Raffles Institution

Year 5 H2 Chemistry 2010

Tutorial 10 – Alkenes

Prepared by: Mrs Kwie Shiao Yin

Discussion Questions

1(a)
CH3
Br
Br

Br
H3C CH2Br

Observation: reddish-brown bromine is decolourised.

(b)
CH3
OH
Br

OH
H3C CH2Br
(MAJOR)

observation: orange bromine is decolorised.

Other products:

CH3 CH3
Br Br
Br OH

Br Br
H3C CH2Br H3C CH2OH

1
 (c)
CH3
Br
I

Br
H3 C CH2I
(MAJOR)

Other product:

CH3
I
Br

I
H3C CH2Br

(d)
CH3
OH
OH

OH
H3C CH2OH

observation: purple MnO4- decolorised, black ppt of MnO2 formed

(e)
C H3

O
COOH

+ C O2 + H 2O

H3C O

Observation:
purple MnO4- decolorised,
colorless odourless gas evolved (CO2) which formed a white precipitate with aq. Ca(OH)2

(f)

2
 CH3
OH

OH
H3C CH3
(MAJOR)

Other product:

CH3
OH

H3C CH2OH

2(a) CH3CH=CH2 + H2O → CH3CH(OH)CH3

Reagents & conditions:

Cold, concentrated H2SO4, followed by warming with H2O

(b) CH3CHClCH3 → CH3CH=CH2 + HCl

Reagents & conditions:

NaOH in ethanol, heat

CH3CH=CH2 + Br2 → CH3CHBrCH2Br

Reagents & conditions:

Br2 in CCl4

(c) CH3CH2CH2CH2OH → CH3CH2CH=CH2 + H2O

Reagents & conditions:

Excess concentrated H2SO4 at 170°C

CH3CH2CH=CH2 + H2O → CH3CH2CH(OH)CH3

Reagents & conditions:

Cold, concentrated H2SO4, followed by warming with H2O

3(a) Reagent: Br2 in CCl4

Condition: dark, room temperature

Bubble a sample of each gas through Br2 dissolved in CCl4.

When ethene is bubbled through Br2 dissolved in CCl4, brown Br2 is decolourised.
CCl4
CH2=CH2 + Br2 
dark
→ CH2BrCH2Br

3
 Brown Br2 does not decolourise when ethane is bubbled through it.

(b) Reagent: KMnO4(aq), H2SO4(aq)

Condition: heat

Bubble a sample of each gas into a mixture containing several drops of KMnO4(aq) dissolved
in excess sulfuric acid. Heat each resultant mixture.

When but-1-ene is heated with acidified KMnO4, the purple KMnO4 is decolourised and a
colourless gas (CO2), which forms a white precipitate when bubbled through Ca(OH)2(aq), is
evolved.
KMnO 4 (aq), H2 SO 4 (aq)
CH3CH2CH=CH2 + 5[O]  heat
→ CH3CH2COOH + CO2 + H2O

CO2 + Ca(OH)2 
→ CaCO3 + H2O

When but-2-ene is heated with acidified KMnO4, the purple KMnO4 is decolourised, but no gas
is evolved.
KMnO 4 (aq), H2SO4 (aq)
CH3CH=CHCH3 + 4[O]  heat
→ 2CH3COOH

4 (a) H H H H
C C H C
H H
C H
H C C H H
H H C C H
C C H
H H H H C H
H
cis-hex-3-ene C H trans-hex-3-ene
H H
(b) Type of reaction: electrophilic addition
Conditions: dark, room temperature
CH2CH3
CH3CH2 H H
δ+ δ– slow
C C Br Br H C C + Br –
+
H CH2CH3 Br CH2CH3

CH2CH3 CH2CH3 Br
H
H C C

Br



– fast
H C C H
+

Br CH2CH3 Br CH2CH3

(c) Regardless of whether cis-hex-3-ene or trans-hex-3-ene reacts with hydrogen bromide, the
carbocation intermediate formed is:
CH2CH3
H
H C C+


–



Br

CH2CH3

H 4
 As the positively charged carbon atom is sp2 hybridised, it is equally probable for the bromide
ion to attack either from the top of or below the trigonal plane containing the positively charged
carbon atom. This would lead to the formation of a pair of enantiomers in a 1 : 1 ratio.

Br Br

C* C*
H3CH2CH2C CH2CH2CH3
H H
H3CH2C CH2CH3

(d) CH3CH2COOH and HOOCCH2COOH

5 (a) The structural formulae and names of the hydrocarbons are:

H3C CH3 H3C H H CH2CH3

A: C C C C C: C C
H B: CH3
H H H H

cis-but-2-ene trans-but-2-ene but-1-ene

H CH3 CH3
D: C C E:
CH3 F:
H

2-methylpropene cyclobutane
methylcyclopropane

(b) H H H
Br H H H
G: H: H C C C H
H C C* C C H
H H
H O H H
H C H
H
H
1-bromobutan-2-ol 2-methylpropane

(c) A is polar (non-zero net dipole moment) while B is non-polar (zero net dipole moment). The
intermolecular forces between molecules of cis-but-2-ene (i.e. permanent dipole – permanent
dipole and instantaneous dipole – induced dipole interactions) are stronger than those
between molecules of trans-but-2-ene (only instantaneous dipole – induced dipole
interactions). Since boiling involves the overcoming of intermolecular forces, cis-but-2-ene has
a higher boiling point than trans-but-2-ene.

(d) KMnO 4 (aq), NaOH(aq)

A → heat
CH3COO–Na+

5
 KMnO 4 (aq), NaOH(aq)
B → heat
CH3COO–Na+
KMnO 4 (aq), NaOH(aq)
C → heat
CH3CH2COO–Na+
KMnO 4 (aq), NaOH(aq)
D → heat
CH3COCH3

6 Attack of the electrophilic carbocation by nucleophiles to give the products.

Aqueous bromine: Nucleophiles present are Br− and H2O. Hence products are 1,2-
dibromoethane and 2-bromoethanol.

Aqueous solution of bromine and sodium chloride: Nucleophiles present are Br−, H2O and Cl−.
Hence products are 1,2-dibromoethane, 2-bromoethanol and 1-bromo-2-chloroethane.
No 1,2-dichloroethane is formed as this would require an attack by chlorine to form the
chloronium ion intermediate in the slow step. The only available chlorine is in the form of Cl−
which is unable to act as an electrophile.

Optional Question

A:
acidified KMnO4 HOOC
heat COOH
hexa-1,5-diene butanedioic acid
10 [O]
2 CO2 2 H2O

B: B exhibits geometric isomerism

acidified KMnO4 HOOC COOH

heat
trans-hexa-1,5-diene
trans–hexa–1, 4–diene CH3CHOOH
CO2 H2 O

cis-hexa-1,5-diene
cis–hexa–1, 4–
diene

C: 3-methylcyclopentene (or any compound with ONE double bond, a ring and ONE chiral
centre)

CH3 H3C

3-methylcyclopentene

The starting sample was a racemic mixture (i.e. contained equal amount of each enantiomer)
⇒ upon oxidation, the chiral centre of the enantiomers remained intact!