Fundamentals of Organic Chemistry (CHEM 231)

Assignment 2 Key

Q1. Daniyal is student of CHEM-231 at SBASSE, LUMS. He is interested in knowing the effect
of resonance on the stability of conjugate base of an acid. He reads some books and articles to
understand the concept and concludes with writing following two points in his notes:

I. Resonance increases the delocalization of negative charge, and hence increases the
stability of conjugate base. Thus, when any acid deprotonates to form a conjugate base,
and resonance is possible in that conjugate base (making it stable)- it implies that the
acid forming this conjugate base was strong.

II. The greater the resonance, the higher would be the stability of conjugate base. Acetic
acid deprotonates to form acetate ion as a conjugate base which has two resonance
structures; On the other hand, phenol deprotonates to form phenoxide ion as a conjugate
base and it has 5 resonance structures- making it very stable. Since conjugate base of
phenol has higher number of resonance structures (5) while the conjugate base of acetic
acid has only 2 resonance structures, it indicates that conjugate base of phenol is more
stable (owing to higher number of resonance structures). Thus Phenol is a stronger acid
as compared to carboxylic acid.

Keeping in mind the above mentioned scenario, please answer the following questions:

A. Write down reaction equation to show deprotonation (loss of H +) and formation of

(2)

B. Draw possible resonance structures of phenoxide and acetate ions.

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 (2) Do you agree with Haider Iqbal’s point of view mentioned in point II? Please give
justification to support or negate his understanding that phenol is a stronger acid than acetic acid.
(4)

No, I don’t agree. Haider’s Iqbal point of view of phenol being a stronger acid than acetic acid
is incorrect, as carboxylic acids are stronger acids than phenol. The reason for this is that Haider
is only considering one factor while drawing his conclusion, that is number of resonance
structures. A factor to consider which is in acetate ion, the negative charge is on oxygen which is
on more electronegative atom than carbon, so the negative charge is stabilized. On the other
hand, in phenoxide ion the negative charge is on carbon in 3 of 5 resonance structures which is
on less electronegative atom. Hence the conjugate base of acetic acid is more stabilized than
phenol, so acetic acid is stronger acid.

Q2. Draw the resonance contributors for each of the following species and rank them in order of
decreasing contribution to the hybrid. Also draw the structure of hybrid in each case. (10)

Resonance contributor i contributes more to the hybrid because of tertiarycarbocation.

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Resonance contributor (i) has greater contribution because it has no formal charge.

Resonance contributor (ii) will contribute more to the resonance hybrid because –ve charge is on
more electronegative atom.

Resonance contributor (ii) will contribute more to the hybrid because +ve formal charge is on
nitrogen that is more stable than the one having +ve charge on oxygen atom.

Resonance Contributor (i) is more stable and will contribute more to the hybrid because it has no
formal charge.

Q3. Which member of each pair is the stronger base and why? (3)

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Structure (i) is stronger base because lone pair is localized on the nitrogen atom so it has greater
ability to accept proton from other specie while in case of ii aniline lone pair is delocalized with
the pi system of benzene ring and thus decrease its strength to act as a base.

(ii) is stronger base because the lone pair on oxygen atom is localized making them more
available for donation. (Lewis base).

(ii) is stronger base because the negative formal charge on oxygen increase the energy of HOMO
of oxygen thus increasing its reactivity as compared to the neutral amine.

Q4. Draw the most stable conformation, its flipped form and the Newman projections of both the
conformations of the following compound while viewing through C1-C3. (4)

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Q5. Draw the Newman and Sawhorse projections of the molecule drawn below. (2)

Q6. For each of the following carbocation’s, determine if they can rearrange, and if so, draw the
rearranged carbocation with a proper curved arrow pushing. (8)

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Structure (b), (d), and (h) will not rearrange.
Q7. List the following species in order from the best nucleophile to the poorest nucleophile in an
aqueous solution. (2)

Q8. a) Rank the following series of molecules based on reactivity in an SN2 reaction
(NaI/acetone).

(1= fastest SN2, 4= slowest SN2) (2)

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b) Rank the following series of molecules based on reactivity in an SN1 reaction (EtOH/heat).

(1= fastest SN1, 4= slowest SN1) (2)

c) Rank the following series of molecules based on reactivity in an E2 reaction (NaO iPr/iPrOH),
and give a justification for the slowest E2 reaction. (1= fastest E2, 4= slowest E2) (4)

In case of structure 4 this would be the least reactive in E2 reaction because both leaving group
and adjacent methyl are on axial positions so, no anti periplaner proton is available.

Q9. For each of the following reactions, figure out the frontiers orbital interaction when
nucleophile attacks an electrophile and their type of interaction. Draw all the lone pairs and use
curved arrows to show how the nucleophile attacks the electrophiles and show the product of
these one step reactions.
(8)

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Q10. Predict which of the following two compounds will undergo an E2 reaction more rapidly
and explain your answer.
(3)

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Q11. The following tertiary alkyl halide was heated in ethanol for several days, and the resulting
mixture of products contained five different elimination products and two substitution products.

(a) Draw the structure of the substitution products and identify their relationship. (2)
(b) Identify which substitution product is expected to be favored, and explain your choice. (2)
(c) Draw all of the elimination products, and identify which products are stereoisomers. (2)
(d) For each pair of stereoisomeric alkenes, identify which stereoisomer is expected to be
favored.
(2)

Q12. Draw the mechanism of the forward reaction clearly showing curly arrows. Determine the
favored direction of the reaction and explain why. (3)

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Favorable direction will be the reverse direction and the reaction equation is represented as
following.

As the iodine is more stable than chloride ion so forward direction in which chlorine act as
leaving group is less favorable. Which can also be explained by energy change for both
directions.

For forward reaction:

∆E = Bonds made – Bonds broken

= -240- (-330)

= +90

For reverse reaction:

∆E = Bonds made – Bonds broken

= -330- (-240)

= -90

Reverse reaction is energetically favorable reaction.

Q13. Draw the structure of the major product of the following reactions while taking care of the
stereochemistry. Name the mechanism yielding major product in each case. (4)

a).

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It will follow SN2 mechanism to yield major product.

b).

It will follow E1cb mechanism because F- is a bad leaving group and less substituted alkene will
be formed because primary carbanion is more stable than secondary or tertiary carbanions.

it will follow an SN2 mechanism to yield the product.

Q14. Which one of the following species will result in E 2 reaction most readily when added to 1-
bromobutane (CH3CH2CH2CH2Br)? Draw the major product of the reaction of 1-bromobutane
with that specie. (2)

a). b). c).

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This specie will result in E2 reaction more rapidly due to the presence of negative charge on
oxygen which will increase the energy of HOMO of oxygen making it more basic and less
nucleophilic due to its bulky nature.

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