3.

a) Synthesize the following alcohols from Grignard reagents and carbonyl compounds, giving all
reagents used in the reaction steps.

i) 2-Methyl-2-propanol

ii) 4-Methyl-1-pentanol

Answer:

i)

ii)

b) Compare and contrast between nucleophilic addition reaction and nucleophilic acyl substitution
reaction, emphasizing on reaction mechanisms and giving examples.

Answer

Nucleophilic addition reaction and nucleophilic acyl substitution reaction are two types of organic
reactions that involve the participation of a nucleophile. Although both reactions involve the attack of a
nucleophile on an electrophilic center, they differ in terms of their reaction mechanisms and the
functional groups involved.

Nucleophilic Addition Reaction:

Nucleophilic addition reactions occur when a nucleophile attacks an electrophilic center, resulting in the
addition of the nucleophile to the substrate molecule. These reactions are commonly observed in
compounds with double or triple bonds, such as alkenes or alkynes. The reaction mechanism typically
involves the following steps:

a. The nucleophile approaches the electrophilic center (e.g., a carbon-carbon double bond) and donates
its electron pair.

b. The electrophilic center forms a new bond with the nucleophile, breaking the existing π bond.

c. The reaction generates a new compound with a saturated functional group.

Example: The addition of hydrogen bromide (HBr) to ethene (C2H4) is a nucleophilic addition reaction.
In this case, the nucleophile is the bromide ion (Br-) and it attacks the electrophilic carbon atom of the
double bond in ethene. The result is the formation of bromoethane (C2H5Br).

Nucleophilic Acyl Substitution Reaction:

Nucleophilic acyl substitution reactions occur when a nucleophile replaces a leaving group in an acyl
group (R-C=O). These reactions are commonly observed in compounds containing acyl derivatives, such
as carboxylic acids, acid halides, acid anhydrides, and esters. The reaction mechanism typically involves
the following steps:

a. The nucleophile attacks the carbonyl carbon of the acyl group, leading to the formation of a
tetrahedral intermediate.

b. The leaving group (usually a halide or an alcohol) departs, resulting in the formation of a new bond
between the nucleophile and the carbonyl carbon.

c. The reaction generates a new compound with a substituted acyl group.

Example: The reaction between acetic acid (CH3COOH) and ammonia (NH3) is a nucleophilic acyl
substitution reaction. In this case, the nucleophile is the ammonia molecule, and it replaces the leaving
group (OH) in the acetic acid molecule. The result is the formation of acetamide (CH3CONH2).

In summary, nucleophilic addition reactions involve the addition of a nucleophile to a substrate, typically
a compound with double or triple bonds. On the other hand, nucleophilic acyl substitution reactions
involve the substitution of a leaving group in an acyl derivative. The reaction mechanisms and the
functional groups involved in these reactions are distinct, leading to different products.

e) Why is acetic acid stronger acid than ethanol? Justify.

answer

Acetic acid is a stronger acid than ethanol because the acetate ion formed by ionization is stabilized by
resonance while the ethoxide ion has no resonance.
5. a) What property of ammonia is utilized for the preparation of primary amines by SN2 reaction of
alkyl halides? Why is this not a good method for its synthesis? Show the reaction of an alternative
method for synthesis of primary amines. 2.0

b) The boiling point of 1-butanol is higher than butane. Justify the statement. 1.0

c) Aryl amines are less basic than alkyl amine. Justify the statement. 1.0

d) Why do carboxylic acids not participate in nucleophilic acid acyl substitution reaction? 1.0

e) Tertiary amines do not form hydrogen hand while primary and secondary amines do Justify

f) Write down the structure of propyl amine and propionamide. Which one is non-basic? Why is so? 1.0

answer a) The property of ammonia utilized for the preparation of primary amines by SN2 reaction of
alkyl halides is its nucleophilicity. However, this method is not ideal due to competing reactions, low
nucleophilicity, and formation of insoluble salts. An alternative method involves the reduction of nitro
compounds, which offers selectivity, mild reaction conditions, and high yield in the synthesis of primary
amines.

R-NO2 + 3H2 → R-NH2 + 2H2O

b) The boiling point of 1-butanol is higher than butane due to the presence of hydrogen bonding in 1-
butanol, which creates stronger intermolecular forces compared to the weaker London dispersion forces
in butane.
c) Aryl amines are generally less basic than alkyl amines because the nitrogen lone-pair electrons are
delocalized by interaction with the aromatic ring π electron system which makes electrons less available.

Or

Aryl amines are less basic than alkyl amines due to the presence of electron-withdrawing groups
attached to the nitrogen atom in aryl amines.

D) Carboxylic acids do not participate in nucleophilic acyl substitution reactions because they are already
in their most stable form and do not easily undergo further substitution.

E) Tertiary amines have no hydrogen atoms bonded to the nitrogen atom and therefore are not
hydrogen bond donors.

F) The structure of propyl amine is: CH3CH2CH2NH2

The structure of propionamide is: CH3CH2CONH2

Propionamide is non-basic compared to propyl amine. This is because the amide group (-CONH2) in
propionamide has a resonance structure that delocalizes the lone pair of electrons on the nitrogen
atom. This resonance stabilization decreases the availability of the lone pair for proton acceptance,
resulting in reduced basicity. In contrast, propyl amine does not have resonance stabilization and thus
exhibits higher basicity.