*

Unit 27

Questions 83-86
Chemists sometimes represent three-dimensional tetrahedral structures (Figure l(a)) with two-dimensional
diagrams called Fischer projections (Figure l(b)). By convention, the vertical lines represent bonds going into the
page and the horizontal lines represent bonds coming out of the page.

w x

w Y
u x
Y

1
\

(a) (b)

Figure 1

To determine if two Fischer projections are superimposable, one can be rotated and compared to the other. Two
types of rotation that will retain the overall arrangement of the molecule are
.
the whole projection is rotated 180° and
one atom or group is fixed and the positions of the other three groups in the Fischer projection are rotated
(clockwise or antic lockwise).
A carbon atom bonded to four diflerent atoms or groups is called a chiral carbon. The arrangement of the atoms
or groups can be designated R or S according to the following rules. /

(i) The atoms bonded onto the chiral carbon are given a priority in the order of their atomic numbers; the higher
the atomic number, the higher the priority. (If two or more atoms bonded to the chiral carbon are identical,
priority is determined by referring to the next atom in each of the groups.)
(ii) The molecule is observed from the side opposite the atom or group with the lowest priority. If the order
of the other three atoms or groups in decreasing priorities is clockwise, the arrangement is designated R; if
anticlockwise, tiie arrangement is designated S.

'...'I;
y- 70
 83 For the compounds I, II, III and IV,

OH 0
CH

0
CH

0:
CH
3
OH
OH CH
3
I II Ill IV

those that have chiral carbons are

A I and II only. c II, III and TV only.
B I, III and IV only. D I, II, HI and FV.

f
84 Which one of the following correctly lists the groups or atoms in order of decreasing priority?
A -CH-CH2 > -C(CH3)3 C -CH2Br> -Br
B -OH > -CHO D -CHs > -NH2

85 Which one of the following statements is true about the Fischer projections of compounds I and II shown
below?

H CH2CH3
HtC
3 CH2CH3 HO H

OH CH
3

I I]
»

Compounds I and II
A are superimposable on each other.
B are mirror images of each other.
c are not related to each other.
D each have more than one chiral carbon.

86 Consider the Fischer projections of the following three compounds I, II, and III.

COOH CH
3 H

H CH
3 HO CH2CH3 HO CHO

Br H CH
3

I 11 Ill

The S configuration is found in

A I only. c Ill only.
B II only. D I and II only.

71
fl

Unit 14

Questions 40 and 41
When a carbon atom is covalently bonded to four different atoms or groups of atoms, it is possible for it to form
two structures that are non-superimposable mirror images. Such structures are called stereoisomers. One method
of representing three-dimensional images on a plane is as follows:
w w
W and X are in the plane,
c-
-^
Y is in front of the plane and ^
c
/
/
^ /.
Y
v Z is behind the plane
/
.^ ^
z z
x x
Y Y
Stmcture (i) and structure (ii) are mirror images
7 and cannot be superimposed onto each other.

Structure (i) Structure (ii)

t
1^

w x Y z

-c. ',
c~ -^
c c-
.^ ^

/
.\

/ s. ',
/ ^
/ .s

v v v v
s s. .^ ',
z 2 x
x Y z w w /

Y w x Y
Structure I Structure II Structure III Structure TV

Figure 1

40 The structure in Figure 1 that cannot be superimposed onto any of the others is
A structure I. c structure III.
B structure II, D structure IV

41 Consider the two organic compounds 2-butanol and 2,2-dichlorobutane.

Stercoisomers are possible for
A both 2-butanol and 2,2-dichlorobutane. f

B 2-butanol but not for 2,2-dichlorobutane,

C 2,2-dichlorobutane but not for 2-butanol.
D neither 2-bufanol nor 2,2-dicblorobutane.

34
f
Questions 92 - 94
Many naturally occurring compounds contain more than one of the same kind offLuictional group. For example,
monosaccharides such as glucose and fi-uctose have several hydroxy groups in each molecule. In general, each
hydroxy group is on a different carbon atom as two hydroxy groups on the same atom is unstable - a loss of water
from the two groups results in the formation of a carbonyl group. With other functional groups, this is not the case.
Chloroform, one of the first anaesthetics, has three chlorine atoms attached to the same carbon atom (CHC^) and
is very stable. Molecules that have different arrangements of the same atoms are called constitutional isomers.

92 What compound is the unstable 3,3-dihydroxypentane most likely to form?

A 2-pentanone
B 3-pentanone
c 3 -methyl-2-butanone
D 3-hydroxy-2-pentene

93 Consider the n-alkyldiols and n-dichloroalkanes; that is, the ^-alkanes that have two hydroxy groups or two
chlorines respectively.
Compared with the number of constitutional isomers of the n-alkyldiols, the number of constitutional isomers
of the Ti-dichloroalkanes is

A the same.
B twice as great.
c greater but less than twice as great.
D greater or fewer, depending on the size of the alkane.

94 How many stable constitutional isomers ofn-pentanediol, C5Hio(OH)2, are there?

A five
B SIX

c seven

D more than seven

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 Questions 59 - 62

An sp3 hybridised carbon atom that has four different groups attached to it has a tetrahedral stereocentre. This
means it can exist in two forms that cannot be superimposed onto each other. An example of a molecule with such
an atom is 2-butanol (CI^CHsCHOHCI^), which can have the two structures shown below.
CH.CH
2 3 CH.CH
2 3

c '» c .s.

."»
v""»
/ /
H v OH
H CH

CH
3 OH

If a molecule has n stereocentres, then it can have up to 2" different non-superimposable structures.

59 Cholesterol has the following structure.

CH
3 CH CH CH
'ss. 2 2 ^ 3
>' .s. ^ .s.
CH CH CH
CH 2
CH
2 CH CH
^ \ ^ \ 3
CH c CH
2
2
CH
CH \c CH
^
2 "s.
c
^ "^ CHCH
^ 2
CH,

CH c CH
^ .s. ^ ^ ^ 2
HO CH CH
2

How many stereocentres does cholesterol have?

A five c seven
B SIX D more than seven

60 Consider these three molecLtles:

the a-amino acid, alanine H2NCHCH3COOH

II the anti-arthritis drug, penicillamine CH3CCH3(SH)CHNH2COOH
m the anti-hypertensive agent, methyldopa (HO)2C6H3CH2CCH3CNH2)COOH

CH CH CH
3

NH
2 CH COOH CH
3
c CH - COOH HO 0 CH-,-
2 C - COOH

SH NH
2 HO NH
2

II Ill

Which of the following is true of I, II and III?

A All three molecules have one stereocentre each.
B Molecule I has one stereocentre but molecules II and HI have two each.
C Molecules I and H have one stereocentre each but molecule III has two.
D Molecule I has no sfereocentre, molecule II has one and molecule III has two.

t- r\ '\v-
'^.-^: 62
 Questions 61 and 62 refer to the following additional information:
The formula of2,4-dibromopentane is Ct^CHBrCHzCHBK^. As this molecule has different groups bonded to
two of its carbon atoms, it has two stereocentres and four possible structures, as shown below.

CH CH
3 CH
3 CH
3
H . Br Br H H Br Br H
<c ^ T
<c »
Vc T
<c > T

a .
. .
a

CH
2 CH
2 CH CH
2 2
» V

c c c c
H
. ^ Br H
^ Br Br
^ H Br
^ H
CH CH
3 CH CH
3 3

Inspection shows that while the middle two structures cannot be superimposed on each other or on the
first structure, the fourth structure rotated 180° is the same as the first. This type of structure is called a meso form.

61 Of the compounds 2,3-dibromobutane and 2,3-dibromopentane

A both have a mesa form.
B 2,3-dibromobutane has a meso form but 2,3-dibromopentane does not.
c 2,3-dibromopentane has a meso form but 2,3-dibromobutane does not.
D neither has a meso form.

62 For a molecule to have a me^o form, it must have a carbon chain that has
A an odd number of carbon atoms in the chain.
B an even number of carbon atoms in the chain.
c a plane of symmetry perpendicular to the chain.
D the same three different groups on the two carbon atoms at the end of the chain.

63
 Questions 18 - 23
In 1825,thefonnulaofbenzenewasdetennmedtobeC6H6. Four early ideas for benzene's structure are shown in
the figure below.

@
^. -/'
H
H c c
y
H\ /
H
H\
/
c \ -/
c c c
/ \ c \
H-C C-H C-CH^ // c c~^ CH3-C=C-C CH
3
\ / c / H \ / ..H-
c c / c \ c
/ \ H
H H H H

Structure I Structure II Structure III Structure TV

One way of determining which one, if any, of these four possible structures is the actual structure for benzene was
by establishing the number of isomers that are produced by a substitution reaction. For example, there are just two
possible isomers for a monosubstituted product of structure I, depending on whether the hydrogen atom that is
replaced is attached to a carbon atom that has only single bonds or a carbon atom that has a double bond. ^

If two or more of the structures produce the same number ofmonosubstituted isomers, the number ofdisubstituted
isomers or trisubstituted isomers may need to be determined.

18 Consider structures II and HI.

How many different monosubstituted isomers can be produced from them'; t?

A one for each of structures II and III

B two for each of structures II and III
c three for structure II and one for structure ID
D three for structure II and two for structure III

19 How many different disubstituted isomers can be produced from structure I?

A two
B three
c four
D SIX

20 If it was found that just one monosubstituted isomer and just two disubstituted isomers could be prepared
from benzene, this would be consistent with benzene having
A structure H only.
B structure III only.
c structure IV only.
D either structure III or structure IV.

--
.</?.;
44
 21 Consider these four trisubstituted isomers of structure HI with the formula 6113X3.

^ H x x x x x H
\
"c ^
/
\
c cf c c" c c
\ x-/ \u/ \J
H/
y \
x
/.
/
c c c c
c c,\ /
c c,\ c ;c \ c c\
H
/
\ / x x \ / H H \
/

./ H H
/
\ / H
c c c c
x H x x

Structure V Structire VI Structure VH Structure VIII

Which one of the following is correct?

A Structures V, VI and VII are equivalent but struchire VID is different.
B Structures V, VI and VIII are equivalent but structure VII is different.
c Structures VI and VIII are the same but structure V and structure VII are different to the other two
and to each other.
D AH four structures are different to each other.

22 How many different tri substituted isomers can be produced from structure IV;
A one

B two
c three
D four

23 Stereoisomers are molecules that are mirror images of each other but that cannot be superimposed onto each
other. Consider disubstituted molecules of structures II and III.
.;
Stereoisomers would be possible for disubstituted molecules of
A structure D but not structure III.
B structure III but not structure II.
c neither structure II nor structure III.
D both structire II and structure III.

45