2º CURSO DEL GRADO EN QUÍMICA - ASIGNATURA: QUÍMICA ORGÁNICA I

EJERCICIOS TEMA 4

1. Write the initiation and propagation steps for the radical monobromination of 2-methylpropane.
a) What are the expected products?
b) Would any of these products be chiral?
c) Which of these products is expected to form faster?

2. A mixture of several products is obtained in the monochlorination reaction of

methylcyclopentane.
a) Draw the structures of the expected isomers.
b) Which of those isomers are chiral?
c) Determine the absolute configuration for the chiral products.

3. Rank the following molecules in a decreasing order of their boiling points (Draw the structures).
a) 3-methylhexane (C7H16); b) 2,3-dimethylpentane (C7H16); c) n-heptane (C7H16);
d) 2,2-dimethylpentane (C7H16).

4. Which of the following products could be efficiently prepared through a radical

monochlorination reaction?
a) (chloromethyl)cyclopentane; b) 3-chloropentane; c) chlorocyclohexane; d) 1-chloropropane;
e) chloroethane

5. ¿Would you expect any differences in the stereochemical outcome of the monochlorination
reaction of (R,R)-3,4-dimethylhexane and (R,S)-3,4-dimethylhexane?

6. The radical monobromination of 2-methylpropane and prop-2-ylbenzene present noticeably

different kinetics. How would you explain this result?

7. In agreement with the expected results for the monobromination of prop-2-ylcyclopentane or

1,2,3,4,5-pentamethylcyclopentane, which reaction would you consider that might have more
synthetic utility?

8. The different isomers of the alkane with formula C5H12 can lead to: a) one monochlorination
products; b) four monochlorination products; c) five monochlorination products.
Identify the isomer that corresponds to each reaction and draw the corresponding products.
9. The monochlorination of 2,3-dimethylbutane gives two different products and one of them is
obtained in a higher yield. However, the monobromination of the same molecule produces almost
exclusively one product. Using the data in the table, answer the following questions:
(Hint: Analyze the propagation steps and draw the reaction energy profile)
a) How do you explain the observed selectivity in the chlorination and bromination reactions?
b) What is the major product in the chlorination reaction?
c) Do you expect any differences in the kinetics of the chlorination and bromination reactions?
d) What is the most stable conformation of the major product in the chlorination reaction
considering the rotation around the C2-C3 bond?

Approximate Bond Dissociation Energies (homolytic cleavage, KJ/mol)

X = Cl X = Br
X‒X 243 193
H‒X 431 368
RCH2‒X 355 303
R3C‒X 357 309
RCH2‒H 423
R3C‒H 404