United States Patent 0 1C6 3,426,358

Patented Feb. 4, 1969

1 2
the longer usefulness of the catalyst; (2) improved direc
3,426,358 tion to monosubstitution over multi-substitution, thus
ALKYLATION 0F PHENOLS avoiding the formation of more highly substituted tar and
Hans L. Schlichting, Grand Island, and Anthony D. residue forming compounds and thereby enhancing the
Barbopoulos and Walter H. Prahl, Buffalo, N.Y., yield of the lower substituted compounds; and (3) an im
assignors to Hooker Chemical Corporation, Niag proved selectivity of reaction to ortho-alkylated products
ara Falls, N.Y., a corporation of New York
No Drawing. Filed Nov. 19, 1965, Ser- No. 508,821 of phenols.
U.S. Cl. 260--621 6 Claims Phenolic reactants which may be effectively utilized in
Int. Cl. C07c 37/16 the process of the invention are those having not more
10 than 25 carbon atoms, preferably containing 6 to 12 car
bon atoms, and also containing at least one reactive posi
ABSTRACT OF THE DISCLOSURE tion, preferably ortho. Such compounds, for example, may
Alkylated phenolic compounds are produced by passing be phenol, isomeric cresols, isomeric xylenols, phenols
in the vapor phase a mixture of a phenolic compound hav having substittued thereon one or more alkyl radicals or
ing at least one reactive position, an alkylating compound, 15 groups such as ethyl, propyl, isopropyl, butyl, amyl, hexyl,
and a small but effective amount of hydrogen halide over cyclohexyl, heptyl, octyl, nonyl, decyl, and the like. Also
an alumina catalyst, .and recovering the alkylation product included are fused ring phenols, such as naphthols and
from the reaction mixture. The process is highly selective similar compounds, as well as polyhydric phenols exempli
to the orthoposition. ?ed by resorcinol, pyrogallol and hydroquinone.
20 The alkylating compounds of the present invention are
selected from the group consisting of alkyl alcohols, alkyl
This invention relates to the alkylation of phenol and halides, alkyl ethers, wherein alkyl is of 1 to 18 carbon
substituted phenols. More particularly, the invention re atoms, and alkenes of 2 to 18 carbon atoms. It is more pre
lates to a catalytic vapor phase alkylation of phenols. ferred to employ those alkyl compounds which have 1 to
It is known that phenols, such as phenol, cresol, xylenol, 25 10 carbon atoms and those alkenes which have 2 to 10
resorcinol, pyrogallol, hydroquinone, and the like, may be carbon atoms, and most preferred to employ those having
alikylated by a vapor phase condensation with alcohols, 1 to 6 carbon atoms and 2 to 6 carbon atoms, respectively.
alkyl halides, dialkyl ethers, or ole?ns, at elevated tem Typical examples of these include methanol, ethanol, pro
peratures, in the presence of alumina as a catalyst. As panol, isopropyl alcohol, butanol, hexanol, cyclohexanol,
previously carried out, these alkylations have been sub heptanol, octanol, decanol, methyl chloride, ethyl chloride,
ject to considerable by-product formation, low yields, for propyl bromide, decyl chloride, dimethyl ether, diethyl
mation of polyalkylated phenols, as well as non-selective ether, ethylene, propylene, butylene, 3,4-dimethyl-2-hex
substitution. ene, and the like.
Selectively substituted phenols are commercially desira The alumina catalysts especially useful in the practice of
ble for various applications. For instance, ortho-cresol is the invention comprise the aluminum oxides having exten
used as an intermediary in the production of plastics, an sive surface areas and great adsorptive capacities. Such
alumina may be obtained from natural sources or may be
tioxidants, and other useful compounds; meta- and para
cresol are useful intermediates for preparing dyes pharma prepared synthetically, as described, for instance, in Ca
ceuticals, antioxidants, and so forth; and 2,6-xylenol is 40 talysis, vol. I, P. H. Emmett, 327 (1954).
The hydrogen halide employed is most conveniently
used as a starting material for polyphenylene oxide plas
tics and bisxylenol plastics. anhydrous hydrogen chloride gas, but aqueous hydrochlo
It is an object of the present invention to provide an ric acid of any concentration to satisfy the required hy
improved process for the alkylation of phenols. Another drogen chloride concentration in the reaction zone may be
object of this invention is to provide a process for the used as well. Other suitable hydrogen halides include an
alkylation of phenols whereby improved selective position~ 45 hydrous or aqueous hydrogen bromide.
ing of the alkyl substituent in the phenolic molecule is The use of a diluent, such as added steam, may offer
achieved. Other objects of the invention will be apparent advantages in particular cases of highly reactive phenol
from the following detailed description. and alkyl components to reduce and control the rate of re
-In accordance with the practice of the invention it has action. In general, steam in excess of the amounts of water
now been found that excellent yields of selectively alkyl 50 formed in the reaction is not required, although such an
ated phenols can be obtained when an alumina catalyst excess is considered as within the scope of the present
containing reaction zone is established to which an alkyl invention.
ating compound and a phenol or phenolic compound are The phenol reactant of the present invention may be
utilized in molar proportions which are stoichiometrically
continuously fed under reaction conditions, and fed simul equivalent to the amount of alkylating compound em
taneously therewith is a small but effective amount of a 55 ployed or may be utilized in molar proportions which are
hydrogen halide. The alkylation product, e.g., the selec substantially in excess of the stoichiometric amount. The
tively alkylated phenolic compound, is thereafter recov excess of phenol may be as much as ?ve or more times
ered from the reaction mixture. the stoichiometric amount, preferably three times the stoi
From a further description of the invention, it will be chiometric amount. It is to be understood, the greater
readily apparent that the novel process offers numerous portion of the excess will be present as unreacted phenol
advantages. The presence of a minor proportion of a hy in the reaction product and may be recycled to the reac
drogen halide, under reaction conditions, provides: (1) tion zone.
reactivity at lower temperature, thus reducing undesirable The hydrogen halide employed as the catalyst activator
decomposition, improving the yield, and contributing to 65 may be introduced to the reaction in molar proportions
 3,426,858
3 4
based on a molar proportion of alkylating agent and may Three reactors were each packed with 400 parts of
range from 0.005 :1 to 1:1, preferably 0.01:1 to 0.05:1. activated alumina granules and placed in electrically
Residence time of the reactants in the reaction zone heated and controlled salt-baths. A mixture of phenol and
may be greater than about one minute, but preferably the methanol (molar proportions PhOH:MeOI-I=2.85 : l)
residence time is maintained between 5 seconds and 20 was fed continuously at the same hourly rate (105 parts/
seconds. Suitable operating temperatures for the reaction 5 hour) through a preheater system into each reactor, over
may range from 150 degrees centigrade to 350 degrees a period of more than 100 hours.
centigrade, although it is preferred to maintain the tem- In Experiment 1, a slow stream of HCl gas (about 1.125
perature in the range of 250 degrees centigrade to 325 parts of gas per hour) was additionally fed to the reactor,
degrees centigrade. While the foregoing temperatures rep- 10 while the reaction temperature was kept at 300 degrees
resent the preferred temperatures, generally they may centigrade. The effluent streams of all three reactors was
vary depending upon the vaporization temperatures of collected as condensate and analyzed by gas chromatog
the reactants. Although the pressure of the recation is raphy. Table I gives the reactants, amounts, and reaction
maintained at atmospheric pressure, it is within the scope conditions employed as well as giving the results obtained.
TABLE I
Example 1 Example 2 Example 3
Total Feed:
Phenol ________________________ __ 4,900 parts ______ __ 9,400 parts ______ __ 9,400 parts.
Methanol____ _ 1,120 parts _ _ _ _ __ 1,120 parts _ _ _
_ __ 1,120 parts.
H01 gas .... ._ __ 56 parts.-. _______________ _.
Temperature. 300 C _____ __ 345 C __________ __ 300 0.
Feed Rate--- 106 parts/hou.r____ 105 parts/hour____ 105 parts/hour.
Condensate:
Water ________ __ __ 630 parts _______ __ 630 parts _______ __ 630 parts.
6,579 parts . . . _ __ 6,580 parts..- ___ 6,579 parts.
105 parts _ _ _ _ _ __ 109 parts _ _ _ _ _ _- 1,080 parts.
2,490 parts _ 864 parts.
110 parts_- _ 325 parts.
115 parts 540 parts.
370 parts - 366 parts.
__ 50 parts _ _ _ _ _ _ __ 100 parts _ _ _ _ _ __ 90 parts.

of this invention to employ subatmospheric and super- The reaction temperature of Example 2 was raised to
atmospheric pressures depending upon the design of the 345 degrees centigrade to obtain a comparable amount
reactor. of anisole in the effluent. Advantageously, these examples
The process of the invention may be carried out in any demonstrate that in accordance with the process of the
suitable catalytic reaction chamber packed with grains or invention (1) the same consumption of methanol was
pellets of alumina catalyst, as such or in combination with 35 effected at a lower temperature, that is, at 300 degrees
carriers, equipped with heating and/or preheating sys- centigrade in Example 1 as compared to the 345 degrees
terns, and having a separating and recovery system, such centigrade required in Example 2; (2) the percentage of
as distillation solumns or extraction columns, whereby undesired polysubstituted compounds, i.e., xylenols and
recovery of the reaction products and recycling of the high boilers, based on mono-substituted and polysubsti
unreacted reactants and/or intermediaries may be ac- 4O tuted compound produced, was substantially reduced to
complished. . 13.4 percent in Example 1 as compared to the 18.7 per
Advantageously, a vertical column packed with alu- cent produced in Example 2 which was conducted in the
mina catalyst and adapted to receive the feed stream, for absence of hydrogen chloride; (3) a substantial selec
instance, at the top and discharge the ef?uent at the bot- tivity to ortho-substitution over meta- and para-substitu
tom may be effectively employed. In some instances, it iS 45 tion is clearly shown in Example 1, wherein 91.7 percent
possible to employ a ?uidized bed reactor, wherein the of mono-substituted products is o-cresol as compared to
catalyst is in a ?uidized form. Additionally, it is within 50.4 percent in Example 2 conducted in the absence of
the scope of the invention to utilize other known and hydrogen chloride; and (4) yields of desirable products
convenient methods. such as the cresols and xylenols was increased as shown
The etfluent of the reaction zone is processed so as to 50 by the reduction of the 3.26 percent yield of high boilers
separate the alkylation products. Suitable methods for the in Example 2 to 1.62 percent yield of high boilers in Ex
separation of said reaction product from the reaction mix- ample 1 which was conducted in the presence of hydro
ture include distillation, fractionation or extraction. gen halide.
It is also within the scope of this invention to process When a phenolic compound, an alcohol and a hydrogen
the e?luent of the reaction zone so as to separate there- halide listed below is used in place of the phenol, metha
from the unreacted phenolic compound and the reaction 1101 and hydrogen chloride, respectively, of Example 1,
products of lower degree of alkylation than desired and similar oitho-alkylation occurs, producing the correspond
to recycle said compounds to the reaction zone to effect ing compounds.
additional alkylation. Phenolic compound: o-Cresol, rrr-cresol, p-cresol, 2,5
The following examples are presented to illustrate fur- 6O xylenol, 3,5-xylenol, catechol, resorcinol, hydroquinone.
ther the novelty and utility of the present invention but Alcohol: Ethanol, propanol, butanol, cyclohexanol,
not with the intention of unduly limiting the same. Un- hexanol, octanol, decanol, methyl chloride, decyl chlo
less otherwise indicated, all temperatures are in degrees ride, methyl ether, ethylene, propylene, isobutylene, 3,4
centigrade and all parts and percentages are by weight. dimethyl-Z-hexene. V
EXAMPLES 1_3 65 Hydrogen halide: Hydrogen bromide.
The advantageous effects of the presence of small EXAMPLES 4"6
amounts of hydrogen chloride on the vapor phase con- Employing the procedures described in Examples 2-4,
densation of phenol and methanol in the presence of alu- the etfects of the presence of small amounts of hydrogen
mina catalyst to form o-cresol are demonstrated by the 70 chloride on the vapor phase condensation reaction of
following three experiments conducted under the herein- o-cresol with methanol to form 2,6-xylenol were demon
after mentioned and listed conditions. Only one reaction strated by the following three experiments. The results
mixture contained hydrogen chloride in accordance with are given in Table II. Experiment #4 illustrates the proc
the present invention. The other two illustrate previously ess conditions in accordance with the present invention,
known reaction conditions and results. 75 while Experiments #5 and #6 illustrate previously known
 3,426,358
5 6
reaction conditions and results. The effluent streams of was treated to recover the 2,6-xylenol as product.
all three reactors was collected as condensate and ana Advantageously, 87 percent of the xylenols formed was
lyzed by gas chromatography. 2,6-xylenol. The yield of 2,6-xylenol expressed as a per
TABLE II
Example 4 Example 5 Example 6
Total Feed:
o-Oresol _______________________ __ 10,800 parts _____ __ 10,800 parts ..... ._ 10,800 parts.
Methanol.

Condensate:
Water ________________________ __ 630 parts _______ __ 630 parts _______ __ 630 parts.
o-Cresol ___________ __ ___ 7,580 parts__ ___ 7,578 parts ...... __ 7,581 parts.
o-Methyl-amsole. 60 parts"- _ 1 220 parts
2,6-xylenol 2,560 parts 918 parts
2,3-xylenol 122 parts _ 182 parts
2,4-xylenol _ 480 parts_ _ 730 parts.
2,5;xylenol _ 120 parts- _ 306 parts.
High Bollers __________________ __ 290 parts _______ __ 410 parts _______ __ 350 parts.

The reaction temperature of Example 5 was raised to centage of all the substituted phenols formed is 74 per
345 degrees centigrade to obtain a comparable amount of cent.
o-methyl-anisole in the effluent. Advantageously, Ex- 2 From the foregoing description and examples, it is
amples 4-6 demonstrate that in accordance with the proc apparent that various modi?cations are possible within the
ess of the invention (1) the same consumption of metha scope of this invention and it is therefore not to be con
nol was obtained at a lower temperature, that is, at 300 strued as limiting the invention except as de?ned by the
degrees centigrade in Example 4 as compared to the 350 appended claims.
degrees centigrade required in Example 5; (2) the per What is claimed is:
centage of undesired polysubstituted compounds, i.e., high 1. The process for the production of alkylated phenolic
boilers, based on monosubstituted compounds, i.e., 2,6-, compounds comprising passing in the vapor phase at a
2,3-, 2,4-, and 2,5-xylenols, and undesired polysubsti temperature between about 150 degrees centigrade and
tuted compounds, was substantially reduced to 8.1 percent about 350 degrees centigrade, a mixture of methanol, 21
in Example 4 as compared to the 11.4 percent produced small but effective amount of a hydrogen halide selected
in Example 5 conducted in the absence of hydrogen chlo from the group consisting of hydrogen chloride and hy
ride; (3) a substantial selectivity to ortho-substitution drogen bromide in molar proportions based on alkylat
over meta- and para-substitution is clearly shown by Ex ing compounds ranging from 0.005:l to 1:1, and a stoi
ample 4, wherein 78.0 percent of the monosubstituted chiometric excess of a phenolic compound selected from
product is 2,6xylenol, as compared to 46.0 percent in Ex the group consisting of phenol and o-cresol, over an alu
ample 5 conducted in the absence of hydrogen chloride; mina catalyst, and recovering the alkylation product from
and (4) yields of desirable products, i.e., xylenols was the reaction mixture.
increased as shown by the reduction of the 11.4 percent 2. A process in accordance with claim 1 wherein the
yield of high boilers in Example 5 to 8.1 percent yield of unreacted phenolic compound and the reaction products
high boilers in Example 4 which was conducted in the of lower degree of alkylation than desired are recycled
presence of hydrogen halide. over the alumina catalyst.
If it is desired to introduce more than one alkyl sub 3. A process in accordance with claim 1 wherein the
stituent to the phenolic compound, it is possible to achieve phenolic compound is phenol.
this result by operating in several steps, that is, isolating 4. A process in accordance with claim 1 wherein the
the partially alkylated intermediate and using it as the phenolic compound is o-cresol.
starting material in a subsequent alkylation operation. 45 5. The process for the production of o-cresol com
However, the preferred method comprises a one step oper prising passing in the vapor phase at a temperature of
ation accomplished by the internal recycling of the inter between about 150 degrees cntigrade and about 350 de
mediate as illustrated by the Example 7 describing the pro grees centigrade, a mixture of methanol, a small but eifec
duction of 2,6-xylenol directly from phenol. tive amount of hydrogen chloride in a molar proportion
50 based on alkylating compound ranging from 0.005 :1 to
EXAMPLE 7 1:1, and a stoichiometric excess of phenol, over an alu
This example was conducted employing the procedure mina catalyst, and recovering o-cresol.
of Examples 24. The feed to the reactor was modi?ed 6. The process for the production of 2,6-xylenol com
to consist of 2820 parts of phenol, 1920 parts of methanol prising passing in the vapor phase at a temperature be
and 95 parts of hydrogen chloride gas. In addition, 6580 55
tween about 150 degrees centigrade and about 350 de
parts of phenol, 12,900 parts of o-cresol, 110 parts of ani grees centigrade a mixture of methanol, a small but
sole, 60 parts of methylanisole all recovered from the effective amount of hydrogen chloride in a molar propor
e?iuent were recycled to the reaction zone. The reaction
tion between about 0.005 :1 to 1:1, and a stoichiometric
temperature was maintained at 300 degrees centigrade,
and the feed rate was 105 parts per hour. 60 excess of phenol and o-cresol, over an alumina catalyst,
and recovering 2,6-xylenol.
Condensate: Parts
Water ______________________________ __ 1,080 References Cited
Phenol _____________________________ __ 6,580
UNITED STATES PATENTS
o-Cresol ____ __ 12,900 65
Anisole ____________________________ __ 110 2,430,190 11/1947 Schmerling et a1. ,
Methyl-anisole ______________________ __ 60 2,448,942 9/1948 Winkler et a1 ______ __ 260621
m-Cresol ___________________________ __ 105
p-Cresol ____________________________ __ 160 LEON ZITVER, Primary Examiner.
2,6-xylenol _______________________ __.___. 2,580 70 H. ROBERTS, Assistant Examiner.
Other xylenols ______________________ __ 370
High boilers __________ _'_ ____________ __ 250
US. Cl. X.R.
The portion of the effluent consisting of phenol, o-cresol, 260624, 625, 626
anisole and methylanisole was isolated and recycled, while
the portion consisting of 2,6-xylenol and high boilers 75