UNIT VIII ALDEHYDES, KETONES AND CARBOXYLIC ACIDS

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ALDEHYDES KETONES CARBOXYLIC
COMPOUNDS CONTAINING PHYSICAL PROPERTIES ACID
R - CHO R-CO-R
R – COOH, R – CO X, R-CO –O-CO-R BOILING POINTS R - COOH

CLASSIFICATION
ALDEHYDES, KETONES AND NOMENCLATURE
CARBOXYLIC ACID

COMPOUNDS
COMPOUNDS CONTAINING
PREPARATION OF CHEMICAL REACTIONS COMMON AND IUPAC
CONTAINING ALDEHYDES, OF ALDEHYDES, NAMES
C=O KETONES AND KETONES AND
R - CHO
CARBOXYLIC ACID CARBOXYLIC ACID

Aldehydes and Ketones: The organic compounds containing carbon-oxygen double bond (>C=O) called
carbonyl group, which is one of the most important functional groups in organic chemistry.
In aldehydes, the carbonyl group is bonded to a carbon and hydrogen while in the ketones; it is bonded to
two carbon atoms.

Nomenclature: There are two systems of nomenclature of aldehydes and ketones.

(a) Common names: Acetaldehyde, Benzaldehyde and β-Bromo-butyraldehyde

Acetone, Acetophenone, Propiophenone and Benzophenone

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(b) IUPAC names: The IUPAC names of open chain aliphatic aldehydes and ketones are derived from the
names of the corresponding alkanes by replacing the ending –e with –al and –one respectively.

Structure of the Carbonyl Group: The carbonyl carbon atom is sp2 -hybridized and forms three sigma (σ)
bonds. The fourth valence electron of carbon remains in its p-orbital and forms a π-bond with oxygen by
overlap with p-orbital of oxygen. In addition, the oxygen atom also has two nonbonding electron pairs.
Thus, the carbonyl carbon and the three atoms attached to it lie in the same plane and the π-electron cloud is
above and below this plane. The bond angles are approximately 120° as expected of a Trigonal coplanar
structure.
Orbital diagram for the formation of carbonyl group:

.
The carbon-oxygen double bond is polarized due to higher electronegativity of oxygen relative to carbon.
Hence, the carbonyl carbon is an electrophilic (Lewis acid), and carbonyl oxygen, a Nucleophilic (Lewis
base) centre. Carbonyl compounds have substantial dipole moments and are polar than ethers. The high
polarity of the carbonyl group is explained on the basis of resonance involving a neutral (A) and a dipolar
(B) structure as shown.

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Preparation of Aldehydes and Ketones:
1. By oxidation of alcohols: Aldehydes and ketones are generally prepared by oxidation of primary
and secondary alcohols, respectively.
CH3CH2OH K2Cr2O7 + dil H2SO4 CH3CHO
By dehydrogenation of alcohols: This method is suitable for volatile alcohols and is of industrial
application. In this method alcohol vapours are passed over heavy metal catalysts (Ag or Cu). Primary
and secondary alcohols give aldehydes and ketones, respectively and Tertiary alcohol gives 2-methyl
propene.
Cu, 573 K
CH3CH2OH CH3CHO + H2
Cu, 573 K
CH3CH (OH) CH3 CH3COCH3 + H2
Cu, 573 K
(CH3)3COH (CH3)2C = CH2 + H2

2. From hydrocarbons:
(i) By ozonolysis of alkenes: Ozonolysis of alkenes followed by reaction with zinc dust and
water gives aldehydes, ketones or a mixture of both depending on the substitution pattern of
the alkene.
CH2 = CH2 + O3 → Ethene ozonide Zn, H2O 2HCHO + H2O2
CH3CH = CH2 + O3 → Propene ozonide Zn, H2O
CH3CHO + HCHO

(ii) By hydration of alkynes: Addition of water to Ethyne in the presence of H2SO4 and HgSO4
gives acetaldehyde. All other alkynes give ketones in this reaction.
Ethyne + H2O H2SO4 (dil), HgSO4 CH3CHO
H2SO4 (dil), HgSO4
Propyne + H2O CH3COCH3

Preparation of Aldehydes:
1. From acyl chloride (acid chloride): Acyl chloride (acid chloride) is hydrogenated over catalyst,
palladium on barium sulphate. This reaction is called Rosenmund’s reduction.

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2. From nitriles: Nitriles are reduced to corresponding imine with stannous chloride in the presence of
hydrochloric acid, which on hydrolysis give corresponding aldehyde. This reaction is called Stephen
reaction.
RCN +SnCl2 +HCl --------> RCH = NH ----------> RCHO
3. From esters: Esters are reduced to aldehydes with DIBAL-H.

4. From hydrocarbons:
(i) By oxidation of methylbenzene
(a) Use of chromyl chloride (CrO2Cl2): This reaction is called Etard reaction.

(b) Use of chromic oxide (CrO3):

(ii) By side chain chlorination followed by hydrolysis:

(iii) By Gatterman – Koch reaction:

Preparation of Ketones:
1. From acyl chlorides:
2RMgX + CdCl2 ------> R2Cd + 2Mg(X) Cl
2R' CO Cl + R2Cd ------> 2R' CO R + CdCl2
2. From nitriles:

3. From benzene or substituted benzenes:

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This reaction is known as Friedel-Crafts acylation reaction.

Physical Properties:
Methanal is a gas at room temperature. Ethanal is a volatile liquid. Other aldehydes and ketones are liquid
or solid at room temperature.
The boiling points of aldehydes and ketones are higher than hydrocarbons and ethers of comparable
molecular masses. It is due to weak molecular association in aldehydes and ketones arising out of the
dipole-dipole interactions. Also, their boiling points are lower than those of alcohols of similar molecular
masses due to absence of intermolecular hydrogen bonding.
The following compounds of molecular masses 58 and 60 are ranked in order of increasing boiling points.
n-Butane < Methoxyethane < Propanal < Acetone < Propan-1-ol
The following compounds of molecular masses 72 and 74 are ranked in order of increasing boiling points.
CH3CH2CH2CH3 < H5C2-O-C2H5 < CH3CH2CH2CHO < CH3CH2CH2CH2OH
The lower members of aldehydes and ketones such as Methanal, Ethanal and Propanone are miscible with
water in all proportions, because they form hydrogen bond with water.

However, the solubility of aldehydes and ketones decreases rapidly on increasing the length of alkyl chain.
All aldehydes and ketones are fairly soluble in organic solvents like benzene, ether, methanol, chloroform,
etc.
The lower aldehydes have sharp pungent odours. As the size of the molecule increases, the odour becomes
less pungent and more fragrant. In fact, many naturally occurring aldehydes and ketones are used in the
blending of perfumes and flavouring agents.

Chemical Properties:
1. Nucleophilic addition and Nucleophilic addition-elimination reactions:
(a) Addition of hydrogen cyanide (HCN):

(b) Addition of sodium hydrogensulphite:

(c) Addition of Grignard reagents:

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H H

HCHO + RMgBr ------> CH3 C – OMgBr ----> CH3 C – OH (Primary alcohol)

H H

H H

CH3CHO + RMgBr ------> CH3 C – OMgBr ----> CH3 C – OH (Secondary alcohol)

CH3 CH3

(d) Addition of alcohols:

(e) Addition of ammonia and its derivatives:

2. Reduction
(i) Reduction to alcohols:

RCHO H2(Ni or Pt or Pd) Na/C2H5OH, LiAlH4 or NaBH4 RCH2OH (Primary alcohol)

RCOR' H2(Ni or Pt or Pd) Na/C2H5OH, LiAlH4 or NaBH4 RCH(OH)R' (Secondary alcohol)

(ii) Reduction to hydrocarbons:

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3. Oxidation:

RCHO [O] RCOOH

The mild oxidising agents mainly Tollen’s’ reagent and Fehling’s’ reagent are used to distinguish aldehydes
from ketones:
(i) Tollen’s’ test: On warming an aldehyde with freshly prepared ammoniacal silver nitrate solution
(Tollen’s’ reagent), a bright silver mirror is produced due to the formation of silver metal.

(ii) Fehling’s test: On heating an aldehyde with Fehling’s reagent, a reddish brown precipitate is obtained.

(iii) Oxidation of methyl ketones by haloform reaction:

4. Reactions due to a-hydrogen: (i) Aldol condensation: Aldehydes and ketones having at least one -
hydrogen undergo a reaction in the presence of dilute alkali as catalyst to form β-hydroxy aldehydes (Aldol)
or β-hydroxy ketones (ketol), respectively. This is known as Aldol reaction.

2CH3CHO dil.NaOH
CH3 –CH (OH) -CH2-CHO (Aldol) heat
CH3 -CH = CH -CHO

2CH3COCH3 Ba(OH)2 CH3 –C (CH3) (OH) -CH2-CO -CHO heat CH3 –C(CH3) = CH –CO –CHO
(Ketol)
(ii) Cross Aldol condensation: When Aldol condensation is carried out between two different aldehydes and
/ or ketones; it is called cross Aldol condensation.

5. Other reactions
(i) Cannizzaro reaction:

(ii) Electrophilic substitution reaction: Aromatic aldehydes and ketones undergo electrophilic substitution at
the ring in which the carbonyl group acts as a deactivating and meta-directing group.
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Uses of Aldehydes and Ketones:
Formaldehyde is well known as formalin (40%) solution used to preserve biological specimens and to
prepare bakelite (a phenol-formaldehyde resin), urea-formaldehyde glues and other polymeric products.
Acetaldehyde is used primarily as a starting material in the manufacture of acetic acid, ethyl acetate, vinyl
acetate, polymers and drugs.
Benzaldehyde is used in perfumery and in dye industries.
Acetone and ethyl methyl ketone are common industrial solvents.
Many aldehydes and ketones, e.g., butyraldehyde, vanillin, acetophenone, camphor, etc. are well known for
their odours and flavours.

Carboxylic Acids:
Carbon compounds containing a carboxyl functional group, –COOH are called carboxylic acids. The
carboxyl group consists of a carbonyl group attached to a hydroxyl group, hence its name carboxyl.
Carboxylic acids may be aliphatic (RCOOH) or aromatic (Ar COOH) depending on the group, (R, alkyl or
Ar, aryl group) attached to carboxylic carbon.
Structure of Carboxyl Group: In carboxylic acids, the bonds to the carboxyl carbon lie in one plane and
are separated by about 120°. The carboxylic carbon is less electrophilic than carbonyl carbon because of the
possible resonance structure shown below:

Methods of Preparation of Carboxylic Acids:

1. From primary alcohols:

2. From aldehydes:
RCHO [O] RCOOH
3. From alkyl benzenes:

4. From nitriles:
RCN H+ or OH- RCONH2 H+ or OH-
RCOOH

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5. From amides:
CH3CONH2 H3O+ CH3COOH + NH3

6. From Grignard reagents:

7. From acyl halides:

8. From anhydrides:

6. From esters: Acidic hydrolysis of ethyl benzoate gives benzoic acid.

H3O+
C6H5 COO C2H5 C6H5 COOH + C2H5OH

Physical Properties:
Aliphatic carboxylic acids up to nine carbon atoms are colourless liquids at room temperature with
unpleasant odours. The higher acids are wax like solids and are practically odourless due to their low
volatility.
Carboxylic acids are higher boiling liquids than aldehydes, ketones and even alcohols of comparable
molecular masses. This is due to more extensive association of carboxylic acid molecules through
intermolecular hydrogen bonding. The hydrogen bonds are not broken completely even in the vapour phase.
In fact, most carboxylic acids exist as dimer in the vapour phase or in the aprotic solvents.

Simple aliphatic carboxylic acids having up to four carbon atoms are miscible in water due to the formation
of hydrogen bonds with water. The solubility decreases with increasing number of carbon atoms. Higher
carboxylic acids are practically insoluble in water due to the increased hydrophobic interaction of
hydrocarbon part. Benzoic acid, the simplest aromatic carboxylic acid is nearly insoluble in cold water.
Carboxylic acids are also soluble in less polar organic solvents like benzene, ether, alcohol, chloroform, etc.
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Chemical Reactions:
Reactions Involving Cleavage of O–H Bond:
Acidity:
Reactions with metals: 2RCOOH + 2Na ---> 2RCOO-Na+ + H2
Reactions with alkalies: RCOOH + NaOH ---> RCOO-Na+ + H2O

Carboxylic acids dissociate in water to give resonance stabilized carboxylate anions and hydronium ion.

For the above reaction:

The dissociation constant is called acidity constant. The stronger the acid, the larger will be its Ka value.

Smaller the value of pKa, stronger the acid is.

The acids have pKa values < 1. Strong acids.
The acids with pKa values between 1 and 5 are considered to be moderately strong acids.
The acids have pKa values between 5 and 15 are extremely weak acids have pKa values >15.

Effect of substituents on the acidity of carboxylic acids:

Electron withdrawing group’s increase the acidity of carboxylic acids by stabilizing the conjugate base
through delocalization of the negative charge by inductive and/or resonance effects.
Conversely, electron donating groups decrease the acidity by destabilizing the conjugate base.

The effect of the following groups in increasing acidity order is

Phenyl < I < Br < Cl < F < CN < NO2 < CF3

Reactions Involving Cleavage of C–OH Bond:

1. Formation of anhydride:

2. Esterification:
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RCOOH + R'OH ----> RCOOR' + H2O

3. Reactions with PCl5, PCl3 and SOCl2:

RCOOH + PCl5 ---> RCOCl + POCl3 + HCl
3RCOOH + PCl3 ---> 3RCOCl + H3PO3
RCOOH + SOCl2 ---> RCOCl + SO2 + HCl
4. Reaction with ammonia:

Reactions Involving –COOH Group:

1. Reduction:
RCOOH (i) LiAlH4/Ether or B2H6 (ii) H3O+ RCH2OH
2. Decarboxylation:
RCOONa NaOH & CaO, heat R – H + Na2CO3

Substitution Reactions in the Hydrocarbon Part:

Hell-Volhard-Zelinsky reaction

2. Ring substitution:

Uses of Carboxylic Acids:

Methanoic acid is used in rubber, textile, dyeing, leather and electroplating industries.
Ethanoic acid is used as solvent and as vinegar in food industry.
Hexanedioic acid is used in the manufacture of nylon-6, 6.
Esters of benzoic acid are used in perfumery.
Sodium benzoate is used as a food preservative.

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Higher fatty acids are used for the manufacture of soaps and detergents.

ASSIGNMENTS:
Q1. Which of these has the least unpleasant Odour?
a) Methanal
b) Butanal
c) Propanal
d) Ethanal
Ans. (b) Because the Odour gets less strong and more fragrant as the size of the aldehyde molecule grows.
Q2. Reactions occur between aldehydes and ketones.
(a) nucleophilic addition
(b) electrophilic substitution
(c) electrophilic addition
(d) nucleophilic substitution
Ans. (a)
Q3. Which of the following is not a formaldehyde application?
(a) Preservation of biological specimens
(b) Preparation of acetic acid
(c) Silvering of mirrors
(d) Manufacturing of Bakelite
Ans. (b)
Explanation: Because formaldehyde has only one carbon atom, it cannot be employed as a starting material
for the production of acetic acid. It is, nevertheless, utilized to make Bakelite, glues, and polymeric items. In
the silvering of mirrors, it also works as a reducing agent.
Q4. Which of the following compounds is formed when benzyl alcohol is oxidized with KMnO4?
(a) CO2 and H2O
(b) Benzoic acid
(c) Benzaldehyde
(d) Benzophenone
Ans. (b)
Q5. The Rosenmund reaction can produce which of the following carbonyl compounds?
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(a) Methanal
(b) Benzaldehyde
(c) Butanone
(d) Acetone
Ans. (b) Benzoyl chloride produces benzaldehyde.
Q6. Name the following compounds according to IUPAC system of nomenclature:
(i) CH3CH(CH3) CH2CH2CHO
(ii) CH3CH2COCH(C2H5) CH2CH2Cl
(iii) CH3CH=CHCHO
(iv) CH3COCH2COCH3
(v) CH3CH(CH3) CH2C(CH3)2COCH3
(vi) (CH3)3CCH2COOH
(vii) OHCC6H4CHO-p

Ans. (i) 4-methyl pentanal

(ii)6-chloro-4-ethyl hexan-3-one
(iii) But-2-enal
(iv) Pentane-2,4-dione
(v) 3,3,5-trimethyl hexane-2-one
(vi) 3,3-dimethyl butanoic acid
(vii) Benzene-1,4-dicarbaldehyde

Q7. Give names of the reagents to bring about the following transformations:
(i) Hexan-1-ol to hexanal
(ii) Cyclohexanol to cyclohexanone
(iii) p-Fluor toluene to p-Fluoro benzaldehyde
(iv) Ethanenitrile to ethanal
(v) Allyl alcohol to propenal
(vi) But-2-ene to ethanal

Ans.
(i) C5H5NH+CrO3Cl- (PCC)
(ii) Anhydrous CrO3 or K2Cr2O7 in acidic medium
(iii) CrO3 in the presence of acetic anhydride or 1. CrO2Cl2 2. H2O
(iv) (Di isobutyl) Aluminium hydride (DIBAL-H)
(v) PCC
(vi) O3 /H2O-Zn dust

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Q8. Arrange the following compounds in the increasing order of their boiling points: CH3CH2CH2CHO,
CH3CH2CH2CH2OH, H5C2 -O-C2H5 and CH3CH2CH2CH3
Ans. Increasing order of boiling points of the given compounds is as follows:
CH3CH2CH2CH3 < H5C2 -O-C2H5 < CH3CH2CH2CHO < CH3CH2CH2CH2OH
Q9. Although phenoxide ion has a greater number of resonating structures than carboxylate ion, carboxylic
acid is a stronger acid than phenol. Why?
Ans. The electronic charge in the carboxylate ion is more dispersed in comparison to phenate ion.
Carboxylate ion is more stable as compared to phenate ion. The release of H+ ion is easier from carboxylic
acid. It behaves as stronger acid than phenol.

Q10. An organic compound (A) with molecular formula C8H8O forms an orange-red precipitate with 2,4-
DNP reagent and gives yellow precipitate on heating with iodine in the presence of sodium hydroxide. It
neither reduces Tollens’ or Fehling’s reagent, nor does it decolourise bromine water or Baeyer’s reagent. On
drastic oxidation with chromic acid, it gives a carboxylic acid (B) having molecular formula C7H6O2.
Identify the compounds (A) and (B) and explain the reactions involved.
Ans. Reactions are as follows:

Q11. Arrange the following compounds in increasing order of their reactivity in nucleophilic addition
reactions.
(i) Ethanal, Propanal, Propanone, Butanone.
(ii) Benzaldehyde, p-Tolualdehyde, p-Nitro benzaldehyde, Acetophenone.

Ans. (i) Butanone < Propanone < Propanal < Ethanal

(ii) Acetophenone < p-Tolualdehyde < Benzaldehyde < p-Nitro benzaldehyde
Q12. An organic compound with the molecular formula C9H10O forms 2, 4-DNP derivative, reduces
Tollens’ reagent and undergoes Cannizzaro reaction. On vigorous oxidation, it gives 1,2-
benzenedicarboxylic acid. Identify the compound.
Ans. 2-Ethyl benzaldehyde

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Q13. An organic compound (A) (molecular formula C8H16O2) was hydrolyzed with dilute Sulphuric
acid to give a carboxylic acid (B) and an alcohol (C). Oxidation of (C) with chromic acid produced (B).
(C) on dehydration gives but-1-ene. Write equations for the reactions involved.
Ans. A = Butyl butanoate, B = Butanoic acid, C = Butanol

Q14. Arrange the following compounds in increasing order of their property as indicated:
(i) Acetaldehyde, Acetone, Di-tert-butyl ketone, Methyl tert-butyl ketone (reactivity towards HCN)
(ii) CH3CH2CH(Br)COOH, CH3CH(Br)CH2COOH, (CH3)2CHCOOH, CH3CH2CH2COOH (acid
strength)
(iii) Benzoic acid, 4-Nitrobenzoic acid, 3,4-Dinitrobenzoic acid, 4-Methoxybenzoic acid (acid
strength)

Ans. (i) Acetaldehyde > Acetone > Methyl tert-butyl ketone > Di-tert-butyl ketone
(ii) (CH3)2CHCOOH < CH3CH2CH2COOH < CH3 CH (Br) CH2 COOH < CH3CH2CH (Br) COOH
(iii) 4-Methoxybenzoic acid < Benzoic acid < 4-Nitrobenzoic acid < 3, 4-Dinitrobenzoic acid
Q15. Give plausible explanation for each of the following:
(i) Cyclohexanone forms cyanohydrin in good yield but 2,2,6-trimethylcyclohexanone does not.
(ii) There are two –NH2 groups in semi carbazide. However, only one is involved in the formation
of semi carbazones.
(iii) During the preparation of esters from a carboxylic acid and an alcohol in the presence of an acid
catalyst, the water or the ester should be removed as soon as it is formed.

Ans. (i) Cyclohexanone forms cyanohydrin in good yield but 2, 2, 6-trimethylcyclohexanone does not
because of presence of three methyl groups at -position w.r.t carbonyl group which hinder the
Nucleophilic attack of CN- group due steric hindrance. No such steric hindrance in Cyclohexanone.
(ii) Semi carbazide has two –NH2 groups but one of these which is directly attached to C=O is involved in
resonance. Electron density on NH2 group decreases hence it does not act as nucleophile.
(iii)It is a reversible reaction. Therefore, to shift the equilibrium in the forward direction, the water or the
ester should be removed as fast as it is formed.

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