73 (1954) RECUEIL 431

____-- ___~_

542.943.5 : 547.652 : 547.521

ON T H E OZONIZATION A N D T H E OZONOLYSIS OF
NAPHTHALENE, 2,3-DIMETHYLNAPHTHALENE, AND
lf4-DIMETHYLNAPHTHALENE I N CONNECTION
W I T H T H E REACTIVITY OF T H E RING SYSTEM.
BY

L. W. F. KAMPSOHMIDT and J. P. WIBAUT1) 2)

(Laboratory for Organic Chemistry, University of Amsterdam).

From a kinetic investigation of the action of ozone on naphthalene and

2,3dimethylnaphthalene it appears that in both cases two molecules of
ozone are rapidly taken up; the diozonide formed continues to react very
slowly with ozone.
From the compounds formed upon ozonolysis of 2,3-dimethylnaphthalene
it follows that upon the action of ozone on 2.3-dimethylnaphthalene two
isomeric diozonides are formed: in one diozonide (main product) the
0, groups are bound in the methylated six-membered ring, the other
diozonide (by-product) contains the 0, groups in the non-methylated six-
membered ring. '

On the strength of theoretical considerations and kinetic investigations of

the ozonization reaction, a reaction mechanism is framed according to which
the first molecule of ozone adds on to an .-,!Ibond of the ring system.
From the reaction mechanism framed it is inferred what aliphatic and
aromatic decomposition products may be formed in the omnolysis of
naphthalene and of 2,Mimethylnaphthalene. The decomposition products
to be expected have all been found and identified. From the aromatic and
aliphatic decomposition products formed in the ozonolysis of 1,4-dimethyl-
naphthalene it follows that also upon the action of ozone on this naphthalene
homologue a molecule of ozone primarily adds on to an a-/l bond.

4 1 . Introduction.
The classical structural theory of organic chemistry mainly discusses
the following valency structures for naphthalene:

1) L. W . F. Kampschmidf, Thesis Amsterdam, 1950.

2) J. P . Wibauf and L. W . F. Kampschmidt, Proc. Koninkl. Ned. Akad. Weten-
schap. 53, 1109 (1950).
432 L. W . F. Kampschmidt and 7. P . Wibaut,

I Ill

On the strength of the chemical behaviour of naphthaIene de-

rivatives, Marckwald 5 ) assumed that the naphthalene ring reacts
exclusively according to structure I. This view was supported by later
investigations of Fries 4 ) and Fieser 5 ) and their collaborators. T h e
argumentation is based, among other things, on the behaviour of
,%naphthol and related compounds in substitution reactions. In the
present paper we are not going into this argumentation any further,
but refer for this to earlier publications.
Fieser's view that a fixed Erlenmeyer-Graebe structure ( I ) is to
be attributed to naphthalene is not in agreement with modern
experimental and theoretical research. Naphthalene is a resonance
hybrid between various limiting structures, of which the structures 1,
11, and 111 are the most important.
From an accurate roentgenographic structure determination of
naphthalene the following values were found for the distances in A
of the C-C bonds in the six-membered ring a ) :

estimated standard deviations for:

a! O.006A
a y 0.005
BB 0.009
y y 0.010

The distances of the exterior C-C bonds in the six-membered ring

are not equal, but exhibit alternating values. The a-@ bond has more
of the double-bond character than the a-y bond, and also more than
the B-B bond.
~~

*) W . Marckwald, Ann. 274, 331 (1893): ibid. 279, 1 (1894).

4) K. Fries and collaborators, Ann. 389, 305 (1912); 404, 50 (1914): M4, 121
(1927); 516, 248 (1935).
5 ) L. F. Fieser in an article on the aromatic character in Gilman, Organic
Chemistry, Vol. I, 155 (1942).
6 ) F. R. Ahmed and D. W . 1. Cruickshank, Acta Cryst. 5, 852 (1952): 9. C.
Abraham, 1. M . Robertson. and S. G. White, Acta Cryst. 2, 233, 238 (1949).
 On the ozonization and the ozonolysis, etc. 73 (1954) RECUEIL 433

In the framework of the investigations of Wibaut and coworkers

on the ozonolysis of aromatic compounds, one of the present authors
(W.) in co-operation with uan Dijk 7 ) investigated the ozonolysis of
2,3-dimethylnaphthalene and of 1,4-dimethylnaphthalene a consider-
able time ago. W e asked ourselves the question whether these
dimethylnaphthalenes would react according to different limiting
structures in the reaction with ozone,
During this investigation, which owing to the war had to be dis-
continued prematurely, the following aliphatic decomposition products
of the ozonolysis of 2,3-dimethylnaphthalene were found: dimethyl-
glyoxal, as well as comparatively small amounts of glyoxal and methyl-
glyoxal. In view of this it was concluded that in the reaction with
ozone 2,3-dimethylnaphthalene mainly reacts according to an Erlen-
meyer-Graebe structure, and to a less extent according to an Erdmann
structure.
The ozonization and the ozonolysis of aromatic compounds have
since been extensively investigated by one of the present authors
(W.) with a number of coworkers. From this and from the theoretical
investigations of Kooyman and Ketelaar a deeper insight into the
nature of these reactions has been gained. It is for this reason that
we have resumed our research on the ozonolysis of naphthalene and
the above-mentioned dimethylnaphthalenes.
5 2. Before proceeding to describe our investigation, we would
make a few remarks on reactions with ozone. From the classical work
of Harries it has appeared that ozone is a specific reagent for an
aliphatic double bond. Rieche 8 ) unambigously determined the structure
of the mono-ozonide of butene-2. In view of this, the ozonization of
alkenes of this type is formulated as follows:

H H
I I
R-c=c-R~+o~--+ R-C-0-C-R,
I I \ /
H H 0-0

In recent work, Criegee and coworkers have described crystalline

mono-ozonides of cyclopentene and of methyl-cyclopentenes; to these
ozonides they assign a structure which is analogous to the structure
of butene ozonide. Criegee points out that only in a few cases have
well-defined mono-ozonides been obtained. During the action of

7) J. P. Wibauf and J. van Dijk, Rec. trav. d i m . 65, 413 (1946).

8) A. Rieche, R. Meisfer, and H. Saufhoff, Ann. 553, 187 (1942).

LXXIII 15
434 I.. W.P. Karnpschrnidt and J. P. Wibaut,

ozone or an ethene derivative of the type R,R,C=CR,R, no ozonide

is formed according to Criegee, but the C = C bond is split up directly,
with the formation of a ketone and a dimeric (or polymeric) ketone
peroxide.
It is striking that the ozonization of alkenes proceeds very rapidly
even at low temperatures, while under very mild conditions the carbon
chain is broken at the double bond, either by the formation of an
ozonide or according to the reaction ,mechanism of Criegee just
mentioned 9 ) . Rieche assumes that the ozone molecule primarily adds
on to a double bond: in this way a highly unstable intermediate
product is supposed to be formed, which is rapidly converted into an
ozonide:

H H H H H H
I 1 I I I I
R-C=C-R’+Oj+ R-C-C-R’+R-C -0-C-RI
I I ‘0-0’
Lo-oo
,J (4

It is obvious that this formulation does not solve the question why
the carbon chain is so readily broken.

4 2.Decomposition of the ozonides.

From the work of several investigators it has appeared that the
hydrolytic decomposition of ozonides may proceed in different ways.
Rieche assumes that primarily a hydroxyalkyl hydroperoxide is
formed, which in the simplest case may react as follows:
,o-0

H
/
R-C-O-CC++HzO+
I
\

H
I
R-
. H
SOH
OOH
+R-C\ I
HL
/OH
OH
R-C=O+H20
I
H

+ R-C=O+H202 or:
I
H H

R-C + R-COOH + HzO

pH
I ‘OH
H

9) R. Criegee, Ann. 583, 1 (1953).

 On the ozoniration and the oronolysis, efc. 73 (1954) RECUEIL 435

In this way there is thus formed an aldehyde and the corresponding

canboxylic acid. Further it is possible that the aldehyde is oxidized to
a carboxylic acid by peroxides formed in the hydrolysis.
A spontaneous decomposition of the mono ozonide is also possible,
involving the formation of a carbonyl compound and a carboxylic acid:
,o-0
R-C - 0 -\C-R -+ R-C-0-0 +R-C=O
HI HI [e,I
R-COOH
5 3. In the discussion of the reaction of ozone with aromatic
hydrocarbons it should be borne in mind that the aromatic ring
system does not contain any double bonds in its ground state.
Considerations based on the ozonization of alkenes cannot therefore
be applied without any modification to the ozonization of aromatics.
Kooyman and Ketelaar’o), who were the first to point out this
difficulty, deal with the reaction of ozone with aromatic hydro-
carbons on the basis of the resonance theory. They assume that
the ozonization is preceded by the formation of one double bond
only (in all probability a polarized one): this double bond
formation is called the “localization” of an aromatic bond. Accord-
ing to Kooyman and Ketelaar the assumption that the naphthalene
molecule is converted into one of its valency structures, which
subsequently reacts with ozone, must be rejected on energetic
grounds. These authors infer from the localization theory that the
ozone will attack the naphthalene molecule at an a-p bond”).
An extension of this theory became possible when it was found
in our laboratory that the ozonization of benzene or chlorobenzene
is accelerated catalytically by AlCI,, BF, or FeCl,, which halides
are typical catalysts for the substitution of halogen in aromatic
rings. This was an indication that the ozonization of aromatics
proceeds according to an electrophilic mechanism. This view was con-
firmed by measurements of the ozonization velocity of benzene and a
number of substitution products 12a, b). In view of this, the theory
about the electrophilic substitution in aromatic compounds, framed by
one of the present authors ( W ) and Sixma, can be extended to the
ozonization of aromatics 1 Z a ) .

lo) E. C. Kooyman and 1. A. A. Ketelaar, Rec. trav .chim. 65, 859 (1946).
11) For a discussion of this matter, cf. Wibauf and Kampschmidt, vide ref. *).
12) a. J. P. Wibauf, F. L. 1. Sixma, L. W. F. Kampschmidt, and H. Boer,
Rec. trav. chim. 69, 1355 (1950); b. J. P. Wibaut and F. L. J. Sixma, ibid. 71, 761
(1952).
436 L. W . F. Kampschmidt and J. P. Wibaut,
___ ____.___

4 4. Ozonization and ozonolysis of naphthalene.

W e assume that the ozone molecule reacts according to a polar
structure, the central 0-atom of which carries a positive charge. The
aromatic nucleus will be polarized under the influence of the polar
ozone molecule, so that in the activated state two n-electrons will be
localized to one of the carbon atoms of the aromatic ring. Thus a
homopolar band may be formed between this carbon atom and the
ozone molecule, resulting in the formation of a reaction complex by an
electrophilic addition.
,The hypothesis of the localization of two n-electrons to a carbon
atom of the naphthtalene ring, which is an extension of the localization
hypothesis of Kooyman and Ketelaar, has been introduced by Wibaut
and Sixma 13) to account for the bromination process of naphthalene.
Sixma 14) demonstrated, by a calculation according to the molecular
orbital method, that localization of two n-electrons to an z-C atom of
the naphthalene ring requires less energy than localization to a
0-C atom. The calculated difference in localization energy for the
u and @ positions is of the same order of magnitude as the difference
in activation energy calculated from the bromination experiments by
Suyver and Wibaut 15).
From this it follows that an ozone molecule will react preferentially
with an a-C atom, the a-@ bond being polarized, for in this case the
primary products formed contain an aromatic ring system. Formation
of a primary product with, polarization of the a-y bond is, on energetic
grounds, less probable. as may be deduced from the localization theory
of Kooyman and Ketelaar. These reactions may be reproduced by the
following mechanism.
Since the reaction B, in which the primarily formed mono-ozonide
arises through polarization of an a-y bond, is less probable than the
reaction A, the ozonization of naphthalene will give rise mainly to a
diozonide IV; this is in agreement with the experimental data.
The action of ozone on naphthalene was first investigated by Harries
and Weiss16); they found that an explosive diozonide C,,H,06 is
formed in the reaction. Upon decomposition of this diozonide, ortho-
phthaldialdehyde is formed, as was demonstrated qualitatively by the

)'1 J. P. Wibaut and F. L. J. Sixma, Proc. Koninkl. Ned. Akad. Wetenschap. 51,
776 (1948); 52, 214 (1949).
1 4 ) F. L. J. Sixme, Rec. trav. Aim. 68, 915 (1949).
16) J. €7. Suyver and J. P. Wibaut, Rec .trav. Aim. 64, 65 (1945).
1') C. Harries and V. Weiss, Ann. 343, 311 ( 1905).
 O n the ozonization and the ozonolysis, etc. 73 (1954) RECUEIL 437

0 3 V

above authors: the other decomposition product to be expected, viz.

glyoxal, was not found by them.
438 L. W . F. Kampschmidt and 1. P . Wibaut,

Seekles 17) investigated the action of ozone on naphthalene once

more with a view to a method for preparing o-phthaldialdehyde. He
obtained this substance in a yield of 10 %, and side by side with it
o-phthalic acid aldehyde in a yield of 70 %; these two products
having been formed by decomposition of naphthalene diozonide, it
appears that this compound is formed as the main product in the
ozonization of naphthalene. This result is confirmed by quantitative
measurements, performed by us in co-operation with Dr. F. L. J.
S'txma.
Fig. 1 represents the consumption of moles of ozone per mole of
naphthalene as a function of the time (solvent chloroform, tempera-
ture -40').

fig. 1

10 20 ' j o . So so 60 70 . 00 wtimc inminula

The rate of reaction drops appreciably after 2.02 moles of ozone

have been taken up per mole of naphthalene. The diozonide formed
continues to react very slowly with ozone, the second six-membered
ring being attacked, with formation of a pentozonide. The fact that
the bend in the curve occurs at 2.02 moles, and not at 2 moles of
ozone, implies that already during the first stage of the reaction some
pentozonide was formed: a rough calculation shows that this quantity
is about 0.1 mole.
If in the mixture of the ozonidcs a triozonide VI should be present.
o-quinone would have to be formed from it by hydrolysis. W e have
not, however, found any indication as to the formation of this quinone.

17) L. Seekles, Rec. trav. chim. 42, 707 (1923).

 O n the ozonization and the oronolysis, etc. 73 (1954) RECUEIL 439

Very little is known as yet about the way in which the oxygen atoms
are bound in ozonides derived from aromatic hydrocarbons; the same
applies to the chemism of the decomposition of these ozonides. At best
we know the final products of the ozonolysis. Thus in the hydrolytic
decomposition of the triozonide of o-xylene are formed glyoxal,
methylglyoxal, dimethylglybxal, side by side with considerable quanti-
ties of formic acid, acetic acid, and oxalic acid.
In the formulae given below we indicate the hydrolytic decomposition
of the ozonides diagrammatically, and ignore the formation of per-
oxides. It has already been mentioned that in the hydrolytic decom-
position of naphthalene diozonide, phthaldialdehyde (VII) or a
derivative thereof has been observed. W e have now also found the
second decomposition product to be expected, viz. glyoxal (VIII).
In the method of working up used by us, naphthalene diozonide is
treated at a low temperature with a soda-alkaline solution of hydroxyl-
amine. The glyoxal formed by the decomposition of the diozonide is
converted into glyoxime, which was identified through the mixed
melting point with an authentic preparation.
From phthaldialdehyde is formed, by the action of hydroxylamine,
the mono-oxime of phthalimide (IX) (melting point 256.5'). which we
identified through the mixed melting point with an authentic pre-
paration 1 8 ) .

93 H

a!
# ,

2HzO -* +H-C-C-H
II II
'. +
0 0
. I
I

0 3
HzNOH
IV

H-C-C-H
II II

1x

18) Cf. L. W . F. Kampschmidf and 1. P. Wibauf, Rec. trav. d i m . 71, 601 (1952).
440 L. W . F. Kampschmidt and J. P. Wibaut,

8 5. Ozonolysis of 2,3-dimethylnaphthalene,
W e determined in the first place the consumption of ozone per
millimole of 2,3-dimethylnaphthalene as a function of the time (vide
Fig. 2).

fig. 2

At -40° the reaction proceeds very rapidly until 2.04 mmoles of

ozone per mmole of hydrocarbon have been taken up: at this point
the curve exhibits a sharp bend, and the action of ozone continues
slowly, with formation of pentozonide. This latter reaction proceeds
slightly more rapidly than with naphthalene.
W e subsequently examined what aromatic decomposition products
are formed in the ozonolysis of 2,3-dimethylnaphthalene. From the
results obtained it appears that two isomeric diozonides ( X and XI)
are formed. The reaction in which the methylated six-membered ring
is attacked is the main reaction A; this was to be expected in view of
the results obtained by Wibaut and van Dijk,who found that the
ozonization velocity increases with the number of methyl groups
substituted in a benzene nucleus. In the side-reaction B, two molecules
of ozone enter the non-methylated six-membered ring.
With dimethylnaphthalene, too, we assume that an ozone molecule
will preferably react with an a-C atom of a six-membered ring; the
primarily formed mono-ozonides possess a double bond, and will be
rapidly converted into the corresponding diozonides, of which X will
give o-phthaldialdehyde and dimethylglyoxal XI1 upon decomposition,
while from XI will be formed 4,5-dimethylphthaldialdehyde (XIII)
and glyoxal.
 I

I
I ,
,'
0;
X XI
442 L. W . F. Kampschmidt and 1. P. Wibaut,

Kooyman 19) already observed on an earlier occasion that the setting

in of the side-reaction B, through which the diozonide XI was
supposed to be formed, may account for the fact that in the ozonolysis
of 2,3-dimethylnapthalene a small amount of methylglyoxal is formed.
He assumes that from XI, in which an aromatic six-membered ring
is present, two isomeric pentozonides XIV and X V may be formed.

XIV xv XVI

From the pentozonide XV, methylglyoxal will be formed upon

hydrolytic decomposition.
W e will now discuss the experimental data forming the basis of
the above-mentioned reaction mechanisms.
a ) We found the following aromatic decomposition products
derived from the diozonide X: phfhalic acid (35 %), phthalirnide
(5 % ) , mono-oxime of phthalimide ( 10 % ) , dioxime of phthalimide
(about 1 %). The phthalic acid may be formed by oxidaton of
primarily formed phthaldialdehyde; the other derivatives have been
formed from this dialdehyde by the action of hydroxylamine in soda-
alkaline medium'*). Each of the compounds mentioned has been
identified through the melting point and the mixed melting point with
an authentic preparation. The figures between brackets indicate the
yield in % of the theory, calculated on the quantity of 2,3-dimethyl-
naphthalene used. These figures represent minimum values, since it
was not possible to perform a quantitative analysis of the mixture of
the reaction products.
b ) We found the following aromatic decomposition products
derived from the diozonide XI: 4,5-dirnefhylphfhalic acid, formed from
primarily produced 45-dimethylphthalic 1,2-dialdehyde ( XI11) , and
probably the imide of 4.5-dimethylphthalic acid. ,This imide, which has
been formed through the action of hydroxylamine on XIII, could not

19) E. C. Kooyman, Rec. trav. chim. 66, 201 (1947).

 O n fhe oronization and the oronolysis, efc. 73 (1954) RECUEIL 443

be separated in the pure state; the presence of this compound in the

mixture of the reaction products has proved very plausible. These
compounds being present in minor amounts in the mixture of the
decomposition products, it is not possible to give figures of the yields.
c) The aliphatic decomposition products found by us were
dirnefhylglyoxal ( 9 "/o ) , glyoxal ( 1.4 % ) , and rnethylglyoxal (XVI)
(about 0.4 % ) , These dicarbonyl compounds were isolated in the form
of the dioximes, and identified through. the mixed melting points. In
addition we found acetic acid (70-75 "/o ). The yields are given in "/o
of the theory, calculated on the quantity of 2,3-dimethylnaphthalene
used.
As to the aliphatic decomposition products dimethylglyoxal, methyl-
glyoxal, and glyoxal, we can confirm the result obtained by Wibaut
and van Dijk 7 ) qualitatively. The total yield of aromatic decomposition
products derived from the diozonide XI amounts to approximately
50 "/o. Since the figures of the yields are to be considered minimum
values, this implies that the action of ozone on 2,3-dimethylnaphthalene
proceeds for more than 50 "/o according to scheme A.
It is striking that the yield of dimethylglyoxal, which is also formed
according to scheme A, is only 9 % of the theory. Perhaps this deficit
is caused by the oxidation to acetic acid of the primarily formed
diacetyl by hydrogen peroxide formed in the hydrolysis of the
ozonides.
In experiment 1, Table I, we found 9.1 % of dimethylglyoxal (as
the dioxime) and 70 % of acetic acid. If the latter compound has
been formed from dimethylglyoxal, the 2,3-dimethylnaphthalene would
have reacted for 79 "/o according to scheme A. Even if the acetic acid
has been formed by the direct decomposition of a diozonide, the latter
diozonide must have been produced by an attack on the methylated
six-membered ring. It may therefore be concluded that the action of
ozone on 2.3-dimethylnaphthalene proceeds for about 80 "/o according
to scheme A.
W e already observed that methylglyoxal is formed by decomposition
of XV, which may be regarded as the pentozonide of an Erdmann
structure. It is to be expected that the ratio methylglyoxal : dimethyl-
glyoxal will increase according as ozone is introduced during a longer
period, because more pentozonide will then be formed. This expectation
is confirmed by the experiment (Table I ) .
It is found that in experiment 1, where exactly two moles of ozone
per mole of dimethylnaphthalene were passed through, a small amount
of methylglyoxal is yet formed. This is in agreement with the form
of curve 2.
444 L. W.P. Kempschmidt and J. P. Wibaut,

T a b l e I.
2.3-dimethyl- ozone pamd dimethyl-
naphthalene through in glyoxime
in mmoles mmoles in mmoles

100 4.55 0.21 0.7

300 1.9 0.19 0.66

Q 6. The ozonolysis of 1,4-dimethylnaphthalene.

In accordance with the reaction mechanism discussed in Q Q 4 and 5
we assume that an ozone molecule reacts with an a-C atom of 1,4-di-
methylnaphthalene, and that the primary product is mainly formed by
polarization of an .-/Ibond. It is conceivable that two isomeric
diozonides XVII and XVIII are formed according as the methylated
six-membered ring or the non-methylated six-membered ring is
attacked by ozone. From an examination of the aromatic decomposition
products of the ozonolysis we found that it is mainly the reaction A
which takes place:
a 3
I

hydrolysis I hydrdyisis I
a 3

+ H-C-C-H
II II
+ H-C-C-H
II II
=O 0 0 o=c
O = Y i 0 0
I I I
a 3 H a 3
XIX xx
non isolated
 O n the ozonizafion and the ozonolysis, etc. 73 (1954) RECUEIL 445
-
If the ozonization is carried out in highly concentrated acetic acid
as solvent, a small amount of a compound may be isolated which
probably consists of impure 1.2-diacetylbenzene (XIX). If the
ozonization is carried out in chloroform, and the solution of the
ozonides is treated with soda-alkaline hydroxylamine, the cyclic
anhydride of the oxime of o-acetylbenzoic acid (XXI) is formed in
a yield of 15 % in respect of 1.4-dimethylnaphthalene. The formation
of this compound may be conceived to be as follows:

-
a 3

oxidation by peroxides HiNOH

\/\c=O
I I
a 3 a 3

XIX

0
/ II
I\/\C=NOH
ar

I
CH3
CH3
XXI

An analogous case presents itself in the ozonolysis of 5,8-dimethyl-

quinoline, where after decomposition of the ozonides by a soda-
alkaline solution of hydroxylamine the cyclic anhydride of the oxime
of 2-acetylpyridine-carboxylic acid is formed 2 0 ) .
From the diozonide XVIII, 3.6-dimethylphthaldialdehyde ( X X )
ought to be formed. W e have not succeeded in isolating this compound
or a derivative thereof, so that it has not strictly been proved that
the side-reaction B takes place.
The occurrence of the side-reaction B is in agreement with the
results obtained by Wibaut and van Dijk7). In a preliminary
investigation about the ozonolysis of 1,4-dimethylnaphthalene, in the
course of which it was examined what aliphatic dicarbonyl compounds

1 0 ) J . P. Wibaut and H . Boer, Proc. Koninkl. Ned. Akad. Wetenschap. 53, 19

(1950).
446 L. W . F. Kampschmidf and I. P. Wibaut,

are thus formed, the said investigators found glyoxal and methyl-
glyoxal in a combined yield of 1-1.5 %. 3-6 moles of glyoxal were
formed to 1 mole of methylglyoxal. T h e formation of glyoxal is in
agreement with reaction scheme A or with reaction scheme B. Methyl-
glyoxal may be formed by decomposition of a pentozonide, derived
from an Erdmann structure. This pentozonide may be formed by
continued action of ozone on the diozonide XVIII (scheme B).
This formation of methylglyoxal in the ozonolysis of 1,4-dimethyl-
naphthalene is analogous to the formation of this ketoaldehyde in the
ozonolysis of 2,3-dimethylnaphthalene. W e have found that thz
ozonides formed from 1,4-dimethylnaphthalenes are not readily
decomposed by water. ,This may be one of the causes why Wibaut
and van Dijk obtained only small amounts of glyoxal and methyl-
glyoxal with the method used by them.
97. Summary and conclusions.
On the strength of the localization theory developed by Kooyman
and Ketelaar, of the extension given to this by Sixma and one of the
present authors (W.), as also of the electrophilic mechanism for the
ozonization reaction as framed by Wibaut, Sixma, Kampschmidf, and
Boer, it is derived that an ozone molecule will preferably react with
an u-b bond of the naphthalene ring.
As a result of this, an unstable mono-ozonide will be formed, from
which a comparatively stable diozonide will rapidly be formed. In
accordance with this requirement of the theory it has been found by
us that naphthalene reacts rapidly with two molecules of ozone, and
that the diozonide thus formed continues to react with ozone much
more slowly. The structure assumed for this naphthalene diozonide
is in agreement with the decomposition products found: phthal-
dialdehyde, or derivatives thereof, and glyoxal.
The fact that in the ozonolysis of naphthalene no o-benzoquinone
is formed is in agreement with the assumption that the first molecule
of ozone reacts with an a-,9 bond, and not with an a-y bond; in the
latter case the formation of a naphthalene triozonide might be expected,
from which o-benzoquinone might be formed by decomposition.
T h e experimental results are in agreement with the roentgenographic
structure determination of naphthalene, from which it follows that an
a-p bond has more of a double-bond character than an .x-y or a
p-p bond.
Upon the action of ozone on 2,3-dimethylnaphthalene, 2 molecules
of ozone are rapidly taken up. Thus two isomeric diozonides are formed,
a possibility which was already pointed out by Kooyman on an earlier
occasion. The main product formed is a diozonide in whch two
 On the ozoniration and the ozonolysis, etc. 73 (1954) RECUEIL 147

0, groups are linked in the methylated six-membered ring: the

by-product is a diozonide in which the 0, groups are linked in the
non-methylated six-membered ring. This has been proved by the
isolation of a number of aromatic and aliphatic compounds, which have
been formed by the decomposition of the two dimethylnaphthalene
diozonides. From the nature of these decomposition products it may
further be concluded that upon the action of ozone on 2,3-dimethyl-
naphthalene the first molecule of ozone adds on to an 2-b bond.
T h e experimentally found fact that mainly the methylated six-
membered ring reacts with ozone is in agreement with measure-
ments I z b ) performed in our laboratory, from which it was found that
the introduction of methyl groups into the benzene nucleus results in
an increased reactivity towards ozone.
T h e diozonides of 2.3-dimethylnaphthalene react slightly more
rapidly with ozone than the naphthalene diozonide. By decomposition
of one of the pentozonides formed upon continued ozonization there
may be formed methylglyoxal, which was found by Wibaut and van
Dijk, and has now been confirmed by us.
Upon the action of ozone on 1,4-dimethylnaphthalene the product
mainly formed is a diozonide in which the 0, groups alp linked in the
methylated six-membered ring.
It is probable that as by-product is formed a diozonide in which the
0, groups are linked in the non-methylated six-membered ring. From
this diozonide, upon continued action of ozone a pentozonide may be
formed, from which methylglyoxal may be produced by hydrolysis:
Wibaut and van Dijk found a small amount of methylglyoxal in the
ozonolysis of 1,4-dimethylnaphthalene.Upon the ozonization of 1.4-di-
methylnaphthalene the first molecule of ozone reacts with an a-0 bond.
T h e results of our investigation are in agreement with the
investigations of Marckwald, Fries, Fieser and others referred to in
9 1, on the reactivity of certain naphthalene derivatives, in particular
on the introduction of substituents into /?-naphthol: in order to account
for the course of this reaction, the said investigators assumed that a
reactive double bond occurs between the a-C atom and the 0-C atom.

9 8. Experimental part+).
Starting materials:
Naphthalene. A commercial product of good quality was distilled over sodium,
and subsequently recrystallized twice from chloroform.

+) All the melting points given are corrected. The analyses were performed at
the Micro-analytical Department of this laboratory by Messrs P. J. Hubers and
H . Pieters.
448 L. W. F. Kampschmidt and J. P. Wibaut,
__-___ __~___.__ - .- -
._ - .-

2,3-Dimefhyfnaphthafenene.A commercial preparation was purified by reuystal-

lization; melting point 104-105", in agreement with our previous statement;
Schroeter 2 1 ) gives 104-104.5".

1,4-Dimethyfnaphthafene was prepared, starting from 1-methylnaphthalene

according to Robinson and Thompson 22). The preparation obtained by us had a
solidification point of 3.2"; Robinson and Thompson give 5.56.5' for the melting
point, and Wibauf and van Djk mention a solidification point of 3.4".
Chloroform. A commercial sample of chloroform pro nercose was shaken with
concentrated sulphuric a d d to remove ethanol, and after washing with dilute alkali
in water was dried over granulated calcium chloride. Immediately before an
ozonization experiment the chloroform was dried by shaking with phosphorus
pentoxide.
Procedure. Mixtures of ozone and oxygen with an ozone content of 12-15%
were obtained by means of the electrolytic method according to Boer-). The
apparatus for the quantitative determination of the amount of ozone taken up has
been described in earlier publications. For the determination of curve 1 and curve 2
respectively, a weighed quantity (about 6 mmoles) of naphthalene or dimethyl-
naphthalene respectively in chloroform solution was reacted at 4"with ozone.
The ozone content of the entering gases was maintained at a constant value. At
successive moments the exit gas mixture was passed through a neutral solution of
potassium iodidei after acidification, the liberated iodine was titrated with 0.1 n
thiosulphate; from this the ozone content of the exhaust gas is found. With the
application of the necessary corrections it can be calculated how much ozone has
been taken up by the naphthalene.

Omnolysis of naphthalene.
Example of an experiment: Ozone-containing oxygen is introduced for 4 hours into
a solution of 4 g (0.031 mole) of naphthalene in 40 ml of chloroform, cooled to
-25"; about 15 mmoles of ozone are passed through the solution per hour. The bulk
of the chloroform is distilled in vacuo; the residual solution (5 ml) is decanted into
dry ether, which has been cooled to -20". The diozonide of naphthalene predpitates
as a white, amorphous product; this is placed on a cooled glass filter, filtered, and
washed with cold ether. The filtrate contains naphthalene which has not reacted. The
diozonide is treated with a solution of hydroxylamine hydrochloride and soda in
water. At ordinary temperature the decomposition proceeds slowly; finally the
mixture is gently warmed.
The aqueous liquid is shaken with ether; from this ethereal solution, glyoxime is
isolated. After evaporation of the aqueous solution and acidification with acetic a d d
a compound is obtained, which after recrystallization from ethanol or from a mixture
of pyridine and water melts at 256-257". and the composition of which corresponds
to the formula C&,O,N,. This compound is the mono-oxime of phthafimide: mixed
melting point with an authentic preparation 256.5".

*I) G. Schoefer, L. Lichtenstd, D. Zrineu, Ber. 51, 1587 (1918).

*) R. Robinson and H. W. Thompson, Chem. SOC.1932, 2016.
**) H. Boer, Rec. trav. chim. 67, 217 (1948).
 O n the oronization and the ozonolysis, etc. 73 (1954) RECUEIL 449
.- - ~ - ~ _ _

Attempts at detecting a-benroquinone.

Jackson and Koch 2') state that from a solution of o-benzoquinone in chloroform can
be formed a black-coloured decomposition product: dioxyphenyloxybenzoquinone;
they prepared a tribenzoyl derivative of this compound, which could not be obtained
in a crystalline form.
a ) W e noted that upon the decomposition of the naphthalene diozonide by means
of a soda-alkaline solution of hydroxylamine hydrochloride there were sometimes
formed black, amorphous products. This amorphous mass contains, among other
compounds, the above-mentioned mono-oxime of phthalimide, which we demonstrated
by treating the black, amorphous product with benzoyl chloride. Thus a crystalline
substance, m.p. 243". is formed, the analysis of which corresponds to a benzoyl
derivate of the mono-oxime of phthalimide (found: C 67.94%. H 3.95% N 10.96%:
C,,H,,O,N, requires C 67.66%, H 3.79%. N 10.52%). W e did not find any indication
as to the presence of the benzoyl derivative described by Jackson and Koch.
b) Willstafter 25) states that o-benzoquinone is converted into pyrocatechol almost
quantitatively by reduction with sulphurous acid at ordinary temperature. W e treated
a solution of naphthalene ozonides in chloroform, such as is obtained in the ozoniza-
tion, with an aqueous solution of sulphurous acid; we did not succeed in demonstrating
the presence of pyrocatechol. either in the aqueous layer or in the chloroform.
A suitable reagent for reducing quinones to the corresponding dioxybenzenes is a
suspension of zinc dust in water, into which some sodium chloride and ferrous
sulphate is dissolved. The chloroform solution of naphthalene ozonides was treated
with the above reagent, but we did not find any indication as to the formation of
pyrocatechol.

Otonolysis of 2Jdimethyhaphthaleme.
W e have carried out an extensive preliminary investigation in order to find the best
methods for the separation of the various compounds, both aliphatic and aromatic,
which are formed upon the decomposition of the mixture of ozonides of 2,2dimethyl-
naphthalene. In the following description of an experiment we mention the way in
which such a mixture of ozonides was worked up and the products were separated.
From the data thus obtained, the figures of the yields mentioned in 4 5 have been
calculated.
Into a solution of 7.8 g (0.05 mole) of 2,3-dimethylnaphthalene in 50 ml of
chloroform, cooled to -25", is introduced ozone-reacting oxygen (21 millimoles
of ozone per hour). The temperature of the reaction mixture is maintained at -25 to
-30". After about 100 millimoles of ozone have been passed through, the chloroform
solution is decanted into a concentrated aqueous solution of 17.5 g of hydroxylamine
hydrochloride and 30 g of soda, which has been cooled to 0". The mixture is stored
for two weeks in the ice-box, after which a crystalfraction (B) has separated. The
mixture is filtered (filtrate A), and the crystals are washed with chloroform and
water. The washing liquors are added to filtrate A.
The crystals B are dried, and extracted with boiling ether until the residue (C)
does not produce any reaction with nickel ions. The ethereal extract gives 0.47 g
of residue (D) of m.p. 230". which consists of nearly pure dimethylglyoxime; fhe
latter was purified by sublimation and identified through the mixed melting point
with an authentic preparation. The residue C, which is insoluble in ether, consists
of the mono-oxime of phthalimide with a small amount of the dioxime.

9 C. J. Jackson and W. Koch, Am. Chem. J. 26, 21 (1901).

25) R. Willstitter and A. P)annenstiel, Ber. 37, 4745 (1904).
450 L. W. F. Kampschmidt and J. P. Wibaut,

In the flitrate A the chloroform layer is separated from the soda-alkaline aqueous
layer (E), and the latter is shaken once more with chloroform. This extract is added
to the bulk of the chloroform solution. This chloroform is evaporated. The residue
F is to be discussed later.
The aqueous layer E is extracted with 5 X 50 ml of ether, and subsequently with
2 X 100 ml of ether. The layer E then left is worked up separately. Upon being
worked up, the ethereal extract yields 0.427 g of a residue, which is separated by
sublimation at 100"/20 mm into a sublimate H (0.167 g) and a residue (J). The
crystal fraction H substantially consists of aliphatic dioximes; the fraction J of the
mono- and the dioxime of phthalimide.

Separation of the mixture of the dioximes of glyoxal, methylglyoxal, and dimethyl-

glyoxal,
The bulk of the dimethylglyoxime formed has been separated in fraction D. Owing
to this the above-mentioned dioximes are present in fraction H in such a proportion
that the separation method of Haayman and Wibauteo) can be applied to this
mixture.
The fraction H is extracted with cold chloroform, 0.022 g going into solution; this
product gives the fluorescein reaction, which points to phthalic anhydride or/and
dimethylphthalic anhydride. The residue, which is insoluble in chloroform, contains
0.060 g of dimethylglyoxime, 0.0213 g of methylglyoxime and 0.0626 g of glyoxime.

Determination of the quantity ot acetic acid, and isolation of phthalic acid and
4,5-dimethylphthalic add.
The aqueous layer E is acidified with dilute sulphuric acid, and perforated with
ether for 4 X 24 hours. After evaporation of the ether, the residue is subjected to
steam distillation until a drop of the distillate no longer shows an acid reaction.
In the distillate the quantity of acetic acid is determined by titration with 0.1 n
sodium hydroxide. In another experiment the acetic acid was identified qualitatively.
Formic acid could not be detected.
The residue of the steam distillation is perforated once more with ether for
4 X 24 hours. The residue (L). obtained after this ethereal extract has been worked
up, consists of a mixture of phthalic acid and 4,5-dimethylphthalic acid. Nothing
else can be isolated from the. remaining aqueous layer.

Separation of the mono- and the dioxime of phthalimide.

T h e crystal fractions C and J are added'together, and the mixture is sublimated
at 17G180" and 20 mm. The sublimate melts at 254" and consists of the mono-
om'me of phthalimide, mixed melting point with an authentic preparation 256.5";
yield 15 yo of the theory, calculated on dimethylnaphthalene.
Analysis:
Found: C 59.64; H 3.59; N 17.11.
Calculated for C,H,O,N,: ,, 59.26; ,, 3.73; ,, 17.28.
The residue left after the sublimation is recrystallized from ethanol, with addition
of a small amount of decolourizing carbon. A crystalline product melting at 262'
is obtained, which consists of not completely pure dioxime of phthalimide la).

*e) P. W. Haagman and J. P. Wibaut, Rec. trav. chim. 60, 842 (1941).
 On the oronization and the ozonolysis, etc. 73 (1954) RECUEIL 451

Analysis:
Found: C 54.81; H 4.34: N 23.21.
Calculated for C,H,O,N,: ,, 54.23: ,, 3.99; ,, 23.72.
From this analysis it appears that the crystal fraction still contains a small amount
of the mono-oxime.
In another experiment we obtained a dioxime preparation of melting point
257-258", the mixed melting point with an authentic preparation (263") being
258-260". The yield of dioxime of phthalimide amounts to about 1 yo of the
yield theoretically calculated.

Separation of phthalic acid and 4,5-&methylphthaIic acid *).

The crystal fraction L is extracted with chloroform (extract L,'). The portion
which is not soluble in chloroform is recrystallized from water and sublimated at
20 mm. The sublimate melts at 1 2 6 1 2 7 " . and very clearly exhibits the fluorescein
reaction, which points to phthalic anhydride: mixed melting point with an authentic
preparation 127-128". The yield of phthalic acid amounts to 3 5 % of the theory,
calculated on dimethylnaphthalene.
The chloroform extract is evaporated, and the residue is recrystallized from
water. W e did not succeed in isolating a pure compound from the first crystallisate.
From the mother liquor we obtained a crystal fraction which, by sublimation
in vacuo, two recrystallizations from ether, and sublimation a t ordinary pressure,
yielded 3.4-dimethylphthalic anhydride: melting point 2 0 6 2 0 7 " ; mixed melting
point with an authentic preparation 207-207.5".

Isolation of phthalimide; probable presence of 4.5-dimethylphthalde.

The crystal fraction F is sublimated at 180"/20 mm. the sublimate F' obtained
consists of a mixture of phthalimide and 4,5-dimethylphthalimide. These phthalimides
have been formed at the temperature of the sublimation from the compounds present
in fraction F, which compounds have been formed by the action of hydroxylamine
on the primary product of the ozonolysis, viz. phthaldialdehyde and 4,5-dimethyl-
phthaldialdehyde respectively. In a previous paper 18) we discussed-he mechanism
of the formation of phthalimide; we assume that 4,5dimethylphthalimide is formed
in an analogous manner.
The sublimate F' is washed at ordinary temperature with chloroform, into which
a small portion dissolves. The portion which is insoluble in chloroform is
recrystallized from ethanol, after treatment with "norit", and subsequently sublimated
at 100"/20 mm. The sublimate obtained consists of phthalimide, as appears from
the melting point of 233-234" and the composition.
Analysis:
Found: C 65.53: H 3.53.
C,H,O,N requires: ,, 65.31; ,, 3.40.

The mixed melting point with an authentic preparation (238") was 234-235";
yield 5 % of the theory.

*) 4.5-Dimethylphthalic acid was prepared by boiling 4.5-dimethylphthalimide

with dilute sodium hydroxide solution and subsequently acidifying, upon which
dimethylphthalic acid is formed (melting point 206") This compound is sublimated
in vacuo, as a result of which the desired anhydride is obtained, which is purified
by sublimation: melting point 208-209", in agreement with the statements in the
literature.
452 L. W.F. Kampschmidt and 1. P. Wibaut,

The portion which is soluble in chloroform is washed with boiling petroleum

ether and then with boiling water, and dried (F"). Melting point 239-242'; this
product exhibits a strong melting point depression (187-222") with phthalimide.
The mixed melting point of equal quantities of the product F" and 45dimethyl-
phthalimide (melting point 245") was 241-244" 9.
This finding makes it probable that the fraction F" mainly consists of 4,5-dimethyl-
phthalimide. In order to obtain a confirmation of this, we determined the infra-red
spectrum *) of phthalimide (Fig. 3), of 4,5ditnethylphthalimide (Fig. 4). and of
fraction F" (Fig. 5).
It is seen that the spectrum of the fraction F" is highly similar to that of
4,Sdimethylphthalimide. Especially the bands at 900 cm-1 are characteristic. The
absorption bands in Fig. 5 are less deep than those in Fig. 4, except for the band
at 1055 cm-1. This may be caused by a superposition of the absorption band at
1055 a - 1 in the spectrum of phthalimide (Fig. 3). W e conclude that the fraction
F" in all probability consists of 4.5dimethylphthalimide. contaminated with
phthalimide.

Oozonolysis 01 1,4dimethylnaphthalene.
When 1,4dimethylnaphthalene is ozonized in chloroform solution at a temperature
of -25" and this solution is subsequently decanted in water, it is found that after
48 hours only a small portion of the ozonides have decomposed. Upon evaporation
of the chloroform layer a solid substance is obtained, which begins to decompose at
about 65". with gas development. The escaping gas contains a constituent which
rapidly liberates iodine from a neutral potassium iodide solution. At 80 to 85" the
decomposition is very violent. When the chloroform solution is evaporated
immediately after the ozonization is completed, syrupy products are obtained,
which decompose with great violence at 60".
A further investigation would be required to ascertain whether the ozonides
formed in the ozonization of 1,4dimethylnaphthalene are readily converted into
polymers. However this may be, it appears from our observations that the ozonides
of 1,4dimethylnaphthalene are not readily decomposed by water.
In view of (his we carried out the ozonization and the further treatment of the
ozonides in another way:
a ) 0.5 g (0.016 mole) of 1,4dimethylnaphthalene are dissolved in 50 cms of glacial
acetic acid, and to this is added 1 cm* of water. Upon this, 0.039 mole of ozone
is passed through in 90 minutes at a temperature of -25".
The liquid is then refluxed for three hours in order to decompose the ozonides
formed: the solution then assumes a dark red colour. The acetic acid is evaporated
in uacuo, and the residue is distilled in VBCIIO. At 110" (0.01 mm) a few drops of
a liquid distil, which are taken up in petroleum ether. The solution is evaporated
until turbidity occurs, and is then cooled to -20". A small quantity is separated
of a colourless crystalline substance, which is filtered off. This substance melts at
about 32". and in alcoholic solution exhibits a red to violet colour reaction with
aminoacids, such as glycine, p-alanine, serine, tyrosine. In addition, this substance

2') 4,s-Dimethylphthalimide was prepared according to the directions given by

H.de Diesbach and B. uon der Weid, Helv. Chim. Acta 10, 886 (1927).
*) The infra-red spectra were observed in the Laboratory for General and
Inorganic Chemistry of the University of Amsterdam. W e thank Prof. Dr.J. A. A.
K e t e h r for putting the apparatus at our disposal, and Mr. W. Vedder for the
performance of the measurements.
O n the ozonization and the ozonolysis, etc. 73 (1954) RECUEIL 453

I. . - . . . ,1455
1900 1700 1500 1300 1117' 900 CM-1

,10,!55
900 1/00 1500 1300 I117 900 CM-1

fig. 5
,1055
00 1700 1500 1300 1117. 900 CM-1
454 L. W. F. Karnpschrnidf and J. P. Wibaut, On the ozonization, etc.

in highly dilute solution also gives a violet-blue reaction on the skin. These reactions
indicate that we have obtained impure 1,2-diacetylbenzene *a); for further identi-
fication the amount was too small.
b) Into a solution of 2.2 g (0.014 mole) of 1,4-dimethylnaphthalene in 50 ml
of chloroform cooled to -25', is introduced 0.030 mole of ozone in 70 minutes.
Then the mixture is decanted in a solution of 7.5 g of hydroxylamine hydrochloride
in 125 ml of pyridine, to which 2 ml of water had been added. This mixture was
left to stand for 24 hours, after which it was boiled for 2 hours; the solution then
became dark red. After evaporation of the solvents at low pressure, a syrupy
residue was left, which was subjected to steam distillation. The distillate was tested
for diacetylbenzene and for 3,6dimethylphthalalChyde; these compounds could not
be detected. The aqueous liquid left behind in the distillation flask was freed from
tarry constituents, and extracted with ether. After being worked up, a solid substance
was left, which was found to be soluble in chloroform. After recrystallization from
ethanol, sublimation at 120'125 mm, recrystallization from water, and a second
sublimation, the substance melts at 158-159". It appears from the analysis and
the mixed melting point that this substance is identical with the anhydroxime
of acetophenone-o-carboxylicacid (XXI)(melting point 159-160') ; mixed melting
point with an authentic preparation, 158-159".
Analysis:
Found: C 67.0 H 3.96;N 8.89
Calculated for C,H,O,N: ,, 67.0; ,, 4.36; ,, 8.69.

The yield of this compound amounts to 15% of the theory, calculated on

1,4-dimethylnaphthalene.

The anhydroxime of acetophenone-o-carboxylica d d (XXI)has been described by

Gabriel *9), who caused hydroxylamine to react on the ester of acetophenone-ortho-
carboxylic acid. W e started from the acid itself, which we obtained by the action
of dimethylcadmium on phthalic anhydride $0).
An aqueous solution of 1.6 g of acetophenones-carboxylic acid and an aqueous
solution of 1 g of hydroxylamine hydrochloride and soda were added together.
left to stand for 24 hours, and boiled for some time. Upon this the mixture is
acidified with acetic acid, the anhydroxime crystallizing in beautiful, felt-like
needles. After crystallization from water the melting point is 159-160"; Gabriel
gives 157-159"; de BenneuiZle gives 158-159" (uncorr.).

Amsterdam, January 1954.

(Received January 22nd 1954).

*a) R. Riemschneider, Gazz. chim. ital. 77, 607 (1947).

20) S. Gabriel, Ber. 16, 1995 (1883).
80) P. L. de Benneville, J. Org. Chem. 6, 462 (1941).