UNIVERSITY OF ZAMBIA

CHEMISTRY DEPARTMENT

CHE 2522: FUNCTIONAL GROUP AND ARENE AROMATICITY

26th Oct 2020

Tutorial Questions on Amines, aromaticity and aromatic reactions

Instructions: Submit answers to the following questions as Assignment: 1(a),(b) & (g); 2(a), (b); 3
(a) & c (i & ii); 4 (a) (i- iii, v, & vii); 4(b)(ii); 4 (c) i & ii; 6b(1&4). These questions should not be
discussed in tutorial sessions

QUESTION ONE

(a) Rank the following compounds in order of increasing basicity.

(b) Devise at least three different methods to prepare N-methylbenzylamine (PhCH2NHCH3) from
benzene, any one-carbon organic compounds, and any required reagents.

(c) Provide the mechanism for the following reaction transformation

NH2 N2Cl
NaNO2/ HCl

(d) Can the amine shown below be prepared by a Gabriel Method or not? Briefly explain your
choice.

(e) What aldehyde or ketone and a nitrogen component are needed to synthesize N-
ethylcyclohexanamine by a reductive amination reaction?
(f) Draw the major product of the following reactions.

NH2 1 . CH3I (excess) N2Cl 1 . CuCN

? (ii) ?
(i) 2 . Ag2O, H2O 2 . LiAlH4
3. Cl 3 . H2O

(g) Devise a synthesis of each compound given below from benzene.

Cl Cl
HO OH
(i) (ii)

Cl

QUESTION TWO

(a) Write the structural formula for each of the following:

(i) m-xylene (vii) 1-chloro-2-(2chloropropyl)benzene

(ii) 3,5-dinitrobenzoic acid (viii) m-bromo-anisole
(iii) 2,4,6-trinitrophenol (ix) Benzyl alcohol
(iv) Chlorotriphenylmethane (x) 4-Phenyl-1-butene
(v) p-ethylaniline (xi) o- p Cresol
(vi) 4-n-butylbenzenesulfonic acid (xii) 2-Phenylethanol

(b) Which of the following molecules would you expect to be aromatic, anti-aromatic or non-aromatic?

CH2
+
(i) (iii) N (vi) (vii)
(ii) (iv) (v)

N N
H H
+ + (xii) (xiii) -
(viii) (ix) (x) (xi) (xiv)

N
O H
QUESTION THREE

(a) Which of the hydrogen atoms shown below is more acidic? Explain your answer.

Cl Cl Cl Cl

H H

A B

(b) Starting with benzene outline the synthesis of each of the following compounds:

(i) m-bromonitrobenzene (iv) p-nitrobenzoic acid

(ii) Ortho-chloronitrobenzene (v) m-toluidine
(iii) p-chlorobenzenesulfonic acid (vi) n-butylbenzene

(c) Provide a detailed mechanism for each of the following reactions. Include contributing
resonance structures and resonance hybrid for the arenium ion intermediate.

(i) HNO3 (ii) (iii) Br2

CH3CH2CH2Cl
? ? ?
H2SO4 FeBr3
AlCl3

QUESTION FOUR

(a) Predict the major product (or products) formed when each of the following reacts with Cl2 and
FeCl3:
(i) Tert-butyl benzene (v) Acetanilide
(ii) Phenol (vi) Benzonitrile
(iii) Iodobenzene (vii) Naphthalene
(iv) Aniline (viii) Trifluoromethylbenzene

(b) Predict the major product (or products) formed when each of the following reacts with HNO3
and H2SO4.

(i) Phenyl benzoate

(ii) Anisole
(iii)Toluene

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 (c) Write a mechanism to account for the products of the following reactions:
CH3 CH3

H3C
(i) H+ H3C

-H2O
OH

CH3
(ii) H2SO4
H3C
CH3

QUESTION FIVE

(a) 2-methylnaphthalene can be synthesized from toluene through the following sequence of
reactions. Write the structure of each intermediate:

O O O

Toluene NH2NH2, KOH SOCl2

+ A, C11H12O3 B, C11H14O2 C, C11H13ClO
AlCl3
heat

AlCl3 NaBH4 H2SO4

D, C11H12O E, C11H14O F, C11H12
heat

G, C11H12Br NaOEt
EtOH heat

(b) Label the following aromatic rings as activated or deactivated based on the substituent attached
to and state whether the group is an ortho-para director or meta director.

OMe O Cl
(i) (ii) (iii)

O
O O O
(iv) H
(v) N (vi) S
OMe OH
O

(c) Use the resonance theory to show how certain substituents are ortho- and para- directing, while
others are meta–directing. Use phenol as an example to explain, by writing the various
resonance forms of phenol as an activated benzene derivate (an electron rich ring).

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 (d) Carry out a similar analysis as in (b), use the resonance theory to show how certain substituents
are meta-directing. As an example, use the nitro group to explain, by writing the various
resonance forms of nitrobenzene as deactivated benzene derivate (an electron deficient ring).
(e) Explain why halogens although they are ring deactivating groups, they are ortho and para
directors.

QUESTION SIX

(a) Outline all steps in a reasonable mechanism for the formation of isopropylbenzene from
propene and benzene in liquid HF.

HF

0 oC

isopropylbenzene (84%)

(b) Outline the methods for the preparation of the following compounds in a reasonable pure state
and good yields from benzene by electrophilic aromatic substitution. Give the mechanism for
the production of these compounds:

O OH NH2
NH2
Br
NO2
Cl
CO2H
NO2
Cl
3 4
1 2