Review questions Chap 17

17.1 (a) 1,1-difluoroethene

(b) 3-bromocyclopentene
(c) 1,6-dichlorohexane
(d) 2-chloro-5-methlyhexane
(e) dichlorodifluoromethane
(f) 3-bromo-3-ethylpentane

17.2 (a) (S)-2-bromobutane

(b) trans-1-bromo-4-methyl-cyclohexane
(c) 3-chlorocyclohexene
(d) (E)-1-chlorobut-2-ene
(e) (R)-2-bromo-2-chlorobutane
(f) meso-2,3-dibromobutane

17.3 (a)
Br

(b)
H Cl

(c)
H H
Br Br

(d)

Br

(e)
Cl
Cl

(f)
Br
17.4 (a) Cl

(b)
Br

(c)
I

(d) CH2Cl2
(e) CHCl3

(f)
Cl

(g)
Cl

17.5 2-Iodooctane and trans-1-chloro-4-methylcyclohexane are 2˚ haloalkanes.

(a) isobutyl chloride: 1˚ haloalkane

(b) 2-iodoctane: 2˚ haloalkane

(c) trans-1-chloro-4-methylcyclohexane: 2˚ haloalkane

17.6 (a)
(b)

3-chloro-1,1-dimethylcyclohexane

(c)

(d)
 1-bromo-2-cyclohexyl-2-methylpropane

1-bromo-4-tert-butylcyclohexane

1-bromo-3-tert-butylcyclohexane

1-bromo-2-tert-butylcyclohexane

17.7 (a) CH2Cl2

(b)

(c) CH3CH2OH

(d)

(e)
17.8 Alkyl groups decrease the polarity of solvents and therefore the order of increasing
polarity is: CH3CH2OH < CH3OH < H2O

17.9 The carbonyl group of acetone is a polar functional group, so acetone is the most polar of
the three. The oxygen atom of diethyl ether adds polarity to this solvent compared to the
hydrocarbon pentane. The order of increasing polarity is:
pentane < diethylether < acetone

17.10 (a) OH–

(b) OH–
(c) CH3S–

17.11 (a) True: both nucleophile and haloalkane are reacting in the rate-determining step.

(b) True: backside attack at the substitution centre results in inversion of

configuration.

(c) True: SN2 reactions result in an inversion of stereochemistry at the substitution

centre, therefore, optical activity is retained in the product. Therefore, the
product is optically active and rotates plane-polarised light to the same extent,
but in the opposite direction of the original.

(d) False: steric crowding influences the order of reactivity in SN2 reactions. As the
number of substituent groups on the substitution centre increases, the reaction
rate decreases. For SN2 reactions, the order of reactivity is: methyl > 1° > 2° > 3°.

(e) False: all nucleophiles are Lewis bases and therefore must have an unshared pair
of electrons. Moderate nucleophiles such as ammonia (NH3) react in SN2
reactions, even though they do not carry a negative charge.

(f) True: the nucleophile is involved in the rate-determining step; therefore, as

nucleophilic strength increases, the rate also increases.

17.12
Br
NaOCH2CH3
(a) + Na+Br-
CH3CH2OH
 NaOCH2CH3
(b) Cl + Na+Br-
CH3CH2OH

Major Minor
product product
Cl
NaOCH2CH3
(c) + Na+Br-
CH3CH2OH

Major Minor
product product

Br NaOCH2CH3
(d) + Na+Br-
CH3CH2OH
Major Minor
product product

17.13
Cl
-HCl
(a)
Major Zaitsev products: cis-trans isomers are possible

Br
-HBr
(b)
Major Zaitsev products: cis-trans isomers are possible

-HCl
(c) Cl No cis-trans isomers are possible

-HCl No cis-trans isomers are possible

(d) Cl

17.14

(a) CH2Br -HBr CH2

 CH3 CH3
-HBr
(b) CH3CHCH2CH2CH2Br CH3CHCH2CH=CH2

17.15 The carbocation that needs to be formed for an SN1 reaction mechanism is too unstable
for this to be a viable route to the product.

17.16 Potassium tert-butoxide is both a strong base and a hindered nucleophile. Consequently
H+ abstraction leading to alkene formation is favoured over substitution.

17.17 The major product is substitution to give 2-ethoxypropane. Elimination to give propene is
a minor side reaction.

17.18 The tertiary haloalkane, 2-bromo-2-methylpropane, is sterically hindered, but sodium

hydroxide is a strong nucleophile and a strong base. This combination leads primarily to E2
elimination to give the alkene. Steric hindrance favours abstraction as the nucleophile is unable to
form a new bond. The increased numbers of C-C bonds in tertiary alkanes such as 2-bromo-2-
methylpropane, favours alkene