H2 Chemistry 2010/11: Tutorial 18 Suggested Solutions Nitro Cpds

Discussion Questions
Question 1
(a)

O2N

NH 2

(b)

CH2NH2

(c)

NH CH3

(d)

NHCOCH3

(e)

NH2

Expected order of increasing basic strength: (d) < (a) < (e) < (b) < (c).
The basic strength of each given compound depends on the availability of the lone pair of electrons on
the nitrogen atom to form a dative covalent bond with a proton. The greater this availability, the greater
the basic strength of the compound.
(d) is an amide and is the least basic (effectively neutral) because its lone pair of electrons on the
nitrogen atom not only partially delocalises into the benzene ring but also interacts with the pi-electron
cloud of the C=O bond. As such, this lone pair is the least available for co-ordination to a proton.
The aromatic amines, (a) and (e), are less basic than the aliphatic amines, (b) and (c), because of the
partial delocalisation of the lone pair of electrons on the nitrogen atom into the benzene ring.
(a) is less basic than (e) because the electron-withdrawing NO2 group increases the extent of this
delocalisation and hence further reduces the availability of the nitrogen lone pair for co-ordination to a
proton.
The aliphatic amines, (b) and (c), are stronger bases because the alkyl groups bonded to the nitrogen
atom are electron-releasing and this increases the electron density at the nitrogen atom, making the lone
pair of electrons on the nitrogen atom much more readily available for co-ordination to a proton.
(c) is a stronger base than (b) since there are two electron-releasing alkyl groups bonded to the nitrogen
atom in (c) compared to only one in (b).

Question 2
(a) CH3CH2Cl CH3CH2CH2NH2
alcoholic KCN
CH3 CH2

CH3 CH2

CN + Cl

CH3 CH2

Cl + -CN
reflux with heat
N + 4[H]

LiAlH4/ dry ether

H
CH3 CH2

N
H

(b) CH2=CH2 CH3CONHCH2CH2NHCOCH3

Synthesis of amine
Br

Br2/CCl4
H2 C

CH2 + Br2

H2 C

CH2

Br
Br
H2 C

CH2

NH2

excess NH3 in alchohol

+ 2NH3

heat in sealed tube

Br

H2 C

CH2

NH2

Synthesis of acyl chloride

-1-

+ 2 HBr

CH2 + H2O

H2 C

CH2

+ 2[O]

K2Cr2O7(aq)/
H2SO4(aq)

CH2

O
H3 C

heat

O
H3C

H3 C

2. Add H2O, warm

OH
H3 C

OH

1. cold conc. H2SO4

+ H2O

C
OH

pyridine
+ SOCl2

H3C

+ SO2 + HCl

OH

Cl

Synthesis of amide
NH2

CH2 + 2 H3 C

H2 C

H3 C

Cl

NH2

CH2 CH2 N

CH3 + 2 HCl

(c) CH3CONH2 CH3CONHCH2CH3

Synthesis of amine
O
H3 C

LiAlH4/dry ether
H3 C

NH2 + 4[H]

C NH2 + H2O
H2

Synthesis of acyl chloride

O
H3 C

NH2 + H+ + H2O

O
H3C

H2SO4 (aq)
H3 C

heat

OH + NH4+

PCl5

H3C

C OH + PCl5

Cl + POCl3 + HCl

Synthesis of amide
O

O
H3 C

Cl

H2 N

H3 C

C CH3
H2

H C COOH

+ HCl

C
N
H

C CH3
H2

(CH3CH2)2NH

(d) 3
Synthesis of acyl chloride

O
H3 C

H3 C

COOH + PCl5

Cl + POCl3 + HCl

Synthesis of amine
O

O
H3 C

O
H3 C

H3 C

Cl + NH3

+ 4[H]

NH2

LiAlH4/dry ether
heat

+ HCl

NH2

H
H3 C

NH2

+ H2O

Synthesis of amide
O

O
H3 C

Cl

H2 NCH2 CH3

H3 C

CH2 CH3 + HCl

O
H3 C

CH2 CH3 + 4[H]

CH2 CH3

(e)

LiAlH4 /dry ether

CH3 CH2

CHO

Chain extension
required.

CH2CH2NH2

-2-

LiAlH4
CHO + 2[H]

CH2OH

dry ether

PCl
PCL55
CH2 Cl + POCl3 + HCl

CH2OH + PCl5

alc. KCN
CH2 CN + KCl

CH2 Cl + KCN

reflux

LiAlH4
CH2 CN + 4[H]

CH2 CH2 NH2

dry ether

Br
Br

(f)

NH2
Br

Conc. H2SO4/
Conc HNO3
+ HNO3

NO2 + H2O

55 oC

Sn/conc. HCl

NO2 + 6[H]

NH2

reflux

Synthesis of
arylamine, MUST
use Sn reagent
with aryl nitro cpd

+ 2H2O

Br
NH2 + 3HBr

Br

NH2 + 3Br2(aq)

Br

NH2

(g)

CHCH
Br
(g)
3CH
2CH
3CH
2CH22Br

CH3CH2

C COOH
H

Br + OH-

CH3 CH2 CH2

O
CH3 CH2 C

OH + [O]
heat with
immediate distillation

OH

HCN/ trace KCN

+ HCN

CH3 CH2

Cl

PCl5
CN + PCl5

CH3 CH2

Cl
C
H

CN + POCl3 + HCl

CH3 CH2

CN

OH
C

+ H2 O
H

CH3 CH2

OH + Br

CH3 CH2 CH2

reflux
K2Cr2O7(aq)/
H2SO4(aq)

CH3 CH2 CH2

CH3 CH2 C

aq NaOH

NH2

ethanol
CN

+ NH3(excess)

CH3 CH2
heat in
sealed tube

C
H

-3-

CN + HCl

NH2
CH3 CH2

NH2

1. HCl(aq) reflux
CH3 CH2

+ 2H2O

CN

2. Neutralise

COOH + NH3

H
+ NH3

CH3 CH2

COO-

Note product is normally zwitterionic

Question 3
(a) phenylamine and (phenylmethyl)amine
Test: Add aqueous bromine to each of the two samples.
Observation: For phenylamine, there would be decolourisation of orange aqueous bromine and the
formation of a white ppt.

NH2

NH2

Br

Br

+ 3Br2(aq)

+ 3 HBr
Br (white ppt.)

Note: 3 moles of Br2 required!

Observation: For (phenylmethyl)amine, there would be no decolurisation of bromine nor formation of

white ppt.

CH2NH2

no reaction
electrophilic substitution
no decolourisation of bromine
no formation of white ppt.

Br2(aq)

(b)

CH3CH2CH2NH3 Cl and CH3CONH2

+

Reagents and conditions: At first, add NaOH(aq) and warm gently, test for any gas evolved with moist
red litmus paper
Observations: Compound which gives a vapour turning moist red litmus paper blue is ammonium salt.
+

CH3CH2CH2NH3 Cl

+ NaOH(aq) CH3CH2CH2NH2 + NaCl(aq) + H2O(l)

Follow up. Heat remaining unknown with NaOH(aq) in boiling water bath. Test for any gas evolved
with moist red litmus paper
Observations: Compound which gives a gas turning moist red litmus paper blue is amide
Amide is hydrolysed on heating, and yields ammonia gas.
-

CH3CONH2 + OH CH3COO + NH3(g)

(c)
(d)

H2N

COCH3

and

CH3CONH

Test: Add 2,4-dinitrophenylhydrazine to each of the two samples.

Observations: An orange ppt will be seen for

No orange ppt will be seen for

H2N

COCH3

CH3CONH

COCH
C O3 + H2N

H 3C

CH3

CH3
H2N

Alternative test can be

iodoform test.

N
H

NO2

H2 N C

H
NO2

-4-

N N

H
+ H2ONO2

H
N
N NO
2 +
O2N

H2O

NO2

Question 4
(a)
A

C
CH3

H
+

HOCH2

CO2CH2CH3

H3N

HO

CH CH2 N R
H

CO2CH2CH3

(b)
A

CO2H

H3N

CH3

NH3

HO2C

CH

CO2H

CH3CH2OH

No reaction.

OH

S
CH
+

C
CH

CH3
CH3
CO2H

H
+

(c)
A

CH3CH2OH

+ RCOOH

CH3 C N

CO2CH2CH3

C
O

No reaction.

CH3 C O CH2

O H
CH3 C O
O

O
O C

CH3

CH CH2 N C
R

CH3

Question 5
Observation
Deduction
A reflux with aq. NaOH gives Alkaline hydrolysis.
salt B and cpd C
A is a amide. B and C are salt of carboxylic acid and amine
respectively.
C: (Mr = 93) with aqueous
bromine gives D: C6H4Br3N
Electrophilic substitution
C has strongly activating group in the benzene ring.
Bromination without catalyst. C is phenylamine.
NH2

Mr = 93
Hence D is
Br
Br

NH2
Br

Since formula for A: C8H9NO

and C has 6 carbons, B therefore has 2 carbons
B is a sodium salt of ethanoate.
O
CH3 C
O-Na+

And hence A is phenylethanamide

O
N

CH3

-5-

E: isomer of A C8H9NO
Reflux E with NaOH(aq)
NH3 evolved, + salt F
F: refluxed with alkaline
KMnO4,
followed
by
acidification yields

Alkaline hydrolysis of primary amide in E to yield carboxylate

and NH3.

HOOC

H3 C

COOH

Oxidation of aryl side chains to COOH.

F is therefore disubstituted.
F is therefore :
COO-Na+
COONa+

Hence E is
O
C NH2

H3 C

G: isomer of A C8H9NO
G refluxed with aq NaOH
obtains alkaline vapour H
and salt I:C7H5O2Na

Hydrolysis of substituted amide (G) to yield amine (H) and

carboxylate (I)
I has 7 carbons, so H has only 1 carbon (G) has 8 carbons
total)

H C NH2
H is methanamine 3
I is a 7 carbon carboxylate, with a benzene ring, so it must
be sodium benzoate.
COONa+
COO-Na+
H reacts with CH3COCl to Reaction of amine H with acyl halide to give amide J
O
give J: C3H7NO
H3 C

J is

CH3

Therefore G is
H
C N CH3
O

-6-

Optional Question
H+/MnO4

CH3

COOH 1. Sn/c.HCl

heat

NO2

COOH

2. NaOH

NO2

F
oxidation of alkyl sidechain
of a benzene ring

NH2
E
reduction of NO2 in F to NH2 in E
B is also a 2 substituted phenylamine compound

Na2CO3

B: C9H9NO2

CO2 gas evolved => B has -COOH group

-gives zwitterions
=>contains COOH
and NH2 groups

Br2/H2O

C: C9H7Br4NO2
- from change in molecular formula
2 H atoms in B replaced by 2 Br atoms, 2 more Br atoms added
=> electrophilic substitution on phenylamine, with aq Br2
no catalyst required. disubstitution, confirms that 2 position
on phyneylamine
occupied
by side
chain;
on phenylamine
occupied
by side
chain;
substitution
at
4
and
6
positions.
substitution at 4 and 6 position

- has
which is also in E
index of unsaturation
is 6. since the benzene
ring and COOH account
for 5 units of unsaturation
a C=C may be in B

- 2 Br atoms added; electrophilic addition on C=C in sidechain

D: CC
BrNO
98H
8Br3NO
9H
3 3
- electrophilic substituition
substitution ofof22HHatoms
atoms ininBBtotogive
similar
-electrophilic
giveD D
similar
to formation
formation of
to
ofCC
- from change in molecular formula
addition of another Br and OH took place. Electrophilic addition
to C=C in B

H+/ MnO4
heat

E + 2 CO2
-B has alkyl side chain and NH2 group on a 1,2-disubstituted benzene ring similar to E
- Oxidative cleavage of C=C in B took place to give COO group in E
-B has a 3 carbon side chain (total 9 carbon atoms) with a C=C and a COOH group

H
C C COOH
H

Br
C

Br

Br

C
H

C
H

OH Br
COOH

Br

C
H

NH2

NH2

C
H

COOH

NH2

Br

Br

Oxidation of B to E
H
C C COOH
H

+ 5[O]

H+/ MnO4

NH2

COOH
+ 2CO2 + H2O
NH2

heat
E

B
Acid-carbonate neutralisation of B
H
C C COOH
H
+ 1/2Na2CO3
NH2

H
+

C C COO Na
H
+ 1/2CO2 + 1/2 H2O
NH2

-7-

Electrophilic substitution and addition of B to give C

H
Br
C C COOH
H
+ 3Br2(aq)
NH2

Br Br
C
H

C
H

COOH
+ 2HBr

NH2
Br

B
Electrophilic substitution and addition of B to give D
H
C C COOH
H
+ 3Br2(aq) + H2O
NH2
B

-8-

C
OH Br
Br

C
H
NH2
Br

C
H

COOH
+ 3HBr