CHM556

Mac – Jun 2017

TEST 3

Name: UiTM ID: Group:

Answer all questions. Total marks: 30

Question 1
Compound A below undergoes Dieckmann cyclization to yield a β,β-diketoester (B) in the presence of
sodium ethoxide as the base.
1. tBuOK, R-Br
NaOCH3
2. dil NaOH, H3O+

H3O+
3. heat

Compound A β,β-Diketoester, B Diketone, C

a) Redraw the structure of compound A and identify in the structure the most acidic hydrogen.
(1 mark)
b) Write a mechanism for the reaction yielding the above β,β-diketoester (B).
(7 marks)
c) If compound B above is reacted with sodium borohydride (NaBH4), draw the structure of the
reduced product. Give reason(s) for your choice of product.
(3 marks)
d) Diketone C can be synthesized from the β,β-diketoester, B.
i) Propose a suitable alkyl halide (R-Br) in the synthesis of C above.
ii) Draw the structures of all intermediates synthesized during the transformation of B to C.
iii) Name the reaction which involves “heat” in the reaction scheme above.
(4 marks)

Question 2
D-Xylose is an aldopentose and widely found in nature. When D-xylose is treated with nitric acid, it
yields an optically inactive aldaric acid. However, when D-xylose is subjected to Ruff degradation, it
yields D-threose, which is upon treatment with nitric acid gives an optically active aldaric acid.

a) Based on the above statement, draw the structures of D-xylose, D-threose and the two aldaric acids.
(6 marks)
b) Provide the reagents required in all the steps involved in Ruff degradation of D-xylose.
(4 marks)

Question 3
a) Draw cyclic Fisher projection and Haworth projection showing the α-D-pyranose form of a D-
aldohexose that is C3-epimer to D-glucose. The structure of D-glucose is shown below.

(4 marks)
b) Based on the Haworth projection above, draw the structure of the product that is expected when
the α-D-pyranose reacts with CH3CH2OH in the presence of HCl. (1 mark)