Organic Chemistry CHEM220 Test 2

Name: Prof. N.A. Koorbanally

Student Number/Barcode
Student Feedback and Solutions

GENERAL FEEDBACK

In general, it is quite evident that a number of students have not prepared well for the test.
This is quite surprising since the examination is only a week and a half away. I know that a
lot happens during this time of the year, but you will find it very difficult to pass the course if
you do not study the material. Remember that studying does not mean reading your work
just once. You need to go through the work in your notes, powerpoint presentations (if
applicable) and textbook and ensure that you understand the concepts. To test that you
understand the material, you should be able to work out the problems. Try and make little
notes and shortnotes, comparisons, tables and figures as you go along. These will be quite
useful when you are revising your work.

In the multiple choice question section, you have fell short in that you have not worked
through the question and then selected an answer. You may use the back or the sides of your
question paper to work through the answer before selecting the correct choice. In many
instances, this may mean scrutinising each of the alternatives. For definitions, look at each
definition and see whether it suits the term being tested. For determining the enantiomer or
the correct Fischer projection, this may mean working out the R and S configuration for each
of the structures in the alternatives. Note that in many cases, you cannot get these questions
right by just reading the alternatives and choosing the one which seems most correct to you.
You have to do some work. For the calculation and mechanistic based questions, work out
the answer or write down the mechanism and then choose the most suitable answer from the
alternatives provided.

Most of the questions in this test are very similar to the examples you have done in class and
in the tutorial. Your examination will be set along the same lines. You need to ensure that
you understand each example in your tutorial and in your notes in order to succeed in the
module.

You all have the ability to pass the module, so let's tackle the module head on and learn some
Organic Chemistry

Prof. N. Koorbanally
Module co-ordinator

PS Model Solutions are included below to show you how to work through problems and to
write good answers.
CHEM220 ORGANIC CHEMISTRY 2 TEST 2

QUESTION 1

Circle the correct entry for each of the following questions

1.1 Which of the following molecules below are chiral

a) CH2Cl2
b) CH3Cl
c) CH3CHClOH
d) CH3CH2OH

Here we need to look at each carbon atom in each molecule and see which among them have
a carbon that is bonded to four different groups. I have highlighted the correct answer and
the chiral carbon.

1.2 Stereoisomers which are not mirror images of each other are termed:

a) enantiomers
b) stereogenic
c) dextrorotatory
d) diastereomers

You can only answer this question by having a good grasp of all the definitions. As an
exercise, define each of the other terms a) through to c).

1.3 How many isomers will the following compound have?

CH2OH CH2OH

*
* Not a stereogenic centre

* since the two methyl

* groups are the same
HO HO

a) 4
b) 8
c) 16
d) 32

I have marked each of the sterogenic centres on the molecule. With 4 stereogenic centres,
you would get 24 = 16 isomers.

1.4 Choose the correct Fischer projection of the molecule drawn below:

H
Cl

H3C OH
You need to switch the H with the Cl to make the H face the back. Your highest priority will
be Cl followed by OH therefore the isomer is R (since you switched groups) and the
compound is S.
CHEM220 ORGANIC CHEMISTRY 2 TEST 2

a) Cl b) Cl c) H d) OH

H3C OH HO H HO CH3 H CH3

H CH3 Cl Cl

a) H on vertical axis. Cl to OH is clockwise therefore R.

b) H on horizontal axis. You must switch the configuration. Cl to OH is anticlockwise (S).
Switch therefore R.
c) H on vertical axis. Cl to OH is clockwise therefore R.
d) H on vertical axis. You must switch the configuration. Cl to OH is clockwise (R),
therefore on switching you get S.

NOTE: You may only bypass the lowest priority group.

The only option with an S configuration is d)

Answer d

1.5 Choose the enantiomer of the compound below from the list given:

NH2
CH2CH3
C
H3C OH

The lowest priority group is the methyl group. You will have to switch this with the ethyl
group in order for it to face the back. The highest priority is hydroxy followed by the amino
group. From OH to NH2 is anticlockwise therefore S for the enantiomer. The orginal
molecules since you swopped the groups around is R.

The molecule from those below that has a S configuration will be the correct answer.

a) b) c) d)
OH CH2CH3 NH2 NH2
CH3 CH3 CH3 CH3
C C C C
H3CH2C NH2 H 2N OH H3 CH2 C OH HO CH2CH3

In each of the four options, the lowest priority group (CH3) is facing away from you.
a) OH to NH2 is clockwise therefore R
b) OH to NH2 is clockwise therefore R
c) OH to NH2 is anticlockwise therefore S
d) OH to NH2 is clockwise therefore R

Answer: c
CHEM220 ORGANIC CHEMISTRY 2 TEST 2

1.6 Which of the following groups can be ranked as having the highest priority in
the Cahn-Ingold Prelog system?

a) CH2OH
b) CH2Cl
c) CHCl2
d) CHClOH

Tip: Identify all the atoms around the carbon. Then add up their atomic masses. The one
with the largest combined atomic masses will have the highest priority. All of the molecules
above have a H as one of its constituents. You can discard this. The remaining two positions
are occupied by either Cl or OH. Since Cl has a higher atomic mass than O, the one with 2
Cl atoms will have the highest priority.

1.7 Pure R-2-butanol has a specific rotation of +60º. How much of S-2-butanol will
be present in a 100 g mixture of R and S 2-butanol which has an optical rotation
of +12º.

a) 60 g
b) 40 g
c) 80 g
d) none of the above

Calculate the enantiomeric excess. Since the optical rotation is +, there must be an excess of
the R isomer. The enantiomeric excess (ee) is therefore calculated as 12/60 = 1/5 or 20%.
This means that 80% is a racemate. Since we are working with 100 g, this can convert nicely
in 80 g racemate of with 40 g is R and 40 g is S. The ee is 20 g R. You have 60 g of the R
isomer and 40 g of the S isomer. Therefore the answer is b.

1.8 Which term best describes the compounds below:

CH3 CH3 CH3 CH3

H 3C Cl Cl CH3 H 3C Cl Cl CH3

H 3C Cl Cl CH3 H 3C Cl Cl CH3

CH3 CH3 CH3 CH3

There is a plane of symmetry as indicated. Symmetrical molecules although possessing

carbons with chiral centres are not optically active and are termed meso compounds.

a) meso compound
b) diastereomers
c) erythro enantiomers
d) achiral

1.9 Which of the following are β–elimination reactions?

a) E1 and E2 reactions
CHEM220 ORGANIC CHEMISTRY 2 TEST 2

b) SN1 and SN2 reactions

c) Decarboxylation reactions
d) Claisen condensation

Here we are testing to see whether or not you know your reactions. The E stands for
elimination and S for substitution. Just by knowing this, you could identify a) as a possible
candidate and rule out b). A claisen condensation is an addition reaction where an enolate
ion adds to a ketone or aldehyde. So this is ruled out. The only other sort of elimination is the
decarboxylation where a molecule of CO2 is eliminated. This is not a β-elimination however.
Therefore the only viable option is a).

1.10 An SN2 reaction takes place with:

a) Retention of configuration
b) Inversion of configuration
c) Racemic mixture
d) Both inversion and retention of configuration

This question tests whether you know the details of the mechanisms you learnt. In an SN2
reaction, the transition state takes on a trigonal bipyramidal shape. Remember that there is no
intermediate in an SN2 reaction. If you look at the trigonal part of the transition state, these
are the bonds that are neither formed nor broken, but just move from one side to the other as
the incoming nucleophile approaches and as the leaving group departs. There is therefore
inversion of configuration.

Retention of configuration is possible where a carbocation intermediate forms for example in

a SN1 reaction. Here, inversion of configuration is also possible and both lead to a racemic
mixture. The other three options therefore all refer to SN1 reactions and not SN2 reactions.

1.11 Define the term ‘intermolecular reaction’:

a) This reaction takes place within a single bi-functional molecule

b) This reaction takes place between two molecules
c) This reaction takes place between kinetically compatible reactants
d) This reaction takes place within a single molecule with one functional group

Intermolecular means between two different molecules. This rules out a and d.
Intermolecular organic reactions have to do with functional groups, not kinetic compatibility.
Moreover, kinetics are measured when molecules react. Therefore c can be ruled out. Your
only and best option is b).

1.12 A solvent has a dielectric constant (ɛ) of 79. What is the solvent?

a) A polar protic solvent (e.g. H2O)

b) An aprotic solvent (e.g. Acetonitrile)
c) A aprotic polar solvent (e.g. DMSO)
d) A nonpolar solvent (e.g. Hexane)
CHEM220 ORGANIC CHEMISTRY 2 TEST 2

A larger ɛ indicates a more polar solvent and a smaller ɛ indicates a non-polar solvent. The
dielectric constant has nothing to do with protic or aprotic solvents.

QUESTION 2

Pure R-2-chlorobutane has a specific rotation of 55º. What would be the observed optical
rotation of a 25.0 g mixture where 5.0 g of the mixture is S-2-chlorobutane? (3)

Answer
If 5.0 g of the mixture is S, this means that 20 g of the mixture is R, 5.0 g of which is part of
the racemic mixture and the enantiomeric excess is 15.0 g/25.0 g = 60%.

Therefore the observed optical rotation would be 60% x 55º = 33º

QUESTION 3

Draw all the stereoisomers for the compound below using the Fischer projection and indicate
which are erythro, threo and enantiomers.

CH2OHCHBrCCH3BrCH2OH (4)

Answer:

CH2OH CH2OH CH2OH CH2OH

H3 C Br Br CH3 Br CH3 H3C Br

H Br Br H H Br Br H

CH2OH CH2OH CH2OH CH2OH

erythro enantiomers threo enantiomers

QUESTION 4

(2R,3S)-3-Phenyl-2-bromobutane undergoes E2 elimination when treated with potassium

tert-butoxide in tert-butanol. Answer the following questions regarding this reaction:

a) Write down the structures of the main products that form. (2)

Answer:
H3C H3C H Ph H
CH C CH2
H
Ph Ph CH3 H3C CH3

A B C
This is an example of a β-elimination reaction that was tested in the MCQ section.
Ordinarily the H with the most number of alkyl groups attached to the carbon to
CHEM220 ORGANIC CHEMISTRY 2 TEST 2

which it is bonded would be abstracted and product B would occur since the H would
orient itself an antiperiplanar position so that the electrons could overlap with the
vacant LUMO orbital. NOT IN THIS CASE. Since the base used to abstract the
proton is bulky, the proton that would be abstracted would be the one that is most
accessible since the tert-butoxide is a bulky base. This, the methyl proton would be
most accessible and product A would be the main product. This would be followed
by B and then C.

b) Write down an acceptable mechanism for the reaction for the formation of the
observed main product.

Answer:

Marks were awarded for the approach of the base and the correct use of arrows; for the
transition state and for the product. The same mechanism can be written with the base
abstracting a proton from the methyl group.