ORGANIC CHEMISTRY

REASONING QUESTIONS
1.Explain why
(i)the dipole moment of chlorobenzene is lower than that of cyclohexyl chloride?
(ii)alkyl halides, though polar, are immiscible with water?
(iii)Grignard reagents should be prepared under anhydrous conditions?
Ans. (i) sp2-hybrid carbon in chlorobenzene is more electronegative than a sp3-hybrid carbon in
cyclohexyl chloride, due to greater s-character. Thus, the C atom of chlorobenzene has less
tendency to release electrons to Cl than the carbon atom of cyclohexyl chloride.
As a result, C – Cl bond in chlorobenzene is less polar than in cyclohexyl chloride. Further, due
to delocalization of lone pairs of electrons of the Cl atom over the benzene ring, C-Cl bond in
chlorobenzene acquires some double bond character while the C – Cl in cyclohexyl chloride is a
pure single bond. In other words, the C-Cl bond in chlorobenzene is shorter than in cyclohexyl
chloride.
Since dipole moment is a product of charge and distance, therefore, chlorobenzene has lower
dipole moment than cyclohexyl chloride due to lower magnitude of negative charge on the Cl
atom and shorter C-Cl distance.
(ii)Alkyl halides are polar molecules, therefore, their molecules are held together by dipole-
dipole attraction. The molecules of H2O are held together by H-bonds. Since the new forces of
attraction between water and alkyl halide molecules are weaker than the forces of attraction
already existing between alkyl halide – alkyl halide molecules and water-water molecules,
therefore, alkyl halides are immiscible (not soluble) in water. Alkyl halide are neither able to
form H- bonds with water nor are able to break the H-bonding network of water.
(iii)Grignard reagents are very reactive. They react with moisture present in the apparatus to
form alkanes

RMgX + H2O RH+ MgX (OH)

That’s why Grignard’s reagent should be prepared under anhydrous conditions.
2.Write the mechanism of the following reaction:

Ans. KCN is a resonance hybrid of the following two contributing structures:

Thus, CN– ion is an ambident nucleophile. Therefore, it can attack the “carbon atom of C-Br
bond in n-BuBr either through C or N. Since C – C bond is stronger than C – N bond, therefore,
attack occurs through C to form n-butyl cyanide.

3.Out of C6H5CH2Cl and C6H5CHCIC6H5which is more easily hydrolysed by aqueous KOH.

Ans. C6H5CH2Cl is 10 aryl halide while C6H5CH(CI)C6H5 is a 2° aryl halide. In SN1 reactions, the
reactivity depends upon the stability of carbocations.
Since the C6H5CH C6H5 carbocation is more stable than C6H5CH2 carbocation,
therefore,C6H5CHCIC6H5 gets hydrolysed more easily than C6H5CH2Cl under SN1 conditions.
However, under SN2 conditions, the reactivity depends on steric hindrance, therefore, under SN2
conditions,C6H5CH2Cl gets hydrolysed more easily than C6H5CHClC6H5.

4.p-Dichlorobenzene has higher m.p. and lower solubility than those of o-and m-isomers.
Discuss.
Ans. The p-isomer being more symmetrical fits closely in the crystal lattice and thus has stronger
inter-
molecular forces of attraction than o- and m-isomers. Since during melting or dissolution, the
crystal lattice breaks, therefore, a large amount of energy is needed to melt or dissolve the p-
isomer than the corresponding o-and m-isomers. In other words, the melting point of the p-
isomer is higher and its solubility lower than the corresponding o-and m-isomers.

5.The treatment of alkyl chlorides with aqueous KOH leads to the formation of alcohols but in
the presence of alcoholic KOH, alkenes are major products. Explain.
Ans. If aqueous solution, KOH is almost completely ionized to give OH– ions which being a
strong nucleophile brings about a substitution reaction on alkyl halides to form alcohols. Further
in the aqueous solution, OH– ions are highly solvated (hydrated). This solvation reduces the basic
character of OH– ions which, therefore, fails to abstract a hydrogen from the P-carbon of the
alkyl chloride to form alkenes. In contrast, an alcoholic solution of KOH contains alkoxide (RO–)
ion which being a much stronger base than OH– ions perferentially eliminates a molecule of HCl
from an alkyl chloride to form alkenes.
6.Explain why propanol has a higher boiling point than that of the hydrocarbon, butane?
Ans. The molecules of butane are held together by weak van der Waals forces of attraction while
those of propanol are held together by stronger intermolecular hydrogen bonding.

7. Alcohols are comparatively more soluble in water than hydrocarbons of comparable molecular
masses. Explain this fact.
Ans. Alcohols can form hydrogen bonds with water and by breaking the hydrogen bonds already
existing between water molecules. Therefore, they are soluble in water.

On the other hand, hydrocarbons cannot form hydrogen bonds with water and hence are
insoluble in water.

8.While separating a mixture of ortho and para nitrophenols by steam distillation, name the
isomer which will be steam volatile. Give a reason.
Ans. O-Nitrophenol is steam volatile due to chelation (intramolecular H – bonding) and hence
can be separated by steam distillation from p-Nitrophenol which is not steam volatile because of
intermolecular H-bonding.
9.Give reason for the higher boiling point of ethanol in comparison to methoxymethane.
Ans. Ethanol undergoes intermolecular H-bonding due to the presence of a hydrogen atom
attached to the electronegative oxygen atom. As a result, ethanol exists as associated molecules.

Consequently, a large amount of energy is required to break these hydrogen bonds. Therefore,
the boiling point of ethanol is higher than that of methoxymethane which does not form H-bonds.
10. Give plausible explanation for each of the following:
(i) Cyclohexanone forms cyanohydrin in good yield but 2,2,2- trimethylcyclohexanone does not
(ii) There are two – NH2 groups in semicarbazide. However, only one is involved in the
formation of semicarbazones.
(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.

The yield of the second reaction is very low because of the presence of three methyl groups at
ex-positions with respect to the C = O, the nucleophilic attack by the CN– ion does not occur due
to steric hindrance. Since there is no such steric hindrance in cyclohexanone, therefore,
nucleophilic attack by the CN– ion occurs readily and hence cyclohexanone cyanohydrin is
obtained in good yield.

Although semicarbazide has two – NH2 groups but one of them (i.e., which is directly attached to
C = O) is involved in resonance as shown above. As a result, electron density on N of this -
NH2 group decreases and hence it does not act as a nucleophile. In contrast, the other -NH2 group
(i.e.. attached to NH) is not involved in resonance and hence lone pair of electrons present on N
atom of this -NH2 group is available for nucleophilic attack on the C = O group of aldehydes and
ketones.’
(iii) The formation of esters from a carboxylic acid and an alcohol in presence of an acid catalyst
is a reversible reaction.

Thus to shift the equilibrium in the forward direction, the water or the ester formed should be
removed as fast as it is formed.

11. Although phenoxide ions have more resonating structures than carboxylate ion, carboxylic
acid is a stronger acid than phenol. Why?
Ans. Consider the resonating structures of carboxylate ions and phenoxide ions.

In case of phenoxide ion, structures (V – VII) carry a negative charge on the less electronegative
carbon atom.Therefore, their contribution towards the resonance stabilization of phenoxide ion is
very small.
In structures I and II, (carboxylate ion), the negative charge is delocalized over two oxygen
atoms while in structures III and IV, the negative charge on the oxygen atom remains localized
only the electrons of the benzene ring are delocalized. Since delocalization of benzene electrons
contributes little towards the stability of phenoxide ion therefore, carboxylate ion is much more
resonance stabilized than phenoxide ion. Thus, the release of a proton from carboxylic acids is
much easier than from phenols. In other words, carboxylic acids are stronger acids than phenols.
12.Account for the following;
(i)pKb of aniline is more than that of methylamine
(ii) Ethylamine is soluble in water whereas aniline is not.
(iii) Methylamine in water reacts with ferric chloride to precipitate hydrated ferric oxide.
(iv)Although the amino group is o and p – directing in aromatic electrophilic substitution
reactions, aniline on nitration gives a substantial amount of m-nitroaniline.
(v)Aniline does not undergo Friedel-Crafts reaction.
(vi)Diazonium salts of aromatic amines are more stable than those of aliphatic amines.
(vii)Gabriel phthalimide synthesis is preferred for synthesizing primary amines.
Ans. (i) In aniline, the lone pair of electrons on the N-atom is delocalised over the benzene ring.
As a result, electron density on the nitrogen atoms decrease. Whereas in CH3NH2,+ I-effect of -
CH3 group increases the electron density on the N-atom. Therefore, aniline is a weaker base than
methylamine and hence its pKb value is higher than that of methylamine.
(ii) Ethylamine dissolves in water due to intermolecular H-bonding. However, in case of aniline,
due to the large hydrophobic part, i.e., hydrocarbon part, the extent of H-bonding is very less
therefore aniline is insoluble in water.

iii)Methylamine being more basic than water, accepts a proton from water liberating OH – ions,

(iv)Nitration is usually carried out with a mixture of cone HNO3 + cone H2SO4. In presence of
these acids, most of aniline gets protonated to form anilinium ion. Therefore, in presence of
acids, the reaction mixture consist of aniline and anilinium ion. Now, -NH2 group in aniline is
activating and o, p-directing while the -+NH3 group in anilinium ion is deactivating and rw-
directing: Nitration of aniline (due to steric hindrance at o-position) mainly gives p-nitroaniline,
the nitration of anilinium ion gives m-nitroaniline. In actual practice, approx a 1:1 mixture of p-
nitroaniline and m-nitroaniline is obtained. Thus, nitration of aniline give

substantial amount of m-nitroaniline due to protonation of the amino group.

13.Why cannot aromatic primary amines be prepared by Gabriel phthalimide synthesis?

Ans. The success of Gabriel phthalimide reaction depends upon the nucleophilic attack by the
phthalimide anion on the organic halogen compound.
Since aryl halides do not undergo nucleophilic substitution reactions easily, therefore,
arylamines, i.e., aromatic, primary amines cannot be prepared by Gabriel phthalimide reaction.

14.Give plausible explanation for each of the following:

(i) Why are amines less acidic than alcohols of comparable molecular masses?
(ii) Why do primary amines have higher boiling point than tertiary amines?
(iii) Why are aliphatic amines stronger bases than aromatic amines?
Ans. (i) Loss of proton from an amine gives an amide ion while loss of a proton from alcohol
give an alkoxide ion.
R—NH2—>R—NH– +H+
R—O —H—>R— O– +H+ .
Since O is more electronegative than N, so it wijl attract positive species more strongly in
comparison to N. Thus, RO~ is more stable than RNH®. Thus, alcohols are more acidic than
amines. Conversely, amines are less acidic than alcohols.
(ii) Due to the presence of two H-atoms on N-atom of primary amines, they undergo extensive
intermolecular H-bonding while tertiary amines due to the absence of H-atom on the N-atom do
not undergo H-bonding. As a result, primary amines have higher boiling points than tertiary
amines of comparable molecular mass.
(iii) Aromatic amines are far less basic than ammonia and aliphatic amines because of following
reasons:
(a)Due to resonance in aniline and other aromatic amines, the lone pair of electrons on the
nitrogen atom gets delocalised over the benzene ring and thus it is less easily available for
protonation. Therefore, aromatic amines are weaker bases than ammonia and aliphatic amines.
(b)Aromatic amines arS more stable than corresponding protonated ion; Hence, they hag very
less tendency to combine with a proton to form corresponding protonated ion, and thus they are
less basic