Kinetic and Organic Reaction Mechanism

Chapter 6

How to Study Reaction Mechanism.

Tutorial

1
How to Study Reaction Mechanism: Tutorial

1. When 14C-labelled allyl 2,6-dimethyl ether undergoes para Claisen rearrangement,

the carbon atom originally attached to oxygen becomes attached to the aromatic ring.
Suggest a mechanism to account for that result
How to Study Reaction Mechanism: Tutorial

2. Hydrolysis of phthalamic acid (1) to phthalic acid (2) was thought to involve
elimination of ammonia and intermediate formation of phthalic anhyride

This possibility was investigated by an analysis of the products of reaction between

phthalamic acid labelled with 13C in the amide group and water enriched with 18O.
Show how this could demonstrate the intermediacy of phthalic anhydride and
suggest how the products might be analysed?
How to Study Reaction Mechanism: Tutorial

3. Hydrolysis of α-acetoxy-p-nitrostyrene is acid-catalysed

In 6 % sulphuric acid there is a kinetic isotope effect k(H2O)/k(D2O) of 0.75 but in 69

% sulphuric acid the size of this effect changed to 3.25.
What may be deduced about the mechanism of hydrolysis from this change?
How to Study Reaction Mechanism: Tutorial

4. The rates of hydrolysis of the three related esters have been studied as a function of
pH, with results shown in Figure 7.
The entropy of activation for the hydrolysis of 1 is -41.0 e.u

Suggest mechanisms for these reactions

How to Study Reaction Mechanism: Tutorial

5. But-2-ene can be converted to 2-bromobut-2-ene by the following two

transformations. What is the structure of the intermediate? Draw mechanisms for
these steps and explain the stereochemistry
How to Study Reaction Mechanism: Tutorial

6. When the amino acid threonine is treated with nitrous acid in the presence of
chloride ions, two isomeric products are formed in addition to the expected product.
What is the mechanism of their formation, and what would you expect their
stereochemistry to be?
How to Study Reaction Mechanism: Tutorial

7. a) We know that it is generally the acyl-oxygen bond that is cleaved in ester

hydrolysis rather than the alkyl-oxygen bond. One of the main pieces of experimental
evidence for this came from an experiment that used 180. How might such an
experiment be carried out? What result would you expect, and how would this be
different if the alkyl-oxygen bond were cleaved?

b) When the alkyl group of an ester is tertiary, hydrolysis under acidic conditions takes
place with alkyl-oxygen cleavage. Could this be distinguished from the above
mechanism kinetically? Apart from 180 labelling, what other evidence might be used to
verify this mechanism?
How to Study Reaction Mechanism: Tutorial

8. Treatment of methyl α-bromopropionate with hydrazine gives a mixture of products

as shown below. A possible mechanism for the reduction is that the hydrazine function
is somehow oxidized to an azo function, which then undergoes an elimination reaction
to give the enolate, and hence the reduced product. Suggest a way of discovering
whether this mechanism is possible.
How to Study Reaction Mechanism: Tutorial

9. When acetone is brominated, the rate of reaction is independent of the

concentration of bromine. Deuteriated acetone is brominated mote slowly than normal
acetone. What do these facts tell us about the mechanism of there action?
How to Study Reaction Mechanism: Tutorial

10. Two possible mechanisms for the Wittig rearrangement of benzyl ethers are
shownbelow. Path 1 involves concerted intramolecular migration of CR3 , whereas Path
2 involves a heterolysis. In either mechanism, the deprotonation step is
ratedetermining. How would you apply the following experiments to distinguish
between the two mechanisms: cross-over, trapping, and stereochemistry?
How to Study Reaction Mechanism: Tutorial

11. The treatment of chlorobenzene with potassium amide in liquid ammonia results in
the formation of aniline. Propose four experiments discussed in this chapter, or others
you can devise, that canbe used to distinguish between the two mechanisms given
below.