CHM556

TUTORIAL 1
ALDEHYDES AND KETONES

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.

i) and

Benzaldehyde Cyclohexanecarbaldehyde

and
ii)

Acetaldehyde Formaldehyde

b) Provide a chemical test to differentiate between acetaldehyde and formaldehyde.

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

i) ii)

iii) iv) CH3CH2CH3

2.
a) Write the mechanism for the conjugate (1,4) addition of methylamine to 2-cyclopentenone.
Include all possible intermediates in the mechanism.

EtOH
CH3NH2 ?

2-Cyclopentenone Methylamine

b) Propose an efficient synthesis for the following transformation.

Ethanol Acetone
c) Provide the major product of each of the following equation

3.
a) Propose the products (A, B and C) of the dicarbonyl compound below with the following reagents.

Ag2O, NH4OH 2 moles CH3NH2

A C
ethanol H3O+

2 moles CH3MgBr
H3O+

4.
a) Provide the required reagents or organic products for the following reactions. Give
intermediate(s) where appropriate.

i) G

H
ii)

iii)

5. Give the reagents that will convert the following compounds to acetophenone. Some reactions
may require more than one step.

(i) (iv)

(ii) (iii)
Acetophenone

a) Suggest the appropriate reducing agent(s) for the following transformation. Provide reasons for
your choice of reagent(s).
 i)

ii)

6.
a) Draw the structures of the products in the following conversions. Draw intermediates where
necessary.
NaBH4 -
(i) Ph3P-CH2 (v)
CH3OH
THF

1. CH3MgBr 1. KMnO4,H+, heat

2. H3O+ 2. SOCl2
Benzaldehyde
(ii) (iv)

1. HCN
2. H2O, H+

(iii)

b) The reaction of a carbonyl compound with semicarbazide yields product A and not B.

X
semicarbazide

i) Give reasons for the above statement.

ii) Write the mechanism for the formation of A.

c) Upon treatment with a catalytic amount of acid, the following compound is converted into a cyclic
hemiacetal. Draw the structure of the hemiacetal and write the plausible mechanism for the
transformation.

H2SO4
7.
a) Carbonyl compounds can easily be attacked by nucleophiles. Suggest the appropriate
nucleophiles/reagents for conversions I, II, III and IV below. Include the necessary reaction
conditions where appropriate.

I IV

II III

b) Provide the major product of each of the following reactions. Include intermediate(s) where
necessary.

8.

a) Give the product(s) of heating PhCOCH2CH3 with the following reagents.

i) NH2NH2 and a strong base, KOH

ii) Zinc amalgam (Zn/Hg) and HCl

b) Name the reactions in (a)(i) and (a)(ii) above.

9.
a) Arrange the following pairs of compounds in order of increasing reactivity with a nucleophile.
Explain your answers.

b) Provide the reagents and reaction conditions for the following reactions. Give the intermediate
where appropriate.
i.

ii. iii.
c) Provide the major product of each of the following equations.

10.
a) i) Use the concept of resonance (charge delocalisation) to explain why benzoic acid,
PhCOOH (pKa = 4.19) is more acidic than phenol, PhOH (pKa = 9.80).
ii) Compare the reactivities of the C=O in benzoic acid, PhCOOH and benzaldehyde,
PhCHO towards nucleophiles.

b) Provide the required reagent(s) or product(s) for the following reactions.

11.
a) The Wittig reaction is a versatile synthetic method for the preparation of an alkene from a
carbonyl compound with a phosphonium ylide as the Wittig reagent. Draw the structure of
the methylene cyclopentane formed in the following synthesis and write the mechanism for
the transformation. (cyclopentanone)

_
(Ph)3P Methylene (Ph)3P=O
cyclopentane
Triphenyl Triphenylphosphine
Cyclopentane phosphonium
ylide