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Amines
Preparation
The primary amines may be prepared by the reduction of nitro compounds,nitriles,amides and oximes. or
H2/Pd
NO 2 NO 2
H2 / Pt
Zn / HCl
or
or
H2 / Ni
Sn/ HCl
or Fe / HCl
or
LiAlH 4
NH 2 NH 2
Sn/ HCl
or
Fe / HCl
Nitro compounds
[Fe/HCl is preferred ,because FeCl2 formed gets hydrolysed to release hydrochloric acid,thus a small amount of HCl is required to initiate the reaction.]
LiAlH 4
C N Nitrile R
or
LiAlH 4
H2 / Ni
or Na(Hg) / C 2H5OH
CH 2 NH2
Br 2
4 NaOH
NH2
Na 2CO 3
2 NaBr
2 H 2O
In this reaction ,the amine formed contain one carbon less than those of amide. [3] Gabriel phthalimide synthesis
O C N C O Phthalimide H KOH O C N K C O N-Alkylphthalimide COO Na COO Na
O C N C O
+
NaOH
Aromatic primary amines can not be prepared by this method because aryl halides do not undergo nucleophilic substitution with the anion formed by phthalimide.
+
+
NH2
[4] Ammonolysis of alkyl halides The process of cleavage of the C-X bond by ammonia molecule is known as ammonolysis.
RX NH3 R NH2 RX R2NH RX R3N RX R4N X
+
The primary amine thus obtained behaves as a nucleophile and can further react with alkyl halide to form secondary and tertiary amines, and finally quaternary ammonium salt.
NH3
xx
Primary amine is obtained as a major product by taking large excess of ammonia. The order of reactivity of halides with amines is RI > RBr > RCl
NH 3 X
NaOH
NH2
H2O
NaX
Page - 1
Class-XII
Amines
Properties
R NH2
HX
NaOH
NH2
H2O
+
NH2
NaX
NH2
NH 3 Cl Anilinium chloride
NaOH
H2O
NaCl
[2] Alkylation
R NH2 RX R2NH RX R3N RX
+
R4N X
[3] Acylation The replacement of hydrogen atom of -NH 2 group by acyl group is known as acylation.
O H3C C Cl H O C2H5 Base H3C C H N C2H5
N-Ethylethanamide
O C2H5 N C2H5 O H3C C H N
The base stronger than amine, like pyridine is used to removes HCl so formed.
O H3C C Cl C2H5
+
O C
C 2H 5 H
Base
H3C
Ethanoyl chloride
O H3C C O CH3
N,N-Diethylethanamide
Aniline
H
N-Phenylethanamide [ acetanilide ]
O H C N CH3 N- methylbenzamide
CH 3
Methanamine
CHCl
3 KOH
Heat
NC
3 H 2O
3 KCl
NH2
CHCl
3 KOH
Heat
NC
3 H 2O
Primary amine
[5] Reaction with Nitrous acid [ Nitrous acid is prepared in situ from mineral acid and sodium nitrite.] H2O NaNO 2 + HCl + R NH2
3 KCl
HNO 2
N2 Cl
OH
Alcohol
N2
HCl
HNO 2
NaNO 2 + HCl
N2 Cl
NaCl
H2O
Page - 2
Class-XII
Amines
[6] Reaction with Hinsberg's reagent Benzenesulphonyl chloride is known as Hinsberg's reagent.
O O R N H S O
Cl
S O
KOH
K
R
O S O
amine
N R
Cl
S O O
2o amine
R N R
N,N-Dialkylbenzenesulphonamide
S
Cl
No reaction
3o amine
K
R
+
O S O
HCl
N H
S O
H2O KOH
N H
Cl
S O O
1o amine
H2O KOH R N H
O R N R S O
Cl
S O
amine
NH2 Br
These days benzenesulphonyl chloride is replaced by p-toluenesulphonyl chloride. [7] Electrophilic substitution
Br 2 / H 2O Br
+
NO 2 ( 51 % ) ( 47 % )
+
NO 2 (2%)
Aniline
+
NH2
NH 3
Aniliniumhydrogensulphate
SO 3H Sulphanilic acid
SO 3 Zw itter ion
Page - 3
Class-XII
NH2
Amines
O
xx
Controlled Bromination
H ( CH 3CO ) 2O Pyridine
N-Phenylethanamide ( Acetanilide )
Br
Br
Controlled Nitration
NH2 ( CH 3CO ) 2O Pyridine
xx
O C CH3
NH2
+
OH / H
NO 2
NO 2
The lone pair of electrons on nitrogen is less available for donation to benzene ring by resonance. Therefore, activating effect of -NHCOCH3 group is less than that of amino group. Aniline and other aryl amines are colourless but get coloured on storage due to atmospheric oxidation. Alcohols are more soluble than amine in water because, alcohols are more polar than amines and form strong intermolecular hydrogen bonds than amine. The intermolecular association is more in primary amine than in secondary amines as there are two hydrogen atoms avilable for hydrogen bond formation in primary. Tertiary amines do not have intermolecular association due to absence of hydrogen atom available for hydrogen bond formation. Therefore, the order of boiling points of isomeric amines : Primary > Secondary > Tertiary The basicity of amines in gaseous phase : 3o amine > 2o amine >1o amine > NH3
H
xx
Explanations
[ Base ]
[ Conjugate acid ]
R R HN
+
The stability of substituted ammonium ion: The positive charge get neutralised by the +I effect of alkyl groups.
NH 2 R
NH 3
NH 4
In aqueous phase the stability of substituted ammonium cation depend upon both the +I effect of alkyl group and solvation by water molecules. The greater the size of the ion lesser will be the solvation and less stabilised is the ion. So the basicity of methyl substituted amines in aqueous phase: When alkyl group is bigger methyl group, there will be steric hindrance to H-bonding with water, so the stability of substituted ammonium ion decreases. So the basicity of ethyl substituted amines in aqueous phase:
H3C NH
CH3 H3C NH2 H3C N CH3 NH3
2o
CH3
1o
C2 H 5
3o
H5C2 NH
H 5 C2 N
H5C2 NH2
NH3
2o
C2 H5
3o C 2 H 5
1o
Page - 4
Class-XII
Amines
Aniline does not undergo Friedel-Crafts reaction (alkylation / acetylation) due to salt formation with aluminium chloride, the Lewis acid, which is used as a catalyst.Due to this , nitrogen of aniline acquires positive charge and hence acts as a strong deactivating group for further reaction. Besides the ortho and para derivatives, significant amount of meta derivative is also formed during nitration of aniline.Because, in the presence of mineral acids,the aniline readily forms anilinium ions. The anilinium ion is a strong electron withdrawing group, which directs the electrophile towards meta position. + NH2 NH 3 NO 3 NH2 Ring deactivator
HNO 3 NO 2
Aniline is less basic than ammonia, because the availability of electron on nitrogen atom of aniline decreases due to delocalisation of electron by resonance In case of aliphatic amine due to +I effect of alkyl group, the xx R > NH2 electron density on nitrogen atom increases, as a result basic Aliphatic amine strength increases.
xx
NH2 Aniline
Amines are less acidic than alcohols, because N-H bond is less polar than O-H bond. Therefore, amine releases H+ ion with more difficulty. Aromatic amines are insoluble in water because, the phenyl group is bulky in size and has -I effect. As a result, its hydrogen bonding with water is negligible. Methylamine forms a soluble hydroxide on reacting with water. The OH- ions released by the hydroxide combine with Fe3+ ions of ferric chloride to give ferric hydroxide or hydrated ferric oxide which is brown in colour.
H3C 2 Fe
3+
xx
NH2
+
6 OH
OH 2 Fe(OH)
H3C
3
NH 3
OH
or Fe 2O 3. 3H2O
( Brown ppt )
Basicity of
NH2 NH2 NH2 NO 2
NO 2 m-Nitroaniline
Incase of aromatic amines, the basicity depends upon: [i] Inductive effect o- > m- > p[ii] Resonance effect, observed at o- & p- positions.
NO 2 p- Nitroaniline
o-Nitroaniline
The electron withdrawing substituents on aromatic ring reduce the basicity of substituted anilines. The -R effect of nitro group is observed maximum at ortho and para positions.Thus, m-nitroaniline is relatively more basic compared to ortho and para isomers as it withdraws electrons through inductive effect(-I effect) only. Out of o-nitroaniline and p-nitroaniline, -I effect is found to be stronger in ortho isomers as compared to para. Thus,o-nitroaniline experiences a strong -R and -I effect and is least basic. So PKb of o-nitroaniline > p-nitroaniline > m-nitroaniline
Page - 5
Class-XII
Amines
Benzenediazonium Chloride
+ N2 Cl + NaCl Diazotisation Benzenediazonium chloride Benzenediazonium chloride is stable due to resonance.
NH2
HNO 2
NaNO 2 + HCl
H2O
Diazonium ion being a weak electrophile,can couple with a strongly activated aromatic system.
+ +
N2
+ +
H3PO 3
+ +
HCl
N2
CH 3CHO
HCl
OH
CuCl / HCl
Cl
+ + +
N2
CuBr / HBr
Br
N2
OH H
+
CuCN / KCN
CN
N2
N Cl Cu / HCl Cl
+ +
N2
+ + + +
CuCl
-+
In strongly alkaline medium, the concentration of diazonium ion ( act as electrophile ) decreases and coupling reaction does not occur.
N N
O Na
KI
N2
KCl
HBF 4
NaOH
N2 BF 4
N2
BF 3
OH N N
H2O
OH
N2
HCl
HBF 4
NaOH
N2 BF 4
NaNO 2 Cu
NO 2
+ N2 + NaBF 4
N N
+
OH
HO
OH
( Orange dye )
Coupling reaction
H NH2 N N NH2
( Yellow dye )
HO
Coupling reaction
p-Aminoazobenzene
Page - 6
Class-XII
Amines
+
-
CHCl
alc. KOH
? ? ? ? ? ? ? ? ?
PhNH 2 Et 2 NH H3C
Br Br
NC
3 KCl
+ 3 H 2O +
HCl
N2 Cl
+ +
H3PO 2
H2O
+ N2 +
HO 3S
H3PO 3
NH2
Conc. H 2SO 4
NH2
N2 Cl
C2H5OH
N2
Br
CH 3CHO
HCl
NH2
aq. Br 2
NH2
3 HBr
O NH C CH3
NH2
+
-
( CH 3CO) 2O
+ CH 3COOH +
N2 Cl
NO 2
/ Cu
+
+
NaBF 4
N2
H3C
CH 2 CH 2 NH2 CH3
+ +
HCl
CH 2 CH 2 NH 3 CH3
Cl
H3C
CH3
HCl
H3C
NH Cl
CH3
PKb value Basic strength Basic strength Basic strength in gaseous phase Boiling point Solubility Basic strength +
N
+
> PhNHCH
> Et NH 2 > Et 2 NH
2
> PhNH 2
p-Toluidine > Et 3N Et OH Et NH
2
> p-Nitroaniline
2
> >
Et 2 NH > Et NH Et NH
2
> NH3
> Et 2 NH
Et NH
2
Et 2 NH >
+
> PhNH 2
N
+
Page - 7
Class-XII
Amines
Page - 8
Class-XII
Amines
Page - 9