + R' OH

Ester Carboxylic acid Alcohol

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[b]By alkaline hydrolysis of ester :- When an ester is heated with dilute aqueous alkali like NaOH or
KOH, it gives water soluble sodium or potassium salt of carboxylic acid. The salt on acidification with
conc. HCl gives corresponding carboxylic acid.

O O O
- + H+
H5C2 C OCH 3 + NaOH H5C2 C O Na
conc. HCl
H5C2 C OH + NaOH
CH3OH

Methyl propanoate Sodium propanoate Propanoic acid

The sodium or potassium salts of higher fatty acids are known as soaps. Hence alkaline hydrolysis
of esters is called saponification.

iv)From alkyl benzenes:- When alkyl benzene is heated with strong oxidizing agents like acidified
K2Cr2O7 or alkaline KMnO4 or dil. HNO3, it gives aromatic carboxylic acid. Irrespective of the chain length,
entire side chain is oxidized to carboxyl group. Tertiary alkyl substituents of benzene are not oxidised.
- + COOH
CH3 COO K
Alkaline KMnO4 Dil. HCl

Toluene Potassium benzoate Benzoic acid

CH3
- + COOH
HC CH3 COO K
Alkaline KMnO4 Dil. HCl

Cumene Potassium benzoate Benzoic acid

v) From alkenes :- Acidic KMnO4 or Acidic K2Cr2O7 oxidizes alkenes to carboxylic acids.
COOH
CH CH2
KMnO4/ Dil. H2SO4

Phenylethene Benzoic acid

KMnO4/ Dil. H2SO4 COOH

 COOH

Cyclohexene Adipic acid

iv)From dry ice(By carboxylation of Grignard reagent):- When solution of Grignard reagent is added
to solid CO2(dry ice) in presence of dry ether, a magnesium salt of carboxylic acid (complex) is obtained
which on acidification gives carboxylic acid.

O O
dry ether + - H-OH
R Mg X + O C O R C OMg X R C OH + Mg-(X)-OH

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Physical Properties:-

1)Colour,state and odour:- Lower aliphatic carboxylic acids(upto C-9) are colorless liquids with irritating
odour. Higher members are colorless, odourless wax like solids.

2) They have higher boiling points than corresponding hydrocarbons, aldehydes, ketones and ethers.

3) Lower aliphatic carboxylic acids (upto C-4) are miscible with water due to formation of hydrogen
bonds with water molecules. Higher carboxylic acids are insoluble in water. They are soluble in organic
solvents.

Reactions of Carboxylic acids:- [A]Acidic properties:-

a)The Carboxyl (―COOH) group imparts acidic character to carboxylic acids. In aqueous solution, H atom
of ―OH of carboxyl group dissociates as H+ and carboxylate ion is formed as the conjugate base.
O
O
+
R C OH + H2O R C O + H3O

Carboxylate ion

b)Carboxylic acids are most acidic amongst the organic compounds. However they are much weaker than
mineral acids like HCl, H2SO4. Carboxylic acids are more acidic than phenols.

Carboxylic acid is a resonance hybrid of two non-equivalent structures (I & II) while carboxylate
ion is a resonance hybrid of two equivalent structures (III & IV). As a result carboxylate anion is more
stable than carboxylic acid. Equilibrium is shifted towards ionization; hence carboxylic acids are acidic in
nature.

O O O
O
+ +
R C O H R C O H H + R C O R C O

(I) (II) (III) (IV)

Influence of electronic effect on acidity of carboxylic acids:- An electron withdrawing substituent

increases the acidity of carboxylic acid by negative inductive (―I)effect. On the contrary, an electron
releasing substituent decreases the acidity of carboxylic acids by positive inductive (+I) effect. In
aliphatic carboxylic acids, inductive effect decreases rapidly as substituent move farther from carboxyl
group. The examples with order of decreasing acidity are given below,

i) Cl3-C-COOH > Cl2-CH-COOH > Cl-CH2-COOH > CH3COOH

trichloro acetic acid dichloro acetic acid chloro acetic acid acetic acid

ii) CH3-CH2-CHCl-COOH > CH3-CHCl-CH2-COOH > Cl-CH2-CH2-CH2-COOH

2-Chlorobutanoic acid 3-Chlorobutanoic acid 4-Chlorobutanoic acid

P B Patil Science Academy, Mudal Nipani. 20 Martand S. S. 9021355181

Acidity of aromatic carboxylic acids :- In aromatic acids, electron withdrawing groups like –Cl,-CN or –
NO2 increases the acidity whereas electron releasing groups like –CH3, -OH, OCH3 or –NH2 decrease the
acidity. The inductive effect of following groups in decreasing order of acidity is,

CF3 > NO2 > CN > F > Cl > Br > I > C6H5

COOH COOH
COOH COOH COOH

NO 2

NO 2
OCH 3
NO 2

Laboratory tests for carboxyl (-COOH) group:

a. Litmus test : (valid for water soluble substances):- Aqueous solution of Organic compound
containing –COOH group turns blue litmus red which indicates the presence of acidic functional group. (It
may be noted that aqueous solutions of water soluble phenols also turn blue litmus red.)
b. Sodium bicarbonate test : When sodium bicarbonate is added to an organic compound containing –
COOH group, a brisk effervescence of carbon dioxide gas is evolved. Water insoluble acid goes in solution
and gives precipitate on acidification with conc.HCl. This indicates the presence of –COOH group.

O O O
CO2 HCl
+ -
R C OH + NaHCO 3
H2O
R C O Na (aq)
R C OH + NaCl

Phenol does not evolve CO2 gas with sodium bicarbonate. Hence, carboxylic acid and phenol are
distinguished by this test.
c. Ester test: One drop of concentrated sulfuric acid is added to a mixture of given organic compound
containing –COOH group and one mL of ethanol, the reaction mixture is heated for 5 minutes in hot water
bath. Hot solution is poured in a beaker containing water, fruity smell of ester confirms the presence of
carboxylic acid.

O O
H+
R C OH + H O C2 H5 R C OC 2H5 + H2O
Warm

[B] Formation of acyl chlorides (Reaction with SOCl2, PCl3 and PCl5):- Carboxylic acids on heating
with thionyl chloride, phosphorous trichloride and phosphorous pentachloride give corresponding acyl
chloride. In these reactions, hydroxyl group of carboxyl group is replaced by chlorine. Thionyl chloride is
preferred as the byproducts are gaseous state which escapes easily.

P B Patil Science Academy, Mudal Nipani. 21 Martand S. S. 9021355181

 O O

R C OH + SOCl 2 R C Cl + SO 2 + HCl

Carboxylic acid Acyl chloride

O O

3R C OH + PCl 3 3R C Cl + H3PO 3

O O

R C OH + PCl 5 R C Cl + POCl 3 + HCl

[C]Reaction with ammonia/Formation of amides:- Carboxylic acids react with ammonia to give
ammonium carboxylate (salts), which on strong heating decomposes to give acid amide.

O O O
- + 
R C OH + NH3 R C O NH 4 R C NH2 + H2O
Carboxylic acid Ammonium salt of acid Amide

Acid amides can also be prepared reacting acid chloride with ammonia.
O O

R C Cl + NH3 R C NH2 + HCl

Acid chloride Acid amide

[D]Formation of acid anhydrides:- When a mono carboxylic acid is heated with strong dehydrating
agent like P2O5 or conc. H2SO4, two molecules of carboxylic acid condense with loss of water to form acid
anhydride.

O O O
O P2O5,
R C O H + H O C R R C O C R + H2O

Carboxylic acid Acid anhydride

The reaction is reversible. Thus anhydride is prepared by heating sodium acetate with acetyl
chloride. This reaction is useful to prepare simple as well as mixed anhydrides.

O O O O
D
R C Cl +
+ -
Na O C R R C O C R + H2O

Acid chloride sodium carboxyate Anhydride.

P B Patil Science Academy, Mudal Nipani. 22 Martand S. S. 9021355181

 [E] Formation of primary alcohol(Reduction):- Carboxylic acids are difficult to reduce, but can be
reduced to primary alcohols by strong reducing agents such as lithium aluminium hydride or diborane.
Diborane does not reduce ‒COOR, ‒NO2, ‒X etc.
O
i)LiAlH4, ether
R C OH
ii)H3O+
R CH2 OH + H2O

Carboxylic acid Primary alcohol

[F]Formation of hydrocarbon (Decarboxylation):- When anhydrous sodium salt of carboxylic acid is

fused with soda lime, it gives hydrocarbon containing one carbon atom less than carboxylic acid.
O
CaO
R C O Na
- +
+ NaOH

R H + Na 2CO 3

O
- + CaO
H3C C O Na + NaOH

CH4 + Na 2CO 3

P B Patil Science Academy, Mudal Nipani. 23 Martand S. S. 9021355181