71 (1952) RECUEIL 473

542.943.5 : 542.955.1 : 547.52 : 541.5

THE MECHANISM OF THE REACTION BETWEEN OZONE
AND AROMATIC BONDS.
A reply to G. M. Badger.
BY
F. L. J. SIXMA and J. P. WIBAUT
A summary is given of experiments which lead to the conclusion that the
addition of ozone is an electrophilic reaction. The points of difference and
agreement in mechanism between the addition of ozone and electrophilic
substitution are discussed. The suggested mechanism is not in opposition
to the interpretation of Kooyrnan and Ketelaar.

1. Introduction.
In his paper on the addition of ozone to aromatic bonds Badger 1 )
starts from the agreement in behaviour between ozone, osmium
tetroxide and diazoacetic ester towards aromatic compounds. T h e
three reagents mentioned are bonded to the most reactive bond in the
molecule and therefore they are designated by him a s "double bond
reagents". This gives no hint however with regard to the mechanism
of these reactions. O n the mechanism of the addition of osmium
tetroxide and diazoacetic acid ester little is known. It is not a
justifiable assumption to assume without more ado that the reaction
velocity of diazoacetic ester with an aromatic bond is greater when
this bond possesses a higher bond order. In the reaction with benzene,
naphthalene and anthracene only one molecule of diazoacetic ester
appears to react 2 ) . T h e dihydrobenzene derivative formed from
benzene, in which the (now practically localised) double bonds
possess. without doubt, a much higher bond order than the bonds
originally present in benzene, reacts nevertheless not a t all or a't least
very much more slowly than benzene with diazoacetic ester, Even if
account is taken of a certain conjugation between the double bonds
*) G . M . Badger, Rec. trav. chim. 71, 468 (1952).
2, Benzene: E. Buchner and Th. Curfius, Ber. 18, 2377 (1885); W . Broren and
E. Buchner, ibid. 34, 982 ( 1 9 0 1 ) ;
naphthalene: E. Buchner and S . Hediger, ibid. 36, 3502 (1903) :
anthracene: G. M. Badger, J. W . Cook and A. R. M. Gibb. referred to in ').
474 F. L. J . Sixma and J. P. Wibauf,

and the cyclopropane ring 3 ) 4 ) , it is still improbable that the bond

orders of the bonds 2.3- and 4 5 in the norcaradiene derivative are
lower than those in benzene * ) :

NzCHz. COOR -----t ‘(F5

\,
2
H

H
CH .COOR

Similar objections can be brought to the addition of diazoacetic

ester to naphthalene:
H CH.COOR
I
(10
\/\Y
+ N2CH2.COOR ----t
. /\/

‘/
(fH
’
The double bond in ring B does not react easily with a second
.molecule of diazoacetic ester, although it easily adds on bromine.
Therefore we prefer to let the discussion of the mechanism of the
addition of diazoacetic ester and osmium tetroxide rest until more
experimental data are available: in the following we shall therefore
limit ourselves to the addition of ozone.

2. The electrophilic character of the ozonisation reaction.

The way in which ozone reacts with aromatic compounds is con-
siderably better known than that in the case of osmium tetroxide and
diazoacetic ester 5 ) . It has been found, for example, that the formation
of benzene triozonide takes place in three successive steps, in which
the formation of the monozonide is the slowest, while this, when once
formed, quickly reacts with two further molecutes of ozone and gives
the triozonide 6 ) . From our kinetic investigations it also appears that
the reaction between benzene, bromobenzene or chlorobenzene and
ozonais accelerated catalytically by substances like aluminium chloride,

s, R. van Volkenburgh, K. W. Greenlee, J. M. Derfer and C . E. Boord, J. Am.

Chem. SOC.71, 3595 (1949).
4, L. N . Ferguson, Chem. Revs. 43, 385 (1948)
*) An investigation into this problem is in progress in our laboratory.
6 ) For a summary of the results obtained in the ozonolysis of aromatic compounds
see J. P. Wibauf, Bull. SOC. chim. France 1950, M. 9%.
e, F. L. J. Sixma. H . Boer and J. P. Wibauf, Rec. trav. chim. 70, 1005 (1951).
 The mechanism of the reaction, efc. 71 (1952) RECUEIL 475

ferric chloride, and boron trifluoride 6 ) 7). This catalytic effect is to

be understood only if the reaction of ozone with these aromatic com-
pounds has a polar character, so that it may be excluded, that the
ozone is added in the form of a diradical. From comparative measure-
ments of the velocity with which a number of benzene and pyridine
derivatives*) react with ozone it has been found further, that the
velocity of ozonisation of these compounds proceeds parallel to the
velocity with which they are brominated, chlorinated or nitrated. T h e
detailed experimental data of these kinetic investigations are already
in part published 6 ) ; the remaining details will appear shortly in this
Journal.
O n the basis of the fact that the addition of ozone obviously takes
place by means of a polar mechanism, and further, on the basis of the
agreement between the relative velocities with which benzene and
pyridine derivatives react on t h e one hand with ozone and on the
other with electrophilic substitution reagents it is, in our opinion, at
least probable that the addition of ozone also occurs by an electro-
philic mechanism. In order to make clear the analogy between
ozonisation and electrophilic substitution the course of these reactions
has been formulated a s follows 7 ) :

addition of ozone to benzene

In order to bring the theory of reaction velocities into this discussion

- even when merely considering the relative velocities with which
different bonds react in one molecule - it is necessary to make certain

7 ) 1. P . Wibaut. F. L. 1. Sixma, L. W . F. Kampschmidt and H . Boer, ibid. 69,

1355 (1950).
*) In preparation.
476 F. L. J. Sixma and J. P. Wibeut,

bromination of benzene

assumptions with regard to the structure of the transition state, the

state of the highest energy content, which is passed during the
reaction. A formulation of the transition state of the addition of ozone
as given in figure 2 brings out the electrophilic character of the
reaction. T h e formation of this .transition state may be preceded by
a n-complex bond ( a s is already assumed in electrophilic sub-
stitution 9 ) .
Although Badger is also of the opinion “that ozonisation may be an
electrophilic reaction”, this author criticises the mechanism suggested
by Wibaut. Sixma, Kampschmidt and Boer 7 ) . because this should
lead to conclusions with regard to the ozonisation of pyrene, which
are in disagreement with experiment. Badger therefore prefers the
suggestions developed by Kooyman and Ketelaar 10). In our opinion,
however, there is no opposition between our ideas and those of
Kooyman and Ketelaar, the former being merely an extension of the
latter, which makes clear the catalytic effect and the relative velocities
with which the benzene derivatives so far investigated react. In the
following paragraphs we will try to elucidate this further; it will
appear also that for the ozonisation of pyrene the experimental results
are not opposed to the picture of the reaction we have suggested.

3. The ozonisation of pyrene.

T h e relative reactivity of the bonds in pyrene towards ozone will
be a result of the different energy contents of the relative transition
states. T h e following three possibilities come into consideration for
more detailed discussion:

0 ) M . J. S . Dewar, “The Electronic Theory of Organic Chemistry”. Oxford

University Press, Oxford (1949), p.. 17, 169.
lo) E. C. Kooyman and J. A. A. Kefelaar, Rec. trav. chim. 65, 859 (1946) : E. C.
Kooyman, ibid. 66, 201 (1947); J. A. A. Ketelaar and J. van Dranen, ibid. 69, 477
(1949).
 The mechanism of the reaction, etc. 71 (1952) RECUEIL 477
__I__

e e
*O o, ; ,o

A B C
Fig. 1.

For a semi-quantitative calculation of the energy content of each of

these transition states we can make use of a wave-mechanical method
described elsewhere, in which, however, the interaction of the charges
on the oxygen atoms and the positive charge in the aromatic nucleus
must be taken into account 11). For the discussion in question however
we shall be satisfied with a qualitative consideration, which will make
the principle sufficiently clear.
Seventeen canonical structures can be set out for the transition state
A. 23 for B and 13 for C. This indicates that the activation energy for
the reaction according to B is the lowest. In the electrophilic bromi-
nation or chlorination this is the effect which has the most important
influence on the energy content o f the transition state, so that it
would be expected that these substitution reactions would take place
according to B. i.e. on carbon atom 3, which is in agreement with
experiments 1 2 ) .
However, in ozonisation we must, in addition, take into account the
interaction of the charges in the transition state which is much greater
here than with bromination. It is found that a stabilisation of the
transition state results from the interaction between the charges e l , e2
and e3 with the positive charges in the nucleus (el en el') (see fig. 2 ) .
A rough calculation shows that this effect is of the order of 17-20
kcal/mol when the charge e4 is equal to the charge of an electron.
Actually e, will be smaller, but it is clear that this effect is large
enough to exert considerable influence on the energy content of the
transition state.

il) For the principle of such calculations. see F. L. 1. Sixme, J. Chem. Phys.
19, 1209 (1951).
le) H . Vollmann, H . Becker. M . Corell and H . Sfrecck, Ann. 531, 1 (1937).
478 F. L. J. Sixma and 1. P. Wibaut,

In our further discussion we can distinguish two models for the

transition state:
( a ) the symmetrical model in which the interaction of the charges
on the ottho-carbon atoms (e4 and e4') is equally great.
( b ) an asymmetrical model in which the influence of the charge e4
is much greater than e4'.

Fig. 2a. Fig. 2b.

T h e choice between these models is not possible without further

knowledge, but on the basis of the results obtained in the ozonolysis
of polycyclic aromatic ring systems we are inclined to prefer the
asymmetrical model. On the basis of- this model it can be explained
why the addition of ozone occurs preferentially on the bond with the
lowest localisation energy.
The stabilisation by electrostatic interaction will be greater in pro-
portion to the charge e4 on the "ortho"-carbon atom, O n considering
the limiting structures of the transition states A, B and C for the
ozonisation of pyrene it follows, that in case A of the 17 limiting
structures 5 have a positive charge on the "ortho"-carbon atoms
(i.e. carbon atom 2 ) . In B this is the case with 3 of the 23 limiting
structures, in C with 3 of the 13 possible structures. The stabilisation
of the transition state due to the electrostatic forces therefore de-
creases in the order A > C > B. Thus, this effect acts in a contrary
direction to the effect of the localisation energy, which is necessary for
the formation of the transition state, Without detailed calculations it
may be seen, that in spite of a certain agreement in the reaction
mechanism, bromination and ozonisation are not necessarily bound to
 The mechanism of the reaction, etc. 71 (1952) RECUEIL 479

..
occur in the same position in the molecule. Finally, under the effect
of the charges on the oxygen atoms not all the limiting structures
which contribute to the transition state will have the same energy
content. The structures with positive charge close by the position where
the O3 will be attached will be of greater significance. This effect also
favours reaction according to A.

4. Some remarks on other reactions.

Although the transition state for the nitration reaction looked at
superficially shows a great similarity to that for the addition of ozone,
it may not be concluded that the nitration and ozonisation will attack
the same place in the molecule. Calculation shows that the interaction
of the charges of the nitrogroup and the nucleus is the reverse of that
coming into consideration for ozonisation, since the repuision el - e4
predominates in the former case. This indicates therefore that the
increase in energy by electrostatic interaction in nitration decreases
in the order A > C > B and therefore in this case substitution accor-
ding to B will be favoured both by this interaction and by the locali-
sation energy.

Fig. 3.

In the semi-quantitative consideration of the transition state of the

ozonisation of naphthalene which we gave previously, the electrostatic
effect appears to be not large enough to exceed the effect of the
localisation energy.
The qualitative considerations developed for pyrene can also be
applied to other polycyclic systems thus in the case of 1,2-benzanthra-
cene the localisation energy for electrophilic substitution appears to
increase in the order 10 < 9 < 5 < 3.4 < remaining positions.
410 F. L: 1. Sixma and 1. P. Wibaut,

7
6- 3
5 10 4
T h e great reactivity of positions 10 and 9 towards most electro-
philic reagents is in agreement with this. T h e effect of the interaction
of the charges (which in ozonisation signifies a lowering of the energy
of the transition state) decreases in the following order:
3,i> 6,7> 8 > 5 > 1’> 3’> 2/> 4/> 10>9
From this it is understandable why the addition of ozone attacks
positions 3 or 4.
If the bond localisation energy is derived from the number of limiting
structures, possible for the remaining n-electron system after locali-
sation. this calculation is strictly analogous to the discussion given
above on the effect of the charge interaction in the transition state.
T h e following figure illustrates this point. T h e connection between

Fig. 4.
For the remaining part For this transition state
of the molecule 5 cano- 5 structures are possible
nical structures are with a positive charge on
possible. carbon atom 2 (for all
other structures the inter-
action of the charges is
smaller on account of the
greater distatice).

the localisation theory of Kooym,an and Ketelaar and the mechanism

suggested by us is clearly apparent from this figure. T h e stabilising
effect of the charges is greatest for that transition state which leads
to the addition of ozone to the bond with the lowest bond localisation
energy (and with the highest bond order).
5. Conclusion.
W e have set out in section 2 the arguments which have lead US to
the conclusion that the addition of ozone to aromatic compounds is a n
 The mechanism of the reaction, efc. 71 (1952) RECUEIL 481
___ _ _ ~ . ~

electrophilic reaction. T h e model of the transition state of the reaction

which accounts for this electrophilic character, is discussed in detail.
Although there is a certain agreement with the transition state of the
electrophilic substitution reactions there are also marked differences,
so that it is not justifiable to conclude from this agreement, that ozone
will attack all aromatic compounds in the same position as electrophilic
substitution reagents. It is pointed out how the strong influence of
the negative charge on two of the oxygen atoms may influence the
energy content of the different transition states, which may lead to the
consequence, that in certain cases ( pyrene. benzanthracene) addition
of ozone to the aromatic nucleus takes place at another position to
that of bromination or nitration. T h e stabilising action of the charges
of the transition state is strongest for that transition state in which
the reaction takes place a t a bond with a high bond order (low bond
localisation energy). W e are of the opinion therefore, that the picture
of the transition state which we have formulated is not in contra-
diction with the interpretation given by Kooyman and Ketelaar, but
is in reality an extension of these views, which makes it possible to
explain the effect of substituents and catalysts on the reaction velocity.
T h e formation of a n-complex may possibly precede the formation
of the transition state. a s is suggested by Dewar 9 ) for electrophilic
substitution. In electrophilic substitution however the cause of the
directing effect is not sought in the 3-complex, but in the transition
state of the reaction, formed from it 1 9 ) . In pyrene also it appears
to us improbable that the formation of the n-complex will determine
the position in the molecule where the attack by ozone will take place.
Indeed a n-bond with a nitronium ion or a Br@-ion should then be
formed also preferably on the 1,2-bond, so that this would not explain
why ozone adds on to a 1.2:bond whereas electrophilic substitution
occurs on carbon atom 3.

(Received September 22nd 1951).

1s) Cf. Dewar, 1.c. page 169.

LXXI 17