U.S. patent application number 09/836216 was filed with the patent office on 2002-02-21 for method for producing ortho-alkylated phenols.
Invention is credited to Goto, Fumisato, Suzuki, Tomoyuki.
Application Number | 20020022750 09/836216 |
Document ID | / |
Family ID | 26590465 |
Filed Date | 2002-02-21 |
United States Patent
Application |
20020022750 |
Kind Code |
A1 |
Suzuki, Tomoyuki ; et
al. |
February 21, 2002 |
Method for producing ortho-alkylated phenols
Abstract
A method for producing ortho-alkylated phenols comprising
reacting phenols represented by the general formula (1) with
monohydric or dihydric alcohol in the presence of germanium oxide
under conditions in which said alcohol is in the supercritical
condition, wherein each of R.sub.1, R.sub.2, R.sub.3, R.sub.4 and
R.sub.5 independently represents a hydrogen atom, or a linear or
branched alkyl group having 1 to 10 carbon atoms. 1
Inventors: |
Suzuki, Tomoyuki;
(Tsukuba-shi, JP) ; Goto, Fumisato; (Tsukuba-shi,
JP) |
Correspondence
Address: |
BIRCH STEWART KOLASCH & BIRCH
PO BOX 747
FALLS CHURCH
VA
22040-0747
US
|
Family ID: |
26590465 |
Appl. No.: |
09/836216 |
Filed: |
April 18, 2001 |
Current U.S.
Class: |
568/780 |
Current CPC
Class: |
Y02P 20/544 20151101;
C07C 37/16 20130101; Y02P 20/54 20151101; C07C 37/16 20130101; C07C
39/07 20130101 |
Class at
Publication: |
568/780 |
International
Class: |
C07C 039/06 |
Foreign Application Data
Date |
Code |
Application Number |
Apr 20, 2000 |
JP |
2000-119398 |
Jul 19, 2000 |
JP |
2000-218858 |
Claims
What is claimed is:
1. A method for producing ortho-alkylated phenols comprising
reacting phenols represented by the general formula (1) with
monohydric or dihydric alcohol in the presence of germanium oxide
under conditions in which said alcohol is in the supercritical
condition, wherein each of R.sub.1, R.sub.2, R.sub.3, R.sub.4 and
R.sub.5 independently represents a hydrogen atom, or a linear or
branched alkyl group having 1 to 10 carbon atoms. 4
2. The method according to claim 1, wherein the method comprises
reacting phenols represented by the general formula (1) with
monohydric or dihydric alcohol in the presence of germanium oxide
and carbon dioxide under conditions in which a mixture of said
alcohol and carbon dioxide is in the supercritical condition.
3. The method according to claim 1, wherein the alcohol is
monohydric alcohol.
4. The method according to claim 2, wherein the alcohol is
monohydric alcohol.
5. The method according to claim 3, wherein the monohydric alcohol
is alcohol represented by the general formula (2), wherein, R.sub.6
represents a linear or branched alkyl group having 1 to 10 carbon
atoms. R.sub.6--OH (2)
6. The method according to claim 4, wherein the monohydric alcohol
is alcohol represented by the general formula (2), wherein, R.sub.6
represents a linear or branched alkyl group having 1 to 10 carbon
atoms. R.sub.6--OH (2)
7. The method according to claim 5, wherein R.sub.6 in the general
formula (2) is a methyl group.
8. The method according to claim 6, wherein R.sub.6 in the general
formula (2) is a methyl group.
9. The method according to claim 1, wherein germanium oxide is
added in the amount of from 0.1 to 30% by weight based on the
phenols of the general formula (1).
10. The method according to claim 2, wherein germanium oxide is
added in the amount of from 0.1 to 30% by weight based on the
phenols of the general formula (1).
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to a method for producing
ortho-alkylated phenols.
[0003] 2. Description of the Related Art
[0004] Aromatic ring alkylated phenols are industrially used as raw
materials or intermediates of medical and agricultural chemicals,
resins, various additives, polymerization inhibitors, antioxidants,
disinfectants, preservatives, industrial chemicals and the like.
For example, thymol having a structure in which an isopropyl group
is bonded to 2-position and a methyl group is bonded to 5-position
of phenol is used as a vermicide.
[0005] Conventionally, for producing ortho-alkylated phenols, a gas
phase reaction in which phenols and alcohol are vaporized and
allowed to flow through a catalyst phase for reaction, a liquid
phase reaction utilizing a Friedel and Crafts' reaction, and other
methods, are known. JP-A No. 2000-38363 discloses a method in which
phenols and alcohol are heated at 400.degree. C. in the
supercritical region using zirconium oxide as a catalyst to produce
ortho-alkylated phenols. However, this method has a problem that
when the reaction is conducted by a batch system, components having
higher boiling points composed of diners of phenols and derivatives
thereof as main components are by-produced in large amount.
SUMMARY OF THE INVENTION
[0006] An object of the present invention is to provide a method
for producing ortho-alkylated phenols from phenols and alcohol,
with high selectivity and by-producing a small amount of components
having higher boiling points even if the reaction is conducted by a
batch system.
[0007] The present inventors have intensively studied a method for
producing ortho-alkylated phenols by a reaction of phenols with
alcohol, and resultantly found that ortho-alkylated phenols can be
produced, by reacting phenols with alcohol using germanium oxide as
a catalyst under the supercritical condition of the alcohol or by
reacting phenols with alcohol in the presence of germanium oxide
and carbon dioxide under conditions in which a mixture of alcohol
and carbon dioxide is in the supercritical condition, with high
selectivity and by-produced a small amount of components having
higher boiling points even if the reaction is conducted by a batch
system, and have completed the present invention.
[0008] Namely, the present invention relates to [I] a method for
producing ortho-alkylated phenols comprising reacting phenols
represented by the general formula (1) with monohydric or dihydric
alcohol in the presence of germanium oxide under conditions in
which said alcohol is in the supercritical condition, wherein each
of R.sub.1, R.sub.2, R.sub.3, R.sub.4 and R.sub.5 independently
represents a hydrogen atom, or a linear or branched alkyl group
having 1 to 10 carbon atoms. 2
[0009] Further, the present invention relates to [II] the method
according to [I], wherein the method comprises reacting phenols
represented by the general formula (1) with monohydric or dihydric
alcohol in the presence of germanium oxide and carbon dioxide under
conditions in which a mixture of said alcohol and carbon dioxide is
in the supercritical condition.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0010] The present invention will be illustrated in detail
below.
[0011] As the linear or branched alkyl group having 1 to 10 carbon
atoms represented by R.sub.1, R.sub.2, R.sub.3, R.sub.4 and R.sub.5
in phenols of the general formula (1) used as a starting raw
material in the present invention, a methyl group, ethyl group,
n-propyl group, isopropyl group, n-butyl group, isobutyl group,
t-butyl group and the like are listed, and as specific examples of
phenols of the general formula (1), phenol, o-cresol, m-cresol,
p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 3,4-xylenol,
3,5-xylenol, anisole, t-butylphenol and the like are listed.
[0012] In the present invention, the alcohol which is another
starting raw material is not particularly restricted providing it
is monohydric or dihydric alcohol, and it is preferably monohydric
alcohol of the general formula (2):
R.sub.6--OH (2)
[0013] (wherein, R.sub.6 represents a linear or branched alkyl
group having 1 to 10 carbon atoms). Here, a methyl group, ethyl
group, n-propyl group, isopropyl group, n-butyl group, isobutyl
group, t-butyl group and the like are listed as R.sub.6.
[0014] As the monohydric alcohol of the general formula (2),
methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol,
t-butanol, pentanol, hexanol, heptanol, n-octanol, n-nonanol,
n-decanol and the like are specifically listed, and because of high
selectivity, methanol, ethanol, n-propanol and n-butanol are
preferable, methanol and ethanol are more preferable, methanol is
further preferable.
[0015] As the dihydric alcohol, ethylene glycol, propylene glycol
and the like are listed.
[0016] In the present invention, the molar ratio of monohydric or
dihydric alcohol to phenols of the general formula (1) is
appropriately determined depending on compounds used, and generally
from 1 to 1000, and ratios from 1 to200 are preferably used.
[0017] Substances have inherent three conditions, gas, liquid and
solid, and further, at the critical temperature or more and
critical pressure or more, a fluid phase exists which is not
condensed even if it is pressed. This condition is called the
supercritical condition.
[0018] When a substance is chemically reacted in fluid under the
supercritical condition, this substance may manifest higher
reactivity than in fluid under gas phase condition and in fluid
under liquid phase condition, the reason for this being not
apparent, and being guessed that the fluid under the supercritical
condition presumably has high density and high diffusion
property.
[0019] Further, under the supercritical condition, the size of a
reaction apparatus can be decreased as compared with the gas phase
reaction since the supercritical condition has a density near
liquid phase.
[0020] In the present invention, the upper limit of the reaction
temperature is not restricted, and preferably 450.degree. C. or
less so that phenols of the general formula (1) are not decomposed.
The upper limit of the reaction pressure also is not restrictive,
and preferably 25 MPa or less since it is expensive to increase
pressure resistance of a reaction apparatus.
[0021] In the production method [I] of the present invention, a
reaction is conducted under conditions in which monohydric or
dihydric alcohol is in the supercritical condition in the presence
of germanium oxide. When methanol is used as this alcohol, the
reaction is conducted under conditions of 240.degree. C. or more
and 8 MPa or more since methanol has a critical temperature of
240.degree. C. and a critical pressure of 8 MPa. When ethanol is
used, the reaction is conducted under conditions of 243.degree. C.
or more and 6.3 MPa or more since ethanol has a critical
temperature of 243.degree. C. and a critical pressure of 6.3 MPa.
When n-propanol is used, the reaction is conducted under conditions
of 264.degree. C. or more and 5 MPa or more since n-propanol has a
critical temperature of 264.degree. C. and a critical pressure of 5
MPa. When isopropanol is used, the reaction is conducted under
conditions of 235.degree. C. or more and 4.8 MPa or more since
isopropanol has a critical temperature of 235.degree. C. and a
critical pressure of 4.8 MPa. When n-butanol is used, the reaction
is conducted under conditions of 287.degree. C. or more and 4.8 MPa
or more since n-butanol has a critical temperature of 287.degree.
C. and a critical pressure of 4.8 MPa.
[0022] Next, the production method [II] of the present invention
will be illustrated.
[0023] In the production method [II] of the present invention, a
reaction is conducted in the presence of germanium oxide and carbon
dioxide under conditions in which a mixture of monohydric or
dihydric alcohol and carbon dioxide is in the supercritical
condition.
[0024] The mixing ratio of the above-mentioned alcohol to carbon
dioxide is not particularly restricted, and determined in view of
the solubility of phenols of the general formula (1) used in the
reaction into the above-mentioned alcohol. The mixing ratio of the
above-mentioned alcohol to carbon dioxide is preferably from 10:90
to 99:1.
[0025] A case in which methanol is used as the above-mentioned
alcohol and phenol is used as the phenols of the general formula
(1) will be specifically illustrated. For example, in the case of a
mixture having a molar ratio of methanol to carbon dioxide of
75:25, this mixture has a critical temperature of 204.degree. C.
and a critical pressure of 12.75 MPa according to J. Chem.
Thermodynamics, vol. 23, p. 970 (1991).
[0026] When ortho-methylation of phenols is conducted under
temperature and pressure conditions in which a mixture of methanol
and carbon dioxide is in the supercritical condition, temperature
and pressure conditions are necessary under which the mixture is in
the supercritical condition. For example, in the case of the
above-mentioned mixture having a molar ratio of methanol to carbon
dioxide of 75:25, it is necessary to conduct the reaction at a
temperature of 204.degree. C. or more and a pressure of 12.75 MPa
or more, and the reaction is preferably conducted at a temperature
of 240.degree. C. or more and a pressure of 12.75 MPa or more.
[0027] The reaction times in the production method [I] of the
present invention and the production method [II] of the present
invention are appropriately determined depending on the kinds of
the phenols and the alcohol, respectively, and the like, and
usually in the range from 1 minute to 24 hours.
[0028] In the respective production methods of the present
invention, it is preferable to effect a batch system reaction of
phenols with monohydric or dihydric alcohol using as germanium
oxide as a catalyst, and by adopting such a reaction embodiment,
by-production of components having higher boiling points composed
of dimers of phenols and derivatives thereof as main components is
suppressed, and selectivity of ortho-alkylated phenols
increases.
[0029] Further, the amount of germanium oxide added as a catalyst
may be small, and the amount of germanium oxide added is preferably
from 0.05 to 50% by weight, more preferably from 0.1 to 30% by
weight, further preferably from 0.5 to 10% by weight based on
phenols of the general formula (1).
[0030] In any of the production method [I] and the production
method [II] of the present invention, it may be conducted by a
batch system or by a flow system, and the batch system is
preferable.
[0031] In any of the production method [I] and the production
method [II] of the present invention, since the reaction mixture
after completion of the reaction may sometimes contain unreacted
raw materials or by-products or impurities in addition to
ortho-alkylated phenols of the general formula (1), the
ortho-alkylated phenols of the general formula (1) can be separated
and purified to purities required for various uses. The separation
and purification methods are not particularly restricted, and
methods industrially usually used such as distillation, extraction
and the like can be applied.
[0032] According to the production method of the present invention,
ortho-alkylated phenols can be produced from phenols of the general
formula (1) and monohydric or dihydric alcohol, using a relatively
small reaction vessel, at high selectivity under conditions in
which by-production of components having higher boiling points such
as dimers of phenols and derivatives thereof and the like is small.
The production methods of the present invention have also
characteristics that a reaction is possible even if the amount of a
catalyst is small, and that by-production of components having
higher boiling points is small particularly in the batch
system.
[0033] According to the method of the present invention,
ortho-alkylated phenols can be produced from phenols and alcohol
using a relatively small reaction vessel with high selectivity
under conditions in which by-production of components having higher
boiling points such as diners of phenols and derivatives thereof,
even if the reaction is conducted by batch system, therefore, the
method of the present invention is industrially useful.
EXAMPLES
[0034] The following examples illustrate the present invention
further in detail, but do not limit the scope of the present
invention.
[0035] Reaction materials and products in examples were identified
by using a gas chromatography mass selective detector, HP-6890 (GC:
manufactured by Yokogawa Electric Corp.)-HP5973 (MS: manufactured
by Yokogawa Electric Corp.), and quantitatively analyzed using a
gas chromatography apparatus, GC-353B (manufactured by GL Science)
equipped with FID (flow ionization detector). Conversions and
selectivities in examples were calculated by the following methods.
The conversion was calculated using the formula:
(conversion)(%)={1-(area of chromatograph of reaction substrate
remaining unreacted in reaction liquid)/(sum of areas of
chromatograph of remaining reaction substrate and all reaction
products)}.times.100. Further, selectivity was calculated,
hypothesizing areas of gas chromatograph per mol of reaction
products are the same, using the formula: (selectivity) (%)={(area
of gas chromatograph of reaction product to be calculated)/(sum of
areas of gas chromatograph of all reaction
products)}.times.100.
Example 1
[0036] 0.460 g of phenol (manufactured by Wako Pure Chemical
Industries Ltd.), 1.451 g of methanol (manufactured by Wako Pure
Chemical Industries Ltd.) and 0.030 g of germanium oxide
(GeO.sub.2, manufactured by Kojundo Kagaku K.K.) were charged in an
autoclave (made of SUS316, inner volume 4.5 ml, no pressure gauge),
the mixture was heated up to 400.degree. C. in a sand bath to
initiate the reaction. 30 minutes after, the autoclave was
quenched, and the temperature was returned to room temperature (ca.
25.degree. C.), then, the reaction liquid was removed out of the
autoclave. Namely, the reaction was conducted by batch system.
Quantification was conducted by the above-mentioned method to find
that the conversion of phenol was 44 mol %, the selectivity of
o-cresol was 71 mol %, the selectivity of 2,6-xylenol was 25 mol %,
the selectivity of anisole was 1 mol %, and the production amount
of components having higher boiling points composed of dimers of
phenol of the following chemical formula (5) and derivative thereof
as main components was as small as 3 mol % in total. p-cresol,
2,4-xylenol and 2,4,6-trimethylphenol were not produced. Components
were separated from the reaction liquid by using liquid
chromatography (elution liquid; water and methanol), and o-cresol
and 2,6-xylenol were separated out from them. The separated liquid
was analyzed by using a gas chromatography mass selective detector,
to confirm that o-cresol and 2,6-xylenol were separated from the
products. Since this autoclave was not equipped with a pressure
gauge, the following experiment was conducted to estimate the
pressure during the reaction. Namely, a pressure gauge was
installed to the same autoclave, phenol and methanol in the same
amounts were charged, and the mixture was heated up to 400.degree.
C. in a sand bath, and the pressure was measured. The estimated
pressure during the reaction was 15.4 MPa.
[0037] A higher boiling point component of the formula: 3
[0038] wherein, each of m and n independently represents an integer
from 0 to 4.
Comparative Example 1
[0039] 0.403 g of phenol, 1.405 g of methanol and 0.031 g of
zirconium oxide (ZrO.sub.2, manufactured by Kojundo Kagaku K.K.)
were charged in an autoclave (made of SUS316, inner volume 4.5 ml,
no pressure gauge), the mixture was heated up to 400.degree. C. in
a sand bath to initiate the reaction. 30 minutes after, the
autoclave was quenched, and the temperature was returned to room
temperature, then, the reaction liquid was removed out of the
autoclave. Quantification was conducted by the above-mentioned
method to find that the conversion of phenol was 3 mol %, the
selectivity of o-cresol was 49 mol %, the selectivity of p-cresol
was 2 mol %, the selectivity of anisole was 13 mol %, and the
production amount of components having higher boiling points
composed of dimers of phenol of the above-described chemical
formula (5) and derivative thereof as main components was 32 mol %
in total. 2,4-xylenol, 2,6-xylenol and 2,4,6-trimethylphenol were
not produced. Pressure was measured in the same manner as in
Example 1 except that phenol and methanol were charged in the same
amounts as described above into the same autoclave, and the
pressure during the reaction was estimated. The estimated pressure
during the reaction was 15.0 MPa.
Comparative Example 2
[0040] 0.411 g of phenol, 1.363 g of methanol and 0.031 g of
titanium oxide (TiO.sub.2, manufactured by Kojundo Kagaku K.K.)
were charged in an autoclave (made of SUS316, inner volume 4.5 ml,
no pressure gauge), the mixture was heated up to 400.degree. C. in
a sand bath to initiate the reaction. 30 minutes after, the
autoclave was quenched, and the temperature was returned to room
temperature, then, the reaction liquid was removed out of the
autoclave. Quantification was conducted by the above-mentioned
method to find that the conversion of phenol was 24 mol %, the
selectivity of o-cresol was 43 mol %, the selectivity of
2,6-xylenol was 2 mol %, the selectivity of p-cresol was 2 mol %,
the selectivity of 2,4-xylenol was 1 mol %, the selectivity of
anisole was 9 mol %, and the production amount of components having
higher boiling points composed of dimers of phenol of the
above-described chemical formula (5) and derivative thereof as main
components was 42 mol % in total. 2,4,6-trimethylphenol was not
produced. Pressure was measured in the same manner as in Example 1
except that phenol and methanol were charged in the same amounts as
described above into the same autoclave, and the pressure during
the reaction was estimated. The estimated pressure during the
reaction was 14.7 MPa.
Comparative Example 3
[0041] 0.407 g of phenol, 1.353 g of methanol and 0.031 g of
niobium oxide (Nb.sub.2O.sub.5, manufactured by Wako Pure Chemical
Industries Ltd.) were charged in an autoclave (made of SUS316,
inner volume 4.5 ml, no pressure gauge), the mixture was heated up
to 400.degree. C. in a sand bath to initiate the reaction. 30
minutes after, the autoclave was quenched, and the temperature was
returned to room temperature, then, the reaction liquid was removed
out of the autoclave. Quantification was conducted by the
above-mentioned method to find that the conversion of phenol was 8
mol %, the selectivity of o-cresol was 16 mol %, the selectivity of
p-cresol was 2 mol %, the selectivity of anisole was 22 mol %, and
the production amount of components having higher boiling points
composed of dimers of phenol of the above-described chemical
formula (5) and derivative thereof as main components was 53 mol %
in total. 2,4-xylenol, 2,6-xylenol and 2,4,6-trimethylphenol were
not produced. Pressure was measured in the same manner as in
Example 1 except that phenol and methanol were charged in the same
amounts as described above into the same autoclave, and the
pressure during the reaction was estimated. The estimated pressure
during there action was 14.7 MPa.
Comparative Example 4
[0042] 0.408 g of phenol, 1.353 g of methanol and 0.032 g of
chromium oxide (Cr.sub.2O.sub.3, manufactured by Wako Pure Chemical
Industries Ltd.) were charged in an autoclave (made of SUS316,
inner volume 4.5 ml, no pressure gauge), the mixture was heated up
to 400.degree. C. in a sand bath to initiate the reaction. 30
minutes after, the autoclave was quenched, and the temperature was
returned to room temperature, then, the reaction liquid was removed
out of the autoclave. Quantification was conducted by the
above-mentioned method to find that the conversion of phenol was 5
mol %, the selectivity of o-cresol was 16 mol %, the selectivity of
p-cresol was 1 mol %, the selectivity of anisole was 6 mol %, and
the production amount of components having higher boiling points
composed of dimers of phenol of the above-described chemical
formula (5) and derivative thereof as main components was 71 mol %
in total. 2,4-xylenol, 2,6-xylenol and 2,4,6-trimethylphenol were
not produced. Pressure was measured in the same manner as in
Example 1 except that phenol and methanol were charged in the same
amounts as described above into the same autoclave, and the
pressure during the reaction was estimated. The estimated pressure
during the reaction was 14.7 MPa.
Comparative Example 5
[0043] 0.410 g of phenol, 1.355 g of methanol and 0.031 g of
molybdenum oxide (MoO.sub.3, manufactured by Wako Pure Chemical
Industries Ltd.) were charged in an autoclave (made of SUS316,
inner volume 4.5 ml, no pressure gauge), the mixture was heated up
to 400.degree. C. in a sand bath to initiate the reaction. 30
minutes after, the autoclave was quenched, and the temperature was
returned to room temperature, then, the reaction liquid was removed
out of the autoclave. Quantification was conducted by the
above-mentioned method to find that the conversion of phenol was 97
mol %, the selectivity of o-cresol was 22 mol %, the selectivity of
2,6-xylenol was 39 mol %, the selectivity of 2,4-xylenol was 3 mol
%, the selectivity of anisole was 2 mol %, the selectivity of
2,4,6-trimethylphenol was 9 mol % and the production amount of
components having higher boiling points composed of dimers of
phenol of the above-described chemical formula (5) and derivative
thereof as main components was 19 mol % in total. p-cresol was not
produced. Pressure was measured in the same manner as in Example 1
except that phenol and methanol were charged in the same amounts as
described above into the same autoclave, and the pressure during
the reaction was estimated. The estimated pressure during the
reaction was 14.7 MPa.
Comparative Example 6
[0044] 0.410 g of phenol, 1.363 g of methanol and 0.031 g of
tungsten oxide (WO.sub.3, manufactured by Wako Pure Chemical
Industries Ltd.) were charged in an autoclave (made of SUS316,
inner volume 4.5 ml, no pressure gauge), the mixture was heated up
to 400.degree. C. in a sand bath to initiate the reaction. 30
minutes after, the autoclave was quenched, and the temperature was
returned to room temperature, then, the reaction liquid was removed
out of the autoclave. Quantification was conducted by the
above-mentioned method to find that the conversion of phenol was 21
mol %, the selectivity of o-cresol was 16 mol %, the selectivity of
2,6-xylenol was 1 mol %, the selectivity of p-cresol was 4 mol %,
the selectivity of 2,4-xylenol was 1 mol %, the selectivity of
anisole was 21 mol % and the production amount of components having
higher boiling points composed of dimers of phenol of the
above-described chemical formula (5) and derivative thereof as main
components was 51 mol % in total. 2,4,6-trimethylphenol was not
produced. Pressure was measured in the same manner as in Example 1
except that phenol and methanol were charged in the same amounts as
described above into the same autoclave, and the pressure during
the reaction was estimated. The estimated pressure during the
reaction was 14.7 MPa.
Comparative Example 7
[0045] 0.405 g of phenol, 1.358 g of methanol and 0.031 g of
manganese oxide (MnO.sub.2, manufactured by Kojundo Kagaku K.K.)
were charged in an autoclave (made of SUS316, inner volume 4.5 ml,
no pressure gauge), the mixture was heated up to 400.degree. C. in
a sand bath to initiate the reaction. 30 minutes after, the
autoclave was quenched, and the temperature was returned to room
temperature, then, the reaction liquid was removed out of the
autoclave. Quantification was conducted by the above-mentioned
method to find that the conversion of phenol was 19 mol %, the
selectivity of o-cresol was 39 mol %, the selectivity of
2,6-xylenol was 1 mol %, the selectivity of p-cresol was 1 mol %,
the selectivity of 2,4-xylenol was 1 mol %, the selectivity of
anisole was 2 mol % and the production amount of components having
higher boiling points composed of dimers of phenol of the
above-described chemical formula (5) and derivative thereof as main
components was 54 mol % in total. 2,4,6-trimethylphenol was not
produced. Pressure was measured in the same manner as in Example 1
except that phenol and methanol were charged in the same amounts as
described above into the same autoclave, and the pressure during
the reaction was estimated. The estimated pressure during the
reaction was 14.7 MPa.
Comparative Example 8
[0046] 0.401 g of phenol, 1.354 g of methanol and 0.031 g of iron
oxide (Fe.sub.2O.sub.3, manufactured by Kojundo Kagaku K.K.) were
charged in an autoclave (made of SUS316, inner volume 4.5 ml, no
pressure gauge), the mixture was heated up to 400.degree. C. in a
sand bath to initiate the reaction. 30 minutes after, the autoclave
was quenched, and the temperature was returned to room temperature,
then, the reaction liquid was removed out of the autoclave.
Quantification was conducted by the above-mentioned method to find
that the conversion of phenol was 21 mol %, the selectivity of
o-cresol was 70 mol %, the selectivity of 2,6-xylenol was 4 mol %,
the selectivity of anisole was 1 mol % and the production amount of
components having higher boiling points composed of dimers of
phenol of the above-described chemical formula (5) and derivative
thereof as main components was 24 mol % in total. p-cresol,
2,4-xylenol and 2,4,6-trimethylphenol were not produced. Pressure
was measured in the same manner as in Example 1 except that phenol
and methanol were charged in the same amounts as described above
into the same autoclave, and the pressure during the reaction was
estimated. The estimated pressure during the reaction was 14.7
MPa.
Comparative Example 9
[0047] 0.413 g of phenol, 1.364 g of methanol and 0.032 g of cobalt
oxide (CoO, manufactured by Wako Pure Chemical Industries Ltd.)
were charged in an autoclave (made of SUS316, inner volume 4.5 ml,
no pressure gauge), the mixture was heated up to 400.degree. C. in
a sand bath to initiate the reaction. 30 minutes after, the
autoclave was quenched, and the temperature was returned to room
temperature, then, the reaction liquid was removed out of the
autoclave. Quantification was conducted by the above-mentioned
method to find that the conversion of phenol was 48 mol %, the
selectivity of o-cresol was 31 mol %, the selectivity of
2,6-xylenol was 2 mol %, the selectivity of p-cresol was 1 mol %
and the production amount of components having higher boiling
points composed of dimers of phenol of the above-described chemical
formula (5) and derivative thereof as main components was 6 mol %
in total. 2,4-xylenol, anisole and 2,4,6-trimethylphenol were not
produced. In this reaction, hydrogenation of an aromatic ring
progressed, and consequently, cyclohexanol was produced in a
selectivity of 15 mol % and cyclohexanone was produced in a
selectivity of 38 mol %. Pressure was measured in the same manner
as in Example 1 except that phenol and methanol were charged in the
same amounts as described above into the same autoclave, and the
pressure during the reaction was estimated. The estimated pressure
during the reaction was 14.7 MPa.
Comparative Example 10
[0048] 0.415 g of phenol, 1.359 g of methanol and 0.031 g of zinc
oxide (ZnO, manufactured by Wako Pure Chemical Industries Ltd.)
were charged in an autoclave (made of SUS316, inner volume 4.5 ml,
no pressure gauge), the mixture was heated up to 400.degree. C. in
a sand bath to initiate the reaction. 30 minutes after, the
autoclave was quenched, and the temperature was returned to room
temperature, then, the reaction liquid was removed out of the
autoclave. Quantification was conducted by the above-mentioned
method to find that the conversion of phenol was 5 mol %, the
selectivity of o-cresol was 27 mol %, the selectivity of p-cresol
was 2 mol %, the selectivity of anisole was 5 mol % and the
production amount of components having higher boiling points
composed of dimers of phenol of the above-described chemical
formula (5) and derivative thereof as main components was 63 mol %
in total. 2,4-xylenol, 2,6-xylenol and 2,4,6-trimethylphenol were
not produced. Pressure was measured in the same manner as in
Example 1 except that phenol and methanol were charged in the same
amounts as described above into the same autoclave, and the
pressure during the reaction was estimated. The estimated pressure
during the reaction was 14.7 MPa.
Comparative Example 11
[0049] 0.414 g of phenol, 1.360 g of methanol and 0.031 g of
aluminum oxide (Al.sub.2O.sub.3, manufactured by Wako Pure Chemical
Industries Ltd.) were charged in an autoclave (made of SUS316,
inner volume 4.5 ml, no pressure gauge), the mixture was heated up
to 400.degree. C. in a sand bath to initiate the reaction. 30
minutes after, the autoclave was quenched, and the temperature was
returned to room temperature, then, the reaction liquid was removed
out of the autoclave. Quantification was conducted by the
above-mentioned method to find that the conversion of phenol was 19
mol %, the selectivity of o-cresol was 17 mol %, the selectivity of
p-cresol was 1 mol %, the selectivity of anisole was 51 mol % and
the production amount of components having higher boiling points
composed of dimers of phenol of the above-described chemical
formula (5) and derivative thereof as main components was 28 mol %
in total. 2,4-xylenol, 2,6-xylenol and 2,4,6-trimethylphenol were
not produced. Pressure was measured in the same manner as in
Example 1 except that phenol and methanol were charged in the same
amounts as described above into the same autoclave, and the
pressure during the reaction was estimated. The estimated pressure
during the reaction was 14.7 MPa.
Comparative Example 12
[0050] 0.415 g of phenol, 1.356 g of methanol and 0.031 g of indium
oxide (In.sub.2O.sub.3, manufactured by Kojundo Kagaku K.K.) were
charged in an autoclave (made of SUS316, inner volume 4.5 ml, no
pressure gauge), the mixture was heated up to 400.degree. C. in a
sand bath to initiate the reaction. 30 minutes after, the autoclave
was quenched, and the temperature was returned to room temperature,
then, the reaction liquid was removed out of the autoclave.
Quantification was conducted by the above-mentioned method to find
that the conversion of phenol was 23 mol %, the selectivity of
o-cresol was 52 mol %, the selectivity of 2,6-xylenol was 2 mol %,
the selectivity of p-cresol was 1 mol %, the selectivity of anisole
was 3 mol % and the production amount of components having higher
boiling points composed of dimers of phenol of the above-described
chemical formula (5) and derivative thereof as main components was
40 mol % in total. 2,4-xylenol and 2,4,6-trimethylphenol were not
produced. Pressure was measured in the same manner as in Example 1
except that phenol and methanol were charged in the same amounts as
described above into the same autoclave, and the pressure during
the reaction was estimated. The estimated pressure during the
reaction was 14.7 MPa.
Comparative Example 13
[0051] 0.402 g of phenol (manufactured by Wako Pure Chemical
Industries Ltd.), 1.353 g of methanol (manufactured by Wako Pure
Chemical Industries Ltd.) and 0.031 g of silicon oxide (SiO.sub.2,
manufactured by Nitto Kagaku K.K.) were charged in an autoclave
(made of SUS316, inner volume 4.5 ml, no pressure gauge), the
mixture was heated up to 400.degree. C. in a sand bath to initiate
the reaction. 30 minutes after, the autoclave was quenched, and the
temperature was returned to room temperature, then, the reaction
liquid was removed out of the autoclave. Quantification was
conducted by the above-mentioned method to find that the conversion
of phenol was 17 mol %, the selectivity of o-cresol was 14 mol %,
the selectivity of p-cresol was 1 mol %, the selectivity of anisole
was 2 mol % and the production amount of components having higher
boiling points composed of dimers of phenol of the above-described
chemical formula (5) and derivative thereof as main components was
81 mol % in total. 2,4-xylenol, 2,6-xylenol and
2,4,6-trimethylphenol were not produced. Pressure was measured in
the same manner as in Example 1 except that phenol and methanol
were charged in the same amounts as described above into the same
autoclave, and the pressure during the reaction was estimated. The
estimated pressure during the reaction was 14.7 MPa.
Comparative Example 14
[0052] 0.389 g of phenol, 1.372 g of methanol and 0.029 g of tin
oxide (SnO.sub.2, manufactured by Wako Pure Chemical Industries
Ltd.) were charged in an autoclave (made of SUS316, inner volume
4.5 ml, no pressure gauge), the mixture was heated up to
400.degree. C. in a sand bath to initiate the reaction. 30 minutes
after, the autoclave was quenched, and the temperature was returned
to room temperature, then, the reaction liquid was removed out of
the autoclave. Quantification was conducted by the above-mentioned
method to find that the conversion of phenol was 24 mol %, the
selectivity of o-cresol was 25 mol %, the selectivity of
2,6-xylenol was 1 mol %, the selectivity of p-cresol was 1 mol %,
the selectivity of anisole was 1 mol % and the production amount of
components having higher boiling points composed of diners of
phenol of the above-described chemical formula (5) and derivative
thereof as main components was 71 mol % in total. 2,4-xylenol and
2,4,6-trimethylphenol were not produced. Pressure was measured in
the same manner as in Example 1 except that phenol and methanol
were charged in the same amounts as described above into the same
autoclave, and the pressure during the reaction was estimated. The
estimated pressure during the reaction was 14.7 MPa.
Comparative Example 15
[0053] 0.408 g of phenol, 1.354 g of methanol and 0.031 g of
magnesium oxide (MgO, manufactured by Kojundo Kagaku K.K.) were
charged in an autoclave (made of SUS316, inner volume 4.5 ml, no
pressure gauge), the mixture was heated up to 400.degree. C. in a
sand bath to initiate the reaction. 30 minutes after, the autoclave
was quenched, and the temperature was returned to room temperature,
then, the reaction liquid was removed out of the autoclave.
Quantification was conducted by the above-mentioned method to find
that the conversion of phenol was 3 mol %, the selectivity of
o-cresol was 23 mol %, the selectivity of p-cresol was 2 mol %, the
selectivity of anisole was 29 mol % and the production amount of
components having higher boiling points composed of dimers of
phenol of the above-described chemical formula (5) and derivative
thereof as main components was 36 mol % in total. 2,4-xylenol,
2,6-xylenol and 2,4,6-trimethylphenol were not produced. Pressure
was measured in the same manner as in Example 1 except that phenol
and methanol were charged in the same amounts as described above
into the same autoclave, and the pressure during the reaction was
estimated. The estimated pressure during the reaction was 14.7
MPa.
Comparative Example 16
[0054] 0.407 g of phenol, 1.357 g of methanol and 0.031 g of
calcium oxide (CaO, manufactured by Wako Pure Chemical Industries
Ltd.) were charged in an autoclave (made of SUS316, inner volume
4.5 ml, no pressure gauge), the mixture was heated up to
400.degree. C. in a sand bath to initiate the reaction. 30 minutes
after, the autoclave was quenched, and the temperature was returned
to room temperature, then, the reaction liquid was removed out of
the autoclave. Quantification was conducted by the above-mentioned
method to find that the conversion of phenol was 10 mol %, the
selectivity of o-cresol was 45 mol %, the selectivity of
2,6-xylenol was 1 mol %, the selectivity of p-cresol was 11 mol %,
the selectivity of 2,4-xylenol was 1 mol %, the selectivity of
anisole was 8 mol % and the production amount of components having
higher boiling points composed of dimers of phenol of the
above-described chemical formula (5) and derivative thereof as main
components was 32 mol % in total. Pressure was measured in the same
manner as in Example 1 except that phenol and methanol were charged
in the same amounts as described above into the same autoclave, and
the pressure during the reaction was estimated. The estimated
pressure during the reaction was 14.7 MPa.
Comparative Example 17
[0055] 0.406 g of phenol, 1.353 g of methanol and 0.031 g of
strontium oxide (SrO, manufactured by Kojundo Kagaku K.K.) were
charged in an autoclave (made of SUS316, inner volume 4.5 ml, no
pressure gauge), the mixture was heated up to 400.degree. C. in a
sand bath to initiate the reaction. 30 minutes after, the autoclave
was quenched, and the temperature was returned to room temperature,
then, the reaction liquid was removed out of the autoclave.
Quantification was conducted by the above-mentioned method to find
that the conversion of phenol was 61 mol %, the selectivity of
o-cresol was 43 mol %, the selectivity of 2,6-xylenol was 6 mol %,
the selectivity of p-cresol was 13 mol %, the selectivity of
2,4-xylenol was 8 mol %, the selectivity of anisole was 13 mol %,
the selectivity of 2,4,6-trimethylphenol was 1 mol %, and the
production amount of components having higher boiling points
composed of dimers of phenol of the above-described chemical
formula (5) and derivative thereof as main components was 13 mol %
in total. Pressure was measured in the same manner as in Example 1
except that phenol and methanol were charged in the same amounts as
described above into the same autoclave, and the pressure during
the reaction was estimated. The estimated pressure during the
reaction was 14.7 MPa.
Comparative Example 18
[0056] 0.411 g of phenol, 1.361 g of methanol and 0.030 g of barium
oxide (BaO, manufactured by Kojundo Kagaku K.K.) were charged in an
autoclave (made of SUS316, inner volume 4.5 ml, no pressure gauge),
the mixture was heated up to 400.degree. C. in a sand bath to
initiate the reaction. 30 minutes after, the autoclave was
quenched, and the temperature was returned to room temperature,
then, the reaction liquid was removed out of the autoclave.
Quantification was conducted by the above-mentioned method to find
that the conversion of phenol was 38 mol %, the selectivity of
o-cresol was 24 mol %, the selectivity of 2,6-xylenol was 1 mol %,
the selectivity of p-cresol was 16 mol %, the selectivity of
2,4-xylenol was 3 mol %, the selectivity of anisole was 8 mol % and
the production amount of components having higher boiling points
composed of dimers of phenol of the above-described chemical
formula (5) and derivative thereof as main components was 46 mol %
in total. 2,4,6-trimethylphenol was not produced. Pressure was
measured in the same manner as in Example 1 except that phenol and
methanol were charged in the same amounts as described above into
the same autoclave, and the pressure during the reaction was
estimated. The estimated pressure during the reaction was 14.7
MPa.
Comparative Example 19
[0057] 0.401 g of phenol, 1.355 g of methanol and 0.030 g of
yttrium oxide (Y.sub.2O.sub.5, manufactured by Wako Pure Chemical
Industries Ltd.) were charged in an autoclave (made of SUS316,
inner volume 4.5 ml, no pressure gauge), the mixture was heated up
to 400.degree. C. in a sand bath to initiate the reaction. 30
minutes after, the autoclave was quenched, and the temperature was
returned to room temperature, then, the reaction liquid was removed
out of the autoclave. Quantification was conducted by the
above-mentioned method to find that the conversion of phenol was 2
mol %, the selectivity of o-cresol was 17 mol %, the selectivity of
p-cresol was 1 mol %, the selectivity of anisole was 10 mol % and
the production amount of components having higher boiling points
composed of dimers of phenol of the above-described chemical
formula (5) and derivative thereof as main components was 66 mol %
in total. 2,4-xylenol, 2,6-xylenol and 2,4,6-trimethylphenol were
not produced. Pressure was measured in the same manner as in
Example 1 except that phenol and methanol were charged in the same
amounts as described above into the same autoclave, and the
pressure during the reaction was estimated. The estimated pressure
during the reaction was 14.7 MPa.
Comparative Example 20
[0058] 0.419 g of phenol, 1.357 g of methanol and 0.030 g of
lanthanum oxide (La.sub.2O.sub.3, manufactured by Wako Pure
Chemical Industries Ltd.) were charged in an autoclave (made of
SUS316, inner volume 4.5 ml, no pressure gauge), the mixture was
heated up to 400.degree. C. in a sand bath to initiate the
reaction. 30 minutes after, the autoclave was quenched, and the
temperature was returned to room temperature, then, the reaction
liquid was removed out of the autoclave. Quantification was
conducted by the above-mentioned method to find that the conversion
of phenol was 4 mol %, the selectivity of o-cresol was 26 mol %,
the selectivity of p-cresol was 2 mol %, the selectivity of anisole
was 9 mol % and the production amount of components having higher
boiling points composed of dimers of phenol of the above-described
chemical formula (5) and derivative thereof as main components was
59 mol % in total. 2,4-xylenol, 2,6-xylenol and
2,4,6-trimethylphenol were not produced. Pressure was measured in
the same manner as in Example 1 except that phenol and methanol
were charged in the same amounts as described above into the same
autoclave, and the pressure during the reaction was estimated. The
estimated pressure during the reaction was 14.7 MPa.
Comparative Example 21
[0059] 0.401 g of phenol, 1.357 g of methanol and 0.030 g of nickel
oxide (NiO, manufactured by Hanni Kagaku K.K.) were charged in an
autoclave (made of SUS316, inner volume 4.5 ml, no pressure gauge),
the mixture was heated up to 400.degree. C. in a sand bath to
initiate the reaction. 30 minutes after, the autoclave was
quenched, and the temperature was returned to room temperature,
then, the reaction liquid was removed out of the autoclave.
Quantification was conducted by the above-mentioned method to find
that the conversion of phenol was 9 mol %, the selectivity of
o-cresol was 27 mol %, the selectivity of p-cresol was 1 mol %, the
selectivity of anisole was 4 mol % and the production amount of
components having higher boiling points composed of dimers of
phenol of the above-described chemical formula (5) and derivative
thereof as main components was 63 mol % in total. 2,4-xylenol,
2,6-xylenol and 2,4,6-trimethylphenol were not produced. Pressure
was measured in the same manner as in Example 1 except that phenol
and methanol were charged in the same amounts as described above
into the same autoclave, and the pressure during the reaction was
estimated. The estimated pressure during the reaction was 14.7
MPa.
Comparative Example 22
[0060] 0.400 g of phenol, 1.352 g of methanol and 0.031 g of
samarium oxide (Sm.sub.2O.sub.3, manufactured by Kojundo Kagaku
K.K.) were charged in an autoclave (made of SUS316, inner volume
4.5 ml, no pressure gauge), the mixture was heated up to
400.degree. C. in a sand bath to initiate the reaction. 30 minutes
after, the autoclave was quenched, and the temperature was returned
to room temperature, then, the reaction liquid was removed out of
the autoclave. Quantification was conducted by the above-mentioned
method to find that the conversion of phenol was 6 mol %, the
selectivity of o-cresol was 17 mol %, the selectivity of p-cresol
was 2 mol %, the selectivity of anisole was 5 mol % and the
production amount of components having higher boiling points
composed of dimers of phenol of the above-described chemical
formula (5) and derivative thereof as main components was 73 mol %
in total. 2,4-xylenol, 2,6-xylenol and 2,4,6-trimethylphenol were
not produced. Pressure was measured in the same manner as in
Example 1 except that phenol and methanol were charged in the same
amounts as described above into the same autoclave, and the
pressure during the reaction was estimated. The estimated pressure
during the reaction was 14.7 MPa.
Comparative Example 23
[0061] 0.404 g of phenol, 1.359 g of methanol and 0.031 g of
tantalum oxide (Ta.sub.2O.sub.3, manufactured by Wako Pure Chemical
Industries Ltd.) were charged in an autoclave (made of SUS316,
inner volume 4.5 ml, no pressure gauge), the mixture was heated up
to 400.degree. C. in a sand bath to initiate the reaction. 30
minutes after, the autoclave was quenched, and the temperature was
returned to room temperature, then, the reaction liquid was removed
out of the autoclave. Quantification was conducted by the
above-mentioned method to find that the conversion of phenol was 5
mol %, the selectivity of o-cresol was 20 mol %, the selectivity of
p-cresol was 1 mol %, the selectivity of anisole was 20 mol % and
the production amount of components having higher boiling points
composed of dimers of phenol of the above-described chemical
formula (5) and derivative thereof as main components was 53 mol %
in total. 2,4-xylenol, 2,6-xylenol and 2,4,6-trimethylphenol were
not produced. Pressure was measured in the same manner as in
Example 1 except that phenol and methanol were charged in the same
amounts as described above into the same autoclave, and the
pressure during the reaction was estimated. The estimated pressure
during the reaction was 14.7 MPa.
Comparative Example 24
[0062] 0.406 g of phenol, 1.441 g of methanol and 0.030 g of copper
oxide (CuO, manufactured by Kojundo Kagaku K.K.) were charged in an
autoclave (made of SUS316, inner volume 4.5 ml, no pressure gauge),
the mixture was heated up to 400.degree. C. in a sand bath to
initiate the reaction. 30 minutes after, the autoclave was
quenched, and the temperature was returned to room temperature,
then, the reaction liquid was removed out of the autoclave.
Quantification was conducted by the above-mentioned method to find
that the conversion of phenol was 43 mol %, the selectivity of
o-cresol was 32 mol %, the selectivity of 2,6-xylenol was 3 mol %,
the selectivity of p-cresol was 2 mol %, the selectivity of
2,4-xylenol was 1 mol %, the selectivity of anisole was 1 mol % and
the production amount of components having higher boiling points
composed of dimers of phenol of the above-described chemical
formula (5) and derivative thereof as main components was 53 mol %
in total. 2,4,6-trimethylphenol was not produced. Pressure was
measured in the same manner as in Example 1 except that phenol and
methanol were charged in the same amounts as described above into
the same autoclave, and the pressure during the reaction was
estimated. The estimated pressure during the reaction was 15.3
MPa.
[0063] The results of Example 1 and Comparative Examples 1 to 24
are summarized in the following Table 1.
1 TABLE 1 Conversion Selectivity (% by mole) No. (% by mole) OCL
26Xyl OMP HBP Ex.1 44 71 25 96 3 Com.1 3 49 0 49 32 Com.2 24 43 2
45 42 Com.3 8 16 0 16 53 Com.4 5 16 0 16 71 Com.5 97 22 39 61 19
Com.6 21 16 1 17 51 Com.7 19 39 1 40 54 Com.8 21 70 4 74 24 Com.9
40 31 2 33 6 Com.10 5 27 0 27 63 Com.11 19 17 0 17 28 Com.12 23 52
2 54 40 Com.13 17 14 0 14 81 Com.14 24 25 1 26 71 Com.15 3 23 0 23
36 Com.16 10 45 1 46 32 Com.17 61 43 6 49 13 Com.18 38 24 1 25 46
Com.19 2 17 0 17 66 Com.20 4 26 0 26 59 Com.21 9 27 0 27 63 Com.22
6 17 0 17 73 Com.23 5 20 0 20 53 Com.24 43 32 3 35 53
[0064] OCL: o-cresol; 26Xyl: 2,6-Xylenol
[0065] OMP: total of all ortho-methylated phenols
[0066] HBP: components having higher boiling points composed of
dimers of phenol of the above-described chemical formula (5) and
derivative
* * * * *