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AS/APR 2011/CHM556

UNIVERSITI TEKNOLOGI MARA FINAL EXAMINATION

COURSE COURSE CODE EXAMINATION TIME

ORGANIC CHEMISTRY II CHM556 APRIL 2011 2 HOURS

INSTRUCTIONS TO CANDIDATES 1. 2. 3. 4. This question paper consists of seven (7) questions. Answer ALL questions in the Answer Booklet. Start each answer on a new page. Do not bring any material into the examination room unless permission is given by the invigilator. Please check to make sure that this examination pack consists of: i) ii) the Question Paper an Answer Booklet - provided by the Faculty

DO NOT TURN THIS PAGE UNTIL YOU ARE TOLD TO DO SO This examination paper consists of 6 printed pages
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AS/APR 2011/CHM556

QUESTION 1 a) Arrange the following pairs in order of their reactivity towards the addition of a nucleophile to a carbonyl group. Give reasons to your answers. o and o

Benzaldehyde

Cyclohexanecarbaldehyde

O ii) H3C H

and

Acetaldehyde

Formaldehyde (6 marks)

b)

Provide a chemical test to differentiate between acetaldehyde and formaldehyde. (2 marks)

c)

Using appropriate reagents, write equations for the steps in the synthesis of the following compounds from acetone.

H 3 C'^CH3

CH, ) H3C

OH CH3

OH iii) H33 C T C H 3 CH3

iv) CH3CH2CH3

(8 marks)

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QUESTION 2

a)

Write the mechanism for the conjugate (1,4) addition of methylamine 2-cyclopentenone. Include all possible intermediates in the mechanism. o
+ CH3NH2 EtOH > ?

to

2-Cyclopentenone

Methylamine (6 marks)

b)

Propose an efficient synthesis for the following transformation. 0 /""OH *>. Ethanol Acetone (10 marks)

QUESTION 3 a) Provide the reagents and reaction conditions for the following reactions. Give the intermediate where appropriate.

OH

A
o

o ii) (^P H
.OH

OH
ii)

OCH,

O iv)
CI

NH2

(10 marks)

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b)

Provide the major product of each of the following equations. 9 i) /^

A

9 -OCH
3

LiAIH4 **

O 2 CH3OH ii) H30+ CO2CH2CH3 iii)

2 CH3MgBr

H30+ (6 marks)

QUESTION 4 Consider the following crossed condensation reactions. 0 1.Base (I) 0

2. H30+

O (II)

NaOH

a)

Draw the structures of the starting compounds for reaction (I). (4 marks)

b)

i) Give a suitable base for reaction (I), ii) Name reactions (I) and (II). iii) Which reaction is also known as the Claisen-Schmidt reaction? (4 marks)

c)

Write the mechanism for reaction (I) yielding to the above (3-keto ester. (9 marks)

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d)

For reaction (II), using curved arrows, show: i) The formation of the enolate ion of the donor. ii) How the enolate in (i) above attacks the acceptor to form the alkoxide intermediate? (6 marks) Referring to reaction (II), draw the structures of the aldol product formed before dehydration and the enone after dehydration. (4 marks)

e)

QUESTION 5 Each compound below is either a dicarbonyl or a diester. o (l) o (II) <X

a)

Draw the structures of the cyclic products expected from the intramolecular condensation reactions of the above compounds. (4 marks) Show the mechanism for the formation of compound (I) above. (7 marks)

b)

c)

Compound (I) is also a product from a Michael reaction. materials required to synthesize (I)?

What are the starting (4 marks)

QUESTION 6 Consider the following acetoacetic ester synthesis. o o

1. NaOEt, CH3CH2CH2Br 2. t-BuOK, CH3CH2CH2Br i 3. Dilute NaOH, H 3 0 + , heat

Acetoacetic ester

Outline the synthesis above by drawing the structures of all intermediates, all side products and the final ketone product. Give the IUPAC name of the final product. (10 marks)

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QUESTION 7 D-Sorbose is a ketohexose. CH2OH O OH HH HOH- OH CH2OH D-Sorbose a) Upon hemiacetal formation, the specific rotation of a-D-sorbose or /3-D-sorbose changes over time to reach equilibrium. Draw the structure of a-D-sorbose in Fisher projection. (2 marks) a-D-Sorbose can exist in both furanose and pyranose rings, i) Draw the Haworth projections of both rings. ii) Draw the structure of the product of the reaction of a-D-sorbose with an excess of CH3I in Ag 2 0, in Haworth projection in pyranose ring. (6 marks) D-Tagatose and D-sorbose are C-3 epimers. i) On reduction with NaBH4, D-tagatose forms optically active alditol P and optically inactive alditol Q. Alternatively, P can be formed by reduction of an aldohexose, R. Suggest the structures of D-tagatose, alditols P and Q, and aldohexose R. ii) Aldohexose R can be used to prepare an aldopentose, D-lyxose, via Ruff degradation. Show the synthetic steps involved in this chain shortening reaction, the structures of all intermediates and D-lyxose, and necessary reagents. (16 marks)

b)

c)

END OF QUESTION PAPER

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