DEDAN KIMATHI UNIVERSITY OF TECHNOLOGY

UNIVERSITY EXAMINATIONS 2014/2015

YEAR THREE SPECIAL/SUPPLEMENTARY EXAMINATION FOR DEGREE OF

BACHELOR OF SCIENCE IN INDUSTRIAL CHEMISTRY

SCH 2358 – ORGANIC SYNTHESIS

DATE: 30TH APRIL 2015 TIME: 11.00AM – 1.00PM

INSTRUCTIONS: Answer Question ONE and any other TWO questions

Question One (30 Marks)

a) Briefly explain each of the following observations. Where appropriate use chemical
equations for clarity.

i. Benzaldehyde does not undergo aldol condensation (2 Marks)

ii. Organomagnesium compounds may not be prepared in the presence of a weakly acidic
compound. (2 Marks)

iii. NaOCH3 is not considered an organometallic. (2 Marks)

iv. A Grignard solution is destroyed by suphur dioxide bubbled through it. (2 Marks)

v. Methyliodide is preferred to methylbromide when preparing the Grignard reagent.

(2 Marks)

vi. The equilibrium constant for the formation of a gem-diol from aldehydes is far much
higher than that of ketones. (2 Marks)

b) Differentiate between an acetal and ketal . (4 Marks)

c) Using retrosynthetic approach show how a Grignard reagent may be used to synthesize the
compound given below. (5 Marks)

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 CH3CHCH2CH2CH2CH3
OH

d) i. Explain three characteristics of an ideal protective group. (3 Marks)

ii. Show how the following conversion may be carried out with the help of a protecting
group.

(6 Marks)
O
O
CH3CCH2CH2CCH CH3CCH2CH2CCCH3

Question Two (20 Marks)

a) What combination of ester and Grignard reagent could you use to prepare the following
tertiary alcohol? (Include the necessary reagents) (4 Marks)
C6H5C(CH2CH3)2
OH

b) Differentiate between an enol and enamine (4 Marks)

c) Triphenylphosphine can be used to convert epoxides to alkenes, for example,

O
+ + -
C6H5CH CHCH3 (C6H5)3P: (C6H5)3P O
C6H5CH CHCH3 +

Propose a plausible mechanism for the above conversion. (4 Marks)

d) Suggest two ways in which organic halides and cuprate reagents may be used to prepare 2-
Methylbutane. (4 Marks)

e) Show that the hydration of ketones is acid catalysed. (4 Marks)

Question Three (20 Marks)

a) Give the IUPAC names for the following organometallics. (3 Marks)

i (CH3CH2)2Mg ii. CH3MgI

(CH3CH2)2AlCl
iii.

b) State the principal products in each of the following reactions. (4 Marks)

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 CH3CH2
CH2CH3 CH2I2, Zn(Cu)
C C
H H diethyl ether
. i.

O C6H5CO20H

CCH3
ii. CHCl3

K2Cr2O7

O CH H2SO4, H20
iii. O

O
LiAlH4 H+

iv.

c) Explain how a Grignard reagent may be used to introduce deuterium into organic
compounds. (2 Marks)

d) i. What are ylides (2 Marks)

ii. Using wittig reaction outline two methods of synthesis of the alkene below. Identify the
alkene that will give higher yield.

CH3
C6H5CH C
CH3 (5 Marks)

e) Write the structural formulas corresponding to enolates of the compound shown below. With
an explanation, identify the most stable enolate. (4 Marks)

O
CH3CCH2CCH3
O

Question Four (20 Marks)

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a) In the following reaction explain the choice of substituted hydrogens and propose a
mechanism for the reaction. (5 Marks)
O
O KOD D
D
+ 4DOH
+ 4D2O D
D
reflux

b) Show how you would synthesize the compounds shown below through aldol condensation:

(6 Marks)
O
NO2 HC CHCCH3
C
CH3

i. ii H3C

c) Show how a thioketal (HSCH2CH2HS) might be used in carrying out the transformation
shown below. (Include the necessary reagents) (5 Marks)

CO2CH3 CH2OH

O O

d) Show that the formation of ethan-1,1-diol is base catalyzed. (4 Marks)

Question Five (20 Marks)

a) In the formation of an acetal in acid media the hemiacetal formed first is converted to an
acetal by way of a cabocation intermediate. With the help of a suitable mechanism how
this occurs. (7 Marks)

b) Outline two ways in which 4-methyl-2-octanone can be prepared by conjugate addition

of an organocuprate to an α,β-unsaturated ketone. (6
Marks)

O
CH3CH2CH2CH2CHCH2CCH3
CH3

4-Methyl-2-octanone

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c) For the following Dieckmann cyclization reaction show with a suitable mechanism how
the conversion takes place. (7 Marks)

O O
O O 1.NaOCH2CH3
CHOCH2CH3
CH3CH2OCCH2CH2CH2CH2COCH2CH3
2.H3O+

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