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Questions:

Generic 5

4 x 5 = 20

Arrange the following
i. In increasing order of solubility in water, C₆H₅ NH₂, (C₂H₅)₂NH, C₂H₅NH₂
ii. In increasing order of basic strength
a) aniline, p- toludine and p – nitroaniline
b) C₆H₅ NH₂, C₆H₅ NHCH₃, C₆H₅NH₂, p-Cl-C₆- H₄-NH₂
iii. In decreasing order of basic strength in gas phase
(C₂H₅)NH₂, (C₂H₅)NH, (C₂H₅)₅N and NH₃
iv. In increasing order of boiling point
C₆H₅OH, (CH₃)₂NH, C₂H₅NH₂
v. In decreasing order of the pK_b values
C₂H₅NH₂, C₆H₅NHCH₃.(C₂H₅)₂ NH and CH₃NH₂
vi. Increasing order of basic strength
C₂H₅NH₂,C₆H₅N(CH₃)₂, (C₂H₅)₂ NH and CH₃NH₂
vii. In decreasing order of basic strength

Account for the following
i. Aniline does not undergo Friedel – Crafts reaction
ii. Diazonium salts of aromatic amines are more stable than those of aliphatic amines
iii. pK_b of aniline is more than that of methylamine
iv. Gabriel phthalimide synthesis is preferred for synthesising primary amines.
v. Ethylamine is soluble in water whereas aniline is not
vi. Amines are more basic than amides
vii.Although amino group is o – and p – directing in aromatic electrophilic substitution reactions, aniline on nitration gives a substantial amount of m – nitroaniline.

Write short notes on the following
i. Hofmann’s bromide reaction
ii. Ammonolysis
iii. Gabriel phthalimide synthesis
iv. Schotten – Baumann reaction
v. Carbylamine reaction
vi. Mustard oil reaction
vii. Coupling reaction
viii. Diazotisation
ix. Gomberg reaction

Identify compounds A, B and C in the following sequence of reactions.
i) \({ C }_{ 6 }{ H }_{ 5 }NO_{ 2 }\overset { Fe/HCL }{ \longrightarrow } A\overset { HN{ O }_{ 2 } }{ \underset { 273K }{ \longrightarrow } } B\overset { { C }_{ 6 }{ H }_{ 5 }OH }{ \longrightarrow } C\)
ii) \({ C }_{ 6 }{ H }_{ 5 }N_{ 2 }cl\overset { CuCN }{ \longrightarrow } A\overset { H_{ 2 }O/H^{ + } }{ \longrightarrow } B\overset { NH_3 }{ \longrightarrow } C\)
iii) \({ C }{ H }_{ 3 }{ C }{ H }_{ 2 }I\overset { NaCN}{ \longrightarrow } A\overset {OH^-}{ \underset {Partial hydrolysis}{ \longrightarrow } } B\overset {NaOH+Br_2 }{ \longrightarrow } C\)
iv) \({ C }{ H }_{ 3 }NH_{ 2 }\overset { CH_3 Br }{ \longrightarrow } A\overset { CH_{ 3 }COCl}{ \longrightarrow } B\overset { B_2H_6 }{ \longrightarrow } C\)
v) \({ C }_{ 6 }{ H }_{ 5 }NH_{ 2 }\overset { (CH_{ 3 }CO)_{ 2 }O }{ \underset { Pyridine }{ \longrightarrow } } A\overset { HNO_{ 3 } }{ \underset { H_{ 2 }SO_{ 4 },288K }{ \longrightarrow } } B\overset { { H }_{ 2 }O/{ H }^{ + } }{ \longrightarrow C } \)
vi)

vii) \({ C }{ H }_{ 3 }CN_{ 2 }NC\overset { HgO }{ \longrightarrow } A\overset { H_{ 2 }O }{ \longrightarrow } B\overset { i) NaN{ O }_{ 2 }/HCL }{ \underset { ii){ H }_{ 2 }O }{ \longrightarrow } } \)

Generic 3

30 x 3 = 90

Arrange the following
vii. In decreasing order of basic strength

Arrange the following
vi. Increasing order of basic strength
C₂H₅NH₂,C₆H₅N(CH₃)₂, (C₂H₅)₂ NH and CH₃NH₂

Arrange the following
v. In decreasing order of the pK_b values
C₂H₅NH₂, C₆H₅NHCH₃.(C₂H₅)₂ NH and CH₃NH₂

Arrange the following
iv. In increasing order of boiling point
C₆H₅OH, (CH₃)₂NH, C₂H₅NH₂

Arrange the following
iii. In decreasing order of basic strength in gas phase
(C₂H₅)NH₂, (C₂H₅)NH, (C₂H₅)₅N and NH₃

10.

Arrange the following
ii. In increasing order of basic strength
a) aniline, p- toludine and p – nitroaniline
b) C₆H₅ NH₂, C₆H₅ NHCH₃, C₆H₅NH₂, p-Cl-C₆- H₄-NH₂

11.

Account for the following
vii. Although amino group is o – and p – directing in aromatic electrophilic substitution reactions, aniline on nitration gives a substantial amount of m – nitroaniline.

12.

Account for the following
vi. Amines are more basic than amides

13.

Account for the following
v. Ethylamine is soluble in water whereas aniline is not

14.

Account for the following
iv. Gabriel phthalimide synthesis is preferred for synthesising primary amines.

15.

Account for the following
iii. pK_b of aniline is more than that of methylamine

16.

Account for the following
ii. Diazonium salts of aromatic amines are more stable than those of aliphatic amines

17.

Write short notes on the following
ix. Gomberg reaction

18.

Write short notes on the following
viii. Diazotisation

19.

Write short notes on the following
vii. Coupling reaction

20.

Write short notes on the following
vi. Mustard oil reaction

21.

Write short notes on the following
v. Carbylamine reaction

22.

Write short notes on the following
iv. Schotten – Baumann reaction

23.

Write short notes on the following
iii. Gabriel phthalimide synthesis

24.

Write short notes on the following
ii. Ammonolysis

25.

Identify compounds A, B and C in the following sequence of reactions.
vii) \({ C }{ H }_{ 3 }CN_{ 2 }NC\overset { HgO }{ \longrightarrow } A\overset { H_{ 2 }O }{ \longrightarrow } B\overset { i) NaN{ O }_{ 2 }/HCL }{ \underset { ii){ H }_{ 2 }O }{ \longrightarrow } } \)

26.

Identify compounds A, B and C in the following sequence of reactions.
vi)

27.

Identify compounds A, B and C in the following sequence of reactions.
v) \({ C }_{ 6 }{ H }_{ 5 }NH_{ 2 }\overset { (CH_{ 3 }CO)_{ 2 }O }{ \underset { Pyridine }{ \longrightarrow } } A\overset { HNO_{ 3 } }{ \underset { H_{ 2 }SO_{ 4 },288K }{ \longrightarrow } } B\overset { { H }_{ 2 }O/{ H }^{ + } }{ \longrightarrow C } \)

28.

Identify compounds A, B and C in the following sequence of reactions.
iv) \({ C }{ H }_{ 3 }NH_{ 2 }\overset { CH_3 Br }{ \longrightarrow } A\overset { CH_{ 3 }COCl}{ \longrightarrow } B\overset { B_2H_6 }{ \longrightarrow } C\)

29.

Identify compounds A, B and C in the following sequence of reactions.
iii) \({ C }{ H }_{ 3 }{ C }{ H }_{ 2 }I\overset { NaCN}{ \longrightarrow } A\overset {OH^-}{ \underset {Partial hydrolysis}{ \longrightarrow } } B\overset {NaOH+Br_2 }{ \longrightarrow } C\)

30.

Identify compounds A, B and C in the following sequence of reactions.
ii) \({ C }_{ 6 }{ H }_{ 5 }N_{ 2 }cl\overset { CuCN }{ \longrightarrow } A\overset { H_{ 2 }O/H^{ + } }{ \longrightarrow } B\overset { NH_3 }{ \longrightarrow } C\)

31.

Identify A,B,and C
CH₃- NO₂ \(\overset { { L }_{ 1 }{AlH }_{ 4 } }{ \underset { {} }{ \longrightarrow } }\) A \(\overset { { 2CH_3 }{Ch_2Br } }{ \underset { {} }{ \longrightarrow } }\) B \(\overset { {H}_{ 2 }{SO}_{ 4 } }{ \underset { {} }{ \longrightarrow } } \) C

32.

How will you prepare propan – 1- amine from
i) butane nitrile
ii) propanamide
ii) 1- nitropropane

33.

Identify A,B and C
\(\overset{SOCl_2}\longrightarrow A \overset{NH_3}\longrightarrow B\overset{LiAlH_4}\longrightarrow (C)\)

34.

How will you convert diethylamine into
i) N, N – diethylacetamide
ii) N – nitrosodiethylamine

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Answers Key:

Generic 5

4 x 5 = 20

i) In increasing order of solubility in water:
\(\mathrm{C}_{6} \mathrm{H}_{5} \mathrm{NH}_{2},\left(\mathrm{C}_{2} \mathrm{H}_{5}\right)_{2} \mathrm{NH}, \mathrm{C}_{2} \mathrm{H}_{5} \mathrm{NH}_{2} \)
\(\mathrm{C}_{2} \mathrm{H}_{5} \mathrm{NH}_{2}>\mathrm{C}_{6} \mathrm{H}_{5} \mathrm{NH}_{2}>\left(\mathrm{C}_{2} \mathrm{H}_{5}\right)_{2} \mathrm{NH}\)
ii) In increasing order of basic strength:
a. Aniline, p - toluidine and p - nitro aniline
p - toluidine > aniline >p - nitro aniline

b. \(\mathrm{C}_{6} \mathrm{H}_{5} \mathrm{NH}_{2}, \mathrm{C}_{6} \mathrm{H}_{5} \mathrm{NHCH}_{3}, \mathrm{p}-\mathrm{Cl}-\mathrm{C}_{6} \mathrm{H}_{4}-\mathrm{NH}_{2} \)
\(\mathrm{C}_{6} \mathrm{H}_{5} \mathrm{NHCH}_{3}>\mathrm{C}_{6} \mathrm{H}_{5} \mathrm{NH}_{2}>\mathrm{p}-\mathrm{Cl}-\mathrm{C}_{6} \mathrm{H}_{4}-\mathrm{NH}_{2}\\ 2^{o} \text { amine } \quad \quad \quad \quad e^{\ominus} \text { with drawing (group) }\)
(iii) In decreasing order of basic strength in gas phase:
\(\mathrm{C}_{2} \mathrm{H}_{5} \mathrm{NH}_{2},\left(\mathrm{C}_{2} \mathrm{H}_{5}\right) \mathrm{NH},\left(\mathrm{C}_{2} \mathrm{H}_{5}\right)_{3} \mathrm{~N} \text { and } \mathrm{NH}_{3} \)
\(\mathrm{NH}_{3}<\mathrm{C}_{2} \mathrm{H}_{5} \mathrm{NH}_{2}<\left(\mathrm{C}_{2} \mathrm{H}_{5}\right)_{2} \mathrm{~N}<\left(\mathrm{C}_{2} \mathrm{H}_{5}\right)_{3} \mathrm{NH}\\ \quad \quad \quad 1^{0} \text { amine } \quad 2^{0} \text { amine } \quad \quad \quad 3^{0} \text { amine }\)
(iv) In increasing order of boiling point:
\(\mathrm{C}_{6} \mathrm{H}_{5} \mathrm{OH},\left(\mathrm{CH}_{3}\right)_{2} \mathrm{NH}, \mathrm{C}_{2} \mathrm{H}_{5} \mathrm{NH}_{2} \)
\(\left(\mathrm{CH}_{3}\right)_{2} \mathrm{NH}>\mathrm{C}_{2} \mathrm{H}_{5} \mathrm{NH}_{2}>\mathrm{C}_{6} \mathrm{H}_{5} \mathrm{OH} \\ 2^{0} \text { amine } \quad \quad1^{0} \text { amine }\)
Generally amines have lower boiling point than alcohol. Due to comparable molecular mass and weaker H-bonds in Amines.
(v) In decreasing order of the pK_b values:
\( \mathrm{C}_{2} \mathrm{H}_{5} \mathrm{NH}_{2}, \mathrm{C}_{6} \mathrm{H}_{5} \mathrm{NHCH}_{3},\left(\mathrm{C}_{2} \mathrm{H}_{5}\right)_{2} \mathrm{NH} \text { and } \mathrm{CH}_{3} \mathrm{NH}_{2} \)
\(\left(\mathrm{C}_{2} \mathrm{H}_{5}\right)_{2} \mathrm{NH}<\mathrm{C}_{2} \mathrm{H}_{5} \mathrm{NH}_{2}<\mathrm{CH}_{3} \mathrm{NH}_{2}<\mathrm{C}_{6} \mathrm{H}_{5} \mathrm{NHCH}_{3} \)
\(\quad \quad \quad 2^{0} \text { amine } \quad 1^{0} \text { amine } 1^{0} \text { amine } \quad 2^{0} \text { amine } \)
\(\mathrm{PK}_{b}: \quad 3.00\quad < \quad 3.29 \quad < \quad 3.38 \quad<\quad 9.30\)
pK_b ,Due to + 1 effect of C₂H₅ group. Higher the value of pK_b lower is the basicity
(vi) Increasing Order of basic strength:
\(\mathrm{C}_{6} \mathrm{H}_{5} \mathrm{NH}_{2}, \mathrm{C}_{6} \mathrm{H}_{5} \mathrm{~N}\left(\mathrm{CH}_{3}\right)_{2},\left(\mathrm{C}_{2} \mathrm{H}_{5}\right)_{2} \mathrm{NH} \text { and } \mathrm{CH}_{3} \mathrm{NH}_{2} \)
\(\mathrm{C}_{6} \mathrm{H}_{5} \mathrm{NH}_{2}>\mathrm{C}_{6} \mathrm{H}_{5} \mathrm{~N}\left(\mathrm{CH}_{3}\right)_{2}>\mathrm{CH}_{3} \mathrm{NH}_{2}>\left(\mathrm{C}_{2} \mathrm{H}_{5}\right)_{2} \mathrm{NH} \\ \left(\mathrm{pK}_{6}: 9.38 \quad > \quad \quad 8.92 \quad \quad > \quad 3.38 \quad > \quad \quad 3.00\right)\)
Due to + 1 effect of C₂H₅ group.
In decreasing order of basic strength:

Aniline does not undergo Friedel - Craft's reaction:
Aniline does not undergo Friedel - Craft's reaction (alkylation and acetylation). Aniline is basic in nature and it donates its lone pair of electrons to the lewis acid AlCl₃ to form an adduct which inhibits further electrophilic substitution reaction.
Diazonium salts of aromatic amines are more stable than those of aliphatic amines:
This is due to resonance
Resonance Structure:
The stability of arene diazonium salt is due to the dispersal of the positive charge over the benzene ring.

pK_b of aniline is more than that of methylamine:
pK_b - methylamine -3.35
pK_b - aniline -9.376
In aniline the lone pair of electrons on N - atom is delocalized over the benzene ring. So, the electron density on the N - atom decreases. In methylamine + 1 effect to CH₃ group increases the electron density on the nitrogen atom Hence aniline is a weaker base than methylamine. Due to this, the pK_bvalue for aniline is more than that of methylamine.
(iv) Gabriel phthalimide synthesis is preferred for synthesising primary amines:
In this method alkyl halides react with pottassium phthalimide to give pure primary amine by nucleophilic substitution. In contrast, Aniline (Aromatic primary amine) can not be prepared by this method because Aryl halides do not undergo nucleophilic substitution with the anion formed by phthalimide. Therefore, this method used for the Aliphatic primary. amines only. Aryl halides do not undergo S_N2 mechanism with the ion formed by the phthalimide.
(v) Ethylamine is soluble in water whereas aniline is not:
(a) Ethylamine is soluble in water, as it can form intermolecular H - bonds with water molecules. In aqueous solution, the substituted ammonium cation get stabilized not only by electron releasing (+I) effect of the alkyl group but also by solvation with water molecules. The greater the size of the ion, the lower will be the solvation.
(b) Amiline doesn't form H - bond with water to a very large extent due to the presence of a large hydrophobic -C₆H₅ group.
(vi) Amines are more basic than amides:
This is because, in amides, the carbonyl group is highly electro negative It has a greater power to attract the electrons towards it. It makes the lone pair of electrons on amide nitrogen (-CONH₂) less available to accept a proton.
(vii) Although amino group is o - and p - directing in aromatic electrophilic substitution reactions, aniline on nitration gives a substantial amount of m - nitro aniline:
In strong acid medium, aniline is protonated to form anilinium ion which is m - directing and hence m - nitro aniline is formed.

Hoffmann's bromide reaction:
When Amides are treated with bromine in the presence of aqueous or ethanolic solution of KOH, primary amines with one carbon atom less than the parent amides are obtained.
\(\underset { \quad \quad \quad amide\\ R=Alkyl(or)Aryl }{ R-\overset { \underset { || }{ O } }{ C } -{ NH }_{ 2 } } \overset { { Br }_{ 2 }/KOH }{ \longrightarrow } \underset { Primary\quad amine }{ R-{ NH }_{ 2 }+{ K }_{ 2 }{ CO }_{ 3 } } +KBr+{ H }_{ 2 }O\)
(ii) Hoffmann's ammonolysis:
When Alkyl halides (or) benzylhalides are heated with alcoholic ammonia in a sealed tube, mixtures of 1°, 2° and 3° amines and quaternary ammonium salts are obtained.
\( { CH }_{ 3 }-Br\overset { \ddot { N } { H }_{ 3 } }{ \underset { \Delta }{ \longrightarrow } } \underset { { 1 }^{ 0 }-amine }{ { CH }_{ 3 }-\ddot { N } { H }_{ 2 } } \overset { { CH }_{ 3 }-Br }{ \longrightarrow } \underset { { 3 }^{ o }-amine }{ \left( { CH }_{ 3 } \right) _{ 2 }\ddot { N } H } \overset { { CH }_{ 3 }Br }{ \longrightarrow } \underset { 3^{ o }-amine }{ \left( { { CH }_{ 3 } } \right) _{ 3 }\ddot { N } } \overset { CH_{ 3 }Br }{ \longrightarrow } \underset { Quartenary \ ammonium\ bromide }{ \left( { CH }_{ 3 } \right) _{ 4 }\overset { + }{ N } { Br }^{ - } } \)
This is a nucleophilic substitution, the halide ion of alkyl halide is substituted by the -NH₂ group. The product primary amine so formed can also has a tendency to act as a nucleophile and hence if excess alkyl halide is taken, further nucleophilic substitution takes place leading to the formation of quarternary ammonium salt. However, if the process is carried out with excess ammonia, primary amine is obtained as the major product. The order of reactivity of alkylhalides with amines
RI > RBr > RCl
(iii) Gabriel phthalimide synthesis:
Gabriel synthesis is used for the preparation of Aliphatic primary amines. Phthalimide on treatment with ethanolic KOH forms potassium salt of phthalimide which on heating with alkyl halide followed by alkaline hydrolysis gives primary amine. Aniline cannot be prepared by this method because the arylhalides do not undergo nucleophilic substitution with the anion formed by phthalimide.

(iv) Schotten - Baumann reaction :
Aniline reacts with benzoylchloride (C₆H₅COCI) in the presence of NaOH to give N - phenyl benzamide. This reaction is known as Schotten - Baumann reaction. The acylation and benzoylation are nucleophilic substitutions.
\(\underset { Aniline }{ { C }_{ 6 }{ H }_{ 5 }-{ NH }_{ 2 } } +\underset { Benzoyl\quad chloride }{ { C }_{ 6 }{ H }_{ 5 }-\overset { \underset { || }{ O } }{ C } -Cl } \overset { Pyridine }{ \longrightarrow } \underset { N-phenyl\quad benzamide }{ { C }_{ 6 }{ H }_{ 5 }-NH-\overset { \underset { || }{ O } }{ C } -{ C }_{ 6 }{ H }_{ 5 } } +HCl\)
(v) Carbylamine reaction :
Aliphatic (or) aromatic primary amines react with: chloroform and alcoholic KOH to give isocyanides (carbylamines), which has an unpleasant smell. This reaction is known as carbylamines test. This test used to identify the primary amines.
\(\underset { Ethylamine }{ { C }_{ 2 }{ H }_{ 5 }-{ NH }_{ 2 } } +\underset { Chloroform }{ { CHCl }_{ 3 }+3KOH } \longrightarrow \underset { Ethylisocyanide }{ { C }_{ 2 }{ H }_{ 5 }-NC } +3KCl+3{ H }_{ 2 }O\)
(vi) Mustard oil reaction:
(a) When primary amines are treated with carbon disulphide (CS₂), N - alkyldithio carbonic acid is formed which on subsequent treatment with HgCI₂, gives an alkyl isothiocyanate.

(b) When aniline is treated with carbon disulphide, or heated together, S-diphenylthio urea is formed, which on boiling with strong HCI, phenyl isothiocyanate (phenyl mustard oil), is formed.

These reactions are known as Hofmann - Mustard oil reaction. This test is used to identify the primary amines.
(vii) Coupling reactions (or) p-hydroxyazobenzene, p-aminoazobenzene, 2-phenyl azo-4-methyl phenol:
Benzene diazonium chloride reacts with electron rich aromatic compounds like phenol, aniline to form brightly coloured azo compounds. Coupling generally occurs at the para position. If para position is occupied then coupling occurs at the ortho position. Coupling tendency is enhanced if an electron donating group is present at the para - position to -N₂CI- group. This is an electrophilic substitution.

Aryl fluorides and iodides cannot be prepared by direct halogenation and the cyano group cannot be introduced by nucleophilic substitution of chlorine in chlorobenzene. For introducing such a halide group. cyano group -OH, NO₂, etc.. benzenediazonium chloride is a very good intermediate Diazo compounds obtained from the coupling reactions of diazonium salts are coloured and are used as dyes.
(viii) Diazotisation :
Aniline reacts with nitrous acid at low temperature (273 - 278 K) to give benzene. Diazonium chloride which is stable for a short time and slowly decomposes even at low temperatures.This reaction is known as diazotization

(ix) Gomberg reaction :
Benzene diazonium chloride reacts with benzene in the presence of sodium hydroxide to give biphenyl. This reaction in known as the Gomberg reaction

+CO₂

Generic 3

30 x 3 = 90

In decreasing order of basic strength:

Increasing Order of basic strength:
\(\mathrm{C}_{6} \mathrm{H}_{5} \mathrm{NH}_{2}, \mathrm{C}_{6} \mathrm{H}_{5} \mathrm{~N}\left(\mathrm{CH}_{3}\right)_{2},\left(\mathrm{C}_{2} \mathrm{H}_{5}\right)_{2} \mathrm{NH} \text { and } \mathrm{CH}_{3} \mathrm{NH}_{2} \)
\(\mathrm{C}_{6} \mathrm{H}_{5} \mathrm{NH}_{2}>\mathrm{C}_{6} \mathrm{H}_{5} \mathrm{~N}\left(\mathrm{CH}_{3}\right)_{2}>\mathrm{CH}_{3} \mathrm{NH}_{2}>\left(\mathrm{C}_{2} \mathrm{H}_{5}\right)_{2} \mathrm{NH} \\ \left(\mathrm{pK}_{6}: 9.38 \quad > \quad \quad 8.92 \quad \quad > \quad 3.38 \quad > \quad \quad 3.00\right)\)
Due to + 1 effect of C₂H₅ group.

In decreasing order of the pK_b values:
\( \mathrm{C}_{2} \mathrm{H}_{5} \mathrm{NH}_{2}, \mathrm{C}_{6} \mathrm{H}_{5} \mathrm{NHCH}_{3},\left(\mathrm{C}_{2} \mathrm{H}_{5}\right)_{2} \mathrm{NH} \text { and } \mathrm{CH}_{3} \mathrm{NH}_{2} \)
\(\left(\mathrm{C}_{2} \mathrm{H}_{5}\right)_{2} \mathrm{NH}<\mathrm{C}_{2} \mathrm{H}_{5} \mathrm{NH}_{2}<\mathrm{CH}_{3} \mathrm{NH}_{2}<\mathrm{C}_{6} \mathrm{H}_{5} \mathrm{NHCH}_{3} \)
\(\quad \quad \quad 2^{0} \text { amine } \quad 1^{0} \text { amine } 1^{0} \text { amine } \quad 2^{0} \text { amine } \)
\(\mathrm{PK}_{b}: \quad 3.00\quad < \quad 3.29 \quad < \quad 3.38 \quad<\quad 9.30\)
pK_b ,Due to + 1 effect of C₂H₅ group. Higher the value of pK_b lower is the basicity

In increasing order of boiling point:
\(\mathrm{C}_{6} \mathrm{H}_{5} \mathrm{OH},\left(\mathrm{CH}_{3}\right)_{2} \mathrm{NH}, \mathrm{C}_{2} \mathrm{H}_{5} \mathrm{NH}_{2} \)
\(\left(\mathrm{CH}_{3}\right)_{2} \mathrm{NH}>\mathrm{C}_{2} \mathrm{H}_{5} \mathrm{NH}_{2}>\mathrm{C}_{6} \mathrm{H}_{5} \mathrm{OH} \\ 2^{0} \text { amine } \quad \quad1^{0} \text { amine }\)
Generally amines have lower boiling point than alcohol. Due to comparable molecular mass and weaker H-bonds in Amines.

In decreasing order of basic strength in gas phase:
\(\mathrm{C}_{2} \mathrm{H}_{5} \mathrm{NH}_{2},\left(\mathrm{C}_{2} \mathrm{H}_{5}\right) \mathrm{NH},\left(\mathrm{C}_{2} \mathrm{H}_{5}\right)_{3} \mathrm{~N} \text { and } \mathrm{NH}_{3} \)
\(\mathrm{NH}_{3}<\mathrm{C}_{2} \mathrm{H}_{5} \mathrm{NH}_{2}<\left(\mathrm{C}_{2} \mathrm{H}_{5}\right)_{2} \mathrm{~N}<\left(\mathrm{C}_{2} \mathrm{H}_{5}\right)_{3} \mathrm{NH}\\ \quad \quad \quad 1^{0} \text { amine } \quad 2^{0} \text { amine } \quad \quad \quad 3^{0} \text { amine }\)

10.

ii) In increasing order of basic strength:
a. Aniline, p - toluidine and p - nitro aniline
p - toluidine > aniline >p - nitro aniline

b. \(\mathrm{C}_{6} \mathrm{H}_{5} \mathrm{NH}_{2}, \mathrm{C}_{6} \mathrm{H}_{5} \mathrm{NHCH}_{3}, \mathrm{p}-\mathrm{Cl}-\mathrm{C}_{6} \mathrm{H}_{4}-\mathrm{NH}_{2} \)
\(\mathrm{C}_{6} \mathrm{H}_{5} \mathrm{NHCH}_{3}>\mathrm{C}_{6} \mathrm{H}_{5} \mathrm{NH}_{2}>\mathrm{p}-\mathrm{Cl}-\mathrm{C}_{6} \mathrm{H}_{4}-\mathrm{NH}_{2}\\ 2^{o} \text { amine } \quad \quad \quad \quad e^{\ominus} \text { with drawing (group) }\)

11.

Although amino group is o - and p - directing in aromatic electrophilic substitution reactions, aniline on nitration gives a substantial amount of m - nitro aniline:
In strong acid medium, aniline is protonated to form anilinium ion which is m - directing and hence m - nitro aniline is formed.

12.

Amines are more basic than amides:
This is because, in amides, the carbonyl group is highly electro negative It has a greater power to attract the electrons towards it. It makes the lone pair of electrons on amide nitrogen (-CONH₂) less available to accept a proton.

13.

Ethylamine is soluble in water whereas aniline is not:
(a) Ethylamine is soluble in water, as it can form intermolecular H - bonds with water molecules. In aqueous solution, the substituted ammonium cation get stabilized not only by electron releasing (+I) effect of the alkyl group but also by solvation with water molecules. The greater the size of the ion, the lower will be the solvation.
(b) Amiline doesn't form H - bond with water to a very large extent due to the presence of a large hydrophobic -C₆H₅ group.

14.

Gabriel phthalimide synthesis is preferred for synthesising primary amines:
In this method alkyl halides react with pottassium phthalimide to give pure primary amine by nucleophilic substitution. In contrast, Aniline (Aromatic primary amine) can not be prepared by this method because Aryl halides do not undergo nucleophilic substitution with the anion formed by phthalimide. Therefore, this method used for the Aliphatic primary. amines only. Aryl halides do not undergo S_N2 mechanism with the ion formed by the phthalimide.

15.

pK_b of aniline is more than that of methylamine:
pK_b - methylamine -3.35
pK_b - aniline -9.376
In aniline the lone pair of electrons on N - atom is delocalized over the benzene ring. So, the electron density on the N - atom decreases. In methylamine + 1 effect to CH₃ group increases the electron density on the nitrogen atom Hence aniline is a weaker base than methylamine. Due to this, the pK_bvalue for aniline is more than that of methylamine.

16.

Diazonium salts of aromatic amines are more stable than those of aliphatic amines:
This is due to resonance
Resonance Structure:
The stability of arene diazonium salt is due to the dispersal of the positive charge over the benzene ring.

17.

Gomberg reaction :
Benzene diazonium chloride reacts with benzene in the presence of sodium hydroxide to give biphenyl. This reaction in known as the Gomberg reaction

18.

Diazotisation :
Aniline reacts with nitrous acid at low temperature (273 - 278 K) to give benzene. Diazonium chloride which is stable for a short time and slowly decomposes even at low temperatures.This reaction is known as diazotization

19.

Coupling reactions (or) p-hydroxyazobenzene, p-aminoazobenzene, 2-phenyl azo-4-methyl phenol:
Benzene diazonium chloride reacts with electron rich aromatic compounds like phenol, aniline to form brightly coloured azo compounds. Coupling generally occurs at the para position. If para position is occupied then coupling occurs at the ortho position. Coupling tendency is enhanced if an electron donating group is present at the para - position to -N₂CI- group. This is an electrophilic substitution.

Aryl fluorides and iodides cannot be prepared by direct halogenation and the cyano group cannot be introduced by nucleophilic substitution of chlorine in chlorobenzene. For introducing such a halide group. cyano group -OH, NO₂, etc.. benzenediazonium chloride is a very good intermediate Diazo compounds obtained from the coupling reactions of diazonium salts are coloured and are used as dyes.

20.

Mustard oil reaction:
(a) When primary amines are treated with carbon disulphide (CS₂), N - alkyldithio carbonic acid is formed which on subsequent treatment with HgCI₂, gives an alkyl isothiocyanate.

(b) When aniline is treated with carbon disulphide, or heated together, S-diphenylthio urea is formed, which on boiling with strong HCI, phenyl isothiocyanate (phenyl mustard oil), is formed.

These reactions are known as Hofmann - Mustard oil reaction. This test is used to identify the primary amines.

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Carbylamine reaction :
Aliphatic (or) aromatic primary amines react with: chloroform and alcoholic KOH to give isocyanides (carbylamines), which has an unpleasant smell. This reaction is known as carbylamines test. This test used to identify the primary amines.
\(\underset { Ethylamine }{ { C }_{ 2 }{ H }_{ 5 }-{ NH }_{ 2 } } +\underset { Chloroform }{ { CHCl }_{ 3 }+3KOH } \longrightarrow \underset { Ethylisocyanide }{ { C }_{ 2 }{ H }_{ 5 }-NC } +3KCl+3{ H }_{ 2 }O\)

22.

Schotten - Baumann reaction :
Aniline reacts with benzoylchloride (C₆H₅COCI) in the presence of NaOH to give N - phenyl benzamide. This reaction is known as Schotten - Baumann reaction. The acylation and benzoylation are nucleophilic substitutions.
\(\underset { Aniline }{ { C }_{ 6 }{ H }_{ 5 }-{ NH }_{ 2 } } +\underset { Benzoyl\quad chloride }{ { C }_{ 6 }{ H }_{ 5 }-\overset { \underset { || }{ O } }{ C } -Cl } \overset { Pyridine }{ \longrightarrow } \underset { N-phenyl\quad benzamide }{ { C }_{ 6 }{ H }_{ 5 }-NH-\overset { \underset { || }{ O } }{ C } -{ C }_{ 6 }{ H }_{ 5 } } +HCl\)

23.

Gabriel phthalimide synthesis:
Gabriel synthesis is used for the preparation of Aliphatic primary amines. Phthalimide on treatment with ethanolic KOH forms potassium salt of phthalimide which on heating with alkyl halide followed by alkaline hydrolysis gives primary amine. Aniline cannot be prepared by this method because the arylhalides do not undergo nucleophilic substitution with the anion formed by phthalimide.

24.

(ii) Hoffmann's ammonolysis:
When Alkyl halides (or) benzylhalides are heated with alcoholic ammonia in a sealed tube, mixtures of 1°, 2° and 3° amines and quaternary ammonium salts are obtained.
\( { CH }_{ 3 }-Br\overset { \ddot { N } { H }_{ 3 } }{ \underset { \Delta }{ \longrightarrow } } \underset { { 1 }^{ 0 }-amine }{ { CH }_{ 3 }-\ddot { N } { H }_{ 2 } } \overset { { CH }_{ 3 }-Br }{ \longrightarrow } \underset { { 3 }^{ o }-amine }{ \left( { CH }_{ 3 } \right) _{ 2 }\ddot { N } H } \overset { { CH }_{ 3 }Br }{ \longrightarrow } \underset { 3^{ o }-amine }{ \left( { { CH }_{ 3 } } \right) _{ 3 }\ddot { N } } \overset { CH_{ 3 }Br }{ \longrightarrow } \underset { Quartenary \ ammonium\ bromide }{ \left( { CH }_{ 3 } \right) _{ 4 }\overset { + }{ N } { Br }^{ - } } \)
This is a nucleophilic substitution, the halide ion of alkyl halide is substituted by the -NH₂ group. The product primary amine so formed can also has a tendency to act as a nucleophile and hence if excess alkyl halide is taken, further nucleophilic substitution takes place leading to the formation of quarternary ammonium salt. However, if the process is carried out with excess ammonia, primary amine is obtained as the major product. The order of reactivity of alkylhalides with amines
RI > RBr > RCl

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+CO₂

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