Quick points to remember : Organic chemistry ( By : Jitender Sir)

Aldehyde , Ketone and Carboxylic acid

1. Aldehyde and ketone undergo nucleophilic addition: The carbon-oxygen double bond is polarized due to higher electronegativity of
oxygen relative to carbon. Hence, the carbonyl carbon carries slightly positive charge and oxygen carry slightly negatively charge so
it’s easy for a nucleophile to attack on carbonyl carbon.

C == O C---- O

2. Aldehydes are generally more reactive than ketones because two alkyl groups (+ INDUCTIVE EFFECT) reduce the electrophilic nature
(or positive charge) of the carbonyl carbon.
3. Following compounds in increasing order of their reactivity in nucleophilic addition reactions.
➢ (i) Ethanal > Propanal > Propanone > Butanone.
➢ (ii) Acetophenone < p-Tolualdehyde < Benzaldehyde < p-Nitrobenzaldehyde

4. Benzaldehyde to be less reactive in nucleophilic addition reactions than propanal: The carbon atom of the carbonyl group of
benzaldehyde is less electrophilic than carbon atom of the carbonyl group present in propanal. The polarity of the carbonyl group is
reduced in benzaldehyde due to resonance and hence it is less reactive than propanal.

5. Oxidation of Toluene with CrO3 to benzaldehyde is carried out in the presence of acetic anhydride: because as soon as
benzaldehyde is formed it react with acetic anhydride to form benzylidene diacetate so thus further oxidation of benzaldehyde to
benzoic acid cab be stopped then benzylidene diacetate can be hydrolysed to corresponding benzaldehyde with aqueous acid.

6. Boiling point of aldehydes are in between of corresponding alcohols and alkane: In aldehydes, dipole-dipole interaction exists
between the molecules. In alkanes Vander Wall’s interaction exists whereas in alcohols hydrogen bonding exists which is stronger than
dipole-dipole interaction and dipole-dipole interaction is stronger than Vander waal force of attraction.
7. Arrange Acc. to their boiling points: CH3CH2CH2CH2CH3 < H5C2-O-C2H5 < CH3CH2CH2CHO < CH3CH2CH2CH2OH
8. Formalin: Formaldehyde is well known as formalin (40%)
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 9. 2,2,6 Trimethyl cyclohexanone will not undergo cyanohydrin formation: due to repulsion by bulky group (alkyl group)
10. Role of dry HCI in the formation of hemiacetal, Acetal and Ketal: Dry hydrogen chloride protonates the oxygen of the carbonyl
compounds and therefore, increases the positive charge (electrophilicity) of the carbonyl carbon facilitating the nucleophilic attack.

11. Why we have to add a base during formation of cyanohydrin with Pure HCN: Aldehydes and ketones react with hydrogen cyanide
(HCN) to yield cyanohydrins. This reaction occurs very slowly with pure HCN. Therefore, it is catalysed by a base and the generated
cyanide ion (CN-) being a stronger nucleophile readily adds to carbonyl compounds to yield corresponding cyanohydrin.

1. Formation of oximes and other ammonia derivatives requires slightly acidic medium (pH = 5-6) for maximum rate, basic or
highly acid conditions lowers the rate: As the acidity increases (means pH will be less than =4.5), the rate of the reaction
decreases because more and more of the amine becomes protonated. As a result, less and less amine is present in the nucleophilic
non-protonated form.

As the acidity decreases (means pH is above 4.5), the rate decreases because the less and less of the tetrahedral intermediate is
present in the reactive protonated form. (Oxygen of carbonyl group will not be protonated so much so reaction become slow)

2. Use of NaHSO3 : When aldehyde and ketone react with NaHSO3 then the position of the equilibrium lies largely to the right-hand side
for most aldehydes and to the left for most ketones due to steric reasons. The hydrogensulphite addition compound is water soluble
and can be converted back to the original carbonyl compound by treating it with dilute mineral acid or alkali. useful for separation and
purification of aldehydes.
3. Boiling Points: Carboxylic acid > Alcohol > Ketone > Aldehyde > Haloalkane > Hydrocarbon
Reason: Extensive H-Bonding Dipole- Dipole interaction Dispersion forces
H-Bonding (Weak vander waal Forces)

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 4. There are two –NH2 groups in semicarbazide. However, only one is involved in the formation of semicarbazones : Because other
two -NH2 groups are taking part in resonance.
O
H2N-NH-C-NH2 O
C=O C=N-NH-C-NH2
Semicarbazide
Semicarbazone
Aldehyde/Ketone
5. Brady's test, the reaction of 2,4-dinitrophenylhydrazine with aldehydes and ketones, fail with carboxylic acids : The carboxylate
anion is resonance-stabilized and the carbonyl carbon is insufficiently electrophilic. You couldn't form a tetrahedral intermediate.
6. Acetic acid can be halogenated in the presence of red P & Br2, but formic acid cannot be halogenated in the same way :
Because in formic acid there is no alpha hydrogen.
7. Formic acid (HCOOH) will not undergo HVZ reaction: because Formic acid has no alpha hydrogen.
8. Formic acid can also give Tollen`s test: because it’s one of the terminal carry aldehydic group.
9. carboxylic acid is more acidic then phenol:
➢ Because the conjugate base of carboxylic acid, a carboxylate ion, is stabilised by two equivalent resonance structures in which
the negative charge is at the more electronegative oxygen atom. The conjugate base of phenol, a phenoxide ion, has resonance
structures in which the negative charge is at the less electronegative carbon atom. Thus, the carboxylate ion is more stabilised
than phenoxide ion, so carboxylic acids are more acidic than phenols.
10. Compounds are arrange according to their acidic nature:

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 11. Arrange the following compound according to their acidic strength?
➢ CH3COOH < Cℓ-CH2COOH (Due to – Inductive effect of Cℓ)
➢ Cℓ-CH2COOH < NO2-CH2COOH ( NO2 group is more EWG so higher – Inductive effect.)
➢ NO2CH2COOH < Cℓ3C-COOH(Number of Chlorine is more then NO2 group so -I effect will be more)
➢ F-CH2CH2CH2COOH < CH3CHFCH2COOH < CH3CH2CHFCOOH(As distance of F increase from COOH group Acidic nature decreses
➢ 3oAlcohol < 2oAlcohol < 1oAlcohol
12. Vinylic and phenylic carboxylic acids are more acidic: because in vinyl and phenyl they attached with carboxylic group with
their sp2 hybrid carbon and if higher the s-character higher will be the acidic nature.

The presence of electron withdrawing group on the phenyl of aromatic carboxylic acid increases their acidity while electron donating
groups decrease their acidity.
13. Arrange the following compounds in decreasing order of their property as indicated:
➢ Acetaldehyde > Acetone > Methyl tert-butyl ketone > Di-tert-butyl ketone, (reactivity towards HCN)
➢ CH3CH2CH(Br)COOH > CH3CH(Br)CH2COOH > CH3CH2CH2COOH > (CH3)2CHCOOH, (acid strength)
➢ 3,4-Dinitrobenzoic acid > 4-Nitrobenzoic acid > Benzoic acid > 4-Methoxybenzoic acid (acid strength)
14. Why benzoic acid do not undergo Fridel craft reaction: because the carboxyl group is deactivating and the catalyst
aluminium chloride (Lewis acid) gets bonded to the carboxyl group).

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