Chemistry 14D Lecture 1

Fall 2012

Final Exam Part A Solutions

Page 1

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1.

OH

NaBH4
CH3OH

2.
H

OCH3

OH

BH3

3.

(a) Molecule A reacts slower than molecule B because it lacks the electron-withdrawing inductive effect of the
fluorine atom, which enhances the +C=O.
(b) Molecule C reacts slower than molecule B because it has more steric hindrance at the C=O. In addition, a
ketone has a smaller +C=O due to the electron-donating methyl group.

4.

Reduction. There is an increase in the number of bonds between carbon and atoms (H) less electronegative
than carbon.
O

O
NaOH

5.
Cl

H2O

O
O

6.

OH
Cl

7.

OH
Cl

OH

(a) Molecule E reacts slower than molecule D because -OCH3 is a poorer leaving group than -Cl. In addition, the
resonance lost upon nucleophilic attack at an ester is more than the resonance stabilization lost upon
nucleophilic attack at an acid chloride.
(b) Molecule F reacts slower than molecule D because -N(CH3)2 is a poorer leaving group than -Cl. In addition,
the resonance lost upon nucleophilic attack at an amide is more than the resonance stabilization lost upon
nucleophilic attack at an acid chloride.
O

8.

CH3(CH2)16

O
O

(CH2)16CH3

(CH2)16CH3

H2SO4
CH3OH

CH3(CH2)16COOCH3

HO

OH
HO

Formed in greatest
amount (3 moles)

Formed in lesser
amount (1 mole)

Chemistry 14D Lecture 1

H

9.

Final Exam Part A Solutions

H

OH2

HO

Ph

Fall 2012

Ph

CH3

OH2

HO

CH3

H
O

OH

Ph

Page 2

HO

CH3

Ph

OH

OH2

CH3

OH2
H
HO

OH

OH

OH2
O

+
Ph

H3C

CH3

OH

Ph

OH

Ph

OH

Initial protonation occurs at the PhC=O because the conjugate acid formed is more stable than the conjugate
acid formed from CH3C=O protonation. Draw resonance contributors to verify.
O

HO
1. LiAlH4

10. (a)
CH3O

N(CH3)2

2. H2O

N(CH3)2

LiAlH4 reduces every C=O to an alcohol, except for an amide, which is reduced to an amine.
H
O

(b)

O
1.

OCH3 2.

HO

CH (excess)

HO

H3O+
C

(c)

Br

Ph

OPh

3. H3O+

OH
O

CH3OH

Ph

OCH3
OH

(e)

1. Mg, ether
2. CO2

NaOCH3

(d)

cat. H2SO4

11. Organometallic, nucleophile, Grignard reagent, polar bond, strong base. Other answers are possible.
12. Keq > 1. An amide has greater resonance stabilization than a carboxylic acid. An equilibrium favors the more
stable side.
13. Glycine's OH group must be converted into a pyrophosphate group before coupling with the next amino acid
because OH is a poor leaving group.
O

14. (a) Fischer esterification:

OH

O
H2SO4
CH3OH

OCH3

Chemistry 14D Lecture 1

Fall 2012

Final Exam Part A Solutions

Page 3

HO

CH2CH3

1. CH3CH2MgBr

(b) Grignard reaction:

2.

CH3

H3O+
CH3

1. NaNH2, NH3 (l)

(c) Chichibabin reaction:

2. H2O

NH2

1. NaOCH2CH3

(d) Claisen condensation:

OCH2CH3

OH

or

2. H3O+

OCH2CH3

OCH2CH3

Other examples are possible in each case.

Ph
O
+

15. Major product:

Ph

NaOH

Ph

CH3OH

Ph
O

Mechanism:
O

Ph

OH

Ph

OCH3 Ph

Ph
Ph
O

OH
Ph

Ph

Ph

Ph

OH

Initial deprotonation occurs at the PhCH2 because this is the most acidic proton (its removal results in the most
stable enolate). NaOH does not convert all of the ketone into the enolate, so we must decided which carbonyl
the enolates attacks. An aldehyde has less steric hindrance and greater +C=O than a ketone, so the ketone
enolate attacks the aldehyde.
16. LDA = Lithium diisopropyl amide
O

17.
Ph

1. LDA
2. H3O+
3. PhCH2Br

OH

or
Ph

Ph

18. The "does not form" product is not formed because the enolate formed by LDA protonated by H3O+. This gives
the starting diketone (or its enol). These do not react with PhCH2Br.
19. Problems 8, 9, 10(e), and 14(a).