82 (1963) RECUEIL

-___-

51

547.461.6.07:547.593.21I ~547.594.3

PREPARATION OF ADIPIC ACID BY OXIDATION OF

CYCLOHEXANOL AND CYCLOHEXANONE WITH NITRIC ACID
Part I. Reaction mechanism
BY

W. 3 . VAN ASSELT and D. W. VAN KREVELEN

(Central Laboratory Staatsmijnen, Geleen and Laboratory for
Chemical Technology, Technological University, Delft)

The oxidation of cyclohexanol with nitric acid to adipic acid proceeds via
two stable intermediates known from the literature 1 viz. 6-hydroxyimino6-nitro hexanoic acid and the hemihydrate of 1,2-cyclohexanedionc, two substances forming beside each other in a given ratio. This ratio can be calculated
as a function of the temperature and of the nitric acid and nitrous acid concentrations. The nitrous acid plays a very important part in the oxidation
process. The oxidation of cyclohexanone proceeds in the same way as that of
cyclohexanol, provided sufficient nitrous acid is present. In the absence of
HNOZ the oxidation does not proceed a t all a t low temperatures.
The catalysts used - ammonium vanadate and copper nitrate - have very
different functions. Under the influence of the vanadate the hemihydrate of
cyclohexanedione is rapidly converted to adipic acid, whereas in the absence of
vanadate this substance is slowly broken down to glutaric acid, succinic acid and
oxalic acid. Copper is effective only at higher tempcraturcs where it prevents the
further break-down of unstable inter mediates.

A. Introduction
The oxidation of cyclohexanol to adipic acid by means of nitric acid
proceeds via some stable and instable intermediates.
In the light of the data and suggestions published by Lindsay1 and
Godt 2 the mechanism of the oxidation can be pictured as set forth below:

Cyclohexanol is first oxidized to cyclohexanone, in which process nitrous

acid is released. Next, the cyclohexanone reacts with the nitrous acid to
yield isonitrosocyclohexanone which, by reaction with nitric acid, gives
2-nitro-2-nitrosocyclohexanone.

A . F. Lindsuy, Chem. Eng. Sci. 1, Suppl. 79 (1951).

H . C.Godt and J. F. Quinn. J. Am. Chem. SOC.78, 1461 (1956).

52

W. J, van Asselt and D. W. van Krevelen

With attendant ring opening and uptake of water the latter compound is
transformed into 6-hydroxyimino-6-nitro hexanoic acid (hereinafter to be
referred to as nitrolic acid), the greater part of which (over 90%) is converted to adipic acid and N20; in addition, slight amounts of glutaric acid
are produced.
By-products may form by introduction of a second nitroso-group into
the intermediately formed isonitrosocyclohexanone.
According to Godt cyclohexanone may moreover yield the hemihydrate
of 1,Zcyclohexanedione (to be referred to as Dione), especially at lower
nitric acid concentrations ; this Dione is converted to adipic acid and
furthermore mainly to succinic acid and glutaric acid.

Nitrolic
acid

'CSN

0H
'NO2

Succinic
acid

Glutaric
acid

Adipic
acid

Preparation of adipic acid by oxidation of cyclohexanol, etc. 82 (1963) RECUEIL

53

The present study was undertaken to verify and elaborate the above
diagram, to investigate the part played by the catalysts in the process and
to measure the reaction kinetics of the various reactions.

B. Methods
1. Standard procedure of the oxidation experiments
The oxidation experiments were carried out in a cylindrical vessel (volume
120 ml) fitted with an electromagnetic stirrer and a cooling jacket. In this
vessel 50 ml of nitric acid, (with or without addition of catalyst) are heated
up to the desired reaction temperature, after which appr. 1 g of cyclohexanol
is added dropwise. The temperature was kept within 0.5" throughout the
oxidation.
In the oxidation of cyclohexanone either HNO2 is dissolved in the nitric
acid beforehand, or, after the addition of cyclohexanone, a KNOz solution
is supplied to the nitric acid slowly and dropwise, or a stream of HNO2
gas is passed through it. Which of these methods has to be used for oxidizing mixtures of cyclohexanone and cyclohexanol depends on the percentage of cyclohexanol in the mixture.
The following catalysts were used : ammonium metavanadate, NH4V03 ,
and copper nitrate, Cu(N03)~.3 aq, mostly in amounts of 0.02 mol/l. The
reaction time was taken so long that the yield of adipic acid and nitrolic
acid (Cs-yield) did not further increase. The amounts of glutaric and
succinic acid, on the other hand, do increase gradually until complete
conversion of the intermediates is reached, but this takes a very long time
at low temperatures.
2. Analysis of the reaction products
Upon completion of the oxidation the reaction mixture is diluted with
water and analysed by the method of liquid-liquid partition chromatography. The column packing in this case consists of 20 g of silicagel (particle
size 0.2-0.4 mm) impregnated with 7.50 ml of water. 1 g of silicagel, impregnated with 0.37 ml of sample, is placed on top of the column after
which the mixture is eluted with chloroform-butanol mixtures (0-20%
butanol). The collected fractions are titrated with 0.02 M alcoholic potassium
hydroxide, phenolphthalein being used as indicator. Nitrolic acid, adipic
acid, glutaric acid and succinic acid can be readily separated in this way.
During the experiments it also appeared that beside the above-mentioned
products a substance X is produced which could afterwards be identified
as an intermediate of the nitrolic acid-adipic acid conversion.
The nitric acid is retained on the column and does not interfere with the
determination. Normally, a column can be used several times provided the
sample is removed after each analysis.

W. .
I
van
. Asselt and D . W. van Kreveleri

54

The accuracy of this analysis varies from 1 to 3 % for nitrolic acid and
adipic acid and from 5 to 20 % for glutaric acid and succinic acid, the latter
two being present in small amounts.
3. Preparation and determination of some intermediates
The intermediates nitrolic acid and Dione were prepared in the way
indicated by Godt 2 and purified by washing and recrystallisation. Elenientary analysis and examination in the mass spectrometer yielded results
consistent with the structure suggested by Godt. It was also shown that
nitrolic acid can be readily separated from the other dicarboxylic acids on
the chromatographic column and, in the form of a dibasic acid, be quantitatively determined in chloroform by titration with alcoholic sodium
hydroxide solution.

C . Results and Discussion

1. Oxidation of cyclohexanol
a) Oxidation experiments according to the standard procedure.
The oxidations were carried out with 30-67% by weight of nitric acid.
The results obtained with 40% nitric acid are illustrated in fig. 1, table 1
showing some complete analytical results. *
By C Sis here to be understood the total yield of products with 6 C-atoms,
100.

80

Yield

60-

(./.Cg)

40-

;O

2b

30

40

50

60

10

80

90

Temp.(*C)

Fig. I . Oxidation of cyclohexanol (1 g) in 40% nitric acid (50 ml).

Influence of catalysts

0 without a catalyst
with 1 mmol HNIVOB
A with 1 mmol Cu(N03)~
1 mmol V
0 with 1 mmol Cu

Table I
Some complete analytical results obtained in the oxidation of cyclohexanol (1 g) in 40% nitric acid (50ml)

Catalyst
(mmol/50 ml)

Reaction
time

Nitrolic
acid

Adipic
acid

(min)

1 cU(NOS)2
1 NH4VOs

lcU+lV

60
60
60
60

Glutanc
acid

Succinic
acid

1 1
Sum

An01
added
-

(mmol/50 ml)
4.69
4.60
4.50
4.36

1.42
1.40
4.80
4.34

0.50
0.28
0.70
0.56

0.37
0.34
0.12
0.06

10.12
9.32

10.13
10.14
9.93
9.53

56

W. J. van Asselt and D. W. van Ki-evelen

so :adipic acid, nitrolic acid and a not further identified intermediate formed
during decomposition of nitrolic acid into adipic acid. The portion of the
oxidation products not shown in the graph (100- % c6) consists of glutaric
acid, succinic acid, lower decomposition products and, as will be demonstrated further, Dione.
The lines found at all other acid concentrations show essentially the same
trend as those in fig. 1. At higher acid concentration the lines shift, divergently, towards the upper 1.h. corner.
At lower concentrations they shift, slightly, convergently, towards the
opposite corner.
At higher temperatures, normally above 40-50", the sum of the products
is indeed appr. 100 %; at lower temperatures and in the absence of vanadate
glutaric acid and succinic acid are formed only in small amounts which
continue to increase with duration of the experiment. The c6 %, however,
remains constant. At low acid concentrations and low temperatures the
reaction is often retarded. In consequence, it was often essential under these
conditions to add a small amount of KNOz to the nitric acid beforehand so
as to make the reaction proceed at a moderate rate.
Fig. 1 clearly shows that copper and vanadate, used as catalysts, produce
quite different effects. Whereas at low temperatures vanadate highly increases the yield, this effect vanishes at elevated temperatures where the
copper begins to play a part. Go& demonstrated that at low temperatures
the hemihydrate of cyclohexanedione is formed ; the yield agrees approximately with the percentage not accounted for by the analysis of the oxidation products obtained without a catalyst at low temperatures.
Consequently, a possible explanation of the effect of vanadate would be
that vanadate converts Dione to adipic acid, whereas in the absence of a
catalyst and under the same conditions this substance is transformed very
slowly into by-products. The fact that vanadate loses its effect at high
temperatures can be ascribed to two causes : 1) Dione is not formed anymore.
2) The further oxidation of this Dione by the nitric acid proceeds more
rapidly than the conversion to adipic acid under the influence ofthe vanadate.
As to the effect of copper at elevated temperatures the following may be
observed: In addition to an improvement of the yield a change is noted in
the distribution of the by-products. Whereas at higher temperatures the
glutaric acid/succinic acid ratio obtained without a catalyst, or with a
vanadate catalyst, is usually 3-4 : 1, the ratio found in experiments using a
copper catalyst is appr. 2 : 1. The absolute amount of succinic acid, however
does not show any appreciable change. This demonstrates that copper
impedes the formation of glutaric acid.
So, whereas vanadate converts a by-product at an increasing rate to adipic
acid, i.e. acts as a true catalyst, copper seems to have an inhibiting effect on
side reactions.

Preparatiori ofadipic acid by oxidation of cyclohexanol, etc.

82 (1963) RECUEIL

57

b. Some special experiments.

Beside the experiments by the standard procedure we performed some
tests of a special character.
These will be discussed separately because each experiment throws light
on a given aspect of the reaction mechanism.
1. To 50 ml of 51 % nitric acid 0.8 mmol of hydrazine sulphate were
added first, to remove dissolved nitrous gases, and subsequently 1 g of
cyclohexanol. Whether or not use was made of a vanadate catalyst, no
oxidation products could be demonstrated in the reaction mixture after
1 hour at 15". If subsequently the hydrazine sulphate was removed with a
small excess of KNOz, the reaction proceeded to completion within appr.
40 min and the yield was equal to those obtained with the standard procedure.

It must be concluded therefore that under the abose reaction conditions

cyclohexanol is not attacked by nitric acid alone.

2. I n the oxidation of cyclohexanol an equimolecular amount of HNOz

is formed first, a portion of which is afterwards consumed during the
formation of nitrolic acid. Experiments in which, upon completion of the
reaction, the amount of HNOz was roughly determined, have shown the
remainder to be approximately equal to the difference between the amount
of cyclohexanol added and the amount of nitrolic acid formed (= yield of
C G without addition of catalyst). I n the presence of NH4V03 under the
same conditions the remaining amount of HNOz was even slightly greater;
in consequence there is good reason to state that in the extra-formation of
adipic acid under the infruence of vanadate no HNOz is consumed. It even
looks as if nitrous acid is formed in this conversion process.
3. If during the oxidation at room temperature part of the excess of
HNOz is removed by addition of small amounts of urea, the yield of C G
obtained without application of a catalyst shows a slight rise. If an additional amount of HNO2 is previously dissolved in the nitric acid, the yield
of C Gis very much lower. So, an excess of H N O z lowers the yield of c6 $
no vanadate catalyst is used.
4. If, upon completion of the oxidation reaction carried out without a
catalyst (at low temperatures) vanadate is added, the degree of conversion
rapidly goes up to 100%. The added percentage is accounted for almost
exclusively by the larger amount of adipic acid formed and not by the
increased nitrolic acid concentration. In this stage much less heat is released
than in the conversion of a corresponding amount of cyclohexanol to
adipic acid.

W. J. van Asselt and D . W. van Krevelett

58

2. Oxidation of cyclohexanone
Cyclohexanone is not oxidized by nitric acid if no nitrous acid is present.
Upon addition of small amounts of nitrite, the ultimate amount of conversion products proves to be equimolecular with the amount of nitrite added.
The way in which the experiments are conducted appears to be very important now. If first 1 g of cyclohexanone is brought into 50 ml of nitric acid
and afterwards a KNOz solution, or HN02 gas is added to it slowly, the
results strongly deviate from those obtained in all other oxidation tests.
(Fig. 2). Low yields are obtained and copper increases the yield under these
conditions, even at low temperatures.

80 -

d
0

10

1 '

20

30

40

>O

60

I
70

Ternp.PC)

Fig. 2. Oxidation of cyclohexanone by addition of a KNOa soluttion dropwise to a

mixture of cyclohexanone (1 g) and nitric acid (50 ml)

A 40% HN03 with 1 mmol C~(N0a)a

0, 40% HNO3 with I mmol Cu(NO3)z
0 40% HNO3 with 1 mmol NHdV03

+ I mmol NH4V0.3

40% HN03 without a catalyst

0 51 % HN03 without a catalyst
0 51 % HN03 with 1 mmol NH4VOy

We must assume here that side reactions take place; these may be due
to the combined effect of NO and NO2 formed from the KNOz added,
and the excess of cyclohexanone present. The effect of copper therefore is
based probably on the suppression of these side reactions by nitrogen
oxides.
However, if first HNOz gas is introduced into the nitric acid and subsequently cyclohexanone is added, the yields show qualitatively the same
trend as those obtained with cyclohexanol. The experimental results are
illustrated in figs. 3, 4 and 5.

Preparatiorr of adipic acid by oxidation of cyclohexanol, etc.

10

20

30

40

30

82 (1963) RECUEIL

I
0

70

Temp.(.C)

Fig. 3. Oxidation of cyclohexanone (1 g) in 51 /, nitric acid (50 ml) containing

dissolved HNOZ
Numbers in figure = mmol of dissolved HNOz
0 without a catalyst
0 with 1 mmol NH4VO3

20 -

Fig. 4. Oxidation of cyclohexanone ( I g) in 40% nitric acid (50 ml)

containing dissolved HNOZ
Influence of catalysts
0 without a catalyst
A with 1 mmol Cu(N03)~
0 with 1 mmol NHaV03
0 with 1 Cu
1V
( x Experiments with cyclohexanol HNO2)

59

W. J. van Asselt and D. W. van Kreveien

60

I :1
0'

10

The products formed are essentially the same, but the yield of c6 obtained
without a catalyst is lower than that obtained with cyclohexanol, because
the average H N 0 2 concentration during the test is lower.
The difference in c6 is also larger according as more HNO2 has been
dissolved a t the start.
The drawn lines in the figures 3, 4 and 5 give the yields obtained with
equimolecular amounts of cyclohexanone and HNO2 (10 mmol). Comparison of these three lines shows that equal yields are obtained at those
temperatures where the partial pressures of nitric acid (PHNOJ are equal.
This is demonstrated also in fig. 7 where, starting from the line for 40%
HN03, the points with equal PHNO, values have been plotted for 51%
and 30% nitric acid.
In the oxidation of mixtures of cyclohexanol and cyclohexanone HNO2
is formed only in the first conversion of cyclohexanol. This nitrous acid is
consumed again during the formation of nitrolic acid; so, if no catalyst is
present, the c6 yield will be equal to the percentage of cyclohexanol in the
mixture. When vanadate is used, the yield is higher, because then also the
Dione formed beside the nitrolic acid is converted to adipic acid without
consumption of HNOz.
These observations have been confirmed experimentally. It should be
borne in mind though that initiation with HNO2 is necessary in all cases,
while sometimes (e.g. at 25 % cyclohexanol) a fairly large amount of HNO2
fails to set the reaction going.

Preparation of adipic acid by oxidation of cyclohexanol, etc.

80 -

82 (1963) RECUEIL

61

(*I.
Yield
c), 6040,

20-

I
I
I

I
I

I
I

I
1

II

I
I

Apparently, this is in contradiction to the assumption that cyclohexanol

is rapidly oxidized to cyclohexanone plus H N 0 2 . This assumption, however, cannot but be correct because kinetic measurements * have demonstrated that cyclohexanol and cyclohexanone are oxidized at equal velocities. Therefore the first step of the oxidation of cyclohexanol should be
considered as a chain reaction proceeding under the influence of H N 0 2 .
If this H N 0 2 is rapidly taken away by the excess of cyclohexanone, the
reaction dies away before all of the cyclohexanol has been converted. The
effect of this phenomenon becomes more pronounced as the nitric acid
concentration is lower. 30 % nitric acid is not capable of oxidizing a mixture
containing an excess of cyclohexanol under these conditions; the amount
of product obtained then corresponds to the quantity of H N 0 2 added.

3. Oxidation of the hemihydrate of 1,2-cyclohexanedione (Dione)

Purified Dione has been subjected to an oxidation test in the same way
as cyclohexanone. The results of the oxidation experiments are represented
in table 11.
The figures clearly show that complete conversion is obtained and
80-90% adipic acid is formed if vanadate is used in the process. Nitrolic
acid has never been demonstrated in the experiments, showing that the

An article on this subject is in preparation.

T a b l e I1
Oxidation of hemihydrate of cyclohexanedione (1.00 g) in nitric acid (50 ml)
~~

Temp.
("C)

25
35
45-46
46
55-57
25
35-36
37
44-47
55-61
55-62

Reaction
time
(min)

55

35
20
60
45
55
35
35
20
10
10

34-36
44-48
35-40
45-51

75
70
20

34
45
55-56
35
45
55-57

105

10

80
75
60
30
25

I
Catalyst
(rnmol/l)

Sum of the
products
determined
chromatographically

Yield
Adipic
acid

Glutaric
acid

( %)

( %)

(%

2.7
1.9
89.1
86.0
83.5
81.8
78.0
64.2

10.8
7.3
8.5
12.2

1.62
3.45
4.55
5.92
5.92
8.21
8.21
8.20
8.13
8.23
8.17

17.0
19.8
31.9

58
63
2
1
1
1
2
3

20 v
20 v

5.72
5.49
8.20
8.15

0.7
0.7
86.0
82.4

4.2
3.7
12.2
15.2

64
62
2
2

2.46
4.96
5.92
8.34
8.29
8.26

1.2
81.6
77.7
73.6

11.6
15.4
19.1
22.2

59
3
3
4

20 v
20 v
20 Vf Cu
20 v
20 v
10

20 v
20 v
20 v

15.0

Suc
ac

Preparation of adipic acid by oxidation of cyclohexanol, efc. 82 (1963) RECUEIL

63

adipic acid cannot have formed via nitrolic acid. It also appears that Cu
has no effect on the oxidation of this intermediate. At lower vanadate
concentrations the amount of glutaric acid increases.
In some cases no complete conversion can be achieved (table 11) without
a catalyst owing to the reaction time being too short then; in other cases,
however, the temperature rise during the reaction suggests that the conversion is indeed complete but that lower decomposition products are formed
(e.g. oxalic acid). In such cases the sum of the products found approaches
5.9 mmol (= 72%).
4. Influence of nitrous acid on the distribution of the reaction products

If, after an oxidation executed without a catalyst, vanadate is added, the

degree of conversion rapidly goes up to 100%; the only product formed
during this stage is adipic acid. We have also seen that under the influence
of vanadate Dione is rapidly converted to adipic acid. We may take it
therefore that the portion of the products which after a low-temperature
oxidation without vanadate is lacking in the analysis (100-% CS), must
have consisted primarily of Dione and also that this Dione forms simultaneously and along with the nitrolic acid.
The influence of nitrous acid is such that the ratio in which nitrolic acid
and Dione are formed (Dione/N.A. ratio) increases with the HNOz-concentration. To make a further study of this influence some oxidation tests
were carried out on cyclohexanone and cyclohexanol with 40 % nitric acid ;

05

0.70.8 1.0

l.5 '2.0
a0 4.0 5.0
+D i o n e l N A r o t l o

70

1'

Fig. 6. Influence of HNOz and temperature on the Dione/N.A. ratio during oxidation
of cyclohexanol and cyclohexanone in 40% nitric acid.

64

W. J. van Asselt and D. W. van Krevelen

Preparation of adipic acid by oxiddon of cyclohexanol, etc. 82 (1963) RECUEIL

65

in these tests the nitrous acid concentration was varied by dissolving more
or less HNOz in the nitric acid prior to the experiment. The HNOz-concentration i n a sample of the liquid was measured before, during, and after
the test. In all cases the final concentration of the HNOz proved to be appr.
10 % below the theoretical value : initial concentration - nitrolic acid
concentration. The results are represented in fig. 6.
The nitrous acid concentration in each test was taken equal to the average
value between the initial and final concentrations.
The points found at 10, 15 and 20" lie on straight lines with a gradient =
1.5. Through the points found at 5" and 25" lines have been drawn running
parallel to the former.
Since the relation between log (Dione/N.A.) - 1/T proves to be also
linear, it is possible to extrapolate towards higher temperatures. Furthermore it appears from fig. 7 that in oxidations without a catalyst a given
P H N O ~is needed for reaching a given yield (or a given Di0nejN.A. ratio).
As the relation between log (PHNO~)
and 1/T is also linear, a plot of log
(PHNOJ versus log (Dione/N.A.) may also be expected to yield straight
lines, with the nitrous acid concentration as parameter.
This has been elaborated further in fig. 8, so that the Dione/N.A. ratio
can be read from the graph for any reaction condition. The Dione/N.A.
ratio can also be calculated by means of the
empirical formula derived from fig. 8 viz. Dione/N.A.
where: (HN02)

= 0.69

= conc.

of nitrous acid in gmol/l

partial pressure of nitric acid in mm Hg.
Both in the chromatographic determination and in the measurement of
the HNOz-concentration fairly large errors can be made. It has appeared,
however, that the calculated Dione/N.A. ratio (fig. S), averaged over a large
number of experiments is only appr. 10% below the value found chromatographically; the difference can be partly accounted for by the fact
that the actual HNO3-concentration was lower than the value taken for
the calculation.
We may assume therefore that the Dione/N.A. ratio calculated from
fig. 8 is a fair approximation of the actual value.
PHNO~ =

D. Conclusions concerning the reaction mechanism

By means of the test results we shall first determine the substances formed
in the oxidation and then examine the way in which they decompose further.
In this way we expect to arrive at a diagram of the reaction mechanism
that can be used in interpreting the kinetic measurement 3 *.

An article on this subject is in preparation.

W. J. van Asselt, Thesis, Delft (1960).

W.J. van Asselt and D. W. van Krevelen

66

CYCLOHEXANONE

CYCLOHEXANOL

0-

High temp.
/'
HN03
koX
I
NO,N02-+
---Via
intermediates

I
i.a.
NOH,
1

Hcmihydratc of
1.2- cyclohexanedione
(Dione

OH

*NOH
H*
'

k ~ . ~ .
kH

1
ADlPlC A C I D
\

I
I

GLUTARIC A C I D

Vanadate

/ ' .

/ '

=O
=0

' i

SUCClNlC A C I D

LOWER DE COM PO SI T ION

PRODUCTS

Fig. 9. Kinetic model

3lYS

Preparation of adipic acid by oxidation of cyclohexanol, erc.

82 (1963) RECUEIL

67

1. Cyclohexanol is oxidized with nitric acid to cyclohexanone nitrous

acid, probably by a chain reaction in which HNO2 plays a part. The reaction
is very fast in most cases.
2. Starting from cyclohexanol and H N 0 3 , we succeeded in stopping the
reaction by removal of the nitrous acid, and in isolating cyclohexanone in
the reaction mixture, so that the conversion of cyclohexanone must be
considered as the rate-determining step. The oxidation products formed are
nitrolic acid and Dione. Also in this reaction HNO2 plays an important
part: cyclohexanone is not attacked by pure nitric acid.
The reaction undoubtedly proceeds via some intermediate products
which, however, are so unstable that they could not be demonstrated.
3. Under the influence of nitric acid the decomposition of nitrolic acid
into adipic acid proceeds at a rate lower than the rate of oxidation. The
reaction also yields a product X of unknown composition which, finally, is
converted again to adipic acid.
4. Under the influence of vanadate the Dione is rapidly converted to
adipic acid whereas glutaric acid is produced as a by-product. If no catalyst
is present, mainly succinic acid and lower decomposition products are
obtained.
5. Cyclohexanone, or the intermediates forming during the transition of
cyclohexanone into nitrolic acid and Dione, may, via side reactions, yield
products which are converted further to glutaric acid and succinic acid.
This suggests introduction of nitro or nitroso groups in the 3 or 4 position
or in the 2 and 6 position.
These reactions, which take place notably at high temperatures in the
presence of large amounts of nitrous gases, are suppressed by addition of
copper.
A diagram of the reaction mechanism is illustrated in fig. 9.

The results of the extensive study by Lubyantshii et al. 59 6 on the

oxidation of cyclohexanol and cyclohexanone with nitric acid under pressure, are difficult to compare with the results presented in this paper because
our experiments were conducted under much more moderate conditions.
Moreover L. did not add extra HNO2 during the oxidation of cyclohexanone, so that the yields of oxidation products differ appreciably. According
to L. the catalyst (a mixture of Cu++ and vanadate) should accelerate the
formation of nitrolic acid. However this can account only for the influence
of copper at high temperature but certainly not for the influence of vanadate.
4 9

(Received July 10th. 1962).

Y. A. Lubyantshii, R. V. Minati and M. S. Furnian, Khim. Prom. 453 (1960).
Y. A. Lubyantshii, R. V. Minati and M. S. Furman, Khim. Prom. 529 (1960).
Y. A. Lubyantshii. C . I. Kostylev, M . S. Furman, Khim. Prom. 533 (1960).