U.S. patent application number 11/299813 was filed with the patent office on 2006-05-04 for process for preparing ruthenium-carrying alumina and process for oxidizing alcohol.
This patent application is currently assigned to SUMITOMO CHEMICAL COMPANY, LIMITED. Invention is credited to Hajime Ishida, Noritaka Mizuno, Kazuya Yamaguchi.
Application Number | 20060094899 11/299813 |
Document ID | / |
Family ID | 29272366 |
Filed Date | 2006-05-04 |
United States Patent
Application |
20060094899 |
Kind Code |
A1 |
Mizuno; Noritaka ; et
al. |
May 4, 2006 |
Process for preparing ruthenium-carrying alumina and process for
oxidizing alcohol
Abstract
A ruthenium-carrying alumina, which is prepared by suspending
alumina in a solution containing trivalent ruthenium and adding a
base to the suspension, is provided. This ruthenium-carrying
alumina is useful as a catalyst for oxidizing alcohols by
contacting the alcohols with molecular oxygen, and can be used for
oxidizing the alcohols at a high conversion to produce ketones,
aldehydes, carboxylic acids, etc. with good productivity.
Inventors: |
Mizuno; Noritaka;
(Nerima-ku, JP) ; Yamaguchi; Kazuya; (Bunkyo-ku,
JP) ; Ishida; Hajime; (Niihama-shi, JP) |
Correspondence
Address: |
SUGHRUE MION, PLLC
2100 PENNSYLVANIA AVENUE, N.W.
SUITE 800
WASHINGTON
DC
20037
US
|
Assignee: |
SUMITOMO CHEMICAL COMPANY,
LIMITED
|
Family ID: |
29272366 |
Appl. No.: |
11/299813 |
Filed: |
December 13, 2005 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10481755 |
Dec 23, 2003 |
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11299813 |
Dec 13, 2005 |
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PCT/JP03/05299 |
Apr 25, 2003 |
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10481755 |
Dec 23, 2003 |
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Current U.S.
Class: |
562/538 ;
502/325; 568/403; 568/471 |
Current CPC
Class: |
C07D 333/22 20130101;
C07C 53/126 20130101; B01J 37/031 20130101; C07C 45/39 20130101;
C07C 51/235 20130101; C07C 51/235 20130101; C07C 45/38 20130101;
B01J 23/462 20130101; B01J 21/04 20130101 |
Class at
Publication: |
562/538 ;
568/471; 568/403; 502/325 |
International
Class: |
C07C 51/245 20060101
C07C051/245; C07C 51/235 20060101 C07C051/235; C07C 51/16 20060101
C07C051/16; C07C 45/29 20060101 C07C045/29 |
Foreign Application Data
Date |
Code |
Application Number |
Apr 26, 2002 |
JP |
P2002-126189 |
Nov 28, 2002 |
JP |
P2002-345108 |
Claims
1. A process for preparing a ruthenium-carrying alumina, the
process comprising the steps of: suspending alumina in a solution
containing trivalent ruthenium and adding a base to the
suspension.
2-6. (canceled)
7. A process for preparing an oxidation catalyst containing a
ruthenium-carrying alumina, the process comprising the steps of:
suspending alumina in a solution containing trivalent ruthenium and
adding a base to the suspension.
8. An oxidation catalyst including a ruthenium-carrying alumina
which is prepared by the process according to claim 1.
Description
FIELD OF THE INVENTION
[0001] The present invention relates to a process for preparing a
ruthenium-carrying alumina, and a process for producing ketones,
aldehydes, carboxylic acids and the like by oxidizing alcohols with
molecular oxygen in the presence of a ruthenium-carrying alumina as
a catalyst.
PRIOR ART
[0002] As a process for oxidizing alcohols, a process of contacting
the alcohols with molecular oxygen in the presence of a ruthenium
catalyst is known. For example, U.S. Pat. No. 4,996,007 proposes to
carry out the above oxidation reaction in the presence of a
ruthenium catalyst such as a ruthenium-carrying alumina, a
ruthenium-carrying carbon, etc. together with an oxygen-activator
such as dihydrodihydroxynaphthalene. JP-A-11-226417 proposes to
carry out the above oxidation reaction in the presence of a
ruthenium catalyst such as
dichlorotris-(triphenylphosphine)ruthenium, tetrapropylammonium
perruthenate salt, a ruthenium-carrying carbon, etc. together with
dioxybenzenes or their oxidized derivatives. Furthermore,
JP-A-2000-70723 proposes to carry out the above oxidation reaction
in the presence of a ruthenium-containing hydrotalcite.
[0003] However, the ruthenium catalysts used in the above
conventional processes do not necessarily have sufficient catalytic
activities so that the desired conversion of the alcohols is not
achieved. Therefore, the conventional processes may not be
satisfactory in the productivity of oxidized products.
SUMMARY OF THE INVENTION
[0004] One object of the present invention is to provide a process
for preparing a ruthenium catalyst having a good activity to
oxidize alcohols.
[0005] Another object of the present invention is to provide a
process for preparing ketones, aldehydes, carboxylic acids and the
like at a high productivity by oxidizing alcohols at a high
conversion using a catalyst prepared by the process described
above.
[0006] Accordingly, the present invention provides a process for
preparing a ruthenium-carrying alumina comprising the steps of
suspending alumina in a solution containing trivalent ruthenium and
adding a base to the suspension, and a process for oxidizing an
alcohol comprising the step of contacting the alcohol with
molecular oxygen in the presence of a ruthenium-carrying alumina
prepared by the process described above. Furthermore, the present
invention provides a process for preparing a carbonyl compound
comprising oxidizing an alcohol by the oxidizing process described
above.
DETAILED DESCRIPTION OF THE INVENTION
[0007] In the process for preparing a ruthenium-carrying alumina
according to the present invention, trivalent ruthenium
(ruthenium(III)) is utilized as a ruthenium source, and alumina is
suspended in a solution containing trivalent ruthenium.
[0008] Examples of ruthenium compounds which can be used as sources
of trivalent ruthenium include ruthenium halides such as
ruthenium(III) chloride, ruthenium(III) bromide, etc.; oxo acid
salts such as ruthenium(III) nitrate, ruthenium(III) sulfate, etc.;
and so on. They may be used as a mixture of two or more of them, if
desired. Among them, ruthenium halides such as ruthenium(III)
chloride are preferable.
[0009] Water is usually used as a solvent of the ruthenium
solution, although a mixed solvent of water and an organic solvent,
or an organic solvent alone may be used, if necessary. The amount
of the solvent is adjusted such that a ruthenium concentration in
the solution is usually from 0.1 mM to 1 M, preferably from 1 mM to
100 mM.
[0010] The kind of alumina to be suspended in the ruthenium
solution is not limited, and various kinds of alumina such as
.alpha.-alumina, .beta.-alumina, .gamma.-alumina, etc. may be used.
Among them, .gamma.-alumina is preferably used. The amount of
alumina is adjusted such that an ruthenium content in the
ruthenium-carrying alumina is usually from 0.1 to 20% by weight,
preferably from 0.5 to 10% by weight.
[0011] Then, a base is added to the suspension of alumina prepared
in the previous step to adjust the pH of the suspension to usually
at least 8, preferably at least 10, more preferably 12 to 14. If no
base is added, the activity of the ruthenium-carrying alumina as a
catalyst for oxidizing alcohols is not sufficiently high.
[0012] Examples of the base include metal hydroxides such as sodium
hydroxide, potassium hydroxide, magnesium hydroxide, etc.; metal
carbonates such as sodium carbonate, potassium carbonate, magnesium
carbonate, etc.; metal acetates such as sodium acetate, potassium
acetate, etc.; ammonia; and the like. They may be used as a mixture
of two or more of them, if desired.
[0013] After the addition of the base, the suspension is subjected
to solid-liquid separation treatment. Thereby, the
ruthenium-carrying alumina is recovered from the suspension. The
solid-liquid separation treatment is usually filtration or
decantation. The recovered ruthenium-carrying alumina may
optionally be post-treated such as washing with water, drying,
etc.
[0014] The ruthenium-carrying alumina prepared by the above process
is preferably used as a catalyst for oxidizing an alcohol with
molecular oxygen. This oxidation reaction may be carried out either
in a liquid phase or in a gas phase. Preferably, it is carried out
in the liquid phase.
[0015] The amount of the ruthenium-carrying alumina used in the
oxidizing process is usually from 0.000001 to 1 mole, preferably
from 0.0001 to 0.1 mole, more preferably from 0.001 to 0.05 mole,
in terms of ruthenium per one mole of the alcohol.
[0016] The alcohol as a substrate to be oxidized may be a primary
alcohol or a secondary alcohol, and may be a monohydric alcohol or
a polyhydric alcohol. The alcohol may be used as a mixture of two
or more of alcohols, if desired.
[0017] Preferably, the alcohol as a substrate is an alcohol
represented by the following formula (1), (2) or (3): ##STR1##
wherein R.sup.1 represents a hydrogen atom; a hydrocarbon group
which may optionally be substituted with at least one substituent
selected from the group consisting of a halogen atom, a nitro
group, an alkoxy group, a phenoxy group and an acyloxy group; or a
heterocyclic group, ##STR2## wherein R.sup.2 and R.sup.3 represent
independently each other a hydrocarbon group which may optionally
be substituted with at least one substituent selected from the
group consisting of a halogen atom, a nitro group, an alkoxy group,
a phenoxy group and an acyloxy group; or a heterocyclic group,
while R.sup.2 and R.sup.3 may be combined to form a ring together
with the carbon atom to which they are bonded, ##STR3## wherein X
represents a single bond or a divalent hydrocarbon group, and
R.sup.4 and R.sup.5 represent independently each other a hydrogen
atom; a hydrocarbon group which may optionally be substituted with
at least one substituent selected from the group consisting of a
halogen atom, a nitro group, an alkoxy group, a phenoxy group and
an acyloxy group; or a heterocyclic group, while R.sup.4 and
R.sup.5 may be combined to form a ring together with the carbon
atoms to which R.sup.4, R.sup.5 and X are bonded.
[0018] When R.sup.1 in the formula (1) is a hydrocarbon group which
may optionally be substituted with at least one substituent
selected from the group consisting of a halogen atom, a nitro
group, an alkoxy group, a phenoxy group and an acyloxy group, the
hydrocarbon group is preferably an alkyl group, a cycloalkyl group,
an alkenyl group, an aryl group, an arylalkyl group or an
arylalkenyl group, each of which has 1 to 20 carbon atoms. The
alkoxyl group and the acyloxy group as a substituent of the
hydrocarbon group may have 1 to 10 carbon atoms.
[0019] When R.sup.1 is a heterocyclic group, it preferably has at
least one hetero atom selected from oxygen, nitrogen and sulfur
atoms. The heterocyclic group is preferably a five- or six-membered
ring.
[0020] When R.sup.2 or R.sup.3 in the formula (2) is a hydrocarbon
group which may optionally be substituted with at least one
substituent selected from the group consisting of a halogen atom, a
nitro group, an alkoxy group, a phenoxy group and an acyloxy group,
the hydrocarbon group is preferably an alkyl group, a cycloalkyl
group, an alkenyl group, an aryl group, an arylalkyl group or an
arylalkenyl group, each of which has 1 to 20 carbon atoms. The
alkoxyl group and the acyloxy group as a substituent of the
hydrocarbon group may have 1 to 10 carbon atoms.
[0021] When R.sup.2 or R.sup.3 is a heterocyclic group, it
preferably has at least one hetero atom selected from oxygen,
nitrogen and sulfur atoms. The heterocyclic group is preferably a
five- or six-membered ring.
[0022] When R.sup.2 and R.sup.3 are combined to form a ring
together with the carbon atom to which they are bonded, the ring is
preferably a monocyclic or polycyclic ring having 5 to 20 carbon
atoms
[0023] When X in the formula (3) is a divalent hydrocarbon group,
it is preferably an alkylidene group, an alkylene group or an
arylene group each of which has 1 to 20 carbon atoms.
[0024] When R.sup.4 or R.sup.5 in the formula (3) is a hydrocarbon
group which may optionally be substituted with at least one
substituent selected from the group consisting of a halogen atom, a
nitro group, an alkoxy group, a phenoxy group and an acyloxy group,
the hydrocarbon group is preferably an alkyl group, a cycloalkyl
group, an alkenyl group, an aryl group, an arylalkyl group or an
arylalkenyl group, each of which has 1 to 20 carbon atoms. The
alkoxyl group and the acyloxy group as a substituent of the
hydrocarbon group may have 1 to 10 carbon atoms.
[0025] When R.sup.4 or R.sup.5 is a heterocyclic group, it
preferably has at least one hetero atom selected from oxygen,
nitrogen and sulfur atoms. The heterocyclic group is preferably a
five- or six-membered ring.
[0026] When R.sup.4 and R.sup.5 are combined to form a ring
together with the carbon atoms to which R.sup.4, R.sup.5 and X are
bonded, the ring is preferably a monocyclic or polycyclic ring
having 5 to 20 carbon atoms.
[0027] Specific examples of the alcohol represented by the formula
(1) include methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol,
1-hexanol, 1-heptanol, 1-octanol, 1-decanol, 1-eicosanol,
3-methyl-1-butanol, 3,3-dimethyl-1-butanol, 4-methyl-1-pentanol,
2-methyl-1-pentanol, 2,2-dimethyl-1-pentanol, 5-methyl-1-hexanol,
3-chloro-1-propanol, allyl alcohol, geraniol, benzyl alcohol,
p-methylbenzyl alcohol, p-methoxybenzyl alcohol, p-chlorobenzyl
alcohol, p-nitrobenzyl alcohol, 2-phenylethanol,
2-(p-chlorophenyl)ethanol, cinnamyl alcohol, furfuryl alcohol,
2-thiophenemethanol, etc.
[0028] Specific examples of the alcohol represented by the formula
(2) include 2-propanol, 2-butanol, 2-pentanol, 2-hexanol,
2-heptanol, 2-octanol, 2-decanol, 2-eicosanol, 3-pentanol,
3-hexanol, 3-heptanol, 3-decanol, 3-eicosanol, 4-heptanol,
4-decanol, 4-eicosanol, 3-methyl-2-butanol, 3,3-dimethyl-2-butanol,
4-methyl-2-pentanol, 2-methyl-3-pentanol, 2,2-dimethyl-3-pentanol,
5-methyl-3-hexanol, 1-chloro-2-propanol, 1-bromo-2-propanol,
1-methoxy-2-propanol, 1-phenoxy-2-propanol, 1-acetoxy-2-propanol,
3-penten-2-ol, 1-phenylethanol, cyclopropylphenylmethanol,
benzhydrol, 1-(p-tolyl)ethanol, 1-(p-chlorophenyl)ethanol,
1-(p-bromophenyl)ethanol, 1-(p-methoxyphenyl)ethanol,
1-(p-phenoxyphenyl) ethanol, 1-(p-acetoxyphenyl) ethanol,
1-phenyl-2-propanol, 1-(p-tolyl)-2-propanol,
1-(p-chlorophenyl)-2-propanol, 1-(p-bromophenyl)-2-propanol,
1-(p-methoxyphenyl)-2-propanol, 1-(p-phenoxyphenyl)-2-propanol,
1-(p-acetoxyphenyl)-2-propanol, cyclopentanol, cyclohexanol,
cycloheptanol, cyclooctanol, cyclododecanol, exo-norborneol,
endo-norborneol, 1-indanol, 1-tetralol, 9-fluorenol, etc.
[0029] Specific examples of the alcohol represented by the formula
(3) include ethylene glycol, propylene glycol, 1,3-propanediol,
1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol,
1,2-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol,
1,2-heptanediol, 1,7-heptanediol, 1,2-octanediol, 1,8-octanediol,
1,2-decanediol, 1,10-decanediol, 3-methyl-1,2-butanediol,
3,3-dimethyl-1,2-butanediol, 4-methyl-1,2-pentanediol,
5-methyl-1,2-hexanediol, 3-chloro-1,2-propanediol,
3-butene-1,2-diol, 4-pentene-1,2-diol, 1-phenylethane-1,2-diol,
1-(4-methylphenyl)ethane-1,2-diol,
1-(4-methoxyphenyl)ethane-1,2-diol,
1-(4-chlorophenyl)ethane-1,2-diol,
1-(4-nitrophenyl)ethane-1,2-diol, 1-cyclohexylethane-1,2-diol,
1,2-cyclohexanediol, etc. oxygen gas or an air can be used as a
molecular oxygen source to be used in the oxidation reaction, and
the oxygen gas or air may be diluted with an inert gas such as
nitrogen, carbon dioxide, helium, etc.
[0030] The contact of the alcohol with molecular oxygen can be
carried out by placing a liquid containing the alcohol and the
ruthenium-carrying alumina in the atmosphere of a molecular
oxygen-containing gas, or by bubbling the molecular
oxygen-containing gas through such a liquid.
[0031] The oxidation reaction may be carried out in the presence of
a solvent, which is less active to the oxidation reaction than
alcohol. Examples of such a solvent include halogenated
hydrocarbons such as dichloromethane, dichloroethane, chloroform,
etc.; esters such as isobutyl acetate, tert-butyl acetate, etc.;
nitrites such as acetonitrile, etc.; aromatic hydrocarbons such as
toluene, etc.; halogenated aromatic hydrocarbons such as
chlorobenzene, trifluorotoluene, etc.; and the like. When the
solvent is used, the amount thereof is usually from 1 to 100,000
parts by weight, preferably from 10 to 10,000 parts by weight, per
100 parts by weight of the alcohol.
[0032] In the oxidation reaction, a reaction temperature is usually
from 20 to 300.degree. C., preferably from 50 to 200.degree. C.,
and a reaction pressure is usually from 0.1 to 10 MPa. The
oxidation reaction may be carried out continuously or
batchwise.
[0033] The above oxidation reaction produces various carbonyl
compounds as oxidation products from the alcohols as the
substrates. For example, when the alcohol is a primary alcohol, a
corresponding aldehyde and/or carboxylic acid can be produced. When
the alcohol is a secondary alcohol, a corresponding ketone can be
produced. When the alcohol is a polyhydric alcohol, a corresponding
polycarbonyl compound can be produced.
[0034] When the alcohol represented by the formula (1) is used, an
aldehyde represented by the formula (4): ##STR4## wherein R.sup.1
is the same as defined above, and/or a carboxylic acid represented
by the formula (5): ##STR5## wherein R.sup.1 is the same as defined
above, can be produced as an oxidation product.
[0035] When the alcohol represented by the formula (2) is used, a
ketone represented by the formula (6): ##STR6## wherein R.sup.2 and
R.sup.3 are the same as defined above, can be produced as an
oxidation product.
[0036] When the alcohol represented by the formula (3) is used, a
compound represented by the formula (7): ##STR7## wherein X is the
same as defined above; and R.sup.6 represents a hydrogen atom or a
hydroxyl group when R.sup.4 is a hydrogen atom or R.sup.6 is the
same as R.sup.4 when R.sup.4 is a group other than a hydrogen atom;
and R.sup.7 represents a hydrogen atom or a hydroxyl group when
R.sup.5 is a hydrogen atom or R.sup.7 is the same as R.sup.5 when
R.sup.5 is a group other than a hydrogen atom, can be produced as
an oxidation product.
[0037] The oxidation product or products can be recovered from the
reaction mixture by optionally subjecting the mixture to
filtration, concentration, washing, alkali treatment, acid
treatment, etc. and then purifying the product or products by
distillation, crystallization, etc.
[0038] When the ruthenium-carrying alumina prepared by the process
of the present invention is used as a catalyst, the alcohols can be
oxidized with molecular oxygen at a high conversion. Thus, the
oxidation products such as ketones, aldehydes, carboxylic acids,
etc. can be produced from the alcohols with a good productivity by
such a process.
EXAMPLES
[0039] The present invention will be illustrated by the Examples,
which do not limit the scope of the invention in any way.
[0040] In the Examples, the reaction mixture was analyzed by gas
chromatography, and the conversion of a substrate and the
selectivity to each product are calculated by the following
formulas: Conversion (%)=(molecular amount of consumed
substrate/molecular amount of used substrate).times.100 Selectivity
(%)=(molecular amount of each product/molecular amount of consumed
substrate).times.100 Preparation of Ruthenium-Carrying Alumina
Examples 1-2 and Comparative Example 1
Example 1
[0041] In 60 ml of aqueous solution of ruthenium(III) chloride (8.3
mM), .gamma.-alumina (2.0 g) (Reference catalyst JRC-ALO-4 of the
Society of Catalyst, specific surface area: 177 m.sup.2/g) was
added and suspended, and the suspension was stirred at room
temperature for 15 minutes. At this time, the suspension had a pH
of 2.1. Thereafter, a 1 M aqueous solution of sodium hydroxide was
added to the suspension to adjust pH to 13.2, and then the
suspension was stirred at room temperature for 24 hours. The
suspension was filtrated, and the residual solid was washed with
water and dried to obtain a ruthenium-carrying alumina (2.1 g)
(ruthenium content: 2.28% by weight, specific surface area: 182
m.sup.2/g).
Example 2
[0042] In 60 ml of aqueous solution of ruthenium(III) chloride (8.3
mM), .gamma.-alumina (2.0 g) (KHS-24 manufactured by Sumitomo
Chemical Co., Ltd., specific surface area: 163 m.sup.2 .mu.g) was
added and suspended, and the suspension was stirred at room
temperature for 15 minutes. At this time, the suspension had a pH
of 2.3. Thereafter, a 1 M aqueous solution of sodium hydroxide
(26.4 ml) was added to the suspension to adjust pH to 13.2, and
then the suspension was stirred at room temperature for 24 hours.
The suspension was filtrated, and the residual solid was washed
with water and dried to obtain a ruthenium-carrying alumina (1.9 g)
(ruthenium content: 2.45% by weight, specific surface area: 187
m.sup.2/g).
Comparative Example 1
[0043] In 60 ml of aqueous solution of ruthenium(III) chloride (8.3
mM), .gamma.-alumina (2.0 g) (Reference catalyst JRC-ALO-4 of the
Society of Catalyst, specific surface area: 177 m.sup.2/g) was
added and suspended, and the suspension was stirred at room
temperature for 24 hours. Then, the resulting suspension having a
pH of 2.4 was filtrated, and the residual solid was washed with
water and dried to obtain a ruthenium-carrying alumina (2.0 g)
(ruthenium content: 1.74% by weight, specific surface area: 180
m.sup.2/g).
Oxidation of Alcohol
Examples 3-25 and Comparative Example 2
Example 3
[0044] The ruthenium-carrying alumina prepared in Example 1 (0.044
g) was added to and suspended in trifluorotoluene (1.5 ml) and
stirred at room temperature for 5 minutes. To the suspension,
benzyl alcohol (0.108 g) was added, and oxidized by flowing oxygen
through the suspension at 83.degree. C. for 24 hours while
stirring. The reaction mixture was analyzed. The conversion of
benzyl alcohol was 84%, and the selectivity to benzaldehyde was
more than 99%.
Example 4
[0045] The ruthenium-carrying alumina prepared in Example 1 (0.11
g) was added to and suspended in trifluorotoluene (1.5 ml) and
stirred at room temperature for 5 minutes. To the suspension,
benzyl alcohol (0.108 g) was added, and oxidized by flowing oxygen
through the suspension at 83.degree. C. for 1 hour while stirring.
The reaction mixture was analyzed. The conversion of benzyl alcohol
was 99%, and the selectivity to benzaldehyde was more than 99%.
Example 5
[0046] The same procedures as in Example 4 were repeated except
that air was flowed through the suspension in place of oxygen, and
the reaction time was changed to be 4 hours. The conversion of
benzyl alcohol was 98%, and the selectivity to benzaldehyde was
more than 99%.
Example 6
[0047] The same procedures as in Example 4 were repeated except
that p-methylbenzyl alcohol was used as a substrate in place of
benzyl alcohol. The conversion of p-methylbenzyl alcohol was more
than 99%, and the selectivity to p-methylbenzaldehyde was more than
99%.
Example 7
[0048] The same procedures as in Example 4 were repeated except
that p-methoxybenzyl alcohol was used as a substrate in place of
benzyl alcohol. The conversion of p-methoxybenzyl alcohol was more
than 99%, and the selectivity to p-methoxybenzaldehyde was more
than 99%.
Example 8
[0049] The same procedures as in Example 4 were repeated except
that p-chlorobenzyl alcohol was used as a substrate in place of
benzyl alcohol. The conversion of p-chlorobenzyl alcohol was more
than 99%, and the selectivity to p-chlorobenzaldehyde was more than
99%.
Example 9
[0050] The same procedures as in Example 4 were repeated except
that p-nitrobenzyl alcohol was used as a substrate in place of
benzyl alcohol, and the reaction time was changed to be 3 hours.
The conversion of p-nitrobenzyl alcohol was 97%, and the
selectivity to p-nitrobenzaldehyde was more than 99%.
Example 10
[0051] The same procedures as in Example 4 were repeated except
that 1-phenylethanol was used as a substrate in place of benzyl
alcohol. The conversion of 1-phenylethanol was more than 99%, and
the selectivity to acetophenone was more than 99%.
Example 11
[0052] The same procedures as in Example 4 were repeated except
that cyclopropylphenylmethanol was used as a substrate in place of
benzyl alcohol. The conversion of cyclopropylphenylmethanol was
more than 99%, and the selectivity to cyclopropylphenylketone was
more than 99%.
Example 12
[0053] The same procedures as in Example 4 were repeated except
that cinnamyl alcohol was used as a substrate in place of benzyl
alcohol, and the reaction time was changed to be 1.5 hours. The
conversion of cinnamyl alcohol was more than, 99%, and the
selectivity to cinnamaldehyde was 98%.
Example 13
[0054] The same procedures as in Example 4 were repeated except
that geraniol was used as a substrate in place of benzyl alcohol,
and the reaction time was changed to be 6 hours. The conversion of
geraniol was 89%, and the selectivity to geranial was 97%.
Example 14
[0055] The same procedures as in Example 4 were repeated except
that 2-pentanol was used as a substrate in place of benzyl alcohol,
and the reaction time was changed to 5 be hours. The conversion of
2-pentanol was 90%, and the selectivity to 2-pentanone was more
than 99%.
Example 15
[0056] The same procedures as in Example 4 were repeated except
that 2-octanol was used as a substrate in place of benzyl alcohol,
and the reaction time was changed to be 2 hours. The conversion of
2-octanol was 91%, and the selectivity to 2-octanone was more than
99%.
Example 16
[0057] The same procedures as in Example 4 were repeated except
that 2-thiophenemethanol was used as a substrate in place of benzyl
alcohol, and the reaction time was changed to be 1.5 hours. The
conversion of 2-thiophenemethanol was more than 99%, and the
selectivity to 2-thiophenecarboxyaldehyde was more than 99%.
Example 17
[0058] The ruthenium-carrying alumina prepared in Example 1 (0.22
g) was added to and suspended in trifluorotoluene (1.5 ml) and
stirred at room temperature for 5 minutes. To the suspension,
cyclohexanol (0.100 g) was added, and oxidized by flowing oxygen
through the suspension at 83.degree. C. for 8 hours while stirring.
The reaction mixture was analyzed. The conversion of cyclohexanol
was 53%, and the selectivity to cyclohexanone was more than
99%.
Example 18
[0059] The same procedures as in Example 17 were repeated except
that 3-penten-2-ol was used as a substrate in place of
cyclohexanol, and the reaction time was changed to be 6 hours. The
conversion of 3-penten-2-ol was 84%, and the selectivity to
3-penten-2-one was more than 99%.
Example 19
[0060] The same procedures as in Example 17 were repeated except
that 1-octanol was used as a substrate in place of cyclohexanol,
and the reaction time was changed to 4 be hours. The conversion of
1-octanol was 80%, and the selectivities to 1-octanal and
1-octanoic acid were 85% and 10%, respectively.
Example 20
[0061] The same procedures as in Example 17 were repeated except
that cyclopentanol was used as a substrate in place of
cyclohexanol. The conversion of cyclopentanol was 92%, and the
selectivity to cyclopentanone was more than 99%.
Example 21
[0062] The same procedures as in Example 17 were repeated except
that cyclooctanol was used as a substrate in place of cyclohexanol,
and the reaction temperature was changed to be 6 hours. The
conversion of cyclooctanol was 81%, and the selectivity to
cycloctanone was more than 99%.
Example 22
[0063] The ruthenium-carrying alumina prepared in Example 1 (0.11
g) was added to and suspended in 1-phenylethanol (3.05 g) and
stirred at room temperature for 5 minutes. Then, 1-phenylethanol
was oxidized by flowing oxygen through the suspension at
150.degree. C. for 18 hours while stirring. The conversion of
1-phenylethanol was 95%, and the selectivity to acetophenone was
more than 99%.
Example 23
[0064] The ruthenium-carrying alumina prepared in Example 1 (0.11
g) was added to and suspended in 2-octanol (3.25 g) and stirred at
room temperature for 5 minutes. Then, 2-octanol was oxidized by
flowing oxygen through the suspension at 150.degree. C. for 24
hours while stirring. The conversion of 2-octanol was 98%, and the
selectivity to 2-octanone was more than 99%.
Example 24
[0065] The ruthenium-carrying alumina prepared in Example 2 (0.11
g) was added to and suspended in trifluorotoluene (1.5 ml) and
stirred at room temperature for 5 minutes. To the suspension,
benzyl alcohol (0.108 g) was added, and oxidized by flowing oxygen
through the suspension at 83.degree. C. for 1 hour while stirring.
The reaction mixture was analyzed. The conversion of benzyl alcohol
was 99%, and the selectivity to benzaldehyde was more than 99%.
Example 25
[0066] The ruthenium-carrying alumina prepared in Example 2 (0.11
g) was added to and suspended in trifluorotoluene (5 ml) and
stirred at room temperature for 5 minutes. To the suspension,
ethylene glycol (0.071 g) was added, and oxidized by flowing air
through the suspension at 83.degree. C. for 5 hours and 10 minutes
while stirring. The reaction mixture was analyzed. The conversion
of ethylene glycol was 72%, and the selectivity to glyoxal was
91%.
Comparative Example 2
[0067] The ruthenium-carrying alumina prepared in Comparative
Example 1 (0.044 g) was added to and suspended in trifluorotoluene
(1.5 ml) and stirred at room temperature for 5 minutes. To the
suspension, benzyl alcohol (0.108 g) was added, and oxidized by
flowing oxygen through the suspension at 83.degree. C. for 24 hours
while stirring. The reaction mixture was analyzed. The conversion
of benzyl alcohol was 23%, and the selectivity to benzaldehyde was
more than 99%.
* * * * *