DEDAN KIMATHI UNIVERSITY OF TECHNOLOGY

UNIVERSITY EXAMINATIONS 2017/2018

YEAR THREE SUPPLIMENTARY/SPECIAL EXAMINATIONS FOR THE DEGREE OF

BACHELOR OF SCIENCE IN INDUSTRIAL CHEMISTRY

SCH 2358 ORGANIC SYNTHESIS

DATE: 19-MARCH 2018 TIME: 2-4PM

INSTRUCTION: Answer ALL questions
QUESTION ONE [25 MARKS]
a) Number the following compounds in order of increasing acidity (1 being least acidic). [3 marks]

CH3CH2OH NH3 HCl C 2H2

b) Define the following terms: [3 marks]

i) Tertiary amine
ii) Aldol condensation
iii) Retrosynthetic analysis

c) Answer the following questions about physical and reactive properties of organic compounds
[3 marks]
Rank the following compounds from O O O O
weakest (1) to strongest (3) base. CH2 O O

Ranking
Rank the following compounds from O O O
weakest (1) to strongest (3) electrophile. H H
Ranking
Rank the following compounds from MgBr
MgBr
weakest (1) to strongest (3) nucleophile. MgBr

Ranking
d) For the following show the reagents, starting material, or product as directed [16 marks]
O ? O

i) OH H

Page 1 of 4
 O 1. Na O in HO
O H+ to neutralize
O
ii) O
O NaOH/H2O
H
HEAT
iii) O
O O
+ KOH/H2O
iv) H heat

Peroxy acid
O
v)
O 1. Li

H 2. H3O+
vi)
O O
HS SH
O
H+
vii)
O O
1. NaBD4
OH
2. H2O/methanol

viii) enough reagent to react with all that will react

O Provide missing C
reagent(s)
ix)

QUESTION TWO: [15 marks]

a) Starting from 1-methyl-1-cyclohexene, a tertiary alcohol, a secondary alcohol, and diols can be
synthesized. With the indicated specific reagents and the reaction conditions, draw
unambiguously the product of each transformation (the stereochemistry needs to be specified for
full credit). [6 marks]

Page 2 of 4
b) i) Show the product of the reaction below. [2 marks]
Na° or Li°

in ammonia
ii) What dictates the stereochemistry of the product?

c) The reaction below is acid catalyzed [3 marks]

H+ + OH
O
OH
H

i) Predict the product of the above reaction.

ii) What role does the acid play? (do not restate what has been given to you)
iii) Why do we add anhydrous acid instead of H O+? 3

d) For the following starting material show product form indicate the absolute configuration of each
product [4 marks]
NaCN
OH TsCl, Pyridine

(S)-4-methylpent-3-en-2-ol Is product S or R?
Is product S or R?

QUESTION THREE: [15 marks]

a) Dr. Tanui tried to make product q shown below using KOH/H2O instead of LDA. Was this a
problem for him? Support your answer using your knowledge about the reaction. In your
answer, include the 2 carbonyl starting materials that lead to the product [4 marks]
H O
C C
C CH3
q
H

Page 3 of 4
 b) Devise retrosynthetic analysis for the following reaction utilizing appropriate retrosynthesis
format. [4 marks]
O O O
starting material
OH
product
HO HO

c) Design a synthetic pathway for carrying out the reaction shown below. [5 marks]
O O

H CH3
d) Compound r reacts to form an Aldol addition product with itself but it cannot form the Aldol
condensation product. Why not? [2 marks]
O
r H

QUESTION FOUR: [15 marks]

a) The ketone shown below can be made from bromobenzene and ethylene. Please show your
synthesis using Grignard reagents as the key component (hint: different types of transformations
including epoxidation and two different Grignard reagents are required). [6 Marks]

b) Answer the following questions about SN2 reactions. [3 marks]

i. What is the problem caused by using NaCN or NaF in normal SN2 conditions?
ii. What is the chemistry strategy for getting around the above problem?
iii. Briefly state how your choice in a. ii above solves the problem you stated in a. i.
c) Predict the product(s) and draw a detailed arrow-pushing mechanism for the following reactions:
[6
Marks]
1) LDA
O
2) Formaldehyde
H 3) H3O+
i)
O
Then
+ 2 MgBr
O
ii) H3O+

Page 4 of 4