JP2000212116A - Production of hydroxyketone - Google Patents

Abstract

PROBLEM TO BE SOLVED: To efficiently produce a corresponding hydroxyketone by oxidizing a secondary alcohol having plural hydroxy groups in the molecule by reacting the specific secondary alcohol with oxygen in the presence of a specified imide compound. SOLUTION: A secondary alcohol having plural hydroxy groups in the molecule, preferably 4-15C linear polyols or 4-15C cyclic polyols (including saccharides) is reacted with oxygen by using an imide compound of the formula (R1 and R2 are each H, a halogen, an alkyl, an aryl, a cycloalkyl, an acyl or the like; X is O or OH) as a catalyst, and a metallic compound as a cocatalyst to provide the objective ketone.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing hydroxyketone useful as an intermediate of various chemical products. More specifically, the present invention relates to a method for producing a corresponding hydroxyketone by oxidizing a secondary alcohol having a plurality of hydroxyl groups in a molecule.

[0002]

2. Description of the Related Art As a method for obtaining a corresponding ketone from a secondary alcohol, a method using chromic acid or manganese dioxide as an oxidizing agent is known. According to these methods, when a secondary alcohol having a plurality of hydroxyl groups in a molecule is oxidized, it is relatively easy to selectively oxidize only one of the hydroxyl groups. However, the above method requires a large amount of the metal compound, which not only complicates the post-treatment but also is not preferable from the viewpoint of resources and the environment.

On the other hand, as a method for oxidizing a substrate without using a large amount of a metal compound, a method using oxygen as an oxidizing agent is widely used. However, there is no known method for efficiently oxidizing a secondary alcohol having a plurality of hydroxyl groups in a molecule with oxygen to obtain a corresponding hydroxyketone. JP-A-8-38909 discloses a method in which a substrate is oxidized with oxygen using a specific imide compound as a catalyst. However, when a diol is used as a substrate, a corresponding hydroxyketone is produced. Not listed.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a method for efficiently obtaining a corresponding hydroxyketone by oxidizing a secondary alcohol having a plurality of hydroxyl groups in a molecule with oxygen. is there.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, have found that when an imide compound having a specific structure is used as a catalyst, a corresponding hydroxyketone can be efficiently produced from a diol. We have found and completed the present invention.

That is, the present invention provides the following formula (1)

Embedded image (Wherein R ¹ and R ² are the same or different and each represents a hydrogen atom,
A halogen atom, an alkyl group, an aryl group, a cycloalkyl group, a hydroxyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or an acyl group; R ¹ and R ² are bonded to each other to form a double bond, or an aromatic or A non-aromatic ring may be formed. X represents an oxygen atom or a hydroxyl group. R ¹ , R ² , or R ¹ and R ²
Are bonded to each other to form a double bond or an aromatic or non-aromatic ring represented by the above formula (1).
A secondary alcohol having a plurality of hydroxyl groups in the molecule is reacted with oxygen in the presence of an imide compound represented by the following formula: Provided is a method for producing a hydroxyketone, which produces a hydroxyketone. In this method, a metal compound may be used as a promoter.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION [Secondary alcohol] The secondary alcohol used as a reaction component (substrate) is an alcohol (polyol) having a plurality of hydroxyl groups in a molecule, and the plurality of hydroxyl groups. The compounds are not particularly limited as long as at least one of them is bonded to a secondary carbon atom, and may be any of a chain polyol such as a chain diol and a cyclic polyol such as a cyclic diol.

Examples of such secondary alcohols include 1,3-butanediol, 1,3-pentanediol, 1,4-pentanediol, 2,4-pentanediol, and 1,3,5-pentanetriol. , 1,3-hexanediol, 1,4-hexanediol, 1,5-hexanediol, 2,4-hexanediol, 1,3-
Heptanediol, 1,4-heptanediol, 1,5
-Heptanediol, 1,6-heptanediol, 2,
4-heptanediol, 2,5-heptanediol,
1,3-octanediol, 1,4-octanediol, 1,5-octanediol, 1,6-octanediol, 1,7-octanediol, 2,4-octanediol, 2,5-octanediol, 1 4-2 carbon atoms such as 1,3-decanediol and 1,3-dodecanediol
Chain polyols having about 0 (preferably about 4 to 15 carbon atoms); 1,3-cyclobutanediol, 1,3-cyclopentanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, About 4 to 15 carbon atoms (preferably 5 to 10 carbon atoms) such as 3-cyclooctanediol and 1,4-cyclooctanediol.
) Cyclic polyols (including saccharides).

The secondary alcohol has various substituents in the molecule, for example, a halogen atom, an oxo group, a substituted oxy group (for example, an alkoxy group, an aryloxy group, an aralkyloxy group, an acyloxy group, etc.), a carboxyl group. A substituted oxycarbonyl group, a substituted or unsubstituted carbamoyl group, a cyano group, a nitro group, a substituted or unsubstituted amino group, a heterocyclic group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, a cycloalkyl group,
It may have a cycloalkenyl group or the like.

Preferred secondary alcohols include polyols (such as diols) in which a hydroxyl group is attached to each of the secondary and primary carbon atoms. When such a compound is oxidized, the secondary carbon atom to which the hydroxyl group is bonded is selectively oxidized, and the corresponding hydroxyketone (a primary alcohol having a ketone group)
Is generated efficiently.

Other preferred secondary alcohols include 1,3-diols and 1,4-diols, especially 1,3-diols. When these secondary alcohols are oxidized, the corresponding hydroxyketone in which only one hydroxyl-bonded carbon atom is oxidized can be obtained with high selectivity.

[Imide compound] In the present invention, an imide compound represented by the above formula (1) is used as a catalyst. In the formula (1), the halogen atom among the substituents R ¹ and R ² includes iodine, bromine, chlorine and fluorine. The alkyl group includes, for example, a linear or C1-C10 linear group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, and decyl groups. Includes branched alkyl groups. Preferred alkyl groups include, for example, lower alkyl groups having about 1 to 6 carbon atoms, particularly about 1 to 4 carbon atoms.

The aryl group includes phenyl and naphthyl groups, and the cycloalkyl group includes cyclopentyl and
And a cyclohexyl group. The alkoxy group includes
For example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, t-butoxy, pentyloxy, hexyloxy group and the like about 1 to 10 carbon atoms, preferably about 1 to 6 carbon atoms, particularly about 1 to 4 carbon atoms Lower alkoxy groups.

The alkoxycarbonyl group includes, for example, carbon atoms of an alkoxy moiety such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, t-butoxycarbonyl, pentyloxycarbonyl and hexyloxycarbonyl. The number includes about 1 to 10 alkoxycarbonyl groups. Preferred alkoxycarbonyl groups include lower alkoxycarbonyl groups having about 1 to 6, particularly about 1 to 4, carbon atoms in the alkoxy moiety.

Examples of the acyl group include those having 1 to 6 carbon atoms such as formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl and pivaloyl groups.
A certain number of acyl groups can be exemplified.

The substituents R ¹ and R ² may be the same or different. In the formula (1), R ¹ and R ² may be bonded to each other to form a double bond or a ring having an aromatic or non-aromatic attribute. The preferred aromatic or non-aromatic ring is a 5- to 12-membered ring, particularly a 6- to 10-membered ring, and may be a heterocyclic ring or a fused heterocyclic ring, but is often a hydrocarbon ring. Such rings include, for example,
Non-aromatic alicyclic ring (cycloalkane ring optionally having a substituent such as cyclohexane ring, cycloalkene ring optionally having a substituent such as cyclohexene ring), non-aromatic bridge A bridged ring (eg, a bridged hydrocarbon ring which may have a substituent such as a 5-norbornene ring),
An aromatic ring (including a condensed ring) which may have a substituent such as a benzene ring and a naphthalene ring is included. The ring is
Often composed of aromatic rings. The ring may have a substituent such as an alkyl group, a haloalkyl group, a hydroxyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, an acyl group, a nitro group, a cyano group, an amino group, and a halogen atom.

In the general formula (1), X represents an oxygen atom or a hydroxyl group, and the bond between the nitrogen atom N and X is a single bond or a double bond.

A double bond or an aromatic or non-aromatic ring formed by bonding R ¹ , R ² or R ¹ and R ² to each other is represented by the above formula (1). One or two N-substituted cyclic imide groups may be further formed. For example, when R ¹ or R ² is an alkyl group having 2 or more carbon atoms, the N-substituted cyclic imide group may be formed to include two adjacent carbon atoms constituting the alkyl group. When R ¹ and R ² are bonded to each other to form a double bond, the N-substituted cyclic imide group may be formed to include the double bond. Further, when R ¹ and R ² are bonded to each other to form an aromatic or non-aromatic ring, the N-substituted cyclic imide group is formed to include two adjacent carbon atoms constituting the ring. It may be.

Preferred imide compounds include those represented by the following formula:

Embedded image (Wherein, R ^{3 to} R ⁶ are the same or different and each represents a hydrogen atom, an alkyl group, a haloalkyl group, a hydroxyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, an acyl group, a nitro group, a cyano group, an amino group, R ^{3 to} R ⁶ may be mutually adjacent groups to form an aromatic or non-aromatic ring, and in formula (1f), A represents a methylene group or Represents an oxygen atom, R ¹ ,
R ² is the same as above. The benzene ring of the formula (1c) has the formula (1
One or two N-substituted cyclic imide groups shown in c) may be further bonded).

In the substituents R ^{3 to} R ⁶ , the alkyl group includes the same alkyl groups as those exemplified above, particularly an alkyl group having about 1 to 6 carbon atoms, and the haloalkyl group includes trifluoromethyl The haloalkyl group having about 1 to 4 carbon atoms such as a group, an alkoxy group includes the same alkoxy group as described above, particularly a lower alkoxy group having about 1 to 4 carbon atoms,
The alkoxycarbonyl group includes the same alkoxycarbonyl group as described above, particularly a lower alkoxycarbonyl group having about 1 to 4 carbon atoms in the alkoxy moiety. Examples of the acyl group include the same acyl groups as described above, particularly those having 1 carbon atom.
About 6 to about 6 acyl groups are exemplified, and examples of the halogen atom include fluorine, chlorine, and bromine atoms. Substituent R ³
To R ⁶ is often a hydrogen atom, a lower alkyl group having about 1 to 4 carbon atoms, a carboxyl group, a nitro group, or a halogen atom. The ring formed by combining R ^{3 to} R ⁶ with each other is the same as the ring formed by combining R ¹ and R ² with each other, and is particularly preferably an aromatic or non-aromatic 5 to 12 ring.
Member rings are preferred.

Representative examples of preferred imide compounds include, for example, N-hydroxysuccinimide, N-hydroxymaleimide, N-hydroxyhexahydrophthalimide, N, N'-dihydroxycyclohexanetetracarboxylic imide, N-hydroxyphthalimide, N-hydroxytetrabromophthalimide, N
-Hydroxytetrachlorophthalimide, N-hydroxyhettimide, N-hydroxyhymic imide, N-hydroxytrimellitic imide, N, N'-
Examples thereof include dihydroxypyromellitic imide and N, N'-dihydroxynaphthalenetetracarboxylic imide.

The imide compound represented by the formula (1) is subjected to a conventional imidization reaction, for example, a reaction between a corresponding acid anhydride and hydroxylamine NH ₂ OH, and a ring opening and ring closing of the acid anhydride group. It can be prepared by an imidization method.

The acid anhydrides include, for example, saturated or unsaturated aliphatic dicarboxylic anhydrides such as succinic anhydride and maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride (1,2-cyclohexanedicarboxylic anhydride). ), Saturated or unsaturated non-aromatic cyclic polycarboxylic anhydrides (alicyclic polycarboxylic anhydrides) such as 1,2,3,4-cyclohexanetetracarboxylic acid 1,2-anhydride, Bridged cyclic polycarboxylic anhydrides (alicyclic polycarboxylic anhydrides), such as hetic anhydride and hymic anhydride, phthalic anhydride, tetrabromophthalic anhydride, tetrachlorophthalic anhydride, nitrophthalic anhydride, Trimetic anhydride, methylcyclohexenetricarboxylic anhydride, pyromellitic anhydride, melittic anhydride, 1,8; 4
Aromatic polycarboxylic anhydrides such as 5-naphthalenetetracarboxylic dianhydride are included.

Particularly preferred imide compounds are alicyclic polycarboxylic acid anhydrides or aromatic polycarboxylic acid anhydrides, especially N-derivatives derived from aromatic polycarboxylic acid anhydrides.
Hydroxyimide compounds, such as N-hydroxyphthalimide, are included.

The imide compound represented by the formula (1) can be used alone or in combination of two or more. The imide compound may be used in a form supported on a carrier. As the carrier, a porous carrier such as activated carbon, zeolite, silica, silica-alumina and bentonite is often used.

The amount of the imide compound to be used can be selected in a wide range, for example, from 0.0001 to 1 mol per mol of the substrate.
1 mol, preferably about 0.001 to 0.5 mol, more preferably about 0.01 to 0.4 mol, and
It is often about 0.35 mol.

[Co-catalyst] In the method of the present invention, a metal compound can be used as a co-catalyst in order to increase the reaction rate. The metal compounds can be used alone or in combination of two or more.

As the metal element constituting the metal compound,
It is not particularly limited, and may be any of the metal elements of Groups 1 to 15 of the periodic table. Note that, in this specification, boron B is also included in the metal element. For example, as the metal elements, Group 1 elements (Li, Na, K, etc.), Group 2 elements (Mg, Ca, Sr, Ba, etc.), Group 3 elements (Sc, lanthanoid elements, actinoid elements, etc.), 4 Group 5 elements (Ti, Zr, Hf, etc.), Group 5 elements (V, etc.), Group 6 elements (Cr, Mo, W, etc.), Group 7 elements (Mn, etc.),
Group 8 element (Fe, Ru, etc.), Group 9 element (Co, Rh, etc.), Group 10 element (Ni, Pd, Pt, etc.), Group 11 element (Cu, etc.), Group 12 element (Zn, etc.), Group 13 Elements (B, Al, In, and the like), Group 14 elements (Sn, Pb, and the like), Group 15 elements (Sb, Bi, and the like), and the like. Preferred metal elements include transition metal elements (periodic table 3 to 3).
Group 12 elements). Among them, elements of the 5 to 11 groups of the periodic table, particularly elements of the 6th, 7th and 9th groups are preferable, and particularly Co such as Mo, Co and Mn is particularly preferable. The valence of the metal element is not particularly limited, but is usually about 0 to 6, preferably 2 to 3.

Examples of the metal compound include simple substances, hydroxides, oxides (including complex oxides), halides (fluoride, chloride, bromide, iodide), oxo acid salts (for example, nitrate) , Sulfate, phosphate, borate,
Inorganic compounds such as carbonates, oxo acids, isopoly acids, and heteropoly acids; and organic compounds such as organic acid salts (eg, acetate, propionate, cyanate, naphthenate, stearate) and complexes. No. The ligands constituting the complex include OH (hydroxo), alkoxy (methoxy, ethoxy, propoxy, butoxy, etc.), acyl (acetyl, propionyl, etc.), alkoxycarbonyl (methoxycarbonyl, ethoxycarbonyl, etc.), acetylacetonato , Cyclopentadienyl group, halogen atom (chlorine, bromine, etc.), CO, CN,
Oxygen atom, H ₂ O (aquo), phosphorus compound of phosphine (triarylphosphine such as triphenylphosphine), NH ₃ (ammine), NO, NO ₂ (nitro),
Nitrogen-containing compounds such as NO ₃ (nitrat), ethylenediamine, diethylenetriamine, pyridine, and phenanthroline. The metal compound can be used alone or
More than one species can be used in combination.

The amount of the metal compound used is, for example, 0.0001 to 0.7 mol, preferably 0.001 to 0.5 mol, more preferably 0.001 to 1 mol, per mol of the substrate.
It is about 5 to 0.1 mol, and often about 0.0015 to 0.05 mol.

[Oxygen] The oxygen may be either molecular oxygen or generator oxygen. As the molecular oxygen, pure oxygen may be used, or oxygen diluted with an inert gas such as nitrogen, helium, argon, or carbon dioxide may be used. It is preferable to use air from the viewpoint of economy as well as operability and safety.

The amount of oxygen used can be appropriately selected according to the type of the substrate, but is usually 0.5 mol or more (eg, 1 mol or more), preferably 1 to 100 mol, and more preferably 1 mol to 1 mol of the substrate. Preferably it is about 2 to 50 mol. Often an excess of oxygen is used relative to the substrate.

[Reaction] The reaction is usually carried out in an organic solvent. Examples of the organic solvent include organic acids such as acetic acid and propionic acid; nitriles such as acetonitrile, propionitrile and benzonitrile; amides such as formamide, acetamide, dimethylformamide (DMF) and dimethylacetamide; hexane, octane and the like Aliphatic hydrocarbons; halogenated hydrocarbons such as chloroform, dichloromethane, dichloroethane, carbon tetrachloride, chlorobenzene and trifluoromethylbenzene; nitro compounds such as nitrobenzene, nitromethane and nitroethane; esters such as ethyl acetate and butyl acetate; And the like. As the solvent, organic acids such as acetic acid, nitriles such as acetonitrile and benzonitrile, halogenated hydrocarbons such as trifluoromethylbenzene, esters such as ethyl acetate, and the like are often used.

The reaction temperature can be appropriately selected according to the type of the substrate and the like, and is, for example, 0 to 200 ° C., preferably 5 to 1 ° C.
50 ° C., more preferably about 10 to 120 ° C.,
Usually, the reaction often takes place at about 10 to 100 ° C. The reaction can be performed under normal pressure or under pressure. When the reaction is performed under pressure, it is usually 1 to 100 atm (for example,
1.5 to 80 atm), preferably about 2 to 70 atm. The reaction time can be appropriately selected depending on the reaction temperature and pressure, for example, from a range of 30 minutes to 48 hours, preferably about 5 to 35 hours. The reaction can be carried out in the presence of oxygen or in the flow of oxygen by a conventional method such as a batch system, a semi-batch system, or a continuous system.

In the method of the present invention, a secondary carbon atom among a plurality of carbon atoms to which a hydroxyl group is bonded (a compound having a plurality of secondary carbon atoms to which a hydroxyl group is bonded, one Atom) is selectively oxidized to form a hydroxyketone having a ketone group and a hydroxyl group in the molecule.

After completion of the reaction, the reaction product is subjected to a conventional method,
For example, it can be easily separated and purified by separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, and column chromatography, or a separation means combining these.

[0037]

According to the method of the present invention, since a specific catalyst is used, a secondary catalyst having a plurality of hydroxyl groups in a molecule is used.
The corresponding hydroxyketone can be efficiently obtained by oxidizing the secondary alcohol with oxygen.

[0038]

The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

Example 1 2,3-butanediol 2 mmol, N-hydroxyphthalimide 0.2 mmol, cobalt (II) acetate 0.0
A mixture of 1 mmol and 4 ml of acetonitrile was stirred at 75 ° C. for 12 hours under an oxygen atmosphere (1 atm). When the reaction solution was analyzed by gas chromatography, 3-
Oxo-1-butanol was produced in a yield of 58%.
The conversion of 1,3-butanediol was 80%.

Example 2 A mixture of 2 mmol of 1,3-butanediol, 0.2 mmol of N-hydroxyphthalimide and 4 ml of acetonitrile was stirred at 75 ° C. for 24 hours in an oxygen atmosphere (1 atm). When the reaction solution was analyzed by gas chromatography, 3-oxo-1-butanol was produced in a yield of 30%. The conversion of 1,3-butanediol is 42
%Met.

Example 3 1,3-Cyclohexanediol 3 mmol, N-hydroxyphthalimide 0.3 mmol, cobalt (III)
Acetyl acetonate [Co (acac) ₃ ] 0.015
A mixture of 8 mmol of benzonitrile was stirred at 75 ° C. for 8 hours under an oxygen atmosphere (1 atm). When the reaction solution was analyzed by gas chromatography, 3-hydroxycyclohexanone was produced in a yield of 73%.
The conversion of 1,3-cyclohexanediol was 78%.

Example 4 1,3-Cyclohexanediol 3 mmol, N-hydroxyphthalimide 0.3 mmol, cobalt acetate (I
I) A mixture of 0.015 mmol and 8 ml of benzonitrile was stirred at 75 ° C. for 8 hours under an oxygen atmosphere (1 atm). When the reaction solution was analyzed by gas chromatography, 3-hydroxycyclohexanone was produced in a yield of 70%. The conversion of 1,3-cyclohexanediol was 73%.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (reference) // C07B 61/00 300 C07B 61/00 300 F term (reference) 4G069 AA06 BA21A BA21B BA27A BA27B BC67A BC67B BE08A BE08B BE11A BE11B BE19A BE19B BE33A BE37A BE37B BE38A BE38B CB07 CB19 CB74 DA02 EE09 4H006 AA02 AC44 BA14 BA16 BA20 BA51 BE30 4H039 CA62 CC20

Claims (2)

[Claims] [Claim 1] The following formula (1) (Wherein R ¹ and R ² are the same or different and each represents a hydrogen atom,
A halogen atom, an alkyl group, an aryl group, a cycloalkyl group, a hydroxyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or an acyl group; R ¹ and R ² are bonded to each other to form a double bond, or an aromatic or A non-aromatic ring may be formed. X represents an oxygen atom or a hydroxyl group. R ¹ , R ² , or R ¹ and R ²
Are bonded to each other to form a double bond or an aromatic or non-aromatic ring represented by the above formula (1).
A secondary alcohol having a plurality of hydroxyl groups in the molecule is reacted with oxygen in the presence of an imide compound represented by the formula: A method for producing a hydroxyketone that produces a hydroxyketone. 2. The method for producing a carboxylic acid according to claim 1, wherein a metal compound is used as a co-catalyst.