28 dec icho

TASK 3
Selectivity of the radical chain reaction

Reactions of alkanes with halogens proceed according to the radical chain mechanism
consisiting of the following general steps: initiation, propagation and termination. The selectivity is
determined by the relative rates of formation of different alkyl radicals from a starting alkane. It
depends strongly on the kind of halogen, as illustrated by reactions of propane with dichlorine and
dibromine, which result in the formation of mixtures of corresponding monohalogenated propane
derivatives in different proportions (reactions conditions were optimized to minimize the formation
of polyhalogenated products):
hν CH2 CHCl
H 3C
CH2
CH3
+ Cl2 ClH2C CH3 + H 3C CH3 + HCl
40% 60%
CH2 hν CH2 CHBr

H3C CH3 + Br2 BrH2C CH3 + H 3C CH3 + HBr
4% 96%
The useful thermochemical data, i.e. enthalpies of bond dissociation ΔHd, are given below:
Bond ΔHd, kJ mol-1

Cl-Cl +242
Br-Br +193
H-Cl +431
H-Br +366
H-(1-propyl) +410
H-(2-propyl) +395
Problems:
a. Calculate the relative reactivities of primary and secondary hydrogen atoms in reactions of
propane with dichlorine and dibromine.
b. Write the mechanism of the reaction of propane with dichlorine yielding 2-chloropropane consisting
of initiation (1 step), propagation (2 steps) and termination (1 of several possible reactions).
c. Based on the proper thermochemical data calculate enthalpies of elemental parallel reactions of
chlorine-induced formation of 1- and 2-propyl radicals (ΔHI, ΔHII), as well as analogous
reactions with bromine (ΔHIII, ΔHIV). Compare results of calculations. What is the difference
of enthalpies of parallel reactions of formation of 1- and 2-propyl radicals?
d. Draw the reaction-energy diagram illustrating the course of parallel reactions of chlorine-
induced formation of 1- and 2-propyl radicals (with energy maxima for corresponding transition
states). Notice that the energy difference changes monotonically. The diagram should be
correctly drawn to scale and properly described. Draw lines related to activation energies and
enthalpies of both reactions. Draw the analogous diagram for the reaction with bromine.
e. Compare both diagrams from the point of view of difference of activation energies. Which
diagram exhibits the bigger difference of activation energies? Is it in agreement with
experimental results concerning the selectivities of propane halogenation? Give the explanation.
f. Calculate the difference of activation energies for both parallel reactions (ΔEa(I,II) and ΔEa(III,IV))
using Arrhenius’ equation and results obtained in a. Assume that the preexponential factor A is
equal for both reactions and that the temperature is T = 298 K.
TASK 5
Peptides and peptidomimetics
In the studies of peptides structure activity relationship (SAR) analogs of parent peptides are
used. Such analogs contain so-called “constrained amino acids” (with restricted rotation of side
chains). Those analogs (peptidomimetics) are useful in the conformation analysis of parent peptide.
It may be helpful in the determination of position of amino acids’ side chains essential for
biological activity.
Give the structure of a peptidomimetic P knowing that:
- a peptidomimetic P is formed by 2 amino acids residues and the X residue ;
- the molar mass of P is 533 g/mol;
- in the reaction of P with 1-fluoro-2,4-dinitrobenzene (DNFB) the derivative with the molar
mass 241 g/mol is obtained
- after digestion with carboxypeptidase the amino acid is isolated; that amino acid is
synthesized as given on the scheme below:
KCN/NH4Cl H2O/HCl
CHO A B
C6H12N2
- compound X is synthesized as given on the scheme below:

COOCH 3
COOH NH2
DCC 1. H2O/NaOH
C D X
NHBoc NaBH3CN (C2H5)3N 2. HCl/AcOEt
N
H CHO
C27H31N3O5 C21H22N3O3Cl
O
Boc - O
(DCC – dicyclohexyl carbodiimide, coupling reagent)

Problems:
a. What is the N-terminus amino acid? Explain briefly your choice.
b. Draw the structural formulas of compounds A, B, C, D (without stereochemistry determination).
c. Draw the structural formula of peptidomimetic P (without stereochemistry determination) and
explain briefly your choice.
d. Peptidomimetic P was designed to determine the conformation of some side chains in parent
linear peptide I (molar mass 521 g/mol). Give the sequence of peptide I and draw its structural
formula. Use the following molar masses: H-1 g/mol, C-12 g/mol, N-14 g/mol, O-16g/mol.

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28 dec icho

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TASK 3

Selectivity of the radical chain reaction

CH2 hν CH2 CHBr

Bond ΔHd, kJ mol-1

- compound X is synthesized as given on the scheme below:

(DCC – dicyclohexyl carbodiimide, coupling reagent)

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