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香 港 中 文 大 學
The Chinese University of Hong Kong
Course Examination 2nd Term, 2011-2012
科目編號及名稱
Course Code & Title : CHEM1280 Introduction to Organic Chemistry & Biomolecules
Time allowed 時間: 2 hours 小時 0 minutes 分鐘

Student I.D. No. 學生編號: Seat No. 座號:

Section 1 (70 points totally)


1. Rank each of the following groups of molecules. (16 points)
1) Rank the following acids in order of decreasing acidity: CF3CH2COOH, CF3COOH,
CH3COOH and CF3SO3H.
2) Rank the following compounds in order of decreasing boiling point: acetone,
propanamide, propene and propanoic acid.
3) Rank the following alcohols in order of decreasing reactivity toward dehydration
reaction with H2SO4:

4) Rank the following compounds in order of decreasing reactivity toward nucleophilic


acyl substitution reaction with water: acetic anhydride, acetamide, ethyl acetate and
acetyl chloride.

2. Oxidation of 1,2-benzenedimethanol with pyridinium chlorochromate (PCC) fails to yield


1,2-benzenedicarbaldehyde, but yields an ester as shown below. Explain this phenomenon
with structures and reactions. (7 points)

3. Oxanamide, a mild sedative with molecular formula of C8H15O2N, is synthesized from


butanal in five steps as shown below. (16 points)
1) Show the necessary reagents used in the 1st to 4th steps;
2) Draw the structure of oxanamide.
Course Code : CHEM1280 Page 2 of 3

4. Reaction of 2-chloro-2-methylpropane, 2-bromo-2-methylpropane or


2-iodo-2-methylpropane in water yields 2-methyl-2-propanol and 2-methylpropene with
the same ratio. Explain why the ratio of products is independent on the halogen atom in the
starting material of alkyl halide. (6 points)

5. Lysine and arginine are two of the 20 natural amino acids that form proteins. The side
chain structures and pKa values of lysine and arginine are shown below. (11 points)
Lysine Arginine

Side chain (the form dominates


at physiological pH)

pKa of side chain 10.79 12.48


pKa of α-NH3+ 8.95 9.04
pKa of α-COOH 2.18 2.17

1) Draw the principle form of lysine at pH = 5 showing the configuration of the


asymmetric center;
2) Draw the principle form of arginine at pH = 11 showing the configuration of
asymmetric center, and calculate the isoelectric point (pI) of arginine;
3) Explain why the side chain of arginine is less acidic than that of lysine (considering the
side chains in the form as shown above).

6. As shown below, adenosine can be hydrolyzed readily by aqueous acid to D-ribose and
adenine. (14 points)
1) Propose a reasonable mechanism for the following reaction using the curved arrows to
show the flow of electrons.
2) Draw the Fischer projection for the open-chain form of D-ribose.
3) Draw the pyranose form of D-ribose in a chair conformation.
Course Code : CHEM1280 Page 3 of 3

Section 2. Choose Three questions only from this section to answer. Please indicate the
questions you want to be graded by circling the question number. If you answer all the four
questions in this section, only the first three answers will be graded. (10 points for each
question and 30 points totally for this section)

7. Draw structures for compounds A, B and C in the following synthetic sequence. It is


known that compound C can not be oxidized by Tollens's reagent. (10
points).

8. Barbital, a long-duration hypnotic and sedative, is synthesized in the following reaction.

1) Propose a reasonable mechanism for this reaction using the curved arrows to show the
flow of electrons.
2) Barbital is weakly acidic with pKa of 7.4. Briefly explain why barbital is acidic.

9. An α-amino acid can be prepared from an aldehyde in the following reactions.


1) Draw the structures of intermediates X and Y;
2) This synthetic sequence yields the amino acid as a racemic mixture. Suggest a method
to separate two enantiomers of the product.

10. Shown below is the synthesis of Bisphenol A from phenol and acetone. Propose a
reasonable mechanism for this reaction using the curved arrows to show the flow of
electrons.