JP2010202555A - Method for producing carbonyl compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing carbonyl compounds from various kinds of alcohols in higher yield. <P>SOLUTION: The method for producing the carbonyl compound includes oxidizing the alcohol represented by one of the formulas: R<SP>1</SP>-Z<SP>1</SP>-CH(OH)-R<SP>2</SP>, R<SP>3</SP>-Z<SP>2</SP>-CH=CH-CH(OH)-R<SP>4</SP>, and R<SP>5</SP>-CH(OH)-CH<SB>3</SB>in the presence of a catalyst of at least one kind of metal selected from ruthenium and platinum, and carried by an activated carbon carrier, and oxygen to afford the carbonyl compound comprising an aldehyde compound or a ketone compound. In the formulas, R<SP>1</SP>and R<SP>3</SP>are each hydrogen, hydroxy, nitro or the like; Z<SP>1</SP>and Z<SP>2</SP>are each a divalent aromatic ring; R<SP>2</SP>and R<SP>4</SP>are each hydrogen, 1-20C alkyl or the like; and R<SP>5</SP>is 1-20C alkyl or the like. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for producing a carbonyl compound. More specifically, the present invention relates to a carbonyl compound comprising an aldehyde compound or a ketone compound by oxidizing alcohol in the presence of a heterogeneous catalyst in which at least one metal selected from ruthenium and platinum is supported on an activated carbon support. It relates to a manufacturing method.

Conventionally, the oxidation of alcohols to carbonyl compounds is one of the important functional group conversion reactions in organic synthesis. For a long time, the method of using a chromium-based oxidizing agent for the oxidation of alcohol [Collins reagent (CrO ₃ · Py ₂ ), Na ₂ Cr ₂ O ₇ -H ₂ SO ₄ system (Jones oxidation), PCC, PDC] and DMSO Techniques combining various DMSO activators (Swern oxidation, Pfitzner-Moffatt oxidation, etc.) have been used. However, the former method is problematic in that the reagent is highly toxic and a large amount of heavy metal (chromium) waste is generated after the reaction. In the latter case, it is necessary to carry out the reaction at a low temperature, and further, there are problems such that dimethyl sulfide produced as the reaction proceeds gives off a bad odor.

Therefore, methods using chromium metal and reactions not using DMSO have been developed. For example, techniques using hypervalent iodine reagents (Dess-Martin oxidation, IBX oxidation), techniques using Ru metal (Ley oxidation) and Pd metal (Uemura oxidation) as catalysts have been developed, and are frequently used due to their wide range of substrate applicability. Has been used. However, Dess-Martin oxidation and IBX oxidation require explosion risk and the addition of an equivalent amount of reagent, and Ley oxidation and Uemura oxidation have problems of residual metals and products due to the use of homogeneous catalysts and cost. Therefore, it is meaningful to develop an oxidation reaction of alcohol using a heterogeneous catalyst that is safe and avoids residual metals and is expected to be reused. In particular, O ₂ whose only by-product is H ₂ O is used. The development of a method using an oxidant is very valuable from an industrial point of view. Many studies have been made on the oxidation reaction of alcohol in the atmosphere of oxygen or air using a heterogeneous catalyst, and a catalyst using Ru or the like has been developed as the heterogeneous catalyst.

  As an example of an immobilized Ru catalyst, Patent Document 1 discloses a catalyst in which ruthenium is supported on a crosslinked polymer, and the crosslinked polymer has an aromatic side chain, a hydrophilic side chain, and a crosslinking group. A homogeneous Ru catalyst is disclosed.

JP 2008-201755 A

In the method using the heterogeneous Ru catalyst described in Patent Document 1, there is a problem in terms of production efficiency, for example, when a carbonyl compound is produced by oxidizing an alcohol, a reoxidant such as TMPO is required. .
Therefore, the method for producing a carbonyl compound having both higher yield and efficiency is not yet sufficient, and further improvement is required.

  An object of the present invention is to provide a method for efficiently producing a carbonyl compound from various alcohols in a higher yield.

The present invention is as follows.
1. In the presence of a catalyst in which at least one metal selected from ruthenium and platinum is supported on an activated carbon support, and oxygen,
A method for producing a carbonyl compound, comprising: oxidizing an alcohol represented by any one of the following general formulas (1) to (3) to produce a carbonyl compound comprising an aldehyde compound or a ketone compound.
R ¹ —Z ¹ —CH (OH) —R ² (1)
[In the general formula (1), R ¹ represents a hydrogen atom, a hydroxy group, a nitro group, an amino group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an acyl group having 1 to 20 carbon atoms. Group, benzoyl group, or halogenated benzoyl group, Z ¹ represents a divalent aromatic ring, R ² represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a phenyl group , A benzoyl group, a halogenated phenyl group, or a halogenated benzoyl group, Z ¹ and R ² may be bonded to each other to form a 3- to 10-membered ring. ]
R ³ —Z ² —CH═CH—CH (OH) —R ⁴ (2)
[In the general formula (2), R ³ represents a hydrogen atom, a hydroxy group, a nitro group, an amino group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an acyl group having 1 to 20 carbon atoms. A benzoyl group or a halogenated benzoyl group, Z ² represents a divalent aromatic ring, R ⁴ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a phenyl group. , Benzoyl group, halogenated phenyl group, or halogenated benzoyl group. ]
R ⁵ —CH (OH) —CH ₃ (3)
[However, in the general formula (3), ^{R 5} represents an alkyl group, or an aralkyl group having 8 to 20 carbon atoms having 1 to 20 carbon atoms. ]
2. The metal content in the catalyst is 1% by mass or more when the entire catalyst is 100% by mass. The manufacturing method of the carbonyl compound as described in above.
3. 1. The reaction temperature in the oxidation is 1.degree. Or 2. The manufacturing method of the carbonyl compound as described in above.
4). The above oxidation is carried out in the presence of a solvent, and the solvent is at least one selected from toluene, isopropyl alcohol and water. To 3. The manufacturing method of the carbonyl compound in any one of.

According to the method for producing a carbonyl compound of the present invention, a carbonyl compound can be produced accurately from a predetermined alcohol. Furthermore, in the method for producing a carbonyl compound of the present invention, the use of a heterogeneous catalyst makes it easy to recover the catalyst after the reaction, and the catalyst can be repeatedly used to produce the carbonyl compound efficiently. I can write.
Further, when the metal content in the catalyst is 1% by mass or more based on 100% by mass of the entire catalyst, the carbonyl compound can be produced more efficiently.
Moreover, when the reaction temperature in oxidation is 10 degreeC-130 degreeC, a carbonyl compound can be manufactured more efficiently.
Furthermore, the oxidation is carried out in the presence of a solvent, and when the solvent is at least one selected from toluene, isopropyl alcohol and water, a carbonyl compound can be produced with a higher yield.

The present invention will be described in detail below.
The method for producing a carbonyl compound of the present invention comprises a catalyst in which at least one metal selected from ruthenium and platinum is supported on an activated carbon support, and oxygen.
It is characterized in that an alcohol represented by any one of the following general formulas (1) to (3) is oxidized to produce a carbonyl compound comprising an aldehyde compound or a ketone compound.
R ¹ —Z ¹ —CH (OH) —R ² (1)
[In the general formula (1), R ¹ represents a hydrogen atom, a hydroxy group, a nitro group, an amino group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an acyl group having 1 to 20 carbon atoms. Group, benzoyl group, or halogenated benzoyl group, Z ¹ represents a divalent aromatic ring, R ² represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a phenyl group , A benzoyl group, a halogenated phenyl group, or a halogenated benzoyl group, Z ¹ and R ² may be bonded to each other to form a 3- to 10-membered ring. ]
R ³ —Z ² —CH═CH—CH (OH) —R ⁴ (2)
[In the general formula (2), R ³ represents a hydrogen atom, a hydroxy group, a nitro group, an amino group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an acyl group having 1 to 20 carbon atoms. A benzoyl group or a halogenated benzoyl group, Z ² represents a divalent aromatic ring, R ⁴ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a phenyl group. , Benzoyl group, halogenated phenyl group, or halogenated benzoyl group. ]
R ⁵ —CH (OH) —CH ₃ (3)
[However, in the general formula (3), ^{R 5} represents an alkyl group, or an aralkyl group having 8 to 20 carbon atoms having 1 to 20 carbon atoms. ]

The catalyst used in the present invention is a catalyst in which at least one metal selected from ruthenium and platinum (hereinafter also simply referred to as “catalytic metal”) is supported on an activated carbon carrier. This catalyst uses activated carbon as a carrier and supports at least one metal selected from ruthenium and platinum (platinum). By using ruthenium and / or platinum, oxidation reaction and reaction from alcohol to aldehyde compound are promoted by catalytic reaction of these metals, and carbonyl compound is efficiently produced with high yield (selectivity). can do.
Among ruthenium-supported catalysts (hereinafter also simply referred to as “ruthenium catalysts”) and platinum-supported catalysts (hereinafter also simply referred to as “platinum catalysts”), a ruthenium catalyst is preferred because of its low cost. .

  The content of the catalyst metal in the catalyst is preferably 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass, and still more preferably 10% by mass with respect to the entire catalyst. Moreover, content of a catalyst metal is 50 mass% or less normally, and can be 30 mass% or less, or 20 mass% or less.

  1-100 nm is preferable and, as for the average particle diameter of the said catalyst metal, 2-20 nm is especially preferable. When the average particle diameter of the catalytic metal is within the above range, the alcohol, oxygen, and catalytic metal as substrates are in a good contact state, and the alcohol can be efficiently oxidized to form a carbonyl compound.

  As the catalyst carrier, activated carbon having a adsorptive capacity is used, which is mostly a substance made of carbonaceous charcoal. The activated carbon is not particularly limited, but a normal one can be used.

The specific surface area of the catalyst is preferably from ^{500~2000m 2 / g, 800~1500m 2 /} g is particularly preferred. When the specific surface area of the catalyst is within the above range, the substrate, the alcohol, oxygen, and the catalyst metal supported on the catalyst are in good contact, and the alcohol is efficiently oxidized to form a carbonyl compound. it can.
Moreover, the shape of the said catalyst is not specifically limited, For example, a powder form, a spherical form, and a cylindrical thing are mentioned.

  A commercial item etc. can be used as said catalyst. Examples of the commercially available products include “A type” manufactured by N.E. Chemcat Co., Ltd., “B type” manufactured by N.E. Chemcat Co., Ltd., “K type” manufactured by N.E. Examples include “NX type” manufactured by the company.

  In the production method of the present invention, the amount of the catalyst to be added is not particularly limited, and is appropriately selected depending on the type of the alcohol (reaction substrate), the reaction temperature, and the like. The blending amount of the catalyst is usually 0.1 to 20 mol%, more preferably 1 mol% or more, further preferably 2 mol% or more, and further preferably 3 mol% or more when the alcohol (reaction substrate) is 100 mol%. 4 mol% or more is more preferable. When the amount of the catalyst to be added is within the above range, the carbonyl compound can be produced efficiently. Further, the reaction rate can be further improved by increasing the amount of the catalyst to be added. However, if the amount is increased more than necessary, the economy becomes poor.

  The alcohol represented by the general formula (1) (hereinafter simply referred to as “alcohol (1)”) is an alcohol having at least one aromatic ring. Examples of the alcohol include primary benzyl alcohol, secondary benzyl alcohol, alcohols having a substituent on these, and derivatives thereof (alcohols).

In the general formula (1), R ¹ is a hydrogen atom, a hydroxy group, a nitro group, an amino group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an acyl group having 1 to 20 carbon atoms, benzoyl Group, or a halogenated benzoyl group.
The alkyl group in R ¹ of the general formula (1) may be a linear alkyl group or a branched alkyl group. The alkyl group has 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms, and particularly preferably 1 to 5 carbon atoms. Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, pentyl, isopentyl, neopentyl, tert -Pentyl group, 1-methylbutyl group, hexyl group, heptyl group, octyl group, 1-methylheptyl group, nonyl group, decyl group and the like.

The alkoxy group in R ¹ of the general formula (1) may be a linear alkoxy group or a branched alkoxy group. Carbon number of this alkoxy group is 1-20, Preferably it is 1-10, More preferably, it is 1-5. Examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group, sec-butoxy group, n-pentoxy group, and neopentoxy group. Can be mentioned.

The acyl group in R ¹ of the general formula (1) may be a linear acyl group or a branched acyl group. The acyl group has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms. Examples of the acyl group include formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, hexanoyl group, octonyl group and the like.

In the halogenated benzoyl group of R ^{1 in} the general formula (1), the type of halogen atom substituted on the benzene skeleton of the benzoyl group is not particularly limited. For example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned.

Z ¹ is a divalent aromatic ring, and this aromatic ring includes a benzene ring, a condensed benzene ring, and a heterocyclic ring.
Examples of the condensed benzene ring include a pentalene ring, an indene ring, a naphthalene ring, an azulene ring, a heptalene ring, a biphenylene ring, an indacene ring, an acenaphthylene ring, a fluorene ring, a phenalene ring, a phenanthrene ring, and an anthracene ring.
Examples of the heterocyclic ring include a furan ring, a thiophene ring, a pyrrole ring, an oxazal ring, a thiazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, and a pyrazine ring.

In the general formula (1), R ² is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a phenyl group, a benzoyl group, or a halogenated phenyl group.
The alkyl group in R ² of the general formula (1) may be a linear alkyl group or a branched alkyl group. The alkyl group has 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms, and particularly preferably 1 to 5 carbon atoms. Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, pentyl, isopentyl, neopentyl, tert -Pentyl group, 1-methylbutyl group, hexyl group, heptyl group, octyl group, 1-methylheptyl group, nonyl group, decyl group and the like.
The alkoxy group in R ² of the general formula (1) may be a linear alkoxy group or a branched alkoxy group. Carbon number of this alkoxy group is 1-20, Preferably it is 1-10, More preferably, it is 1-5. Examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group, sec-butoxy group, n-pentoxy group, and neopentoxy group. Can be mentioned.

In the halogenated phenyl group represented by R ^{2 in} the general formula (1), the type of halogen atom substituted with a phenyl group (benzene skeleton) is not particularly limited. For example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned.

また、Ｚ^１がピリジン環の場合、下記一般式（５）に表されるアルコールが挙げられる。尚、一般式（５）のＲ^１及びＲ^２は一般式（１）のＲ^１及びＲ^２と同様である。

また、Ｚ^１がチオフェン環の場合、下記一般式（６）に表されるアルコールが挙げられる。尚、一般式（６）のＲ^１及びＲ^２は一般式（１）のＲ^１及びＲ^２と同様である。

Examples of the alcohol (1) include alcohols represented by the following general formula (4) when Z ¹ is a benzene ring. Incidentally, ^{R 1} and ^{R 2} in the general formula (4) is the same as ^{R 1} and ^{R 2} in general formula (1).

Also, when Z ¹ is a pyridine ring, include alcohols represented by the following general formula (5). Incidentally, ^{R 1} and ^{R 2} in the general formula (5) is the same as ^{R 1} and ^{R 2} in general formula (1).

Also, when Z ¹ is a thiophene ring, alcohols represented by the following general formula (6). Incidentally, ^{R 1} and ^{R 2} in the general formula (6) is the same as ^{R 1} and ^{R 2} in general formula (1).

In the case where the alcohol (1) is a secondary alcohol, R ¹ is a hydrogen atom and Z ¹ is a benzene ring. Specific examples of the case where R ² is a methyl group include the following formula (7): 1-phenylethanol represented, R ² is a t-butyl group, 1-phenyl-2,2-dimethyl-1-propanol represented by the following formula (8), and R ² is a pentyl group 1) -phenyl-1-pentanol represented by 9), benzhydrol represented by the following formula (10) in which R ² is a phenyl group, and formula (11) in which R ² is a 4-chlorophenyl group 4-chlorobenzhydrol represented, and benzoin represented by the following formula (12) in which R ² is a benzoyl group.
In addition, as a specific example when R ² is a methyl group and Z ¹ is a benzene ring, 1- (4-methoxyphenyl) ethanol represented by the following formula (13) in which R ¹ is a methoxy group, 1- (4-nitrophenyl) ethanol represented by the following formula (14) in which R ¹ is a nitro group, 1- (2-methylphenyl) represented by the following formula (15) in which R ¹ is a methyl group Examples include ethanol.

In the alcohol (1), examples of the primary alcohol in which Z ¹ is a benzene ring and R ² is a hydrogen atom include alcohols represented by the following general formula (16). Further, in the case where R ² is a primary alcohol which is a hydrogen atom, a specific example of the case where Z ¹ is a benzene ring is benzyl alcohol represented by the following formula (17) wherein R ¹ is a hydrogen atom. Is mentioned. A specific example in the case where R ² is a hydrogen atom and Z ¹ is a pyridine ring includes pyridine-3-methanol represented by the following formula (18).

Moreover, Z < ¹ > and R < ² > in the said General formula (1) may couple | bond together, and may form a 3-10 membered ring (preferably 4-7 membered ring, More preferably, 5-6 membered ring). Examples of the alcohol in which Z ¹ and R ² are bonded to each other to form a ring include 9-fluorenol represented by the following formula (19) and 1-indanol represented by the following formula (20). Can be mentioned.

The alcohol represented by the general formula (2) (hereinafter, simply referred to as “alcohol (2)”) is an allyl alcohol having at least one aromatic ring and having a vinylene group bonded to the aromatic ring. is there.
In the general formula (2), R ³ is a hydrogen atom, a hydroxy group, a nitro group, an amino group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a benzoyl group, or a halogenated benzoyl group. .

The alkyl group in R ³ of the general formula (2) may be a linear alkyl group or a branched alkyl group. The alkyl group has 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms, and particularly preferably 1 to 5 carbon atoms. Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, pentyl, isopentyl, neopentyl, tert -Pentyl group, 1-methylbutyl group, hexyl group, heptyl group, octyl group, 1-methylheptyl group, nonyl group, decyl group and the like.

The alkoxy group in R ³ of the general formula (2) may be a linear alkoxy group or a branched alkoxy group. Carbon number of this alkoxy group is 1-20, Preferably it is 1-10, More preferably, it is 1-5. Examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group, sec-butoxy group, n-pentoxy group, and neopentoxy group. Can be mentioned.

The acyl group in R ³ of the general formula (2) may be a linear acyl group or a branched acyl group. The acyl group has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms. Examples of the acyl group include formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, hexanoyl group, octonyl group and the like.

In the halogenated benzoyl group of R ^{3 in} the general formula (2), the type of halogen atom substituted on the benzene skeleton of the benzoyl group is not particularly limited. For example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned.

Z ² is a divalent aromatic ring, and this aromatic ring includes a benzene ring, a condensed benzene ring, and a heterocyclic ring.
Examples of the condensed benzene ring include a pentalene ring, an indene ring, a naphthalene ring, an azulene ring, a heptalene ring, a biphenylene ring, an indacene ring, an acenaphthylene ring, a fluorene ring, a phenalene ring, a phenanthrene ring, and an anthracene ring.
Examples of the heterocyclic ring include a furan ring, a thiophene ring, a pyrrole ring, an oxazal ring, a thiazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, and a pyrazine ring.

In the general formula (2), ^{R 4} is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a phenyl group, a benzoyl group, or a halogenated phenyl group.
The alkyl group in R ⁴ of the general formula (2) may be a linear alkyl group or a branched alkyl group. The alkyl group has 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms, and particularly preferably 1 to 5 carbon atoms. Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, pentyl, isopentyl, neopentyl, tert -Pentyl group, 1-methylbutyl group, hexyl group, heptyl group, octyl group, 1-methylheptyl group, nonyl group, decyl group and the like.

The alkoxy group in R ⁴ of the general formula (2) may be a linear alkoxy group or a branched alkoxy group. Carbon number of this alkoxy group is 1-20, Preferably it is 1-10, More preferably, it is 1-5. Examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, tert-butoxy group, sec-butoxy group, n-pentoxy group, and neopentoxy group. Can be mentioned.

In the halogenated phenyl group and halogenated benzoyl group of R ^{4 in} the general formula (2), the type of halogen atom substituted on the benzene skeleton of the phenyl group or benzoyl group is not particularly limited. For example, fluorine, chlorine, bromine, iodine and the like can be mentioned.

〔但し、一般式（４）におけるＲ^６は炭素数２〜１２の二価の炭化水素基を示す。〕
上記一般式（４）のＲ^６は、二価の飽和炭化水素基が好ましく、アルキレン基がより好ましい。このアルキレン基は、直鎖でも、分岐を有するアルキレン基でも構わないが、直鎖のアルキレン基が好ましい。 The alcohol represented by the general formula (3) (hereinafter simply referred to as “alcohol (3)”) is an aliphatic secondary alcohol.
In general formula (3), ^{R 5} is an alkyl group, or an aralkyl group having 8 to 20 carbon atoms having 1 to 20 carbon atoms.
The alkyl group in R ⁵ of the general formula (3) may be a linear alkyl group or a branched alkyl group. The alkyl group has 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms, and more preferably 1 to 10 carbon atoms. Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, pentyl, isopentyl, neopentyl, tert -Pentyl group, 1-methylbutyl group, hexyl group, heptyl group, octyl group, 1-methylheptyl group, nonyl group, decyl group and the like.
Further, aralkyl group in R ⁵ in the general formula (3) is a hydrocarbon group having a benzene ring represented by the following general formula (26). The aralkyl group has 8 to 20 carbon atoms, preferably 8 to 15 carbon atoms, and more preferably 8 to 10 carbon atoms. Examples of the aralkyl group include a phenylethyl group (phenethyl group), a phenylpropyl group, a phenylbutyl group, a phenylpentyl group, and a phenylhexyl group.

[However, R ⁶ in the general formula (4) represents a divalent hydrocarbon group having 2 to 12 carbon atoms. ]
R ^{6 in the} general formula (4) is preferably a divalent saturated hydrocarbon group, and more preferably an alkylene group. The alkylene group may be linear or branched, but is preferably a linear alkylene group.

Oxygen [refers to simple molecular oxygen (oxygen gas). The same applies hereinafter. ] Functions as an oxidizing agent in the present invention. This oxygen may be present in the reaction system of the present invention and be in contact with the reaction substrate. Specifically, the reaction system can be in an air atmosphere, and the oxidation reaction in the present invention can be performed in an air atmosphere. Moreover, since it can oxidize the said alcohol more efficiently, it is preferable that it is under oxygen atmosphere. In this oxygen atmosphere, for example, a gas other than oxygen such as air may be contained, oxygen may be 100%, and oxygen and an inert gas such as nitrogen, helium, and argon are included. It may be. In an oxygen atmosphere, the oxygen gas concentration is preferably 70% by volume or more, and more preferably 80% by volume or more. A high concentration of oxygen is preferably present, and the reaction efficiency can be increased by the high concentration of oxygen. Specifically, oxygen can be present in the reaction system by blowing oxygen into a closed reaction vessel (reaction system) with an oxygen balloon (oxygen balloon).
The amount of oxygen in the oxidation reaction may be equal to or more than the equivalent of the compound, but a large excess of 5 times equivalent or more is preferable with respect to the alcohol (1) to (3) which is the reaction substrate, and more than 10 times equivalent is more. Preferably, 30 times equivalent or more is more preferable.

  In the present invention, the alcohol can be oxidized in the presence of a solvent to produce a carbonyl compound. As said solvent, what can melt | dissolve said alcohol (1)-(3) which is a reaction substrate is preferable, and water, an organic solvent, etc. are mentioned. Examples of the solvent include water, acetonitrile, toluene, propyl alcohol, isopropyl alcohol, butanol and the like. These solvents can be used alone or in combination of two or more. Of these, toluene, isopropyl alcohol and water are preferred. Reactions using these solvents are highly soluble in the reaction substrate, and the reaction speed is fast due to the small molecules. Furthermore, since it has a low boiling point, it can be easily removed (evaporated) from the reaction mixture, so that a carbonyl compound can be produced more efficiently.

  The reaction temperature in the present invention is not particularly limited. It is appropriately selected depending on the other reaction conditions such as the type of reaction substrate, the solvent used and the reaction time. Usually, the temperature is preferably room temperature (18 ° C.) or higher, and the reaction can be promoted by heating. However, the heating temperature is preferably equal to or lower than the boiling point of the solvent used. Specifically as said reaction temperature, 10 to 130 degreeC is preferable, More preferably, it is 20 to 120 degreeC, More preferably, it is 20 to 100 degreeC, More preferably, it is 30 to 80 degreeC.

  The reaction time in the present invention is not particularly limited. It is appropriately selected depending on the other reaction conditions such as the type of reaction substrate, the solvent used and the reaction time. This reaction time is usually 30 minutes to 72 hours, and the reaction time can be shortened by heating as described above. Further, the reaction time can be shortened by placing the reaction system in an oxygen atmosphere.

According to the present invention, a carbonyl compound comprising an aldehyde compound or a ketone compound is produced. For example, the carbonyl compound formed from the alcohol (1) according to the present invention is represented by the following general formula (21). However, ^R 1, ^{Z 1} and ^{R 2} in the following general formula (21) is the same as ^R 1, ^{Z 1} and ^{R 2} in the general formula (1).
^{R 1 -Z 1 -C (O)} -R 2 (21)
Moreover, the carbonyl compound formed from the said alcohol (2) by this invention is represented by the following general formula (22). However, ^R 3, ^{Z 2} and ^{R 4} in the following general formula (22) is the same as ^R 3, ^{Z 2} and ^{R 4} in the general formula (2).
^{R 3 -Z 2 -CH = CH-} C (O) -R 4 (22)
In addition, the carbonyl compound formed from the alcohol (3) according to the present invention is represented by the following general formula (23). However, ^{R 5} in the following general formula (23) is the same as ^{R 5} in the general formula (3).
_{^{R 5 -C (O) -CH 3}} (23)

For example, in the method for producing a carbonyl compound of the present invention, as shown by the following formula (24), the carbonyl compound (b) is produced from the alcohol (a) represented by the general formula (4).

As a manufacturing method of this invention, it can carry out as follows, for example.
As shown by the following formula (25), for example, 10 mol of 1-phenyl-1-pentanol (9) as a reaction substrate and 10% by mass of ruthenium were supported on a reaction vessel of an organic synthesizer as a reaction substrate. A catalyst (10% Ru / C) and toluene as a solvent are charged. The amount of the catalyst added is, for example, 0.5 mol (ruthenium 5 mol% with respect to 100 mol% of the reaction substrate). And a reaction product is obtained by providing the reaction process which heats and stirs for 24 hours at 70 degreeC of reaction temperature in oxygen atmosphere, and can manufacture a carbonyl compound. Further, after the reaction is completed, disappearance of the raw material can be confirmed by thin layer chromatography or the like.
Furthermore, in this invention, as shown by the following Formula (25), the recovery process of a catalyst can be provided. Moreover, a concentration process, a purification process, etc. can be provided.

  The catalyst recovery step is a step of filtering the reaction product obtained above and filtering the catalyst from the reaction product. As the catalyst recovery step, for example, the catalyst can be recovered by filtering the reaction product obtained above using a Kiriyama funnel or the like. Furthermore, the catalyst separated by filtration can be washed with an organic solvent such as toluene or ethanol. Then, the filtered or washed catalyst can be used again in the method for producing a carbonyl compound by drying for 10 to 24 hours.

  The concentration step is a step of producing a concentrated solution of a carbonyl compound by concentrating the filtrate obtained by the recovery step (including the organic solvent in which the catalyst is washed out). As the concentration step, for example, the filtrate obtained by the recovery step (including the organic solvent in which the catalyst is washed out) is further filtered using a membrane filter or the like, and the membrane filter is filtered with an organic material such as ether. Wash with solvent. Then, the obtained filtrate (including the organic solvent that washed the membrane filter) is concentrated under reduced pressure to obtain a concentrated solution.

  The purification step is a step of purifying the carbonyl compound from the concentrated solution. As the purification step, for example, the concentrated solution can be purified by silica gel column chromatography to obtain a carbonyl compound.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to such examples as long as the gist of the present invention is not exceeded. Yields in the following experimental examples ( %) Was calculated by the following measurement method.
(1) Yield by ¹ H-NMR The obtained reaction product was measured with “JNM AL-400 spectrometer” manufactured by JEOL Ltd. and calculated from the obtained spectrum. The solvent is CDCl ₃ and the internal standard is tetramethylsilane.
(2) Isolation yield The fraction obtained by separating the obtained reaction product by column chromatography (hexane: ethyl acetate) was concentrated under reduced pressure and calculated from the numerical value obtained after weighing.

The catalysts used are as follows.
(1) 10% Ru / C (K): a catalyst (“K type” manufactured by N.E. Chemcat Co., Ltd.) in which activated carbon is used as a carrier and 10% by mass of ruthenium is supported on the whole catalyst.
(2) 10% Ru / C (NX): a catalyst (“NX type” manufactured by N.E. Chemcat Co., Ltd.) in which activated carbon is used as a carrier and 10% by mass of ruthenium is supported on the whole catalyst.
(3) 5% Ru / C (A); a catalyst (“A type” manufactured by N.E. Chemcat Co., Ltd.) in which activated carbon is used as a carrier and 5% by mass of ruthenium is supported with respect to the whole catalyst. .
(4) 5% Ru / C (WAKO); a catalyst in which activated carbon is used as a carrier and 5% by mass of ruthenium is supported on the entire catalyst (“Ruthenium-activated carbon (Ru 5%)” manufactured by Wako Pure Chemical Industries, Ltd.) ).
(5) 10% Pd / C; catalyst using activated carbon as a carrier and 10% by mass of palladium supported on the entire catalyst (“K type” manufactured by N.E. Chemcat Co., Ltd.).
(6) 10% Rh / C; a catalyst (“K type” manufactured by N.E. Chemcat Co., Ltd.) in which activated carbon is used as a carrier and 10% by mass of rhodium is supported on the whole catalyst.
(7) 10% Au / C: A catalyst (“K type” manufactured by N.E. Chemcat Co., Ltd.) in which activated carbon is used as a carrier and 10% by mass of gold is supported on the whole catalyst.
(8) 10% Ir / C: a catalyst (“K type” manufactured by N.E. Chemcat Co., Ltd.) in which activated carbon is used as a carrier and 10% by mass of iridium is supported on the whole catalyst.
(9) 5% Pt / C: a catalyst in which 5% by mass of platinum is supported on activated carbon as a carrier (“Platinum-activated carbon (Pt 5%)” manufactured by Wako Pure Chemical Industries, Ltd.).

[1] Experimental examples 1-1 to 1-6 (catalyst study)
As shown in the following formula (31), 1-phenyl-1-pentanol (51) is used as an alcohol (secondary alcohol) as a reaction substrate, and various catalysts shown in Table 1 below and oxygen In the presence of carbonyl compound (valerophenone) (52) was produced by oxidizing the alcohol at a reaction temperature of 50 ° C. Toluene was used as the solvent. ^The yield obtained by ¹ H-NMR is also shown in Table 1. Note that Experimental Example 1-1 and Experimental Example 1-6 are examples, and Experimental Example 1-2 to Experimental Example 1-5 are comparative examples.

Experimental Example 1-1
164 mg (171 μl, 1.0 mmol) of 1-phenyl-1-pentanol, 50.5 mg (ruthenium 50.0 μmol) of 10% Ru / C (K), and 2.0 ml of toluene (Toluene) were placed in an oxygen atmosphere. Were put into a test tube of an organic synthesizer equipped with an oxygen-filled balloon and a stirrer (“Chemist Plaza” manufactured by Shibata Chemical Co., Ltd.), and the reaction was performed by stirring at a temperature of 50 ° C. for a reaction time of 24 hours. Thereafter, the obtained reaction solution was filtered using a membrane filter (Millipore, Millex-LH, 0, 45 μm), and the membrane filter was further washed with 15 ml of ether. The obtained filtrate was concentrated to obtain a colorless oily substance (carbonyl compound-containing composition). The obtained oily substance was measured by the ¹ H-NMR, and the yield of the obtained carbonyl compound (valerophenone) was calculated. The oxygen-filled balloon is a balloon filled with oxygen, and the oxygen balloon is filled with 1 l of oxygen gas (corresponding to about 40 mmol at 25 ° C. at 0.1 MPa).

Experimental Example 1-2
A carbonyl compound (similar to Experimental Example 1-1) except that 10% Pd / C 52.2 mg (palladium 50.0 μmol) was used instead of the catalyst in Experimental Example 1-1 instead of 10% Ru / C (K). Valerophenone).

Experimental Example 1-3
Similar to Experimental Example 1-1 except that 51.5 mg (rhodium 50.0 μmol) of 10% Rh / C (K) was used in place of the catalyst in Experimental Example 1-1 instead of 10% Ru / C (K). A carbonyl compound (valerophenone) was obtained.

Experimental Example 1-4
A carbonyl compound (similar to Experimental Example 1-1) except that 10% Au / C 98.5 mg (gold 50.0 μmol) was used instead of the catalyst in Experimental Example 1-1 instead of 10% Ru / C (K). Valerophenone).

Experimental Example 1-5
A carbonyl compound (as in Experimental Example 1-1) was used except that 10% Ir / C 96.1 mg (iridium 50.0 μmol) was used instead of the catalyst in Experimental Example 1-1 instead of 10% Ru / C (K). Valerophenone).

Experimental Example 1-6
A carbonyl compound (similar to Experimental Example 1-1) except that 55.0 Pt / C 195.0 mg (platinum 50.0 μmol) was used instead of the catalyst in Experimental Example 1-1 instead of 10% Ru / C (K). Valerophenone).

[2] Experimental examples 2-1 to 2-4 (examination of ruthenium catalyst)
As shown in the following formula (32), using 1-phenyl-1-pentanol (51) as an alcohol as a reaction substrate, various catalysts supporting Ru shown in Table 2, and the presence of oxygen, The mixture was stirred for 24 hours at a reaction temperature of 70 ° C., and the alcohol was oxidized to produce a carbonyl compound (valerophenone) (52). Further, the catalyst was blended so that ruthenium was 5 mol% when the alcohol was 100 mol%. Toluene was used as a solvent. ^The yields obtained by ¹ H-NMR are also shown in Table 2. Experimental examples 2-1 to 2-4 are examples.

Experimental Example 2-1
A carbonyl compound (valerophenone) was obtained in the same manner as in Experimental Example 1-1 except that the reaction temperature in Experimental Example 1-1 was changed to 70 ° C. instead of 50 ° C.

Experimental Example 2-2
Experimental Example 1-1 except that the reaction temperature in Experimental Example 1-1 was changed to 70 ° C. instead of 50 ° C., and 5% Ru / C (WAKO) was used instead of 10% Ru / C (K). In the same manner as above, a carbonyl compound (valerophenone) was obtained.

Experimental Example 2-3
Experimental Example 1-1 except that the reaction temperature in Experimental Example 1-1 was changed to 70 ° C. instead of 50 ° C., and 10% Ru / C (NX) was used instead of 10% Ru / C (K). In the same manner as above, a carbonyl compound (valerophenone) was obtained.

Experimental Example 2-4
Experimental Example 1-1 except that the reaction temperature in Experimental Example 1-1 was changed to 70 ° C. instead of 50 ° C., and 5% Ru / C (A) was used instead of 10% Ru / C (K). In the same manner as above, a carbonyl compound (valerophenone) was obtained.

[3] Experimental examples 3-1 to 3-8 (solvent study)
As shown in the following formula (33), 1-phenyl-1-pentanol (51) is used as an alcohol as a reaction substrate, 50% in the presence of 10% Ru / C (K) and oxygen as a catalyst, The alcohol was oxidized at a reaction temperature of 0 ° C. to produce a carbonyl compound (valerophenone) (52). Various solvents shown in Table 3 were used as the solvent. ^The yields obtained by ¹ H-NMR are also shown in Table 3. Experimental examples 3-1 and 3-3 to 3-8 are examples, and experimental example 3-2 is a comparative example.

Experimental example 3-1
In Experimental Example 3-1, 2.0 ml of toluene was used as a solvent. Experimental example 3-1 is the same as experimental example 1-1.

Experimental Example 3-2
A carbonyl compound (valerophenone) was obtained in the same manner as in Experimental Example 1-1 except that 2.0 ml of dimethyl sulfoxide (DMSO) was used instead of toluene as the solvent in Experimental Example 1-1.

Experimental Example 3-3
A carbonyl compound (valerophenone) was obtained in the same manner as in Experimental Example 1-1 except that 2.0 ml of acetonitrile (MeCN) was used instead of toluene as the solvent in Experimental Example 1-1.

Experimental Example 3-4
A carbonyl compound (valerophenone) was obtained in the same manner as in Experimental Example 1-1 except that 2.0 ml of water (H ₂ O) was used instead of toluene as the solvent in Experimental Example 1-1.

Experimental Example 3-5
A carbonyl compound (valerophenone) was obtained in the same manner as in Experimental Example 1-1 except that 2.0 ml of isopropyl alcohol (i-PrOH) was used instead of toluene as the solvent in Experimental Example 1-1.

Experimental Example 3-6
A carbonyl compound (valerophenone) was obtained in the same manner as in Experimental Example 1-1 except that 2.0 ml of 2-methyl-2-propanol (t-BuOH) was used instead of toluene as the solvent in Experimental Example 1-1. .

Experimental Example 3-7
A carbonyl compound (valerophenone) was prepared in the same manner as in Experimental Example 1-1, except that 2.0 ml of 50% by volume isopropyl alcohol aqueous solution (50% i-PrOH) was used instead of toluene as the solvent in Experimental Example 1-1. Obtained.

Experimental Example 3-8
Instead of toluene as the solvent in Experimental Example 1-1, carbonyl was used in the same manner as in Experimental Example 1-1, except that 2.0 ml of 50% by volume 2-methyl-2-propanol aqueous solution (50% t-BuOH) was used. A compound (valerophenone) was obtained.

[4] Experimental examples 4-1 to 4-10 (reaction temperature study)
As shown in the following formula (34), 1-phenyl-1-pentanol (51) is used as an alcohol as a reaction substrate, 10% Ru / C (K) as a catalyst, and oxygen in the presence of The above alcohol was oxidized at various reaction temperatures shown in 4 to produce a carbonyl compound (valerophenone) (52). As a solvent, toluene was used in Experimental Examples 4-1 to 4-5, and isopropyl alcohol (i-PrOH) was used in Experimental Examples 4-6 to 4-10. ^The yields obtained by ¹ H-NMR are also shown in Table 4. Experimental examples 4-1 to 4-10 are examples.

Experimental example 4-1
In Experimental Example 4-1, the reaction temperature was 50 ° C. Experimental Example 4-1 is the same as Experimental Example 1-1.

Experimental example 4-2
A carbonyl compound (valerophenone) was obtained in the same manner as in Experimental Example 1-1 except that the reaction temperature in Experimental Example 1-1 was changed to 50 ° C. instead of 50 ° C.

Experimental Example 4-3
A carbonyl compound (valerophenone) was obtained in the same manner as in Experimental Example 1-1 except that the reaction temperature in Experimental Example 1-1 was changed to 70 ° C. instead of 50 ° C.

Experimental Example 4-4
A carbonyl compound (valerophenone) was obtained in the same manner as in Experimental Example 1-1, except that the reaction temperature in Experimental Example 1-1 was changed to 120 ° C. instead of 50 ° C.

Experimental Example 4-5
A carbonyl compound (valerophenone) was obtained in the same manner as in Experimental Example 1-1 except that the reaction temperature in Experimental Example 1-1 was changed to room temperature (18 ° C.) instead of 50 ° C.

Experimental Example 4-6
A carbonyl compound (valerophenone) was obtained in the same manner as in Experimental Example 1-1 except that 2.0 ml of isopropyl alcohol (i-PrOH) was used instead of toluene as the solvent in Experimental Example 1-1. Experimental Example 3-6 is the same as Experimental Example 3-6, with a reaction temperature of 50 ° C.

Experimental Example 4-7
As in Experimental Example 1-1, 2.0 ml of isopropyl alcohol (i-PrOH) was used instead of toluene as the solvent in Experimental Example 1-1, and the reaction temperature was changed to 60 ° C. instead of 50 ° C. A carbonyl compound (valerophenone) was obtained.

Experimental Example 4-8
As in Experimental Example 1-1, 2.0 ml of isopropyl alcohol (i-PrOH) was used instead of toluene as the solvent in Experimental Example 1-1, and the reaction temperature was changed to 70 ° C. instead of 50 ° C. A carbonyl compound (valerophenone) was obtained.

Experimental Example 4-9
As in Experimental Example 1-1, 2.0 ml of isopropyl alcohol (i-PrOH) was used instead of toluene as the solvent in Experimental Example 1-1, and the reaction temperature was changed to 90 ° C. instead of 50 ° C. A carbonyl compound (valerophenone) was obtained.

Experimental Example 4-10
Experimental Example 1-1 except that 2.0 ml of isopropyl alcohol (i-PrOH) was used instead of the solvent toluene in Experimental Example 1-1, and the reaction temperature was changed to room temperature (18 ° C.) instead of 50 ° C. In the same manner as above, a carbonyl compound (valerophenone) was obtained.

[5] Experimental Examples 5-1 to 5-6 (Examination of catalyst amount for secondary alcohols)
As shown in the following formula (35), 1-phenyl-1-pentanol (51) is used as an alcohol as a reaction substrate, 70% in the presence of 10% Ru / C (K) as a catalyst, and oxygen. The alcohol was oxidized at a reaction temperature of 0 ° C. to produce a carbonyl compound (valerophenone) (52). The catalyst compounding amount shown in Table 5 (mol% of ruthenium when the alcohol is 100 mol%) was added to 10% Ru / C (K) as the catalyst. Toluene was used as the solvent. ^The yield obtained by ¹ H-NMR is also shown in Table 5. Experimental examples 5-1 to 5-6 are examples.

Experimental Example 5-1
A carbonyl compound (valerophenone) was obtained in the same manner as in Experimental Example 1-1 except that the reaction temperature in Experimental Example 1-1 was changed to 70 ° C. instead of 50 ° C. Experimental Example 5-1 is the same as Experimental Example 4-3 except that the catalyst compounding amount is 5 mol% [add 50.5 mg of 10% Ru / C (K) (ruthenium 50.0 μmol)].

Experimental Example 5-2
The reaction temperature in Experimental Example 1-1 was changed to 70 ° C. instead of 50 ° C., and the catalyst compounding amount was changed to 4 mol% instead of 5 mol% [added 40.4 mg of 10% Ru / C (K) (ruthenium 40.0 μmol)] A carbonyl compound (valerophenone) was obtained in the same manner as in Experimental Example 1-1 except that.

Experimental Example 5-3
The reaction temperature in Experimental Example 1-1 was changed to 70 ° C. instead of 50 ° C., and the catalyst blending amount was changed to 5 mol%, and 3 mol% [10% Ru / C (K) 30.3 mg (ruthenium 30.0 μmol) added] A carbonyl compound (valerophenone) was obtained in the same manner as in Experimental Example 1-1 except that.

Experimental Example 5-4
The reaction temperature in Experimental Example 1-1 was changed to 70 ° C. instead of 50 ° C., and the catalyst compounding amount was changed to 5 mol%, and 2 mol% [10% Ru / C (K) 20.2 mg (ruthenium 20.0 μmol added)] A carbonyl compound (valerophenone) was obtained in the same manner as in Experimental Example 1-1 except that.

Experimental Example 5-5
The reaction temperature in Experimental Example 1-1 was changed to 70 ° C. instead of 50 ° C., and the catalyst compounding amount was changed to 5 mol%, and 1 mol% [10% Ru / C (K) 10.1 mg (ruthenium 10.0 μmol) added] A carbonyl compound (valerophenone) was obtained in the same manner as in Experimental Example 1-1 except that.

Experimental Example 5-6
The reaction temperature in Experimental Example 1-1 was changed to 70 ° C. instead of 50 ° C., and the catalyst compounding amount was changed to 5 mol% to 0.5 mol% [10% Ru / C (K) 5.05 mg (ruthenium 5.0 μmol). A carbonyl compound (valerophenone) was obtained in the same manner as in Experimental Example 1-1 except that

[6] Experimental examples 6-1 to 6-3 (examination of oxygen existence conditions)
As shown in the following formula (36), 1-phenyl-1-pentanol (51) is used as an alcohol as a reaction substrate, 10% Ru / C (K) (catalyst blending amount 5 mol%) as a catalyst, The alcohol was oxidized at a reaction temperature of 70 ° C. to produce a carbonyl compound (valerophenone) (52). Toluene was used as the solvent. As for the oxygen existence conditions, Example 6-1 uses an oxygen-filled balloon, Example 6-2 opens the reaction system to the atmosphere, and Example 6-3 fills with an inert gas (argon). The reaction was performed under an inert gas atmosphere (oxygen-free state) using a balloon. The yield obtained by ¹ H-NMR is also shown in Table 6. Experimental examples 6-1 and 6-2 are examples, and experimental example 6-3 is a comparative example.

Experimental Example 6-1
A carbonyl compound (valerophenone) was obtained in the same manner as in Experimental Example 1-1 except that the reaction temperature in Experimental Example 1-1 was changed to 70 ° C. instead of 50 ° C. Experimental example 6-1 uses an oxygen-filled balloon under an oxygen atmosphere and is the same as experimental example 4-3.

Experimental Example 6-2
The reaction temperature in Experimental Example 1-1 was changed to 70 ° C. instead of 50 ° C., and in an atmospheric atmosphere, the organic synthesis apparatus was not equipped with an oxygen-filled balloon, and was the same as in Experimental Example 1-1 except that the reaction was performed in an open state. A carbonyl compound (valerophenone) was obtained.

Experimental Example 6-3
A carbonyl compound (valerophenone) was used in the same manner as in Experimental Example 1-1 except that the reaction temperature in Experimental Example 1-1 was changed to 70 ° C. instead of 50 ° C., and a balloon filled with argon (Ar) was used instead of the oxygen-filled balloon. )

[7] Experimental Examples 7-1 to 7-11 [Examination of reaction substrate (secondary alcohol)]
As shown in the following formula (37), various alcohols (53) shown in Table 7 are used as secondary alcohols as reaction substrates, and 10% Ru / C (K) as a catalyst (catalyst blending amount 5 mol%). The above alcohol was oxidized at a reaction temperature of 70 ° C. in the presence of oxygen to produce a carbonyl compound (54). As for the oxygen existence conditions, in all of Experimental Examples 7-1 to 7-11, there are two types of oxygen existence, one using an oxygen-filled balloon under an oxygen atmosphere and one conducted in an open air atmosphere. Performed under conditions. Toluene was used as the solvent. The yields obtained from the isolated yields are also shown in Table 6. Table 7 shows R and R ′ in the reaction substrate (55) represented by the following formula (37) in Experimental Examples 7-1 to 7-8. Moreover, the structural formulas of the reaction substrates in Experimental Examples 7-9 to 7-11 are also shown in Table 7. Experimental examples 7-1 to 7-11 are examples.

Experimental Example 7-1
Instead of 1-phenyl-1-pentanol which is the reaction substrate in Experimental Example 1-1, 1.0 mmol of 1-phenylethanol was used, the reaction temperature was changed to 70 ° C. instead of 50 ° C., and the oxygen presence condition was in an oxygen atmosphere. Obtained a carbonyl compound (acetophenone) in the same manner as in Experimental Example 1-1 except that the reaction time was 5 hours and the reaction time was 18 hours when the oxygen presence condition was atmospheric.

Experimental Example 7-2
Instead of 1-phenyl-1-pentanol which is the reaction substrate in Experimental Example 1-1, 1.0 mmol of 1-phenyl-2,2-dimethyl-1-propanol was used, and the reaction temperature was changed to 50 ° C. and 70 ° C. In the same manner as in Example 1-1, except that the reaction time was 2 hours when the oxygen presence condition was in an oxygen atmosphere, and the reaction time was 24 hours when the oxygen presence condition was in an air atmosphere, the carbonyl compound (2 , 2-dimethylpropiophenone).

Experimental Example 7-3
Instead of 1-phenyl-1-pentanol which is the reaction substrate in Experimental Example 1-1, 1.0 mmol of benzhydrol was used, the reaction temperature was changed to 70 ° C. instead of 50 ° C., and the oxygen presence condition was in an oxygen atmosphere. A carbonyl compound (benzophenone) was obtained in the same manner as in Experimental Example 1-1, except that the reaction time was 16 hours, and the oxygen presence condition was 16 hours under atmospheric conditions.

Experimental Example 7-4
Instead of 1-phenyl-1-pentanol which is the reaction substrate in Experimental Example 1-1, 1.0 mmol of benzoin is used, the reaction temperature is set to 70 ° C. instead of 50 ° C., and the oxygen presence conditions are an oxygen atmosphere and an atmospheric atmosphere. A carbonyl compound (benzyl) was obtained in the same manner as in Experimental Example 1-1 except that the test was performed under the following two conditions.

Experimental Example 7-5
Instead of 1-phenyl-1-pentanol which is the reaction substrate in Experimental Example 1-1, 1.0 mmol of 4-chlorobenzhydrol was used, the reaction temperature was changed to 70 ° C., and the oxygen presence condition was oxygen. A carbonyl compound (4-chlorobenzophenone) was obtained in the same manner as in Experimental Example 1-1 except that the reaction time was 1 hour under the atmosphere and the reaction time was 3 hours under the oxygen presence condition in the air atmosphere.

Experimental Example 7-6
In place of 1-phenyl-1-pentanol which is the reaction substrate in Experimental Example 1-1, 1.0 mmol of 1- (4-nitrophenyl) ethanol was used, the reaction temperature was changed to 70 ° C., and oxygen was present. A carbonyl compound (4-nitroacetophenone) was obtained in the same manner as in Experimental Example 1-1, except that the conditions were two conditions under an oxygen atmosphere and an air atmosphere. In addition, when the oxygen presence condition was in an air atmosphere, the reaction was further performed at a reaction temperature of 90 ° C. (reaction time: 24 hours).

Experimental Example 7-7
In place of 1-phenyl-1-pentanol, which is the reaction substrate in Experimental Example 1-1, 1.0 mmol of 1- (4-methoxyphenyl) ethanol was used, the reaction temperature was changed to 70 ° C., and oxygen was present. A carbonyl compound (4-methoxyacetophenone) was obtained in the same manner as in Experimental Example 1-1 except that the conditions were changed under two conditions: an oxygen atmosphere and an air atmosphere.

Experimental Example 7-8
Instead of 1-phenyl-1-pentanol, which is the reaction substrate in Experimental Example 1-1, 1.0 mmol of 1- (4-methylphenyl) ethanol was used, the reaction temperature was changed to 70 ° C., and oxygen was present. A carbonyl compound (4-methylacetophenone) was obtained in the same manner as in Experimental Example 1-1 except that the conditions were changed under two conditions: an oxygen atmosphere and an air atmosphere.

Experimental Example 7-9
Instead of 1-phenyl-1-pentanol, which is the reaction substrate in Experimental Example 1-1, 1.0 mmol of 9-fluorenol was used, the reaction temperature was changed to 70 ° C. instead of 50 ° C., and the oxygen presence condition was in an oxygen atmosphere. A carbonyl compound (9-fluorenone) was obtained in the same manner as in Experimental Example 1-1, except that the reaction time was 3 hours, and the reaction was 3 hours under an oxygen atmosphere.

Experimental Example 7-10
Instead of 1-phenyl-1-pentanol, which is the reaction substrate in Experimental Example 1-1, 1.0 mmol of 1-indanol was used, the reaction temperature was changed to 70 ° C., and the oxygen presence conditions were set in an oxygen atmosphere and A carbonyl compound (1-indanone) was obtained in the same manner as in Experimental Example 1-1, except that the test was performed under two conditions under an air atmosphere.

Experimental Example 7-11
In place of 1-phenyl-1-pentanol, which is the reaction substrate in Experimental Example 1-1, 1.0 mmol of α-methyl-2-thiopheneethanol was used, the reaction temperature was changed to 50 ° C., and the oxygen presence condition was changed to 70 ° C. Was carried out in the same manner as in Example 1-1, except that the carbonyl compound (2-acetylthiophene) was obtained.

[8] Experimental Examples 8-1 to 8-3 [Examination of reaction substrate (primary benzyl alcohol)]
As shown in the following formula (38), 4-methoxybenzyl alcohol (55) is used as a primary alcohol as a reaction substrate, and 10% Ru / C (K) (catalyst blending amount 5 mol%) is used as a catalyst. The above alcohol was oxidized at room temperature (18 ° C.) or 50 ° C. in the presence of oxygen to produce a carbonyl compound (4-methoxybenzaldehyde) (56). As the solvent, toluene or a mixed solvent of toluene and water was used. The isolated yield or the yield obtained by ¹ H-NMR is also shown in Table 8. Experimental examples 8-1 to 8-3 are examples.

Experimental Example 8-1
An experiment was conducted except that 4-methoxybenzyl alcohol was used instead of 1-phenyl-1-pentanol which is a reaction substrate in Experimental Example 1-1, and the reaction time was changed to two reaction times of 4 hours and 24 hours. A carbonyl compound (4-methoxybenzaldehyde) was obtained in the same manner as in Example 1-1. The yield was determined by isolation yield and ¹ H-NMR yield.

Experimental Example 8-2
Experimental example except that 4-methoxybenzyl alcohol was used instead of 1-phenyl-1-pentanol, which is the reaction substrate in Experimental Example 1-1, and the reaction temperature was changed to room temperature (18 ° C.) instead of 50 ° C. A carbonyl compound (4-methoxybenzaldehyde) was obtained in the same manner as in 1-1. In Experimental Example 8-2, 8% of a homo-coupled product represented by the following formula (61) was obtained as a by-product.

Experimental Example 8-3
Instead of 1-phenyl-1-pentanol, which is the reaction substrate in Experimental Example 1-1, 4-methoxybenzyl alcohol was used, and the solvent was toluene, water, and a mixed solvent. Similarly, a carbonyl compound (4-methoxybenzaldehyde) was obtained. In addition, the volume ratio of toluene and water of the mixed solvent is 1: 1.

[9] Experimental examples 9-1 to 9-6 (Examination of catalyst amount for primary benzyl alcohols)
As shown in the following formula (39), 4-methoxybenzyl alcohol (55) is used as the reaction substrate alcohol, and the reaction is carried out at 50 ° C. in the presence of 10% Ru / C (K) as the catalyst and oxygen. The alcohol was oxidized according to temperature to produce a carbonyl compound (4-methoxybenzaldehyde) (56). The catalyst compounding amount shown in Table 9 (mol% of ruthenium when the alcohol is 100 mol%) was added to 10% Ru / C (K) as the catalyst. Toluene was used as the solvent. The isolated yield or the yield obtained by ¹ H-NMR is also shown in Table 9. Experimental examples 9-1 to 9-6 are examples.

Experimental Example 9-1
Experimental Example 1-1 except that 4-methoxybenzyl alcohol was used instead of 1-phenyl-1-pentanol, which is the reaction substrate in Experimental Example 1-1, and the reaction time was changed to 4 hours instead of 24 hours. In the same manner as above, a carbonyl compound (4-methoxybenzaldehyde) was obtained. In Experimental Example 9-1, the catalyst blending amount was 5 mol% [added 10% Ru / C (K) 50.5 mg (ruthenium 50.0 μmol)]. Experimental Example 9-1 is the same as Experimental Example 8-1.

Experimental Example 9-2
Instead of 1-phenyl-1-pentanol which is the reaction substrate in Experimental Example 1-1, 4-methoxybenzyl alcohol was used, the reaction time was changed to 24 hours, and the compounding amount of the catalyst was changed to 5 mol%. A carbonyl compound (4-methoxybenzaldehyde) was obtained in the same manner as in Example 1-1, except that the amount was 4 mol% [10% Ru / C (K) 40.4 mg (ruthenium 40.0 μmol).

Experimental Example 9-3
Instead of 1-phenyl-1-pentanol which is the reaction substrate in Experimental Example 1-1, 4-methoxybenzyl alcohol was used, the reaction time was changed to 6 hours instead of 24 hours, and the catalyst compounding amount was changed to 5 mol%. A carbonyl compound (4-methoxybenzaldehyde) was obtained in the same manner as in Experimental Example 1-1, except that the amount was 3 mol% [10% Ru / C (K) 30.3 mg (ruthenium 30.0 μmol).

Experimental Example 9-4
Instead of 1-phenyl-1-pentanol which is the reaction substrate in Experimental Example 1-1, 4-methoxybenzyl alcohol was used, the reaction time was changed to 25 hours instead of 24 hours, and the catalyst compounding amount was changed to 5 mol%. Thus, a carbonyl compound (4-methoxybenzaldehyde) was obtained in the same manner as in Experimental Example 1-1 except that 20.2 mg (10% Ru / C (K) 20.2 mg (ruthenium 20.0 μmol) was used.

Experimental Example 9-5
Instead of 1-phenyl-1-pentanol which is the reaction substrate in Experimental Example 1-1, 4-methoxybenzyl alcohol was used, the reaction time was changed to 25 hours instead of 24 hours, and the catalyst compounding amount was changed to 5 mol%. A carbonyl compound (4-methoxybenzaldehyde) was obtained in the same manner as in Experimental Example 1-1 except that the amount was 1 mol% [10% Ru / C (K) 10.1 mg (ruthenium 10.0 μmol). In Experimental Example 9-5, 11% of the homocoupled body represented by the above formula (61) was obtained.

Experimental Example 9-6
In place of 1-phenyl-1-pentanol, which is the reaction substrate in Experimental Example 1-1, 4-methoxybenzyl alcohol was used, the reaction time was changed to 4 hours instead of 24 hours, and the oxygen presence condition was changed to atmospheric conditions. A carbonyl compound (4-methoxybenzaldehyde) was obtained in the same manner as in Experimental Example 1-1 except that. In Experimental Example 9-1, the catalyst blending amount was 5 mol% [added 10% Ru / C (K) 50.5 mg (ruthenium 50.0 μmol)]. Table 9 shows the isolated yield and the yield obtained by ¹ H-NMR. In Experimental Example 9-6, 1% of the homocoupled body represented by the above formula (61) was obtained.

[10] Experimental Examples 10-1 to 10-4 (Examination of ruthenium catalyst for primary alcohols)
As shown in the following formula (40), 4-methoxybenzyl alcohol (55) was used as the reaction substrate alcohol, and various catalysts supporting Ru shown in Table 10 and oxygen were present at 50 ° C. The mixture was stirred at the reaction temperature for 2 hours, and the alcohol was oxidized to produce a carbonyl compound (4-methoxybenzaldehyde) (56). Further, the catalyst was blended so that ruthenium was 5 mol% when the alcohol was 100 mol%. Toluene was used as a solvent. ^The yield obtained by ¹ H-NMR is also shown in Table 10. Experimental examples 10-1 to 10-4 are examples.

Experimental Example 10-1
Experimental Example 1-1 except that 4-methoxybenzyl alcohol was used instead of 1-phenyl-1-pentanol, which is the reaction substrate in Experimental Example 1-1, and the reaction time was changed to 2 hours instead of 24 hours. In the same manner as above, a carbonyl compound (4-methoxybenzaldehyde) was obtained.

Experimental Example 10-2
Instead of 1-phenyl-1-pentanol, which is the reaction substrate in Experimental Example 1-1, 4-methoxybenzyl alcohol was used, the reaction time was changed to 2 hours instead of 24 hours, and the catalyst was 10% Ru / C ( A carbonyl compound (4-methoxybenzaldehyde) was obtained in the same manner as in Experimental Example 1-1 except that 5% Ru / C (WAKO) was used in place of K).

Experimental Example 10-3
Instead of 1-phenyl-1-pentanol, which is the reaction substrate in Experimental Example 1-1, 4-methoxybenzyl alcohol was used, the reaction time was changed to 2 hours instead of 24 hours, and the catalyst was 10% Ru / C ( A carbonyl compound (4-methoxybenzaldehyde) was obtained in the same manner as in Experimental Example 1-1 except that 10% Ru / C (NX) was used instead of K).

Experimental Example 10-4
Instead of 1-phenyl-1-pentanol which is the reaction substrate in Experimental Example 1-1, 4-methoxybenzyl alcohol was used, the reaction time was changed to 2 hours instead of 24 hours, and the catalyst was 10% Ru / C ( A carbonyl compound (4-methoxybenzaldehyde) was obtained in the same manner as in Experimental Example 1-1 except that 5% Ru / C (A) was used instead of K).

[11] Experimental examples 11-1 to 11-7 [Examination of reaction substrate (primary alcohol)]
As shown in the following formula (41), using various primary alcohols (57) shown in Table 11 as reaction substrates, 10% Ru / C (K) (catalyst blending amount 5 mol%) as a catalyst, oxygen, In the presence of, the above alcohol was oxidized at the reaction temperature shown in Table 7 to produce the carbonyl compound (58). As for the oxygen existence conditions, in all of Experimental Examples 11-1 to 11-7, there are two types of oxygen existence: one using an oxygen-filled balloon under an oxygen atmosphere and one conducted in an open air atmosphere. Performed under conditions. Toluene was used as the solvent. The yields obtained by the isolated yield are shown in Table 11. Table 11 shows the structural formula of R ′ in the reaction substrate (57) represented by the following formula (41) in Experimental Examples 11-1 to 11-4 and the reaction substrate (57) in Experimental Examples 11-5 to 11-7. It is written together. Experimental examples 11-1 to 11-7 are examples.

Experimental Example 11-1
Instead of 1-phenyl-1-pentanol, which is the reaction substrate in Experimental Example 1-1, 1.0 mmol of 4-butoxybenzyl alcohol was used, and the oxygen presence conditions were two conditions: an oxygen atmosphere and an air atmosphere. A carbonyl compound (4-butoxybenzaldehyde) was obtained in the same manner as in Experimental Example 1-1 except that the test was performed.

Experimental Example 11-2
Instead of 1-phenyl-1-pentanol, which is the reaction substrate in Experimental Example 1-1, 1.0 mmol of 4-chlorobenzyl alcohol was used, and the reaction time was 6 hours under an oxygen atmosphere under an oxygen atmosphere. A carbonyl compound (4-chlorobenzaldehyde) was obtained in the same manner as in Experimental Example 1-1, except that the reaction time was 6 hours under atmospheric conditions.

Experimental Example 11-3
Instead of 1-phenyl-1-pentanol, which is the reaction substrate in Experimental Example 1-1, 1.0 mmol of 4-nitrobenzyl alcohol was used, and the oxygen presence conditions were two conditions: an oxygen atmosphere and an air atmosphere. went. Furthermore, the one where the oxygen presence condition was in the atmosphere was also the one where the reaction temperature was 90 ° C. A carbonyl compound (4-nitrobenzaldehyde) was obtained in the same manner as in Experimental Example 1-1 except for the above.

Experimental Example 11-4
Instead of 1-phenyl-1-pentanol, which is the reaction substrate in Experimental Example 1-1, 1.0 mmol of 2-hydroxybenzyl alcohol was used, and the oxygen presence conditions were two conditions: an oxygen atmosphere and an air atmosphere. went. Further, a carbonyl compound (2-hydroxybenzaldehyde) was obtained in the same manner as in Experimental Example 1-1, except that the reaction temperature was 70 ° C. under oxygen atmosphere.

Experimental Example 11-5
In place of 1-phenyl-1-pentanol, which is the reaction substrate in Experimental Example 1-1, 1.0 mmol of 1-naphthalenemethanol was used, and the oxygen presence condition was performed under two conditions: an oxygen atmosphere and an air atmosphere. A carbonyl compound (1-formylnaphthalene) was obtained in the same manner as in Experimental Example 1-1.

Experimental Example 11-6
Instead of 1-phenyl-1-pentanol, which is the reaction substrate in Experimental Example 1-1, 1.0 mmol of pyridine-3-methanol was used, and the oxygen presence condition was in an oxygen atmosphere, and the oxygen presence condition was an atmospheric atmosphere. With respect to the case below, three types of reactions were performed: reaction temperature 50 ° C. reaction time 24 hours, reaction temperature 70 ° C. reaction time 24 hours, and reaction temperature 90 ° C. reaction time 24 hours. A carbonyl compound (3-formylpyridine) was obtained in the same manner as in Experimental Example 1-1 except for the above.

Experimental Example 11-7
Instead of 1-phenyl-1-pentanol, which is the reaction substrate in Experimental Example 1-1, 1.0 mmol of thiophene-2-methanol was used, and the oxygen presence conditions were two conditions: an oxygen atmosphere and an air atmosphere. went. Furthermore, the one having an oxygen presence condition in an air atmosphere was also performed at a reaction temperature of 70 ° C. A carbonyl compound (2-formylthiophene) was obtained in the same manner as in Experimental Example 1-1 except for the above.

[12] Experimental examples 12-1 to 12-2 [Examination of reaction substrate (benzyl type allyl alcohol)]
As shown in the following formula (42), using various benzyl type allyl alcohols (59) shown in Table 12 as reaction substrates, 10% Ru / C (K) (catalyst blending amount 5 mol%) as a catalyst, oxygen, In the presence of carbonyl compound (60) was produced by oxidizing the alcohol at a reaction temperature of 50 ° C. As for the oxygen existence conditions, in all of Experimental Examples 12-1 to 12-2, there are two types of oxygen existence, one using an oxygen-filled balloon under an oxygen atmosphere and one carried out in an open atmosphere. Performed under conditions. Toluene was used as the solvent. The yields obtained from the isolated yields are also shown in Table 12. Moreover, the structural formula of the reaction substrate (59) in the following formula (42) in Experimental Examples 12-1 to 12-2 is also shown in Table 12. Experimental examples 12-1 and 12-2 are examples.

Experimental Example 12-1
Instead of 1-phenyl-1-pentanol, which is the reaction substrate in Experimental Example 1-1, 1.0 mmol of 4-nitrocinnamyl alcohol was used, and the oxygen presence conditions were two conditions: an oxygen atmosphere and an air atmosphere. A carbonyl compound (cinnaldehyde) was obtained in the same manner as in Experimental Example 1-1 except that the procedure was performed in the same manner as in Experimental Example 1-1.

Experimental Example 12-2
Instead of 1-phenyl-1-pentanol, which is the reaction substrate in Experimental Example 1-1, 1.0 mmol of cinnamyl alcohol was used, and the oxygen presence condition was performed under two conditions: an oxygen atmosphere and an air atmosphere. Except for the above, a carbonyl compound (cinnamaldehyde) was obtained in the same manner as in Experimental Example 1-1.

[13] Experimental examples 13-1 to 13-4 [Examination of reaction substrates (aliphatic secondary alcohol and aliphatic primary alcohol)]
Using various aliphatic secondary alcohols and primary alcohols shown in Table 13 as reaction substrates, the reaction temperature was 90 ° C. in the presence of 10% Ru / C (K) (catalyst blending amount 5 mol%) and oxygen as the catalyst. Thus, the above alcohol was oxidized to produce a carbonyl compound. As for the oxygen existence conditions, in all of Experimental Examples 13-1 to 13-4, there are two types of oxygen existence: one using an oxygen-filled balloon under an oxygen atmosphere and one conducted in an open air atmosphere. Performed under conditions. As the solvent, toluene or a mixed solvent of toluene and water was used. The yields obtained from the isolated yields are also shown in Table 13. Table 11 also shows the structural formulas of the reaction substrates in Experimental Examples 13-1 to 13-4. Further, “ND” in Table 13 indicates that the yield could not be measured. Experimental examples 13-1 and 13-2 are examples, and experimental examples 13-3 and 13-4 are reference examples.

Experimental Example 13-1
Instead of 1-phenyl-1-pentanol which is the reaction substrate in Experimental Example 1-1, 1.0 mmol of 4-phenyl-2-butanol was used, the reaction temperature was changed to 70 ° C., and the oxygen presence condition was changed. A carbonyl compound (benzylacetone) was obtained in the same manner as in Example 1-1, except that the test was performed under two conditions under an oxygen atmosphere and an air atmosphere.

Experimental Example 13-2
Instead of 1-phenyl-1-pentanol, which is the reaction substrate in Experimental Example 1-1, 1.0 mmol of 2-decanol was used, the reaction temperature was changed to 70 ° C., and the oxygen presence conditions were set in an oxygen atmosphere and A carbonyl compound (2-decanone) was obtained in the same manner as in Experimental Example 1-1 except that the test was performed under two conditions under an atmospheric atmosphere.

Experimental Example 13-3
Instead of 1-phenyl-1-pentanol, which is the reaction substrate in Experimental Example 1-1, 1.0 mmol of 1-decanol was used, the reaction temperature was changed to 70 ° C., and the oxygen presence condition was set in an oxygen atmosphere and A carbonyl compound (decanal) was obtained in the same manner as in Experimental Example 1-1, except that the test was performed under two conditions under an air atmosphere.

Experimental Example 13-4
Instead of 1-phenyl-1-pentanol, which is the reaction substrate in Experimental Example 1-1, 1.0 mmol of 1-decanol was used, the reaction temperature was changed to 70 ° C., and the oxygen presence condition was set in an oxygen atmosphere and A carbonyl compound (decanal) was obtained in the same manner as in Experimental Example 1-1 except that the reaction was performed under two conditions under an air atmosphere, and toluene, water, and a mixed solvent were used as the solvent. In addition, toluene, water, and a mass ratio of the said mixed solvent are 1: 1. In Experimental Example 13-4, decanoic acid, which is a carboxylic acid, was obtained in a 59% yield under an oxygen atmosphere.

  From the results of the above Experimental Examples 1-1 to 1-6 (Table 1), the yield of the catalyst on which ruthenium (Ru) was supported in Experimental Example 1-1 was 93%. The yield of the catalyst carrying platinum (Pt) was 100%. On the other hand, in the catalyst loaded with a metal other than ruthenium (Ru) and platinum (Pt), the yield of the catalyst loaded with iridium (Ir) in Experimental Example 1-5 was 21%. The yield was less than%. When a catalyst carrying ruthenium (Ru) or platinum (Pt) is used, a carbonyl compound is obtained in a high yield. If the catalyst metal is ruthenium (Ru) or platinum (Pt), a predetermined alcohol is used. It can be seen that it has an excellent catalytic effect in the oxidizing reaction.

  From the results of Experimental Examples 2-1 to 2-4 (Table 2), any catalyst in which ruthenium (Ru) is supported on an activated carbon carrier can be used in the reaction of oxidizing a predetermined alcohol. It can be seen that it has an excellent catalytic effect. In all cases where the catalyst metal content was 5% or more, the yield in the carbonyl compound production was an excellent value.

  From the results of Experimental Examples 3-1 to 3-8 (Table 3), when DMSO in Experimental Example 3-2 was used, the yield was a low value of 4%. On the other hand, when toluene of Experimental Example 3-1 was used, the yield was 93%, 57% with acetonitrile of Experimental Example 3-3, 75% with water of Experimental Example 3-4, and Experimental Example 3- With 5 isopropyl alcohol, the yield was as high as 73%. Although the oxidation reaction proceeds in any solvent, it can be seen that among these solvents, toluene, water and isopropyl alcohol are preferable, and toluene and isopropyl alcohol are more preferable.

From the results of Experimental Examples 4-1 to 4-10 (Table 4), when toluene was used as a solvent, the yield at room temperature in Experimental Example 4-5 was 16%. The yield was 93% at 50 ° C. in -1, and a high yield of 100% in Experimental Example 4-3. On the other hand, in Experimental Example 4-4 in which the reaction temperature was 120 ° C., the reactivity (yield) decreased. This is presumably because the solubility of oxygen was reduced by boiling the solvent (toluene).
When isopropyl alcohol was used as the solvent, the yield at room temperature in Experimental Example 4-10 was a low value of 6%, but the high value of 73% was obtained at 50 ° C. in Experimental Example 4-6. Met. However, when isopropyl alcohol was used as the solvent, the yield decreased with increasing temperature at a reaction temperature of 60 ° C. or higher. This is because although the oxidation reaction of alcohol proceeds with an increase in the reaction temperature, the oxidation reaction of isopropyl alcohol also proceeds at the same time, and the ketone body in which the alcohol is oxidized is reduced by the Ru-H complex formed accordingly. Conceivable.

  From the results of the above Experimental Examples 5-1 to 5-6 (Table 5), the yield was 100% when the catalyst compounding amount in Experimental Example 5-1 was 5 mol%. However, it can be seen that, under the same reaction temperature and reaction time, the yield decreases as the catalyst formulation decreases.

  From the results of the above Experimental Examples 6-1 to 6-3 (Table 6), the yield was 100% in both the oxygen atmosphere in Experimental Example 6-1 and the atmospheric atmosphere in Experimental Example 6-2. there were. However, the yield was as low as 18% under the argon atmosphere in Experimental Example 6-3.

From the results of Experimental Examples 7-1 to 7-11 (Table 7), substrates having no substituent on the benzene ring in Experimental Examples 7-1 to 7-4, Experimental Example 7-9, and Experimental Example 7-10 Then, steric hindrance (Experimental Example 7-2), cyclic (Experimental Example 7-9), non-cyclic (Experimental Example 7-1 and Experimental Example 7-3), electronic factors (Experimental Example 7-4), etc. The reaction proceeded without any problem in an oxygen atmosphere or an air atmosphere. On the other hand, with the substrate of Experimental Example 7-10, the yield was only moderate.
In Experimental Example 7-5, a ketone body could be obtained in a high yield from a substrate substituted with chlorine. On the other hand, with the benzyl alcohol having a nitro group in Experimental Example 7-6, the desired ketone body was obtained in high yield, but the oxidation reaction was delayed and the reaction time was 24 hours.
In addition, in the substrate having a methyl group at the 2-position in Experimental Example 7-8, the oxidation reaction proceeded efficiently without being sterically hindered by the methyl group.
Further, since the reaction proceeded without any problem even in the alcohol having a thiophene ring in Experimental Example 7-11, it is considered that this reaction is not easily affected by the catalytic poisoning action such as a sulfur atom.
From the above, it can be seen that the method for producing a carbonyl compound according to the present invention enables an efficient oxidation reaction of various alcohols (secondary benzyl alcohols and the like) in an oxygen atmosphere or an air atmosphere.

  From the results of the above Experimental Examples 8-1 to 8-3 (Table 8), in the secondary benzyl alcohols, the progress of the oxidation reaction progressed at a predetermined reaction temperature (see Table 4). For primary benzyl alcohols, the oxidation reaction proceeded sufficiently even when the reaction temperature was 50 ° C. Furthermore, the raw material disappeared even in the reaction at room temperature. However, the homo-coupled product was produced. The formation mechanism of the above-mentioned homo-coupled body is considered to be a nucleophilic attack of the alcohol substrate on the benzyl cation generated by the high valence Ru generated by Ru / C oxygen oxidation acting as the Lewis acid of the alcohol.

  From the results of the above Experimental Examples 9-1 to 9-6 (Table 9), when the amount of the catalyst was decreased, the yield was decreased as the reaction time was extended. However, it has been found that a sufficient yield can be obtained by increasing the reaction time. In addition, even when the oxygen condition was an air atmosphere, a slight amount of homo-coupled body was confirmed, but it was found that application to an air atmosphere was sufficiently possible.

  From the results of Experimental Examples 10-1 to 10-4 (Table 10), even when the reaction substrate is a primary benzyl alcohol, any catalyst in which ruthenium (Ru) is supported on an activated carbon carrier can be used. It can be seen that even this catalyst has an excellent catalytic effect in the reaction of oxidizing a predetermined alcohol. In all cases where the catalyst metal content was 5% or more, the yield in the carbonyl compound production was an excellent value.

From the results of Experimental Examples 11-1 to 11-7 (Table 11), even in the case where the reaction substrate is a primary benzyl alcohol, the substrate in which the electron donating group was substituted in Experimental Example 11-1, The oxidation reaction proceeded without problems in both oxygen and air.
Moreover, in Experimental Example 11-2 and Experimental Example 11-3, the target aldehyde compound could be obtained in high yield even with benzyl alcohol substituted with an electron withdrawing group such as a chlorine atom or a nitro group. Furthermore, in Experimental Example 11-3, it was necessary to raise the temperature to 90 ° C., but the substrate substituted with a nitro group could be oxidized even under oxygen conditions in an air atmosphere.
In Experimental Example 11-6 and Experimental Example 11-7, the reaction temperature may need to be increased even with a substrate having a heterocycle such as pyridine or thiophene, but the target aldehyde compound can be obtained in high yield. It was.

From the results of Experimental Examples 12-1 and 12-2 (Table 12), even when the reaction substrate is alcohol (2) (benzylic alcohol), the yield is high under oxygen conditions in an oxygen atmosphere and an air atmosphere. The desired aldehyde was obtained at a high rate.
In addition, in the case of 4-nitrocinnamyl alcohol in which the nitro group was substituted in Experimental Example 12-1, the target aldehyde compound could be obtained with higher yield. In the case of cinnamyl alcohol in Experimental Example 12-2, a temperature increase to 70 ° C. or 90 ° C. may be necessary, but the target aldehyde compound was obtained in good yield.

  From the results of Experimental Examples 13-1 to 13-4 (Table 13), the reaction substrate in Experimental Examples 13-1 and 13-2 is alcohol (3) (aliphatic secondary alcohol). Also, the desired aldehyde was obtained in good yield under oxygen conditions in an oxygen atmosphere and an air atmosphere. On the other hand, when the reaction substrate in Experimental Example 13-3 and Experimental Example 13-4 is an aliphatic primary alcohol, under the oxygen condition in the oxygen atmosphere of Experimental Example 13-3, the target carbonyl compound The yield could not be measured. This is thought to be due to the complicated progress of the reaction. On the other hand, the yield of the target carbonyl compound was 57% under the oxygen condition in the atmosphere of Experimental Example 13-3. In the reaction system to which water was added in Experimental Example 13-4, the yield was slightly reduced.

Claims (4)

In the presence of a catalyst in which at least one metal selected from ruthenium and platinum is supported on an activated carbon support, and oxygen,
A method for producing a carbonyl compound, comprising: oxidizing an alcohol represented by any one of the following general formulas (1) to (3) to produce a carbonyl compound comprising an aldehyde compound or a ketone compound.
R ¹ —Z ¹ —CH (OH) —R ² (1)
[In the general formula (1), R ¹ represents a hydrogen atom, a hydroxy group, a nitro group, an amino group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an acyl group having 1 to 20 carbon atoms. Group, benzoyl group, or halogenated benzoyl group, Z ¹ represents a divalent aromatic ring, R ² represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a phenyl group , A benzoyl group, a halogenated phenyl group, or a halogenated benzoyl group, Z ¹ and R ² may be bonded to each other to form a 3- to 10-membered ring. ]
R ³ —Z ² —CH═CH—CH (OH) —R ⁴ (2)
[In the general formula (2), R ³ represents a hydrogen atom, a hydroxy group, a nitro group, an amino group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an acyl group having 1 to 20 carbon atoms. A benzoyl group or a halogenated benzoyl group, Z ² represents a divalent aromatic ring, R ⁴ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a phenyl group. , Benzoyl group, halogenated phenyl group, or halogenated benzoyl group. ]
R ⁵ —CH (OH) —CH ₃ (3)
[However, in the general formula (3), ^{R 5} represents an alkyl group, or an aralkyl group having 8 to 20 carbon atoms having 1 to 20 carbon atoms. ]   The method for producing a carbonyl compound according to claim 1, wherein the metal content in the catalyst is 1% by mass or more when the entire catalyst is 100% by mass.   The method for producing a carbonyl compound according to claim 1 or 2, wherein a reaction temperature in the oxidation is 10 ° C to 130 ° C.   The method for producing a carbonyl compound according to any one of claims 1 to 3, wherein the oxidation is performed in the presence of a solvent, and the solvent is at least one selected from toluene, isopropyl alcohol, and water.