OXIDATION OF TOLUENE AND OTHER
ALKYLATED AROMATIC HYDROCARBONS
TO BENZOIC ACIDS AND PHENOLS
WARREN W. KAEDING, ROBERT 0 . L I N D B L O M ,
R. G. T E M P L E , AND H . I . M A H O N
The Dow Chemical Go., Walnut Creek, Calif.
A new process utilizes air for the conversion of toluene to phenol by a two-step catalytic oxidation process.
Benzoic acid is the intermediate. The hydroxyl group becomes attached to the aromatic ring a t a position
adjacent to thle departing carboxyl group. Meta-substituted phenols, therefore, are obtained from both
ortho- and para-substituted benzoic acids.
ETROLEUM is the most important source of aromatic raw
Pmaterials which are utilized by the chemical industry.
Advanced technology has made available increasing numbers
and larger quantities of pure derivatives of this type a t lower
cost. Toluene remains the cheapest and potentially the most
abundant primary source of the aromatic ring.
.4ir is an exceedingly desirable substance to use as a chemical
reagent. No other material is so readily and conveniently
available. has such a uniform and reliable composition, and
(except for sea water) is so abundant. Disposal of the un-
rracted or undesired fractions is usually simple. The search
for new ways to control and increase the specificity of its chemi-
cal reactivity will continue to challenge the imaginations of
marly chemists and engineers.
This phenol process combines air and toluene in a two-step
oxidation process, where benzoic acid is the intermediate.
Oxidation of Toluene tot Phenol
T h e conversion of toluene to phenol can be visualized as a
complete oxidation of the methyl group to form carbon dioxide
and water (Equation 1).
CHJ
OH
Stable intermediates which represent successive stages of
oxidation are benzyl alcohol, benzaldehyde, and benzoic acid.
The latter is the most stable compound. Although certain
reagents and conditions of reaction permit the formation of
the other intermediates. benzoic acid is the usual end product
for a considerable variety of oxidizing agents such as persulfate
( 7 1 ) . chromic acid (7411, alkaline permanganate (79), dilute
nitric acid (73), chlorine followed by hydrolysis (4, 70), and
oxygen (5, 76, 20).
Oxygen in air is not only the most attractive oxidizing agent
from a cost standpoint, but also appears to present the simplest
system for product isolation when toluene can be used as the
solvent. A catalytic. liquid-phase method utilizing this system
has been reported (27). T h e yield of benzoic acid was low
and a study to optimize the conditions of reaction was required.
The conversion of benzoic acid to phenol and carbon dioxide
itas a more formidable problem. The desired product was
not only very sensitive to further oxidation but the chemistry
of this transformation was unknown.
It has been reported that small amounts of phenol and related
compounds, such as salicylic acid and phenyl benzoate, were
produced when cupric benzoate was pyrolyzed (3. 7 7 , 77)
or when benzoic acid was heated with a variety of copper salts
( 7 , 9 ) . These experiments were verified. Phenol was pro-
duced, although the yields were low and decomposition to
form tar was predominant.
Subsequent studies designed to elucidate the chemistry of
this reaction eventually proved that attractive yields of phenol
could be obtained in dilute aqueous solutions utilizing cupric
ion as the specific oxidizing agent (7).
T h e desired reaction also occurred in various organic solvents
with the cupric salt of benzoic acid. Much subsequent work
has led to the proposal that cupric benzoate is the key reactant
for this transformation (2: 8, 78). Molten benzoic acid was
the most attractive solvent because its high boiling point per-
mitted the reaction to proceed a t atmospheric pressure, it had
excellent solvent properties for the catalyst and promoters,
and it provided a large reservoir of starting material.
Experimental
Benzoic Acid Production. The apparatus utilized for the
production of benzoic acid is shown schematically in Figure 1.
Since elevated pressures were required, metal construction
was used throughout the system. T h e 8-cm. tubular reactor
had an operating liquid level of 110 cm. and a volume of 5
litt=rs
OPERATION PROCEDURE.The reactor was charged with 5
liters of toluene, in which the soluble cobalt catalyst was dis-
solved, by means of the toluene feed reservoir, F. A smaller
feed reservoir, Q, was available for the addition of other liquids
to the reactor. After the desired temperature had been
reached, air was introduced into the bottom of the reactor.
R, through a d i p tube, A . T h e reactor temperature was meas-
ured by a thermocouple inserted in a well, W . The reactor
was heated electrically by means of Nichrome resistance tape.
T h e pressure was allowed to build u p to the desired value
and maintained at a constant reading by adjusting the exit
valve leading from the phase separator vapor space, S. Two
pressure-control switch mechanisms (not shown on the draw-
ing) were attached to the system. A warning bell sounded if
the pressure varied 1 2 p.s.i.g. from the desired value.
Vapors leaving the reactor were separated from the air not
used in the oxidation with a condenser, K Two phases sepa-
rated, a lower aqueous phase which contained some formic
acid, and an upper toluene layer. The toluene was returned
to the reactor by means of a seal leg. T h e water was periodi-
cally drained. Make-up toluene was added by means of
reservoir, F. to maintain the proper level, indicated by the sight
glass, G. A dry ice trap and charcoal absorber. T . was used
to remove the last traces of toluene from the noncondensable
gas stream.
VOL. 4 NO. 1 JANUARY 1965 97

Figure 1. Apparatus
T h e concentration of oxygen in the effluent gas stream and
the water production rate were sensitive indicators of the rate
of reaction. T h e induction period before reaction began
could usually be measured in minutes.
T h e concentration of benzoic acid increased a t a steady rate
u p to a level of 50 to 55% by weight. However, a lower value
of 25 to 30% was usually maintained by draining 600 to 700
ml. of reactor liquid each hour into a large flask. T h e liquid
level in the reactor was re-established by the immediate addi-
tion of toluene (and/or recycle filtrate). T h e reactor liquid
accumulated over a n 8-hour period was allowed to stand for
an additional 4 hours (to reach room temperature) and the
benzoic acid which had precipitated was then removed by
filtration .and washed with a portion of the make-up toluene.
T h e filtrate was recycled to the reactor. A small amount of
fresh cobalt catalyst (13 mg. per hour in run 17) was added
each hour in the recycle toluene filtrate. T h e solid benzoic
acid on the Buchner filter contained from 15 to 20% (by weight)
of toluene, which was removed by heating in a 100' C . oven
or by distillation. T h e benzoic acid was a finely divided white
solid with a purity of better than 99%. T h e equipment was
operated on a 24-hour-per-day basis.
METHODS O F ANALYSIS. A weighed sample of benzoic acid
(ca. 10 grams) was placed in a 600-ml. beaker and dissolved in
100 ml. of methylene chloride. After 300 ml. of water were
added, the two-phase mixture, rapidly stirred, was titrated to
p H 7.8 with standard base.
A weighed sample of benzaldehyde (10 grams) was dissolved
in a 100-ml. aliquot of standard hydroxylamine hydrochloride
solution. This reagent was prepared by dissolving 35 grams of
hydroxylamine hydrochloride in 160 ml. of water and diluted
98 l&EC PROCESS DESIGN AND DEVELOPMENT
with a n equal volume of ethanol. T h e pFI was adjusted to
2.6 with HCI. When the oxime was formed, an equivalent
amount of HC1 was liberated. This was titrated to the p H of
the original reagent (2.6). .4 blank sample was also run.
Separate analyses, where benzoic acid and benzyl alcohol
were added in amounts expected in actual samples, were run.
No interference was detected.
Toluene was determined by distilling a 150, to 200-gram
sample through a 1 5-tray, Sls-inch Oldershaw column. A
sharp break in the distillation curve appeared when the toluene
was removed.
Neutral material, determined by difference, was primarily
benzyl alcohol and benzyl benzoate.
T h e composition of the filtrate recycled (not including tolu-
ene added to rinse the benzoic acid or for additional make-up)
was benzoic acid, 11 to 167,; benzaldehyde. 2 to 37,; benzyl
alcohol, benzyl benzoate (and other unidentified hydrocarbons),
4 to 9%. The remainder was toluene.
PHENOLPRODUCTION. T h e apparatus and procedure for
the oxidation of benzoic acid to phenol and carbon dioxide
have been described (8). T h e only modification for the
experiments reported here was in the reactor design.
Agitation was achieved entirely by the flow of air through
the molten benzoic acid solution. T h e tubular reactor, with a
diameter of 2l!2 inches and a n operating volume of 1500 ml.,
was constructed of glass and electrically heated with Nichrome
resistance tape. 'The phenol and water used for hydrolysis
were collected together as a two-phase liquid system.
Results and Discussion
Oxidation of Toluene to Benzoic Acid. Early experiments
indicated that toluene could be oxidized to benzoic acid a t
$20" to 175' C., with a n air rate of 0.1 to 1.0 liter per minute
per kilogram of toluene, with a soluble cobalt catalyst a t a
concentration of 0.1 to 0.37, by weight. With the establish-
ment of practical conditions of reaction, operating techniques
and equipment were quickly perfected to the point where
process conditions could be simulated. T h e product was
separated and purified by crystallization, unconverted inter-
mediates were recycled, catalyst activity was maintained in-
definitely, a n d yield and conversion rates were calculated. A
number of typical runs of this type are summarized in Table I.
Reasonably good material balances were obtained despite
large inventories outside the equipment. Runs 16 and 17
(Table I) were actually a continuation of run 15. T h e reactor
was shut down over the week end and restarted with the filtered
reactor liquid the following week. This demonstrated that
catalyst activity could be maintained indefinitely and that a
considerable fraction of the intermediates recycled eventually
was converted to benzoic acid. A yield approaching 90%
was indicated.
This work confirmed for us that benzoic acid of high quality
could be prepared from toluene by oxidation with air in a con-
tinuous manner, with acceptable yields and rates. T h e condi-
tions and characteristics of the reaction were defined and
materials of construction were tested. Economic evaluations
could be calculated and a preliminary plant design developed.
Oxidation of Benzoic Acid to Phenol. A similar approach
was adopted for the oxidation of benzoic acid to phenol.
This was a more difficult system to study because of the high
melting point of the benzoic acid solvent (120' C.) and its
tendency to sublime with large volumes of air bubbling
through the molten liquid.
Cupric benzoate was recognized as the key reagent which
thermally decomposed to produce phenol precursors (Equa-
tion 2). In benzoic acid solution, this decomposition began
a t approximately 190' C. The half life a t the operating
temperature of 230' to 240' C. is measured in minutes.
 The presence of benzoylsalicylic acid was first indicated by
observing the rate of carbon dioxide evolution. It began
slowly, reached a maximum value. and then declined in a
manner typical of consecutive reactions. The presence of this
intermediate was verified by identification with a high resolu-
tion infrared spectrophotometer. In the presence of steam.
c
the benzoylsalicylic acid hydrolyzed to give benzoic and sali-
d
2
a
* -
c
3
cylic acids (Equation 3). The latter decarboxylated very
rapidly in the reaction medium to give phenol and carbon
dioxide (Equation 4). T h e half life for this reaction is meas-
ured in seconds.
r-
h
G.
oc
d When air. was bubbled through the benzoic acid solution
m 3
containing the reduced copper salts, cupric benzoate was
rapidly regenerated (Equation 5). Copper metal \vas also
oxidized under these conditions of reaction.
0 m m
m
r- 3
m
d

m d
hl d
N
c

m
c'! G. COOH 0 COOH COOH
d m c

a m m
N 0 0

m m t
u m m
m
r- hi

a m c
m m hl

r-
d
m
ir,
m.
m

m m 0
m
hl
r-
N
m
N
COOH ?H

m 0 m
m
3
f *
m

When water was introduced simultaneously with the air,

m F m the principal reaction product was free phenol. This net
m 0
reaction is shown by Equation 6 as the sum of all of the previous
reactions. The fortunate difference in boiling points of the
m m
9
rr,
product and starting material and the relatively high tem-
m m
m
2 perature of reaction permitted the immediate and convenient
removal of phenol from the reaction zone by distillation.
m m c An alternative mechanism of reaction would involve de-
m r- 0 carboxylation of the benzoylsalicylic acid prior to hydrolysis.
m
c
0 m
3
N
I n this event, phenylbenzoate would be an intermediate.
This ester would be the principal product if the reaction \vere
m W d
N
0 N
N N carried out in the absence of water.
The results of a number of runs are summarized in Table 11.
A working set of conditions and rates of reaction was estab-
0
N r-
N d
N
0 9 0 lished and yields were calculated. An ample supply of phenol
0 0 0 was also made available for product evaluation.
A complex mixture of nonvolatile products, appropriately
m labeled "tars," slowly accumulated in the reactor. A con-
fm m
hl
m
0
tinuous reaction would ultimately require some processing to
remove tars. This was accomplished subsequently by distilla-
.c tion of the volatile components or by selective solvent extrac-
a 4
e h
c
e * si tion.
T h e rate of reaction was affected by the concentration of
cupric benzoate. When the concentration was doubled (Table
In a
3 i= 11), the phenol production rate increased by approximately
30%. The concentration of oxygen in the reactor inlet gas

VOL. 4 NO. 1 JANUARY 1965 99

 Table II. Oxidation of
Reactor Benzoic Acid, G r a m Moles Phenol Carbon Dioxide
Inlet Gas Water AV. AV. Ai.. .Mole
Time Reactor Rate, Rate, Catalyst, addn. rate, rate, ratio
Run Run, Temp., I./ Oxygen, MI./ - ~ Gram Moles Initial Make- rate, Totalb mole/ Total mole/ COzl
No. Hr. a p
b. min. yo Min. Gun Mg charge up Total molelhr. moles hr. moles hr. PhOH
3 33 230 2.7 21 1.55 0.40 1.17 12.3 25.9 38.2 0.79 22.6 0.69 25.6 0.78 1.13

6 39 230 2.7 21 1.82 0.80 1.17 12.3 37.2 49.5 0.96 35.4 0.91 36.1 0.93 1.02

7 23 230 2.7 21 1.71 0.80 2.34 12.3 22.6 34.9 0.98 20.9 0.91 22.2 0.97 1.06

8 40.5 230 2.7 21 1.80 0.40 1.17 12.3 33.2 45.5 0.82 31.0 0.77 34.3 0.85 1.10

9 16.5 230 2.7 21 1.60 0.40i 1.2 12.3 12.3 24.6 0.75 12.2 0.74 12.2 0.74 1.00

10 21 240 2.7 21 1.70 0.80 1.2:',12,3 24.6 36.9 1.17 22.4 1.07 23.0 1.10 1.02

11 18 230 2.7 42b 1.61 0.80 1.2 12.3 24.6 36.9 1.37 22.6 1.25 25.2 1.40 1.11

12 6.8 230 2.7 70k 1.00 0.96 1.2 13.1 13.3 26.4 1.97 l5,l 2.22 14.9 2.21 0.99

14 45 230 2.7 21 1.41 0.40 1.2 11.11 28.3 39.4 0.63 26.6 0.59 28.7 0.64 1.08

a Gram moles. b Includes phenol present as phenyl benzoate. c Recovered f r o m dry ice trap. d Includes benzoic acid presmt in phenol distilled and in
samples withdrawn for analysis. 6 Includes samples of reactor liquid w i t h d ~ a w nf o r analysis, approx. 75-150 g. f Assume GO? = ' / z 02, all of neutral
+
fraction wasphenyl benzoate, andmol. w t . of tar = 100. 0 Molar yield = l O O X (Phenol) (phenyl benzoate)/(total B z O H a d d e d ) - (BzOHrecovered) -

stream had a more dramatic effect, not completely reflected
in the average production rate shown in Table 11. T h e
column size and perhaps the amount of water added did not
permit removal of the phenol a t a n optimum rate. Phenyl
benzoate rapidly accumulated in the reactor a t the expense
of benzoic acid needed for the reoxidation. With run 12
(Table 11) the rate of reaction was increased to the point where
the heat of reaction maintained the reactor liquid a t the oper-
ating temperature a n d provided the column reflux. No
external heat source was required. I t was even necessary to
reduce the oxygen conce7tration somewhat to prevent the
reactor temperature from increasing above the desired value.
T h e presence of soluble iron salts of benzoic acid had a
definite retarding effect on the phenol production rate (run 14,
Table 11). A slight decrease was also observed with run 9,
where the iron was added as finely divided metal. T h e rate
of solution was very slow. Most of the iron did not dissolve.
Derivatives of T o l u e n e a n d Benzoic Acid. Cresols were
obtained as products when the toluic acids were oxidized in a
similar manner. However, rn-cresol was the exclusive phenolic
product isolated from both o- and p-toluic acids. A mixture
of 0- and p-cresol was obtained from rn-toluic acid. This steric
result can be explained by postulating an attack by a n oxygen
atom a t a position adjacent to the original carboxyl group
during the decomposition of the cupric salt (R = CGHSCO)
(Equation 7). This accounts for the formation of the benzoyl-
salicylic acid intermediate found in the reaction medium.
0
procedure by starting with the appropriate substituted toluene
a n d benzoic acid derivative. There are certain practical
limitations as the type and degree of substitution become more
complex. For example. the iilitial oxidation of pseudocumene
to the corresponding monocarboxylic acid would produce a
mixture of three isomeric dimethvlbenzoic acids. Conversion
of the acid mixture would give four xylenol isomers. Certain
specific compounds, however, such as mesitylene or durene
would give only one monocarboxylic acid and phenol (2>4-
dimethylphenol and 2,3,j-trimethylphenol, respectively).
When toluene is substituted with alkyl groups containing
two or more carbon atoms, an indiscriminate attack occurs to
give a mixture of products, with the notable exception of the
tert-butyl group. The latter is very resistant to oxidation
under the conditions of reaction described for this process
(6). p-tert-Butyltoluene may be converted to p-tert-butyl-
benzoic acid a n d the latter subsequently oxidized to m-tert-
butylphenol by a similar procedure and with identical equip-
ment used to produce phenol from toluene.
When a methyl group is located a t a position ortho to the
carboxyl group, partial oxidation may occur to give a n ester
eventually by reaction with the adjacent carboxyl group.
For example, phthalide is a significant side reaction product
in the production of rn-cresol from 0-toluic acid (Equation 8 ) .

Since phenols are sensitive to further oxidation, it is impera-

tive to remove them immediately from the reaction zone.
I This is most easily accomplished with phenol because of its
R R relatively low boiling point in comparison \\ ith the tempera-
This mechanism has been verified conclusively for benzoic ture of reaction. Alkyl-substituted benzoic acids are oxidized
acid itself by Schoo and coworkers utilizing C14-labeled benzoic to their corresponding phenols in the same tcmperature range
acid (75). A series of alkyl-substituted benzoic acids and (220' to 250' C . ) required for the parent compound. The
phenols, therefore, may be prepared by the same general additional substituents increase the boiling point of the product

100 l&EC PROCESS DESIGN A N D DEVELOPMENT

Benzoic Acid to Phenol

.\laterial Balance1
~~ PhenolQ
Benzoic ~ ~-
Final Reactor Liquid -~
~~~ ~~
Aromatic
Benzene, Acid, Total. Tar, Benzoic Phenol, .Yeutral, Grams rings,/ Yield, Attack, Shut-
.Molec ‘Vfolesd g.e /c
c7 acid, CL 5 c; in out znjout 76 yo doionsh
0 19 12.6 1602 5.6 77.6 5.7 7.5 1.8 2.0 5167
~
3 ~-
8.2 ~~
89 67 4
4935 36.3
0 36 11.7 1-88 13.8 66.8 5.7 10 7 2.18 0.98 6707
- ~~
4 9.. 5. ~ 94
~
77 0
6646 49.9
0 36 12.3 1676 2.9 80.6 4 1 6 2 2.90 3.21 4722 34.9 ~~~
93 65 0
4607 3410
0 38 11.3 1643 9.1 73.4 5 5 9.3 1.3 1.3 6109-
45.5
~-
91 75 0
5999 44.1
0 02 11.4 1536 3.6 82.0 2.7 6.5 1.7 1.91 3282
~-
24.6 92 54 2
3203 24.2
0 37 13.2 1629 5.4 77 6 4.6 8.3 2.7 1.4 4946 36.7 ~~~
95 64 2
4887 36.8
0 27 12.1 1830 11.7 64.2 6.5 13.9 2.5 1.2 ~
4981 36.9 91 61 2
4982 37.0
8.8 1622 10.7 42.8 11.8 30.5 2.8 1.4 3568
~~ _2 6_. 5 85 67 1
3386 26.0
0 38 10.9 1 706 13.5 69.6 4.2 8 6 2.0 l.lm 5525 39 4
-~
93 12 0
5403 40.2
‘*
(phenyl benzoate); attack = 7OOX ( B z O H consumed)!(BzOH ~ u , t ) p / ? e d ) . Shut doion ourmight. .Vat a continuous run. 24 g . of powdered iron added
initially. 2 Plus l.6yoiron. k Inlet air (27cI,)enriched w i t h p u r e o.xypen 10 obtain concentration shoion. 1 0.48 mole of ferric benroat? addrd initially.
m Plus 7.0cIc iron.

and it is more difficult to remove it from the reaction z o ~ i rby
distillation. This promotes tar formation and adversely afl-ects
the yield.
If dicarboxylic acids are oxidized by this method, an iriter-
mediate hydroxyhenzoir: acid is formed: Jvhich tends to d r -
carboxylate to give phenol rather than produce a dihydroxy-
benzene.
Sitrobenzoic acids produce the corresponding nitrophenols.
T h e high melting and boiling points of the compounds, how-
ever. presented serious operating difficulties. T h e hydroxyl
group became attached a t a position adjacent to the original
carboxyl group. This rule has applied without variation to
every benzoic acid derivative tested.
Commercial Production. At the time of writing. three
commercial phenol plants utilizing this process are under
construction or in production. T h e first to be started i s
located a t Ladner, British Columbia, Canada, and is being
operated by Dow Chemical of Canada, Ltd. T h e second is
located a t Kalama, Wash.. and is being operated by the
\.Vestern Division of T h e Dow Chemical Co. T h e third plant
is located a t Rosenburg. T h e Netherlands, and is operated by
Dutch State Mines.
Ac knowledgrnent
A number of people have given valuable advice and asTist-
ance \$ith the early process research work and with studies
draling with the oxidation of benzoic acid to phenol Grate-
ful acknolvledgment is given to W. Hirschkind, T. R. Norton
R . D. Barnard, R. H. Meyer, and TY. E. Brown.
literature Cited
(1) Bamdas, E. M., Shemyakin, M. M., Z h . Obshch. K h i m . 18, 324
(1948).
(2) Barnard, I<. D.: Meyer, K. H. (to Dow Chemical Co.), U. S.
Patent 2,852,567(Sept. 16, 1948).
(3) Ettling, A n n . 53, 77 (1845).
(4) George, ,\., U. S. Patent 1,557,153 (Oct. 13, 1925).
(3) Haefele. LV. R., Hearne, G. W.,Ballard, S. A . (to Shell
Urvelopnient C o . ) ,Ibid., 2,723,994(Nov. 15, 1955).
(6) Hearrie, G. LV., Evans, T. Mi., Buls, V. LV’. (to Shell Develop-
ment ‘20.).Ibid., 2,578,654 (Dec. 18, 1951).
(7) Kaeding, W. LV., J . Or?. Chem. 26, 3144 (1961).
(8) Kaeding, W.LV., Lindblom, R. O., Temple, R. G., Znd. En,?.
Chem. 53, 805 (1961).
(9) Kinney, C . K., L.anglois: D. P., J . Am. Chem. SOL.53, 2191
(1931).
(10) Kyrides, L. P., C . S. Patent 1,345,373 (July 6, 1920).
(11) List, K., Limpricht, H., Ann. 90, 190 (1854).
(12) Moritz, C., Wolffenstein, R., Ber. 32, 432 (1899).
(13) Nazarov, I. N.: Kuznetov, N . V., Semenoziskii Dokl. A k a d . Nauk
.SS.SR 99, 1003 (1954).
(14) Schneider, J . Chem. Obzar (Chem. Prumysl) 14, 153 (1939).
(15) Schoo. \V,. Veenland, J. V., Bigot, J. A,,. Sixma, F. L. J . ,
R e t . Tim. C h i m . 80, 134 (1961).
(16) Sluis. K. .J. H. van, Chem. Prods. 20, 191 (1957).
(17) Stenhouse, J.; Ann. 53,91 (1845).
(18) Tola:id, LV. G., J . A m . Chem. Soc. 83, 2507 (1961).
(19) Ullman, F., Uzbachian, J. B., Ber. 36, 1798 (1903).
(20) Uri, N.. .Yuture 187, 746 (1960).
(21) U. S. Dept. Commerce, Office ofTechnical Services, P. B. 564
(1946).
RECEIVEDfor review February 24, 1964
ACCEPTEDMay 27, 1964

VOL. 4 NO. 1 JANUARY 1965 101