Raffles Institution (Junior College)

H2 Chemistry 2010/11
Tutorial 18 Organic Nitrogen Compounds

Self-Check Questions
1.

Place the following compounds in the expected order of increasing boiling point.
Give reasons for your answer.
(a)
(b)

2.

CH3CH2CH2NH2
CH3CH2CH2CH3

(c)
(d)

CH3CH2CH2OH
CH3CH2NHCH3

(e)

(CH3)3N

(a) Explain why phenylalanine although only slightly soluble in water, dissolves readily in
aqueous acid and aqueous alkali.
(b) To which electrode in an electrolytic cell would you expect the ions of phenylalanine to
migrate in a solution of (i) pH = 1 and (ii) pH = 13?
(c) In a solution of pH range 6-8, there is very little movement of phenylalanine towards the
electrodes. What do you think is the nature of the species present in the solution at this
pH?

Discussion Questions
1.

Place the following compounds in the expected order of increasing basic strength.
Give reasons for your answer.
(a)

O2N

(b)

2.

NH 2

CH2NH2

(c)

NH CH3

(d)

NHCOCH3

(e)

NH2

Suggest the reagents and conditions required to carry out the following conversions.
Write balanced equations for each step carried out.
(a)

CH3CH2Cl CH3CH2CH2NH2

(b)

CH2=CH2 CH3CONHCH2CH2NHCOCH3

(c)

CH3CONH2 CH3CONHCH2CH3

(d)

H3C COOH

(CH3CH2)2NH

(e)
(e)

CHO

CH2CH2NH2

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Br

(f)
Br

(f)

NH2
Br

(g)

(g)CHCH
3CH
2CH2Br
3CH2CH2Br

NH2
CH3CH2

C COOH
H

3.

Suggest simple chemical tests which can be carried out to distinguish between the
members of the following groups of compounds. Write relevant equations for any reactions
which occur.
(a) phenylamine and (phenylmethyl)amine
(b) CH3CH2CH2NH3+Cl and CH3CONH2
(c)(d) H N
2

COCH3

and

CH3CONH
HOCH2

4.

CO2CH2CH3

H2N

HO

OH
CH CH2 NH R

Salbutamol (R = an alkyl group)

benzocaine

CH3

D
R

C
CO2CH2CH3

S
NH

CH

CH

CH

CH3
CH3
CO2H

O
penicillin (R = an aryl grouo)

pethidine

Write down the structural formula(e) of the organic product(s) obtained when
(a) A, B, C and D are each treated with dilute hydrochloric acid at room temperature,
(b) A, B and D are each heated with dilute hydrochloric acid,
(c) A, B and C are each treated with ethanoyl chloride.

5.

A neutral compound A, C8H9NO, on refluxing with concentrated aqueous sodium hydroxide

gives a solution of salt, B and a compound C (Mr = 93). With aqueous bromine, C forms a
white precipitate D, C6H4Br3N.
E is an isomer of A. On refluxing E with aqueous sodium hydroxide, ammonia gas is
evolved and a salt F can be isolated from the reaction mixture. When F is refluxed with
alkaline potassium manganate(VII) solution and the resulting mixture subsequently
acidified, benzene-1,4-dicarboxylic acid is obtained.
G is another isomer of A. On refluxing G with aqueous sodium hydroxide, an alkaline
vapour, H, is obtained together with a salt solution I, C7H5O2Na. H reacts with ethanoyl
chloride to form J, C3H7NO.
Identify the compounds A to J with giving your reasons, and explaining all reactions using
balanced equations.

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Optional Question
This question is about compound B, C9H9NO2, which forms zwitterions in aqueous solution
and conducts electricity when a potential difference is applied across an aqueous solution
of B at pH = 3.
- On warming B with aqueous Na2CO3, a colourless gas which gave white precipitate with
Ca(OH)2 is evolved.
- With bromine water, B gives white precipitate, C, C9H7Br4NO2 and D, C9H6Br3NO3.
- Treatment of 1 mole of B with hot acidified potassium permanganate gives a colourless
solution and 2 moles of carbon dioxide gas. Controlled neutralization of the colourless
solution gives a white precipitate, E, C7H7O2N.
Compound E, dissolves in both NaOH(aq) and HCl (aq). Compound E can also be
synthesized as indicated in the following sequence.
CH3

(i) Sn(s)/conc. HCl, reflux

H+(aq)/MnO4F

NO2

heat

E
(ii) controlled addition of NaOH(aq)

Deduce the structures of compounds B to F. Explain the chemistry of the reactions

described, with the aid of equations where appropriate.

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Self-Check Answers
1.

(a)
(b)

CH3CH2CH2NH2
CH3CH2CH2CH3

(c)
(d)

CH3CH2CH2OH
CH3CH2NHCH3

(e)

(CH3)3N

Expected order of increasing boiling point: (b) < (e) < (d) < (a) < (c).
The 5 compounds have approximately the same Mr.
(b) has the lowest b.p.. As the molecules are essentially non-polar, only id-id interactions exist between
them.
For (e), the molecules are polar and pd-pd interactions exist between them (no H-bonding because of
absence of N-H group).
For (d), the molecules can interact with each other through hydrogen bonding which is stronger than the
van der Waals forces of attraction in (b) and (e).
Hydrogen bonding between molecules of (a) is more extensive compared to that for (d) because the lone
pair of electrons on the secondary amine is more sterically hindered for the formation of the H-bond.

(c) has the highest b.p. because the molecules can interact with each other through OH ----O hydrogen
bonding. This type of hydrogen bond is stronger than the NH ----N hydrogen bond since the OH bond is
more polar (due to the more electronegative oxygen atom compared to the nitrogen atom) than the NH
bond.
2 (a)Phenylalanine is only slightly soluble in water because it contains the benzene ring which is
hydrophobic.

OH- (aq)

CH2
III

H3N CH COO-

H2N CH COO -

H3N CH COOH
H+ (aq)

CH2
I

CH2
II

In aqueous acids and alkalis, phenylalanine exists as a cation (II) and an anion (III) respectively.
In each case, a charged species is formed which can be more easily solvated by water molecules
and thus solubility is enhanced.
(b) (i) At pH=1, phenylalanine exists as cations and hence would migrate to the cathode (i.e. the
negatively charged electrode).
(ii) At pH=13, phenylalanine exists as anions and hence would migrate to the anode (i.e. the
positively charged electrode).
(c) At pH 6-8, phenylalanine exists predominantly as zwitterions. Such species possess no net
charge (i.e. electrically neutral) and hence exhibits little movement towards the electrodes.

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