CHE1502/203/2/2018

Tutorial Letter 203/2/2018

General Chemistry 1B
CHE1502

Semester 2

Department of Chemistry

This tutorial letter contains the key to assignment 05.

BARCODE
 SECOND SEMESTER

KEY TO ASSIGNMENT 5

1. The Lewis structure for boric acid, B(OH)3:

B has 3 valence electrons; O has 6 valence electrons and H has 1 valence electron.

Formal Charge, FC, calculation:

FC = Group Number – no of lone pair of electrons – ½ (no of bonding electrons)

= 3 – 0 -½ (6) = 3 – 3 = 0

2. The resonance delocalization takes place as follows:

Note that electrons move from the electron rich pi bond to the electron deficient carbocation.

Guidelines for Drawing Resonance Structures:

1) Do not change the connection of atoms - leave the atoms in the structure exactly where
they are located.
2) Draw complete Lewis structures to start with – i.e. draw in all hydrogens and lone pairs of
electrons
3) ONLY the position of electrons change when drawing resonance structures
4) The electrons in π bonds or non-bonding (unshared) pairs can freely participate in
resonance. Therefore, anions and lone pairs of electrons on for example, nitrogen,
oxygen, halogens, etc. can participate in resonance.

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5) The total number of electrons does not change.

6) Obey the octet rule on any atom - do not exceed the octet rule.
7) The electrons move towards the positive atom.
8) Electrons can only move if the π bonds are conjugated and/ or if a charge (positive or
negative) is conjugated to π bond(s).
9) In the case of carbanions, the electrons move from the negative charge.

3. The movement of electron pairs in the reaction:

A Lewis base is a species that have a pair of electrons that can be donated to form a new bond.
A Lewis acid is a species that can accept a pair of electrons. Species having a positive charge
or an empty orbital are examples of Lewis acids. In the above example, the Lewis base is the
compound having the negatively charged N with lone pairs of electrons, which can be donated
to the Lewis acid (created when the C=O bond breaks). The curved arrow always starts at the
center/ atom that donates electrons and ends at the atom that accepts the electrons.

4. The structural formulas of the four structural (constitutional) isomers must all have a
molecular formula of C5H10 but the atoms must be connected differently. Possible structural
isomers with carbon-carbon double bonds:

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Possible isomers with cyclic structures:

Try to draw the other isomers not shown.

5. (a) Consider the compound with the proposed name:

The structure consistent with the proposed name, 2-methyl-1-1, dichloropent-3-yne is:

(b) The numbering is from the wrong side of the molecule. This is an alkyne and the
numbering should start at the end that would give the C≡C the lowest possible number.
Therefore, the parent name should be pent-2-yne and not pent-3-yne. The change in
numbering will change the location of the other substituents.
The substituents in the given name are not listed in alphabetical order. The ‘dichloro’ atoms
should be named before the methyl group. The 1-1,-dichloro is incorrect since there should be
commas and not a dash between two numbers i.e. 1,1.

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There is a comma between the 1 and ‘di’ it should be 1-dibromo. The methyl group is on C-4
and not on C-2 and should be 4-methyl not 2-methyl. The ending of the name should be ‘yne’
and not ‘yne)I’.

The correct IUPAC name for the compound is thus: 5,5-dichloro-4-methylpent-2-yne

6. The structures for MAJOR product of each reaction/ reaction sequence is shown below:

(a)

(b)

(c)

(d)
H

CH3
CH CH2OH
H
CH3
(e)

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(f)

(g)

(h)

7. The detailed reaction mechanism for the reactions shown in:

(i) Question 6(a)

Initiation:

Propagation:

First step:

The halogenation reaction of alkanes proceeds via a radical intermediate. The propagation step
shown above gives a radical intermediate. There are different possible radicals that can form in
the reaction which are shown below:

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The halogenation reaction of alkanes proceeds via a radical intermediate.

Some reaction with different types of carbon atoms in the alkane molecule,
can form more than one radical. Below is the ranking of the radicals in order
of INCREASING stability i.e. from the least stable to the most stable.

The tertiary carbon radical is the most stable radical and the primary radical is
the least stable.

The tertiary carbon radical is the most stable radical (has the lowest energy) and will produce
the major product in the second propagation step.
Second step:

There are also termination reactions in a halogenation reaction. Please consult the textbook on
how these steps are drawn.

(ii) Question 6(b)

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Water (H2O) is a poor nucleophile, which promotes nucleophilic substitution via an SN1 reaction
mechanism. This mechanism involves more than one step. The mechanism for the reaction of
2-bromobutane with water:
Firstly, carbocation formation:

The carbocation is planar and the nucleophile can attack from either side of the carbocation.

Secondly, we redraw the carbocation (in 3-D format) and show the nucleophile attacking from
the bottom:

The nucleophilic attack is followed by removal a proton from the oxonium ion by the bromide ion
to give the corresponding ether molecule, which has a (R)-configuration.

Similarly, the nucleophile attacking from the top is shown below. The above nucleophilic attack
from the top gives the (S)-isomer. [See question 9 below for an explanation on how to determine
the (R)- and (S)- configurations.

Methanol, CH3OH, reacts similar to water.

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(iii) Question 6(c)

Cyanide ion is a strong nucleophile and the reaction with the secondary alkyl halide proceed via
the SN2 reaction mechanism.

(iv) Question 6(e)

The reaction mechanism of the reaction of HBr with CH3CH=CH2 is:

The secondary carbocation is more stable and lower in energy than the primary carbocation and
the secondary carbocation will mostly form in the reaction.

(v) Question 6(g)

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(vi) Question 6(h)

The complete mechanism of the reaction above is:

8. The different Newman projections for the molecule, CH2ClCH2Br are:

9. (a) When the OH group is attached to a primary carbon i.e. the carbon is attached to
ONE other carbon. The alcohol below is therefore a primary alcohol.

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CH3

CH3 C CH2OH

CH3

IUPAC name: 2,2-Dimethylpropan-1-ol

When the OH group is attached to a secondary carbon i.e. the carbon is attached to TWO other
carbon atoms. The alcohol below is therefore a secondary alcohol.

CH3
CH OH

IUPAC name: 1-Phenylethanol

When the OH group is attached to a tertiary carbon i.e. the carbon is attached to THREE other
carbon atoms. The alcohol below is therefore a tertiary alcohol.

CH3

CH3CH2 C OH

CH3

IUPAC name: 2-Methylbutan-2-ol

(b) A chiral molecule must have a chiral center, i.e. a carbon containing four different groups
or atoms.

According to the Cahn-Ingold-Prelog rule, assigning priorities to the groups/atoms around the
chiral center:

Group Priority

Br 1

CH2CH3 2

CH3 3

H 4
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The 3-dimensional structures of the enantiomers of the above compound:

The enantiomers are:

(R)-2-bromobutane (S)-2-bromobutane

10. (a) The major organic product formed in the reaction is:

(b) The reaction proceeds via the following mechanism:

N.B. The mechanism above uses the ethoxide (CH3CH2O-) ion as base. The ethoxide ion reacts
in the same way as the methoxide (CH3O-) ion. Draw the same mechanism but change the
base.

This is an E2 elimination reaction because the base is a strong base. According to Zaitsev’s
rule, the product with the most substituted double bond will predominate. Therefore, the product
formed above is the major product.

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11. The correct name of the following compound according to the IUPAC rules is
5-ethyl-2,3-dimethylhept-6-enal

Explanation:

According to the IUPAC convention, the longest continuous carbon chain containing the
carbonyl group and the C=C has 7 C’s → heptane. The compound has a carbonyl group
characteristic of an aldehyde; begin numbering at the end of the C-chain of the C=O; so the
ending ‘ane’ changes to ‘al’ → heptanal. But there is a C=C bond in the chain at C-6 → change
the ‘an’ to ‘en’ → hept-6-enal or 6-heptenal. At each of C-2 and C-3, there is a CH3 group/
methyl group → two methyl’s: ‘di-methyl’ → 2,3-dimethyl and at C-5 there is an CH2CH3 group
i.e. ethyl group → 5-ethyl. Write the substituents in alphabetical order.

12. Correct Answer: (4)

The above does NOT represent keto-enol tautomerism.

A ketone or aldehyde can undergo keto-enol tautomerism if the carbon atom which is adjacent
to the carbonyl group has at least one H atom attached to it. In the compound above, there are
no H’s attached to the adjacent C (the α-carbon) – hence it will not exhibit keto-enol
tautomerism.

The other representations of keto-enol tautomerism are correct. In Option (1) the C=O of the
aldehyde [(C=O)H, CHO] group is more reactive than the C=O of the ketone group,
[C-(C=O)-C]. Hence, the keto-enol tautomerism of only the one C=O group. Redraw the
process to start with the ‘keto-form’.

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13. The correct name of the following compound according to the IUPAC rules is

(E)-4-ethyl-2,5-dimethylhept-4-enoic acid

Explanation:

According to the IUPAC convention, the longest continuous carbon chain has 7 C’s → heptane.
The compound has a carboxyl group, COOH at the end of the chain; so the ending ‘ane’
changes to ‘oic acid’. Start numbering from the carboxylic acid functional group and consider
the chain that contains the most substituents:

But there is a C=C bond in the chain at C-4 → change the ‘an’ to ‘en’ → 4-heptenoic acid. At
C-2 and C-5 there are methyl groups → 2,5-dimethyl; at C-4 is an ethyl group →4-ethyl. Name
the substituents in alphabetical order.

The Z/E nomenclature is used when the groups attached to the C=C are different. Assign
priority order to the groups attached to the each carbon of the C=C. Assign priority in terms of
atomic number of atom attached to C=C:

On C-4: -CH2CH3 and -CH2CHCOOH(CH3); -CH2CHCOOH(CH3) has higher priority

On C-5: -CH3 and -CH2CH3; -CH2CH3 has higher priority

The two priority groups are on the opposite sides of the C=C, therefore E - isomer.

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14. The nucleophilic -OH will attack the carbonyl carbon as follows:

15. (a) The IUPAC name of the compound below is: S-2-chlorobutane

(b) Because water is a weak nucleophile, the reaction will proceed via the S N1 mechanism.

The C-Cl bond breaks and the intermediate secondary carbocation is formed.

CH3CH2 CH3CH2
C Cl C

H H
CH3 CH3
planar structure

The secondary carbocation intermediate contains a C atom with an empty p orbital. The water
molecule can attack the carbocation intermediate on both lobes of the empty p orbital. [See 7(ii)
above for the illustration of the attack on the lobes.]

The attack occurs from both the top and bottom to give the products shown below. This is a
multistep process.

Attack from the top:

H H H
CH3CH2
O O
H2O
C H2 O
H CH3CH2 C CH3CH2 C
CH3
H CH3 H CH3
S-

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Attack from the bottom:

H CH3 CH3
H
CH3CH2 CH3CH2 C CH3CH2 C
C
O H2 O O
H H2 O
CH3 H H H
R-

CHECKLIST OF KEY CONCEPTS

 From a given structure of a conjugated species (carbocation or carbanion) you should be

able to draw the structures of the other possible resonance forms of that structure. Can
you also show the movement of electrons when one structure changes to another with
arrows?
 From the given molecular formula, can you draw the structures of compounds that are
constitutional / structural isomers? Can you also give the IUPAC names for the
structures that you have drawn?
 Can you draw the different Newman projections of the different conformations of
alkanes and halo alkanes (alkyl halides) from a given structural formula? Are you
also able to identify the most stable and least stable conformations amongst those
that you drew and label these conformations?
 Do you understand the halogenation reaction of alkanes to draw the structure of
the major product in the reaction?
 If you are given the structures of different compounds will you be able to identify the
molecule that contains a chiral or asymmetric carbon?
 If you are given the 3-dimensional structure of a chiral compound can you identify its
correct IUPAC name according to the Cahn-Ingold-Prelog rules (R- or S-)?
 If you are given the structural formula of a substituted alkene, can you draw the
geometric isomer (E- and Z-) and name the compound according to the IUPAC
nomenclature rules?
 If you are given the IUPAC name of an alkene (a diene), can you identify the correct
structure?

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 Can you identify the correct mechanistic step in a hydration reaction of a given alkene
molecule?
 From the structure of a given alkene reacting with a symmetrical reagent such as a
halogen, can you propose the mechanism of the formation of the major product(s) of the
reaction? Can you identify the stereochemistry of the product in such a reaction and
name the product (according to the IUPAC and Cahn-Ingold Prelog rules?
 If you are given the reaction of a given alkene with a hydrogen halide, can you draw the
mechanism for the reaction? Are you able to use curved arrows to show how the
electrons move?
 Will you be able to identify the major product that will form in the reaction of a given
alkene with a hydrogen halide in the presence of peroxides?
 Can you identify the structure of the major product formed in a hydration reaction of a
given alkene molecule? (for example, oxymercuration - demercuration)

 In a given reaction of a terminal alkyne with strong base and the subsequent reaction
with an alkyl halide (i.e. the reaction with the acetylide ion that formed in the first
reaction), will you be able to identify the structure of the major product that will form in
each reaction? Can you determine whether or not a reaction will occur?
 Can you identify whether or not a alkyne will form in an elimination reaction of a halogen
substituted alkene?
 Can you draw the structure of carbonyl containing compounds and give their IUPAC
name – ketone/aldehyde/esters?
 Do you understand the concept of keto-enol tautomerism; can you illustrate the concept
with the correct representation and structures?
 Comparing the acidities of substituted carboxylic acids; from the given structures of
different compounds can you identify the weakest / strongest acid?

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