JP2001239171A - Catalyst separation and recovery method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for efficiently separating an N-substituted cyclic imide-type catalyst or its decomposition products by using a simple means from a mixture of reaction products obtained in the presence of the N- substituted cyclic imide-type catalyst with either the N-substituted cyclic imide- type catalyst or its decomposition products. SOLUTION: The separation and recovery method of the present invention is to separate and recover an N-substituted cyclic imide-type catalyst or its decomposition products from a mixture of reaction products obtained in the presence of the N-substituted cyclic imide-type catalyst with either the N- substituted cyclic imide-type catalyst or its decomposition products. The N- substituted cyclic imide-type catalyst or its decomposition products are recovered as solids by precipitating or re-pulping the mixture in a solvent selected from a hydrocarbon, a chain type ether or water.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a mixture comprising a reaction product obtained by using an N-substituted cyclic imide catalyst such as N-hydroxyphthalimide and the N-substituted cyclic imide catalyst or a decomposition product thereof. And a method for separating and recovering an N-substituted cyclic imide-based catalyst or its decomposition product from the catalyst.

[0002]

2. Description of the Related Art N-hydroxyphthalimides and other N-
BACKGROUND ART Substituted cyclic imide-based catalysts have attracted attention as catalysts that smoothly proceed various reactions such as oxidation with molecular oxygen, carboxylation, nitration, sulfonation, acylation, and radical coupling reactions under mild conditions.

For example, JP-A-8-38909 and JP-A-9-327626 disclose that a substrate such as a hydrocarbon or an alcohol is oxidized with molecular oxygen in the presence of an N-substituted cyclic imide-based catalyst. Methods for producing the corresponding alcohols, aldehydes, ketones, carboxylic acids and the like are disclosed. JP-A-9-278675 discloses that the N-
A method for oxidizing a conjugated compound using a substituted cyclic imide-based catalyst is disclosed. JP-A-10-316610 describes that oxidation of ethers in the presence of the N-substituted cyclic imide-based catalyst produces esters, acid anhydrides, lactones, and the like. WO 99/50204
A method for producing a corresponding epoxide by oxidizing a compound having a non-aromatic ethylene bond with molecular oxygen in the presence of the N-substituted cyclic imide catalyst and a co-oxidizing agent; and A method is described for producing a corresponding ester or lactone by oxidizing a ketone with molecular oxygen in the presence of a cyclic imide-based catalyst and a co-oxidant.

JP-A-11-239730 discloses a method for obtaining a corresponding nitro compound by reacting a substrate with a nitrogen oxide in the presence of an N-substituted cyclic imide-based catalyst. A method for producing a corresponding carboxylic acid by reacting a substrate with carbon monoxide and oxygen is disclosed. WO 99/41219 discloses that in the presence of an N-substituted cyclic imide-based catalyst, a substrate is reacted with 1,2 such as oxygen and biacetyl.
It is described that an acylation reaction proceeds under mild conditions when reacted with a 2-dicarbonyl compound or the like. Proceedings of the 1999 Annual Meeting of the Chemical Society of Japan show that when N-hydroxyphthalimide is used as a catalyst to react an α, β-unsaturated ester with an alcohol and oxygen, a radical coupling reaction proceeds and α-hydroxy It has been reported that -γ-butyrolactone is produced in good yield. In addition, the same report reports that when a hydrocarbon such as adamantane is reacted with oxygen and sulfur dioxide using N-hydroxyphthalimide as a catalyst, a corresponding sulfonic acid is generated.

As described above, the N-substituted cyclic imide-based catalyst is extremely useful as a catalyst for a wide range of organic synthesis reactions such as an oxidation reaction. There have been few reports on the method of separation from the catalyst. For example, JP
JP-A-114702 discloses an aqueous solvent and a non-aqueous solution which can be separated from the aqueous solvent when the reaction product and the catalyst are separated from an oxidation reaction mixture obtained using an N-substituted cyclic imide-based catalyst. A method has been proposed in which an oxidative reaction product is distributed to an aqueous solvent layer and a catalyst is distributed to a water-insoluble solvent layer by using an aqueous solvent. However, this method is extremely effective when the reaction product is a compound having extremely high polarity such as adipic acid, but is always useful when separating the reaction product having a relatively low polarity from the catalyst. It's not an easy way. Further, in order to recover the catalyst as a solid, it is necessary to evaporate the water-insoluble solvent, which is costly.

When the N-substituted cyclic imide catalyst is used in a reaction, it may be partially decomposed depending on the reaction conditions and the like. When the decomposition product of the catalyst is mixed into the product of the reaction product, the quality of the product may be deteriorated. However, a method for separating such a decomposition product has not been known.

[0007]

Accordingly, an object of the present invention is to provide a reaction product obtained by reacting in the presence of an N-substituted cyclic imide-based catalyst with the N-substituted cyclic imide-based catalyst or a decomposition product thereof. It is an object of the present invention to provide a method capable of efficiently separating an N-substituted cyclic imide-based catalyst or a decomposition product thereof from a mixture containing:

Another object of the present invention is to provide a reaction product obtained by reacting in the presence of an N-substituted cyclic imide catalyst with the N-substituted cyclic imide catalyst.
An object of the present invention is to provide a method capable of easily recovering an N-substituted cyclic imide-based catalyst or its decomposition product as a solid from a mixture containing the substituted cyclic imide-based catalyst or its decomposition product.

[0009]

Means for Solving the Problems The present inventors have studied the physical properties of the catalyst and its decomposed product in order to achieve the above object, and found that the N-substituted cyclic imide-based catalyst and its decomposition product have a medium polarity. Has been found to be easily soluble in solvents having the following formulas, but difficult to dissolve in very low polarity solvents or extremely high polarity solvents. Therefore, as a result of further study, when the mixture containing the reaction product and the N-substituted cyclic imide-based catalyst or its decomposition product is subjected to a specific treatment using a specific solvent, the N-substituted cyclic imide-based catalyst is obtained. The present inventors have found that a catalyst or a decomposition product thereof can be efficiently separated and recovered as a solid, and have completed the present invention.

That is, the present invention provides a reaction product obtained by reacting in the presence of an N-substituted cyclic imide-based catalyst with the N-substituted cyclic imide-based catalyst.
A method for separating and recovering an N-substituted cyclic imide-based catalyst or a decomposition product thereof from a mixture containing a substituted cyclic imide-based catalyst or a decomposition product thereof, wherein the mixture is obtained from a hydrocarbon, a chain ether and water. A method for separating and recovering a catalyst for recovering the N-substituted cyclic imide-based catalyst or a decomposition product thereof as a solid by subjecting to crystallization or repulping operation using a selected solvent.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The N-substituted cyclic imide catalyst of the present invention is represented by 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, in which one or two N-substituted cyclic imide groups shown in the above formula may be further formed.) An imide compound represented by

In the formula (1), the halogen atom among the substituents R ¹ and R ² includes iodine, bromine, chlorine and fluorine. Alkyl groups include, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s
Linear or branched alkyl groups having about 1 to 10 carbon atoms, such as -butyl, t-butyl, pentyl, hexyl, heptyl, octyl, and decyl 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 above 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.

The above-mentioned R ¹ , R ² , or a double bond or an aromatic or non-aromatic ring formed by bonding 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 and X are the same as above. (In the benzene ring of the formula (1c), one or two N-substituted cyclic imide groups shown in the formula (1c) may be further formed.)

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, by reacting a corresponding acid anhydride with hydroxylamine NH ₂ OH, and opening and closing 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, and in particular, N-derivatives derived from aromatic polycarboxylic acid anhydrides.
Hydroxyimide compounds, such as N-hydroxyphthalimide, are included.

In the present invention, the reaction product obtained by using the N-substituted cyclic imide-based catalyst may be any compound produced by a reaction utilizing the catalyst. For example, an oxidation reaction product (for example, Alcohol, aldehyde, ketone, carboxylic acid, epoxy compound, lactone,
Acid anhydride, acetal, etc.), carboxylation reaction product (carboxylic acid), nitration reaction product (nitro compound), sulfonation reaction product (sulfonic acid), acylation reaction product (aldehyde, ketone), radical Examples include, but are not limited to, coupling reaction products (lactones and other compounds). Each reaction product (alcohol, aldehyde, ketone, carboxylic acid, etc.) may be any of an aliphatic compound, an alicyclic compound, an aromatic compound, and a heterocyclic compound. Further, alcohols include monools, diols and polyhydric alcohols, and carboxylic acids include monocarboxylic acids, dicarboxylic acids and polycarboxylic acids. In addition, specific examples of the reaction product include a reaction product described in the prior art described in the section of the prior art.

In the present invention, the decomposition product of the N-substituted cyclic imide-based catalyst is not particularly limited as long as it is a compound formed by decomposition or modification of the N-substituted cyclic imide-based catalyst during each of the above reactions. For example, an N-unsubstituted cyclic imide compound represented by the following formula (2), a cyclic acid anhydride represented by the following formula (3), various ring opening And the like.

Embedded image (Wherein R ¹ and R ² are the same as above)

The N-unsubstituted cyclic imide compound represented by the above formula (2) is a compound which is considered to be formed by reduction of the N-substituted cyclic imide-based catalyst in the reaction system. Examples include phthalic acid imide. Further, it is presumed that the cyclic acid anhydride represented by the above formula (3) was formed by the compound hydrolyzed in the reaction system of the N-substituted cyclic imide-based catalyst or a derivative thereof by ring closure with dehydration or the like. And a typical example thereof is phthalic anhydride. Examples of the ring-opening compound include dicarboxylic acids such as phthalic acid, and derivatives thereof.

An important feature of the present invention is that a mixture containing the reaction product and the N-substituted cyclic imide-based catalyst or a decomposition product thereof is used in a solvent selected from hydrocarbons, chain ethers and water. The present invention is characterized in that the N-substituted cyclic imide-based catalyst or a decomposition product thereof is recovered as a solid by subjecting to the crystallization or repulping operation. Hereinafter, the N-substituted cyclic imide-based catalyst and its decomposition product may be collectively referred to as “N-substituted cyclic imide-based catalyst or the like”. In this specification, “crystallization” is used in a broad sense that includes not only crystallization in a narrow sense but also “precipitation”.

When the reaction product is a low-polarity compound, it is preferable to use a hydrocarbon or a chain ether as the solvent, and when the reaction product is a high-polarity compound (a water-soluble compound), Preferably, water is used as the solvent.

The reaction product and the N-substituted cyclic imide-based catalyst are contained in the mixture subjected to the crystallization or repulping operation.
Two or more kinds may be contained respectively. The mixed solution contains a reaction product, an N-substituted cyclic imide catalyst, a reaction raw material, a reaction solvent, and a co-catalyst such as a metal compound used in combination with the N-substituted cyclic imide catalyst. And a solvent used in the purification step. The mixture may be a reaction mixture at the end of the reaction, or after subjecting the reaction mixture to a conventional separation and purification operation such as filtration, concentration, dilution, liquid property adjustment, extraction, washing, crystallization, and drying. May be used.

In the present invention, examples of the hydrocarbon used in the crystallization or repulping operation include aliphatic hydrocarbons such as pentane, hexane, isohexane, heptane, octane, isooctane, 2-ethylhexane and decane; cyclopentane and cyclohexane And alicyclic hydrocarbons such as cyclooctane; and aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene. Examples of the chain ether include diethyl ether, diisopropyl ether, t-butyl methyl ether, dibutyl ether, and anisole. These solvents can be used alone or in combination of two or more. Among these, particularly preferred solvents include aliphatic hydrocarbons such as hexane, alicyclic hydrocarbons such as cyclohexane, chain ethers such as t-butyl methyl ether, and mixed solvents thereof.

The amount of hydrocarbon, chain ether or water used in the crystallization or repulping operation is determined by the type of operation (repulp or crystallization), the type and content of the reaction product, the type and content of the catalyst, etc. N-substituted cyclic imide-based catalyst contained in the mixture and its decomposition product 100
The amount can be appropriately selected, for example, in the range of about 50 to 100,000 parts by weight with respect to parts by weight.

The process liquid during the crystallization or repulping operation may contain a solvent other than the hydrocarbon, chain ether and water as long as the separation efficiency is not impaired. For example, a reaction solvent or a solvent used in an operation such as an extraction performed in a step prior to the crystallization or repulp operation of the present invention or a crystallization operation may be included in the process liquid, In order to enhance the property, another solvent (for example, an organic solvent compatible with these hydrocarbons or chain ethers, or a water-soluble solvent with water) is used together with the hydrocarbon, chain ether or water. Crystallization or repulping operation may be performed by addition.

As such a solvent, for example, acetic acid,
Organic acids such as propionic acid; nitriles such as acetonitrile, propionitrile and benzonitrile; N, N-
Amides such as dimethylformamide; chloroform,
Halogenated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chlorobenzene and trifluoromethylbenzene; nitro compounds such as nitrobenzene and nitromethane; esters such as ethyl acetate, butyl acetate, methyl benzoate and ethyl benzoate; tetrahydrofuran and dioxane Cyclic ethers; alcohols such as methanol, ethanol and isopropyl alcohol; ketones such as acetone and ethyl methyl ketone.

In order to efficiently separate the reaction product from the N-substituted cyclic imide-based catalyst and the like, the amount (total amount) of hydrocarbons, chain ethers or water in the process liquid during the crystallization or repulping operation is considered. ) Is, for example, 50% by weight or more, especially 70% by weight or more (particularly 90% by weight or more) of the entire solvent (volatile component) in the process liquid.

The processing temperature varies depending on the type of processing, but is usually about -10 ° C. to + 150 ° C., preferably 0 to 150 ° C.
The range is about + 100 ° C. The above processing can be performed by any method such as a batch method and a continuous method. The processing may be performed once or a plurality of times.
More than one kind may be combined. Crystallization can be performed by cooling and / or concentrating the solution. Repulp can be performed by stirring a mixture of a solid and a solvent.
The solid obtained by crystallization or repulping can be separated by using a conventional solid-liquid separation operation such as filtration and centrifugation. The separated N-substituted cyclic imide-based catalyst or the like can be reused as a catalyst as it is or after an appropriate regeneration treatment. Further, the filtrate (or mother liquor) from which the N-substituted cyclic imide-based catalyst and the like have been removed is separated into conventional separation and purification means,
For example, the reaction product can be isolated by subjecting it to concentration, crystallization, recrystallization, extraction, distillation, column chromatography and the like.

Embodiments of the method of the present invention include, for example, (i)
Using a hydrocarbon, chain ether or water as a reaction solvent (or an excess amount of reaction components), an N-substituted cyclic imide-based catalyst or the like can be obtained by changing the composition of the system during the reaction, or by cooling or concentrating after the reaction is completed. (Ii) The reaction mixture is subjected to appropriate treatment such as filtration, concentration, drying, liquid property adjustment, extraction, washing, crystallization and the like, if necessary, and then the hydrocarbon, chain An embodiment in which ether or water is added to crystallize or repulp the N-substituted cyclic imide-based catalyst or the like is included.

As a more specific example of the above embodiment (ii), for example, a precipitate is removed by filtration from a reaction mixture such as an oxidation reaction, and the filtrate is concentrated. Or chain ether (if the product is a non-polar compound)
Alternatively, the N-substituted cyclic imide-based catalyst or the like can be recovered as a solid by adding water (when the product is a polar compound) and crystallizing or repulping the N-substituted cyclic-imide-based catalyst or the like. Further, after concentrating a reaction mixture such as an oxidation reaction, water is added to crystallize a reaction product and an N-substituted cyclic imide-based catalyst and the like, and a hydrocarbon or a chain ether is added to the obtained crystals. By crystallizing or repulping the N-substituted cyclic imide-based catalyst or the like, the N-substituted cyclic imide-based catalyst or the like can be recovered as a solid.

[0038]

According to the present invention, the reaction product obtained by reacting in the presence of an N-substituted cyclic imide-based catalyst and the N-substituted cyclic imide catalyst
The N-substituted cyclic imide-based catalyst or its decomposition product can be efficiently separated from the mixture containing the substituted cyclic imide-based catalyst or its decomposition product by simple means. Further, the N-substituted cyclic imide-based catalyst or a decomposition product thereof can be easily recovered as a solid from the mixture.

[0039]

EXAMPLES The present invention will be described below in more detail with reference to Examples, but the present invention is not limited to these Examples.

Example 1 A 1-L titanium tube equipped with a cooling pipe and a pressure regulator
In an autoclave, 50 g of cyclohexane (0.594
Mol), 9.692 g of N-hydroxyphthalimide
(0.059 mol), cobalt (II) acetate tetrahydrate 0.
296 g (0.0012 mol) and acetonitrile 40
0 g, and pressurized with nitrogen (33 kgf / cm ^Two3.2
4MPa) and the temperature was raised while stirring. Stable at 75 ° C
When done, 40kgf / cm^Two(3.92 MPa)
Under the pressure of, air was allowed to flow and reacted for 4 hours. In the system
Replaced with nitrogen and cooled. Gas chromatographic reaction mixture
Analyzed by Raffy and high performance liquid chromatography.
As a result, the cyclohexane conversion was 19.5%,
Hexanone yield 14.5% (selectivity 74.4%)
Clohexanol in 1.6% yield (8.2% selectivity)
Had been generated. In the reaction mixture, it is used as a catalyst.
9.080 g of N-hydroxyphthalimide
Phthalimide, which is a modified product of hydroxyphthalimide,
0.109 g, also of N-hydroxyphthalimide
0.138 g of phthalic anhydride was present.
After filtering the reaction mixture to remove insolubles, the filtrate
To remove cyclohexane and acetonitrile.
Was. Add 100 ml of cyclohexane to the concentrated residue,
After stirring for a while, the catalyst and its decomposition
Products (N-hydroxyphthalimide, phthalimide and
And phthalic anhydride) were collected as a solid. Touch the filtrate
The medium and its decomposition products were not included.

Example 2 25 g (164 mmol) of adamantanol, 5.36 g (32.8 mmol) of N-hydroxyphthalimide,
Vanadium acetylacetonate [V (acac) ₃ ]
0.11 g (0.328 mmol), acetic acid 150 ml,
And a mixture of 150 ml of chlorobenzene at 1 atm.
The mixture was stirred at 85 ° C. for 20 hours under an oxygen atmosphere of 101 MPa). After the reaction was completed, the reaction mixture was analyzed by gas chromatography and high performance liquid chromatography. The conversion of adamantanol was 95.6%, the yield of adamantanediol was 50.5% (selectivity 52.8%),
Adamantane triol yield 40.7% (selectivity 4
2.6%). Also, in the reaction mixture,
N-hydroxyphthalimide used as a catalyst is 1.8
5 g, phthalimide 1.51 g, phthalic anhydride 0.
It contained 40 g. Concentrate the reaction mixture and add 1.2 L of water
After stirring at 50 ° C. for 2 hours and cooling, the insolubles were filtered to recover the catalyst and its decomposition products as solids. The filtrate was extracted three times with 3 L of ethyl acetate. The extract was concentrated to 170 g, and the crystals were filtered to obtain 11.2 g of adamantanediol.
The catalyst and its decomposition products were not contained in the crystals. Further, the raffinate was concentrated to 100 g, and acetone 20
0 g was added, and the crystals were filtered to obtain 9.9 g of adamantanetriol. The catalyst and its decomposition products were not contained in the crystals.

Example 3 27 g (200 mmol) of adamantane, 3.25 g (20 mmol) of N-hydroxyphthalimide, V ₂ O ₅
0.183 g (0.1 mmol), 240 m anisole
1 and 60 ml of acetic acid at 1 atm (0.101 M
The mixture was stirred at 85 ° C. for 3 hours under an oxygen atmosphere of Pa). After the reaction was completed, the reaction mixture was analyzed by gas chromatography and high performance liquid chromatography. The conversion of adamantane was 13.0%, the yield of adamantanol was 11.3% (selectivity: 86.9%), and Tanone was produced in a yield of 0.9% (selectivity 6.9%). Also,
In the reaction mixture, N-hydroxyphthalimide used as a catalyst was 2.12 g, phthalimide was 0.68 g,
0.18 g of phthalic anhydride was contained. The reaction mixture was concentrated, 400 ml of hexane was added, the mixture was stirred at 50 ° C. for 2 hours, and after cooling, the insolubles were filtered to collect the catalyst and its decomposition product as a solid. The filtrate contained no catalyst and its decomposition products.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) C07C 35/08 C07C 35/08 35/37 35/37 45/33 45/33 49/403 49/403 A 49/453 49/453 F-term (reference) 4G069 AA10 GA13 4H006 AA02 AC41 AC44 BA20 BA30 BA51 BA83 BE30 FC22 FC36 FE12 4H039 CA60 CA62 CC30

Claims (1)

[Claims] 1. An N-substituted cyclic imide-based catalyst comprising a mixture containing a reaction product obtained by reacting in the presence of an N-substituted cyclic imide-based catalyst and the N-substituted cyclic imide-based catalyst or a decomposition product thereof. Or a method for separating and recovering a decomposition product thereof, wherein the mixture is subjected to crystallization or repulping using a solvent selected from hydrocarbons, chain ethers and water, and the N-substituted cyclic imide-based A method for separating and recovering a catalyst, which recovers the catalyst or a decomposition product thereof as a solid.