JPH11188265A - Method for regenerating imide catalyst and production process using imide catalyst - Google Patents

Abstract

PROBLEM TO BE SOLVED: To easily regenerate an imide catalyst deactivated by use in a reaction. SOLUTION: An imide catalyst of the formula (e.g. N-hydroxyphthalimide) deactivated by use in a reaction is regenerated by treatment with hydroxylamine or an acid. In the formula, R<1> and R<2> are each H, halogen, alkyl, aryl, cycloalkyl or the like, R<1> and R<2> may bond to each other to form a double bond or an arom. or nonarom. ring and (n) is 1-3. The deactivated catalyst includes N-hydroxyphthalimide, at least part of which is changed into phthalimide and/or N-substd. oxyphthalimide by use in oxidation, carboxylation or nitration reaction.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method and an apparatus for regenerating an imide-based catalyst used in an oxidation reaction, a carboxylation reaction, a nitration reaction, etc., a method for producing the imide-based catalyst, and a method using the imide-based catalyst. The present invention relates to a manufacturing process and a manufacturing apparatus for organic compounds.

[0002]

2. Description of the Related Art It is known that imide compounds act as excellent oxidation reaction catalysts. For example, JP-A-8-
38909 discloses that a substrate is oxygen-oxidized in the presence of an oxidation catalyst composed of a specific imide compound to generate a corresponding carboxylic acid, alcohol or ketone. However, the above imide compounds, especially N-
When a hydroxyimide compound is used in the reaction as a catalyst,
As the reaction progresses, the imide-based compound changes to an imide compound in which an oxygen atom adjacent to a nitrogen atom is eliminated, or an N-alkoxyimide compound in which a substrate is bonded to an oxygen atom adjacent to a nitrogen atom. Greatly decreases.
Therefore, even if the catalyst used for the reaction is recycled to the reaction system as it is, desired reaction results cannot be obtained. The imide compound is produced by reacting a corresponding acid anhydride with hydroxylamine.

[0003]

An object of the present invention is to provide a method and an apparatus for easily regenerating a deactivated imide-based catalyst. Another object of the present invention is to provide a simple method for producing an imide-based catalyst. Still another object of the present invention is to provide an efficient and economical organic compound production process and apparatus using an imide-based catalyst.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, when the imide catalyst deactivated by the reaction is treated with hydroxylamine or an acid, the imide catalyst is decomposed. It has been found that the reproduction can be performed efficiently, and the present invention has been completed. That is, the present invention provides the following formula (1)

[0005]

Embedded image (Wherein, R ¹ and R ² are the same or different and represent 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, an acyl group; R ¹
And R ² may combine with each other to form a double bond or an aromatic or non-aromatic ring. n is an integer of 1 to 3) is a method for regenerating the imide-based catalyst from the deactivated catalyst using an imide-based catalyst represented by the following formula:
Provided is a method for regenerating an imide-based catalyst, wherein the deactivated catalyst is treated with hydroxylamine or an acid. In the imide catalyst represented by the formula (1), R ¹ and R ² may combine with each other to form an aromatic or non-aromatic 5- to 12-membered ring. In the reproducing method, the following formula (2)

[0006]

Embedded image [Wherein, R ¹ , R ² and n are the same as above. X represents a hydrogen atom or -OY (Y represents an organic group)], and the deactivated catalyst can be regenerated by treating with hydroxylamine.

[0007]

Embedded image (Wherein R ¹ , R ² , Y and n are the same as above), and the deactivated catalyst containing the compound represented by the formula ( ¹ ) can be regenerated by treating with an acid. The imide-based catalyst regenerating apparatus of the present invention is an apparatus for regenerating the imide-based catalyst from a deactivated catalyst using the imide-based catalyst represented by the formula (1) in the reaction, wherein the deactivated imide-based catalyst is used. A treatment device for treating the catalyst with hydroxylamine or an acid is provided. The present invention further provides a method for producing an imide compound, which comprises reacting a compound represented by the formula (2) with hydroxylamine to produce an imide compound represented by the formula (1), and The compound represented by the formula (3) is treated with an acid to give the compound of the formula (1)
Provided is a method for producing an imide compound which produces the imide compound represented by the formula: The production process of the present invention includes a reaction step of subjecting an organic substrate to a reaction in the presence of the imide-based catalyst represented by the formula (1), a separation step of separating a reaction product generated in the reaction step from a catalyst, The method includes a regeneration step of regenerating the imide-based catalyst by treating the catalyst deactivated in the reaction step with hydroxylamine or an acid, and a recycling step of recycling the regenerated imide-based catalyst to the reaction step. Examples of the reaction include an oxidation reaction in which an organic substrate is oxidized by molecular oxygen, a carboxylation reaction in which an organic substrate is reacted with carbon monoxide and oxygen to cause carboxylation, and a nitration reaction in which an organic substrate is reacted with nitrogen oxide. And other nitration reactions. As an organic substrate, for example,
(A) a compound having a methyl group or a methylene group at a site adjacent to an unsaturated bond, (b) a homo- or heterocyclic compound having a methylene group, (c) a compound having a methine carbon atom,
Examples of the compound include (d) a compound having a methyl group or a methylene group at a position adjacent to an aromatic ring, (e) a compound having a methylene group at a position adjacent to a carbonyl group, and (f) a conjugated compound. In the reaction step, a co-catalyst may be used together with the imide-based catalyst as a catalyst. As the co-catalyst, a compound containing at least one element selected from the group consisting of a group 2A element of the periodic table, a transition metal element and a group 3B element of the periodic table can be used. The present invention provides a reaction apparatus for subjecting an organic substrate to a reaction in the presence of the imide-based catalyst represented by the formula (1), a separation apparatus for separating a reaction product generated in the reaction from a catalyst, Also includes a regenerating apparatus for regenerating the imide-based catalyst by treating the deactivated catalyst with hydroxylamine or an acid, and an apparatus for producing an organic compound having a recycle unit for recycling the regenerated imide-based catalyst to the reactor. It is.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION [Imide-based catalyst] In the imide-based catalyst represented by the above formula (1), halogen atoms among the substituents R ¹ and R ² include 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 a phenyl group, a naphthyl group and the like, and the cycloalkyl group includes a cyclopentyl, cyclohexyl, cyclooctyl group and the like. Alkoxy groups include, for example, methoxy, ethoxy,
Propoxy, isopropoxy, butoxy, isobutoxy, t-butoxy, pentyloxy, hexyloxy groups and the like, preferably containing a lower alkoxy group having about 1 to 10 carbon atoms, preferably about 1 to 6 carbon atoms, particularly about 1 to 4 carbon atoms. It is.

The alkoxycarbonyl group includes, for example, a carbon atom 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 an aromatic or non-aromatic ring. Preferred aromatic or non-aromatic rings are about 5 to 12 membered rings, especially about 6 to 10 membered rings, and may be a heterocyclic ring or a fused heterocyclic ring,
Often it is a hydrocarbon ring. Examples of such a ring include a non-aromatic alicyclic ring (a cycloalkene ring which may have a substituent such as a cyclohexane ring and a cycloalkene which may have a substituent such as a cyclohexene ring). Ring), a non-aromatic bridged ring (eg, a bridged hydrocarbon ring which may have a substituent such as a 5-norbornene ring), a benzene ring, a naphthalene ring or the like. And aromatic rings. The ring is often composed of an aromatic ring.

Preferred imide-based catalysts include compounds represented by the following formula.

[0014]

Embedded image (Wherein, R ^{3 to} R ⁶ are the same or different and are each a hydrogen atom,
It represents an alkyl 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. R ¹ ,
R ² and n are the same as described above. In the substituents R ^{3 to} R ⁶ , the alkyl group includes the same alkyl group as the above-described alkyl group, particularly an alkyl group having about 1 to 6 carbon atoms, and an alkoxy group. Include the same alkoxy group as described above, particularly a lower alkoxy group having about 1 to 4 carbon atoms, and the alkoxycarbonyl group includes the same alkoxycarbonyl group as described above, particularly a lower alkoxy group having about 1 to 4 carbon atoms in the alkoxy moiety. Includes carbonyl groups.
Examples of the acyl group include the same acyl groups as described above, particularly, an acyl group having about 1 to 6 carbon atoms. Examples of the halogen atom include fluorine, chlorine, and bromine atoms. The substituents R ^{3 to} R ⁶ are usually a hydrogen atom, a lower alkyl group having about 1 to 4 carbon atoms, a carboxyl group, a nitro group, or a halogen atom in many cases. In the above formula (1), n is
Usually, it is about 1 to 3, preferably 1 or 2. One or more compounds represented by the formula (1) can be used in the reaction.

The acid anhydride corresponding to the imide compound represented by the formula (1) includes, for example, a saturated or unsaturated aliphatic dicarboxylic anhydride such as succinic anhydride and maleic anhydride, tetrahydrophthalic anhydride, Hexahydrophthalic anhydride (1,2-cyclohexanedicarboxylic anhydride),
1,2,3,4-cyclohexanetetracarboxylic acid
A saturated or unsaturated non-aromatic cyclic polycarboxylic anhydride (alicyclic polycarboxylic anhydride) such as 1,2-anhydride;
Crosslinked cyclic polycarboxylic anhydrides (alicyclic polycarboxylic anhydrides) such as hetic anhydride and hymic anhydride, phthalic anhydride, tetrabromophthalic anhydride, tetrachlorophthalic anhydride, nitrophthalic anhydride, Aromatic polycarboxylic anhydrides such as trimellitic anhydride, methylcyclohexenetricarboxylic anhydride, pyromellitic anhydride, melittic anhydride, 1,8; 4,5-naphthalenetetracarboxylic dianhydride are included. 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. Particularly preferred compounds include N-hydroxyimide compounds derived from alicyclic polycarboxylic anhydrides, especially aromatic polycarboxylic anhydrides, such as N-hydroxyphthalimide.

Such imide compounds have high catalytic activity and promote various reactions even under mild conditions. Such reactions include, for example, oxidation of organic substrates with molecular oxygen, carboxylation of organic substrates with carbon monoxide and oxygen, nitration of organic substrates with nitrogen oxides, and the like. Hereinafter, these reactions will be described.

[Oxidation reaction] In the presence of the imide compound,
By contacting the organic substrate with molecular oxygen, ketones, alcohols, aldehydes,
Oxidation products such as carboxylic acids can be obtained. Organic substrates include a wide range of saturated or unsaturated compounds, such as hydrocarbons (aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons), heterocyclic compounds, alcohols, ethers , Esters, ketones, aldehydes, amines and the like can be used. Preferred substrates include, for example, (a) a compound having a methyl group or a methylene group at a site adjacent to an unsaturated bond, (b) a homo- or heterocyclic compound having a methylene group, (c) a compound having a methine carbon atom, (D) a compound having a methyl group or a methylene group adjacent to an aromatic ring, (e) a compound having a methylene group adjacent to a carbonyl group, and (f) a conjugated compound. (A) The compound having a methylene group at a site adjacent to an unsaturated bond includes an organic compound having a double bond and / or a triple bond. Such compounds include those having 3 to 3 carbon atoms.
About 12 chain unsaturated hydrocarbons, for example, propylene, 1-butene, 2-butene, butadiene, 1-pentene, 2-pentene, isoprene, 1-hexene, 2-hexene, 1,5-hexadiene, 2 , 3-dimethyl-2
-Butene, 3-hexene, 1-heptene, 2-heptene, 1,6-heptadiene, 1-octene, 2-octene, 3-octene, 1,7-octadiene, 2,6-octadiene, 2-methyl-2 -Butene, 1-nonene, 2
-Nonene, decaene, decadiene, dodecaene, dodecadiene, dodecatriene, undecaene, undecadiene, undecatriene and the like.

(B) Examples of the homocyclic compound (b1) having a methylene group include cycloalkanes (cyclopropane, cyclobutane, cyclopentane, cyclopentene, cyclohexane, methylcyclohexane, 1,2-
Dimethylcyclohexane, isopropylcyclohexane, cycloheptane, cyclooctane, C _3-30 cycloalkane such as methyl cyclooctane, cyclononane, cyclodecane, cyclododecane, cyclotridecane, cyclotetradecane, cyclopentadecane, cyclohexadecane, cycloalkyl octadecane, cyclononadecane) , Cycloalkenes (cyclopropene, cyclobutene, cyclopentene, cyclohexene, 1-methyl-1
-Cyclohexene, cycloheptene, cyclooctene,
Cyclononene, Shikurodekaen, C _3-30 cycloalkenes such as cyclododecatriene ene), cycloalkadiene compound (cyclopentadiene, cyclohexadiene, cycloheptadiene, cyclooctadiene, cycloalkyl decadiene,
_C5-30 cycloalkadienes such as cyclododecadienes), cycloalkatrienes, cycloalkatetraenes, and condensed polycyclic aromatic hydrocarbons obtained by condensing a 5- to 8-membered ring (dihydronaphthalene, indene, fluorene) Such)
And the like.

(B) The heterocyclic compound having a methylene group (b2) includes a 5- or 6-membered ring compound having a hetero atom selected from a nitrogen atom, an oxygen atom and a sulfur atom, or a 5- or 6-membered ring compound having a hetero atom. Examples include fused heterocyclic compounds in which a member ring is fused to an aromatic ring, such as dihydrofuran, tetrahydrofuran, pyran, dihydropyran, tetrahydropyran, piperidine, piperazine, pyrrolidine, and xanthene.

(C) The compound having a methine carbon atom (methylidyne group) includes, for example, chain hydrocarbons having tertiary carbon atoms, bridged cyclic hydrocarbons, and the like.
Examples of chain hydrocarbons having a tertiary carbon atom include, for example, isobutane, isopentane, isohexane, 3-methylpentane, 2,3-dimethylbutane, 2-methylhexane, 3-methylhexane, 2,3-dimethyl Pentane, 2,4-dimethylpentane, 2,3,4-trimethylpentane, 3-ethylpentane, 2,3-dimethylhexane, 2,4-dimethylhexane, 3,4-dimethylhexane, 2,5-dimethylhexane , 2-propylhexane, 2-methylheptane, 4-methylheptane, 2
Aliphatic hydrocarbons having about 4 to 10 carbon atoms, such as -ethylheptane, 3-ethylheptane, 2,6-dimethylheptane, 2-methyloctane, 3-metaloctane, 2,7-dimethyloctane, and 2-methylnonane And the like. The bridged cyclic hydrocarbons include bridged cyclic hydrocarbons (eg, bicyclic hydrocarbons such as decalin, hexahydroindane, carane, bornane, norbornene, vinyl norbornene, norbornadiene, norbornane, formyl norbornene, homobledan, and adamantane). , Methyl adamantane, 1,3-dimethyl adamantane, ethyl adamantane, chloro adamantane, adamantanol, adamantanone, methyl adamantanone, dimethyl adamantanone, formyl adamantane, tricyclo [4.
3.1.1 ^2,5 ] tricyclic hydrocarbons such as undecane,
Tetracyclo [4.4.0.1 ^2,5 . [ ^7,10 ] dodecane, etc.), diene dimers or hydrogenated products thereof (dicyclopentane, dicyclohexane, dicyclopentene, dicyclohexadiene, dicyclopentadiene, etc.), terpenes (Limonene, Mentene, Pinane, Pinene, Menthol, Camphor, Bornene, Caryophyllene, Mentone, etc.).

Preferred methine carbon atom (methylidyne group)
Include cross-linked cyclic hydrocarbons having about 7 to 16 carbon atoms (particularly about 6 to 14 carbon atoms) (particularly cross-linked cyclic hydrocarbons such as adamantane or derivatives thereof).

(D) Examples of the compound having a methyl group or a methylene group at a position adjacent to the aromatic ring include aromatic hydrocarbons having an alkyl group (toluene, xylene,
Mesitylene, durene, ethylbenzene, propylbenzene, cumene, methylethylbenzene, methylnaphthalene, dimethylnaphthalene, methylanthracene, dimethylanthracene, trimethylanthracene, dibenzyl, diphenylmethane, triphenylmethane, etc.), and a heterocyclic compound having an alkyl group (methylfuran, Methylpyran, methylchroman, methylpyridine (picoline), dimethylpyridine (lutidine), trimethylpyridine (collidine), ethylpyridine, methylquinoline,
Methylindole, indane, indene, tetralin,
Fluorene). Preferred compounds include those having a methyl or methylene group at the benzyl position.

(E) At the site adjacent to the carbonyl group (active)
Examples of the compound having a methylene group include aldehydes, ketones, carboxylic acids and derivatives thereof. Aldehydes include aliphatic aldehydes (acetaldehyde,
C _2-12 alkyl monoaldehydes such as propionaldehyde, butyraldehyde, isobutyraldehyde, pentylaldehyde, hexylaldehyde, heptylaldehyde, octylaldehyde, nonylaldehyde, decylaldehyde, malonaldehyde, succinaldehyde, adipaldehyde, sebacaldehyde, etc. Aliphatic aldehydes), aromatic aldehydes (benzaldehyde, anisaldehyde, etc.), alicyclic aldehydes (formylcyclohexane, cycloneral, etc.), bridged cyclic ketones (formylnorbornene, formyladamantane, etc.), heterocyclic aldehydes ( Nicotinaldehyde, furfural, etc.).

Examples of the ketones include aliphatic ketones (acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl tert-butyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, 3-hexanone, 2-heptanone. , 3-heptanone, 4-heptanone, 2-octanone, 3-octanone, 4-octanone, 2-nonanone, 2-decanone, etc., cyclic ketones (cyclopentanone, cyclohexanone, methylcyclohexanone, dimethylcyclohexanone, cycloheptanone) , Isophorone, cycloheptanone, cyclooctanone, cyclononanone, cyclodecanone, cyclohexadione, cyclooctadione and other non-aromatic cyclic mono- or polyketones, α-tetralone,
cyclic ketones having an aromatic ring such as β-tetralone and indanone), bridged cyclic ketones (adamantanone, methyladamantanone, dimethyladamantanone,
Mentones), aromatic ketones (acetophenone, propiophenone, etc.), heterocyclic ketones (indene-
1-one, fluoren-9-one, etc.). Examples of the carboxylic acid or a derivative thereof include an aliphatic dicarboxylic acid or a derivative thereof (malonic acid or an ester thereof, succinic acid or an ester thereof, glutaric acid or an ester thereof), and the like.

(F) Conjugated compounds include conjugated dienes,
α, β-unsaturated nitriles, α, β-unsaturated carboxylic acids or derivatives thereof are included. As conjugated dienes,
For example, butadiene, isoprene and the like can be mentioned.
Examples of the α, β-unsaturated nitrile include (meth) acrylonitrile. The α, β-unsaturated carboxylic acid or its derivative includes (meth) acrylic acid, (meth) acrylate, (meth) acrylamide derivative and the like.

These substrates include suitable substituents such as halogen atoms, alkyl groups, alkenyl groups, oxo groups, hydroxyl groups, alkoxy groups, hydroxyalkyl groups, mercapto groups, carboxyl groups, alkoxycarbonyl groups, and cycloalkyl groups. Group, aryl group, amino group,
Substituted amino group, carbamoyl group, nitro group, cyano group,
An acyl group or the like may be substituted.

The oxygen used for oxidizing the substrate may be active oxygen, but it is economically advantageous to use molecular oxygen. The molecular oxygen is not particularly limited, and 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 selected according to the type of the substrate, and is usually 0.5 to 1 mol of the substrate.
Mol or more (for example, 1 mol or more), preferably 1 to 10
It is about 0 mol. In many cases, an excess molar amount of oxygen relative to the substrate is used, and it is particularly advantageous to carry out the reaction under an atmosphere containing molecular oxygen such as air or oxygen.

In the oxidation reaction, the amount of the imide compound to be used can be selected in a wide range, for example, 0.0001 to 1 mol (0.01 to 100 mol%), preferably 0.001 to 1 mol per mol of the substrate. To 0.5 mol, more preferably about 0.01 to 0.3 mol,
It is often about 0.25 mol.

A co-catalyst may be used in the oxidation reaction. Examples of the co-catalyst include metal compounds such as Group 2A elements of the periodic table (magnesium, calcium, strontium, barium, etc.), transition metal elements, and Group 3B elements of the periodic table (boron B,
Including aluminum (Al). The cocatalyst can be used alone or in combination of two or more. Examples of the element of the transition metal include a Group 3A element in the periodic table (for example, lanthanide elements such as lanthanum La, cerium Ce, and samarium Sm, actinoid elements such as actinoid Ac, in addition to scandium Sc and yttrium Y), and a group 4A element. (Titanium Ti, zirconium Zr, hafnium Hf, etc.), group 5A element (vanadium V, niobium Nb, tantalum Ta, etc.), group 6A element (chromium C, etc.)
r, molybdenum Mo, tungsten W, etc.), group 7A element (manganese Mn, technetium Tc, rhenium Re, etc.), group 8 element (iron Fe, ruthenium Ru, osmium Os, cobalt Co, rhodium Rh, iridium Ir,
Nickel Ni, palladium Pd, platinum Pt, etc.), 1B
Group 2 elements (copper Cu, silver Ag, gold Au, etc.), and Group 2B elements (zinc Zn, cadmium Cd, etc.).
Preferred co-catalysts include transition metal elements (for example, lanthanoid elements such as Ce, group 3A elements such as actinoid elements, group 4A elements, group 5A elements, group 6A elements, group 7A elements, group 8A elements, and the like). Group element, group 1B element,
Group 2B element) and Group 3B element.

The co-catalyst may be a simple metal, a hydroxide or the like, but is usually a metal oxide containing the above-mentioned element (including a double oxide, an oxyacid or a salt thereof), and an organic acid salt (for example, Acetate, etc.), an inorganic acid salt, a halide, a coordination compound (complex) containing the metal element, a polyacid (heteropolyacid or isopolyacid) or a salt thereof in many cases.

Examples of ligands forming a complex include alkoxy groups such as OH (hydroxo), methoxy, ethoxy, propoxy and butoxy groups, acyl groups such as acetyl (OAc) and propionyl, methoxycarbonyl (acetato), ethoxycarbonyl and the like. Alkoxycarbonyl group, acetylacetonato (AA), cyclopentadienyl group, halogen atom such as chlorine, bromine, CO, CN, oxygen atom, H ₂ O (aquo), phosphine (eg, triphenylphosphine, etc.) Phosphorus compounds such as triarylphosphine); and nitrogen-containing compounds such as NH ₃ (ammine), NO, NO ₂ (nitro), NO ₃ (nitrat), ethylenediamine, diethylenetriamine, pyridine, and phenanthroline. In the complex or complex salt, the same or different ligands may be coordinated by one kind or two or more kinds. Preferred ligands include, for example, phosphorus compounds such as OH, alkoxy group, acyl group, alkoxycarbonyl group, acetylacetonate, halogen atom, CO, CN, H ₂ O (aquo) and triphenylphosphine;
Nitrogen-containing compounds are included, including H ₃ , NO ₂ , and NO ₃ . The amount of the cocatalyst used can be selected within a range that does not impair the reactivity and the selectivity.
0001 to 1 mol, preferably 0.00005 to 0.7
Mole, more preferably about 0.0001 to 0.5 mole, and often about 0.0002 to 0.1 mole. The ratio of the co-catalyst to the imide-based catalyst represented by the formula (1) can be selected within a range that does not impair the reaction rate or the selectivity.
001 to 10 mol, preferably about 0.003 to 5 mol. The activity of the imide compound may decrease as the amount of the cocatalyst increases. Therefore, in order to maintain a high activity of the catalyst system, the ratio of the cocatalyst is not less than an effective amount and not more than 0.1 mol (for example, 0.001 to 0.1 mol) per 1 mol of the imide catalyst. Mol, preferably about 0.003 to 0.08 mol).

The oxidation reaction is usually performed in an organic solvent inert to the reaction. As the organic solvent, for example, organic carboxylic acids and oxycarboxylic acids such as formic acid, acetic acid and propionic acid, acetonitrile, propionitrile, nitriles such as benzonitrile, formamide, acetamide,
Amides such as dimethylformamide (DMF) and dimethylacetamide, alcohols such as t-butanol and t-amyl alcohol, aliphatic hydrocarbons such as hexane and octane, aromatic hydrocarbons such as benzene, chloroform, dichloromethane, dichloroethane, Halogenated hydrocarbons such as carbon tetrachloride and chlorobenzene; nitro compounds such as nitrobenzene, nitromethane and nitroethane; esters such as ethyl acetate and butyl acetate; ethers such as diethyl ether, diisopropyl ether and dioxane; and mixed solvents thereof. No.
The substrate may be used as a reaction solvent by using an excess amount of the substrate. Organic solvents such as acetic acid and nitriles such as acetonitrile and benzonitrile are often used as the solvent.

When the reaction is carried out in the presence of a protonic acid, the oxidation reaction can be carried out smoothly. This protonic acid may be used as a solvent as described above. Examples of the protic acid include organic acids (organic carboxylic acids such as formic acid, acetic acid, and propionic acid; oxycarboxylic acids such as oxalic acid, citric acid, and tartaric acid; alkyl sulfonic acids such as methanesulfonic acid and ethanesulfonic acid; Acids, arylsulfonic acids such as p-toluenesulfonic acid, etc.), and inorganic acids (eg, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, etc.).

The reaction temperature is, for example, 0 to 300 ° C., preferably 30 to 250 ° C., more preferably 50 to 200 ° C.
C., and usually reacts at about 70 to 150 C. in many cases. The reaction can be performed under normal pressure or under pressure,
When reacting under pressure, usually 1 to 100 atm
(For example, 1.5 to 80 atm), preferably 2 to 70 atm.
tm. 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 1 to 36 hours, more preferably 2 to 24 hours. The reaction can be performed, for example, in the presence of molecular oxygen or in the flow of molecular oxygen by a conventional method such as a batch system, a semi-batch system, or a continuous system.

The reaction produces ketones, alcohols, aldehydes, carboxylic acids and the like corresponding to the substrate. For example, when (a) a compound having a methyl group or a methylene group adjacent to an unsaturated bond is oxidized, a compound in which an oxo group or a hydroxyl group is introduced into the methyl or methylene carbon atom is mainly generated. (B) Oxidation of a homo- or heterocyclic compound having a methylene group produces a compound in which an oxo group or a hydroxyl group has been introduced into the methylene carbon atom, and the ring is oxidatively cleaved to form a corresponding dicarboxylic acid. May be generated. For example,
Oxidation of cyclohexane produces adipic acid or cyclohexanone. (C) When a compound having a methine carbon atom is oxidized, a compound having a hydroxyl group introduced into the methine carbon atom is produced. When (d) a compound having a methyl group or a methylene group at a site adjacent to the aromatic ring is oxidized, a compound having a hydroxyl group or an oxo group introduced into the methyl or methylene carbon atom is produced. Further, when the conjugated dienes of the (f) conjugated compounds are oxidized, the corresponding alkene diols are produced,
Oxidation of (meth) acrylonitrile, (meth) acrylic acid or a derivative thereof produces 3,3-dihydroxypropionitrile, 3,3-dihydroxypropionic acid or a derivative thereof.

After completion of the reaction, the reaction product is subjected to a conventional method,
For example, separation and purification can be easily performed by separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, and column chromatography, or a separation means in which these are combined.

[Carboxylation reaction] The substrate can be carboxylated by contacting the organic substrate with carbon monoxide and oxygen in the presence of the imide compound. Organic substrates include a wide range of saturated or unsaturated compounds, for example,
Hydrocarbons (aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons), heterocyclic compounds, alcohols, ethers, esters, ketones, aldehydes, amines, etc. can be used. . Preferred substrates include, for example, (a) a compound having a methyl group or a methylene group at a site adjacent to the unsaturated bond, (b) a homo- or heterocyclic compound having a methylene group, and (c) a compound having a methine carbon atom. , (D) a compound having a methyl group or a methylene group adjacent to an aromatic ring, and (e) a compound having a methylene group adjacent to a carbonyl group. The carbon monoxide and oxygen may be pure carbon monoxide or oxygen, or may be diluted with the inert gas. In addition,
The oxygen source may be air. The carboxylation reaction is
It can be performed in the presence or absence of a solvent. As the solvent, the solvents exemplified in the above oxidation reaction and the like can be used. Preferred solvents include organic acids (eg, acetic acid,
Propionic acid), halogenated hydrocarbons (eg, dichloroethane, etc.), nitriles (eg, acetonitrile, etc.) and the like. Also in the carboxylation reaction, the cocatalyst exemplified in the above-mentioned oxidation reaction can be used.

The amounts of the imide compound and cocatalyst used are as follows:
This is the same as in the case of the oxidation reaction.

The amount of carbon monoxide to be used can be selected, for example, from the range of 1 mol or more (for example, 1 to 100 mol) with respect to 1 mol of the substrate, and is preferably an excess mol.
It is 1.5 to 100 mol, more preferably about 2 to 30 mol. The amount of oxygen used is, for example, 0.5 mol or more (for example, 0.5 to 100 mol), preferably 0.5 to 30 mol, more preferably 0.5 to 100 mol per mol of the substrate.
It can be selected from a range of about 25 mol. In the case of using an excessive amount of carbon monoxide and oxygen in the continuous reaction,
Carbon monoxide and oxygen can be continuously supplied to the reaction system by circulation or the like for use.

Carbon monoxide (CO) and oxygen (O_Two)
If it is, a wide range such as CO / O _Two(Molar ratio) = 1 /
99-99.99 / 0.01 (for example, 70 / 30-9
9/1) can be selected from the range.
It is advantageous to use a large amount of carbon oxide. CO and O_TwoWith
The ratio is usually CO / O_Two(Molar ratio) = 1 / 99-99
/ 1 (for example, 10/90 to 99/1), preferably 3
0/70 to 98/2, more preferably 50/50 to 9
It is about 5/5, especially about 60/40 to 90/10.

The reaction temperature is, for example, from 0 to 200 ° C., preferably from 10 to 15 ° C., depending on the type of the imide compound or the substrate.
0 ° C. (for example, 10 to 120 ° C.), more preferably 1 ° C.
It can be selected from a range of about 0 to 100 ° C (for example, 10 to 80 ° C). Further, the reaction can be carried out under normal pressure or under pressure. The reaction can be performed in any of a batch system, a semi-batch system, and a continuous system.

By the carboxylation reaction, a compound having a carboxyl group introduced into the substrate is produced. For example,
When the substrates (a) to (e) are subjected to a carboxylation reaction, a carboxyl group can be introduced into a carbon atom of a methyl group or a methylene group or a carbon atom of a methine group. Especially,
Compounds having a methine carbon atom of the substrate (c), for example,
When a bridged cyclic hydrocarbon such as adamantane is carboxylated, a carboxyl group is smoothly introduced into a cyclic methine carbon atom, and a carboxyl group-containing compound such as 1-carboxyadamantane is produced in a high yield. After completion of the reaction, the reaction product is easily separated and purified by conventional separation and purification means, for example, filtration, concentration, distillation, extraction, crystallization, recrystallization, adsorption, column chromatography, and the like, or a combination thereof. Can be separated and purified.

[Nitration reaction] By contacting an organic substrate with nitrogen oxide in the presence of the imide compound,
The substrate can be nitrated. Organic substrates include a wide range of saturated or unsaturated compounds, such as hydrocarbons (aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons), heterocyclic compounds, alcohols, ethers , Esters, ketones, aldehydes, amines and the like can be used. Preferred substrates include, for example, (a) a compound having a methyl group or a methylene group at a site adjacent to an unsaturated bond, (b) a homo- or heterocyclic compound having a methylene group,
Examples include (c) a compound having a methine carbon atom, (d) a compound having a methyl group or a methylene group at a site adjacent to an aromatic ring, and (e) a compound having a methylene group at a site adjacent to a carbonyl group. Nitrogen oxides are of the formula N _x O _y (wherein x is an integer of 1 or 2, y is an integer of 1 to 6)
Can be represented by In the compound represented by the above formula, when x is 1, y is usually an integer of 1 to 3,
When x is 2, y is usually an integer of 1 to 6. Such nitrogen oxides include, for example, N ₂ O, NO, N ₂ O
₃ , NO ₂ , N ₂ O ₄ , N ₂ O ₅ , NO ₃ , N ₂ O _{6 and the} like. These nitrogen oxides can be used alone or in combination of two or more.

Preferred nitrogen oxides include nitrogen oxides (particularly N ₂ O) formed by the reaction of oxygen with at least one nitrogen compound selected from nitrous oxide (N ₂ O) and nitric oxide (NO). ₃ ) or nitrogen oxide, nitrogen dioxide (NO ₂ ) or NO ₂ containing N ₂ O ₃ as a main component
Nitrogen oxides containing as a main component. Nitrogen oxide N ₂ O ₃ can be easily obtained by the reaction of N ₂ O and / or NO with oxygen. More specifically, it can be prepared by introducing nitric oxide and oxygen into the reactor to generate a blue liquid N ₂ O ₃ . Therefore, the nitration reaction may be performed by introducing N ₂ O and / or NO and oxygen into the reaction system without previously generating N ₂ O ₃ . In addition, oxygen may be pure oxygen, and inert gas (carbon dioxide, nitrogen, helium, argon, etc.)
May be used after dilution. Further, the oxygen source may be air.

The amount of the imide compound used is the same as in the case of the oxidation reaction. The amount of nitrogen oxide used can be selected according to the amount of nitro group introduced. For example, it can be selected from the range of about 1 to 50 mol, preferably about 1.5 to 30 mol, per mol of the substrate. It is often about 25 mol. The nitration reaction can be performed in the presence or absence of a solvent. As the solvent, various solvents inert to the reaction, for example, the solvents exemplified as the solvent used in the oxidation reaction can be used. The reaction temperature is, for example, 0 ° C. to 150 ° C., preferably 25 to 12 ° C., depending on the type of the substrate.
It can be selected from the range of 5 ° C, more preferably about 30 to 100 ° C. The method of the present invention can be used at relatively low temperatures, e.g.
It proceeds smoothly even at 0-60 ° C. The reaction pressure may be usually normal pressure or under pressure. The reaction can be performed in any of a batch system, a semi-batch system, and a continuous system.

By the nitration reaction, a compound having a nitro group introduced into the substrate is produced. For example, when the substrates (a) to (e) are subjected to a nitration reaction, a nitro group can be introduced into a carbon atom of a methyl group or a methylene group or a carbon atom of a methine group. In particular, when a compound having a methine carbon atom of the substrate (c), for example, a bridged cyclic hydrocarbon such as adamantane is carboxylated, a carboxyl group is smoothly introduced into the cyclic methine carbon atom.
Carboxyl group-containing compounds such as nitroadamantane are produced in high yields. After completion of the reaction, the reaction product is subjected to conventional separation and purification means, for example, filtration, concentration, distillation, extraction,
Separation and purification can be easily performed by separation and purification means such as crystallization, recrystallization, adsorption, and column chromatography, or a combination thereof.

As described above, the imide compound is oxidized,
It is useful as a reaction catalyst for carboxylation and nitration. However, when the imide compound is used as a catalyst, during the reaction, for example, the compound represented by the formula (2) [for example, a (N-unsubstituted) phthalimide compound and an N-substituted oxyphthalimide compound, due to a radical mechanism or the like. ], A compound represented by the formula (3) (for example, N-
(Substituted oxyphthalimide compounds), ring-opened imide compounds, polycarboxylic acids corresponding to the imide compounds and their acid anhydrides (eg, phthalic acid, phthalic anhydride, etc.), and the catalytic activity is greatly reduced. In the formulas (2) and (3), Y representing an organic group corresponds to not only a residue obtained by removing a proton from an organic substrate used as a reaction raw material but also a residue obtained by cleavage with a radical. The catalyst with reduced catalytic activity can be regenerated as follows.

[Method and apparatus for regenerating imide-based catalyst]
In the present invention, in order to regenerate the deactivated catalyst (hereinafter sometimes simply referred to as “deactivated catalyst”), particularly the imide catalyst deactivated by subjecting the imide catalyst to a reaction, the deactivated catalyst is used. Treat with hydroxylamine or acid.
Further, the regenerating device of the present invention includes a treatment device for treating the deactivated catalyst with hydroxylamine or an acid. The regeneration method of the present invention is applied to a deactivated catalyst in which at least a part of the imide-based catalyst has been changed to another compound, in particular, a compound represented by the formula (2) or (3). When the deactivated catalyst contains the compound represented by the formula (2), a method of treating with hydroxylamine is advantageous. When the deactivated catalyst contains the compound represented by the formula (3), The method of treating with an acid is advantageous.

In this method, the reaction mixture containing the deactivated catalyst may be subjected to catalyst regeneration as it is, and the desired product, by-products, solvent, insolubles, and the like are separated from the reaction mixture by conventional separation means, For example, after separation by filtration, concentration, distillation, extraction, crystallization, or the like, the catalyst mixture (catalyst mixture) may be subjected to catalyst regeneration.

The regeneration treatment of the deactivated catalyst can be carried out, for example, by mixing the deactivated catalyst with hydroxylamine or an acid in a suitable solvent and reacting them. A treatment apparatus for catalyst regeneration includes, for example, a reactor for reacting a deactivated catalyst with hydroxylamine or an acid, and supply means for supplying the components to the reactor (eg, a charging line, a charging pump, etc.). Mixing means (for example, a stirrer, etc.) for mixing the above components, and, if necessary, reaction temperature adjusting means for adjusting the reaction temperature;
It can be constituted by a pH adjusting means for adjusting H, a discharging means for discharging the reaction mixture from the reactor, and the like.

As the solvent, water or an organic solvent can be used. Examples of the organic solvent include alcohols such as methanol, ethanol and isopropanol; aromatic hydrocarbons such as benzene and toluene; halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane and 1,2-dichloroethane; pentane and hexane , Heptane, octane and other aliphatic hydrocarbons; cyclohexane, methylcyclohexane and other alicyclic hydrocarbons;
Esters such as ethyl acetate and butyl acetate; ethers such as diethyl ether, dioxane, and tetrahydrofuran; aprotic polar solvents such as acetonitrile, N, N-dimethylformamide, and dimethyl sulfoxide; The solvents can be used alone or in combination of two or more. Preferred solvents include water and mixed solvents of water and organic solvents.

As hydroxylamine, free hydroxylamine may be used, or hydroxylamine released by reacting a salt of hydroxylamine with a base in the reaction system may be used. The hydroxylamine salts include inorganic acid salts such as hydrochloride, sulfate, nitrate and phosphate; and organic acid salts such as acetate. Examples of the base include hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide; hydroxides of alkaline earth metals such as magnesium hydroxide and calcium hydroxide; carbonates of alkali metals such as sodium carbonate; Alkaline earth metal carbonates such as magnesium; and alkali metal bicarbonates such as sodium bicarbonate. When hydroxylamine is used for the regeneration treatment of the deactivated catalyst, the amount of the hydroxylamine used is usually 1 mol per 1 mol of the total amount of the compounds of the formulas (2) and (3) contained in the deactivated catalyst. As described above, it is preferably about 1 to 5 mol, more preferably about 1 to 2 mol, and 1 to 1.5 mol (particularly 1.
(2 to 1.5 mol) in many cases. If necessary, hydroxylamine may be used as a regeneration solvent.

The acid used for the regeneration treatment of the deactivated catalyst includes:
Inorganic acids such as hydrogen fluoride, hydrogen chloride, hydrogen bromide, hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid; methanesulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfone Examples thereof include sulfonic acids such as acids. Preferably, the acid is anhydrous. The amount of the acid used is, for example, 1 mol per 1 mol of the compound of the formula (3).
About 5 mol, preferably about 1 to 3 mol, and more preferably about 1 to 2 mol. Acids may be used as regeneration solvents. The treatment of the deactivated catalyst with an acid may be carried out in the presence of water, and the amount of water to be used is generally about 0 to 100 mol, preferably 0, mol per 1 mol of the compound of the formula (3).
You may select from the range of about 50 mol. The regeneration treatment with an acid is advantageously performed in the absence of water.

Treatment temperature with hydroxylamine or acid (reaction temperature between deactivated catalyst and hydroxylamine or acid)
Is, for example, about 0 to 100 ° C., preferably 5 to 50 ° C.
It is about. The regeneration treatment of the deactivated catalyst is performed at room temperature (for example, 1
(About 0 to 40 ° C.) in many cases. After treatment with hydroxylamine or acid, conventional separation and purification means, for example,
The regenerated imide catalyst can be separated and purified by filtration, concentration, extraction, crystallization, recrystallization and the like. The imide catalyst can be easily separated and purified by crystallization or recrystallization under acidic conditions (for example, pH = about 2 to 6). According to the regenerating method and the regenerating apparatus, the imide catalyst represented by the formula (1) can be regenerated at a high yield, and the regenerated imide catalyst can be reused in the reaction system.

[Production method of imide compound] In the production method of the imide compound of the present invention, the compound represented by the formula (2) is reacted with hydroxylamine or represented by the formula (3). The compound is treated with an acid. Equation (2)
Alternatively, when the compound represented by formula (3) is used as a catalyst for a reaction such as oxidation, carboxylation, or nitration, the imide compound represented by formula (1) is used as described above. Obtained as a modified product of the compound. The reaction between the compound represented by the formula (2) and hydroxylamine, and the treatment of the compound represented by the formula (3) with an acid include:
It can be carried out according to the method described for the method for regenerating the deactivated catalyst. After the reaction, the imide compound represented by the formula (1) can be separated and purified by a conventional separation and purification means, for example, filtration, concentration, extraction, crystallization, recrystallization, or a combination thereof.

[Production Process and Apparatus for Organic Compound] The production process of the present invention comprises a reaction step of an organic substrate in the presence of a catalyst, a separation step of a target compound and a catalyst component from a reaction mixture, and a separation step. It includes a step of regenerating the separated catalyst component and a step of recycling the regenerated catalyst component to the reaction system. Further, the production apparatus of the present invention includes a reaction apparatus, a separation apparatus, a regenerating apparatus, and a recycling unit. FIG. 1 is a schematic process diagram showing an example of the manufacturing process of the present invention.

In the reaction step, the organic substrate supplied from the line 1 is subjected to a reaction in the presence of the imide catalyst. The imide catalyst is regenerated in the regeneration step and
May be used, and if necessary, an unused new catalyst may be used, or a regenerated catalyst and an unused new catalyst may be used in combination. Examples of the type of reaction include the above-described oxidation reaction, carboxylation reaction, nitration reaction, and the like, as described above. The reaction apparatus used in the reaction step includes, for example, a reactor for reacting an organic substrate, supply means for supplying a reaction component and a catalyst to the reactor (for example, a charging line, a charging pump, and the like), and a reaction component and a catalyst. Mixing means for mixing (eg,
A stirrer, etc.), and if necessary, a reaction temperature adjusting means for adjusting the reaction temperature, a discharge means for discharging the reaction mixture from the reactor, and the like. In the separation process,
The reaction product and catalyst are separated from the reaction mixture supplied by line 2 from the reaction step. Separation of the reaction product from the catalyst can be performed by the above-described separation / purification means or separation apparatus (for example, a filtration apparatus, a concentration apparatus, a distillation apparatus, an extraction apparatus, an adsorption apparatus, a column chromatograph, etc.). The separated reaction product is recovered through a line 4 and further purified if necessary. Part or all of the separated catalyst is subjected to a regeneration step through a line 3 and is regenerated. When a part of the catalyst used in the reaction is supplied to the regeneration step, the remaining catalyst can be recycled to the reaction step without regeneration.

In the reproducing step, the above-mentioned reproducing apparatus is used,
The deactivated catalyst supplied from the separation step through line 3 is
In the same manner as described above, the catalyst can be regenerated by treating with hydroxylamine or an acid. In the recycling step, the regenerated catalyst recovered from the regeneration step through the line 5 is recycled to the reaction step. The regenerated catalyst can be recycled by a conventional method, for example, as it is, or by dissolving or suspending it in a suitable solvent and supplying it to the reaction system. Recycling means, for example,
Pumps, belt conveyors, etc. can be used. The operation in each of the above steps may be performed by any of a continuous system and a batch system.

[0059]

According to the regeneration method and the regeneration apparatus of the present invention, the deactivated imide-based catalyst can be easily regenerated. According to the production method of the present invention, an imide-based catalyst can be produced in a high yield by a simple means. Further, in the manufacturing process and the manufacturing apparatus of the present invention,
In a method for producing an organic compound using an imide-based catalyst, the target compound can be produced efficiently and economically.

[0060]

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 Hydroxylamine sulfate 2NH ₂ OH.
H ₂ SO ₄ (1.03 g, 6.3 mmol) and water 1
After dissolving with 0 ml, 5% aqueous sodium hydroxide solution 10
ml was added to liberate the hydroxylamine. To the obtained aqueous solution, a powdery phthalimide (1.4
(7 g, 10 mmol) was added slowly and stirred at room temperature for 1 hour. Dilute hydrochloric acid was added to the mixture to adjust the pH to about 3, and a crystalline precipitate was formed. After stirring for an additional hour, the mixture was left overnight. The generated crystals are filtered,
By washing with 5% diluted acetic acid, N-hydroxyphthalimide (1.28 g, yield 78%) was obtained.

Example 2 Hydroxylamine sulfate 2NH ₂ OH.
H ₂ SO ₄ (1.03 g, 6.3 mmol) and water 1
After dissolving with 0 ml, 5% aqueous sodium hydroxide solution 10
ml was added to liberate the hydroxylamine. To the obtained aqueous solution, powdery N-cyclohexyloxyphthalimide (2.45 g, 10 mmol) was slowly added with stirring, and the mixture was stirred at room temperature for 1 hour. Dilute hydrochloric acid was added to the mixture to adjust the pH to about 3, and a crystalline precipitate was formed. After stirring for an additional hour, the mixture was left overnight. The generated crystals were filtered and washed with 5% diluted acetic acid to obtain N-hydroxyphthalimide (1.08 g, yield 66%).

Example 3 N-cyclohexyloxyphthalimide (2.45 g, 10 mmol) was placed in a flask and dissolved in benzene. To this solution was added 7 g of ethanol containing 10% by weight of hydrochloric acid, and the mixture was refluxed for 6 hours. The precipitate formed is filtered,
By washing with benzene, N-hydroxyphthalimide (1.06 g, yield 65%) was obtained.

Example 4 In a flask, N-hydroxyphthalimide (1.63) was added.
g, 10 mmol), cyclohexane (8.41 g, 1
00 mmol), cobalt acetylacetonate Co
(AA) ₂ (0.015 g, 0.05 mmol) and 250 ml of acetic acid were charged and stirred at 100 ° C. for 6 hours under an oxygen atmosphere. When the products in the reaction mixture were analyzed by gas chromatography and high performance liquid chromatography, cyclohexanone (yield 13%) and adipic acid (yield 11%) were obtained at a cyclohexane conversion of 40%. Of the N-hydroxyphthalimide used, 42
% Remain as is, 24% is in phthalimide, 14%
Was changed to N-cyclohexyloxyphthalimide. The reaction mixture was concentrated by a concentrator to remove acetic acid, and 10 g of a 5% by weight aqueous hydroxylamine solution (15 mmol of hydroxylamine) was added thereto, followed by stirring at room temperature for 6 hours. The reaction mixture was analyzed by high performance liquid chromatography to find that it contained 1.16 g (7.1 mmol) of N-hydroxyphthalimide.
The regeneration rate of N-hydroxyphthalimide (the ratio of regenerated N-hydroxyphthalimide to altered N-hydroxyphthalimide) was 50%. After the mixture was neutralized, water was distilled off, and N-hydroxyphthalimide was separated by silica gel coloro chromatography (hexane / ethyl acetate = 5/1).

[Brief description of the drawings]

FIG. 1 is a schematic process diagram showing an example of a manufacturing process of the present invention.

Claims (13)

[Claims] [Claim 1] The following formula (1) (Wherein, R ¹ and R ² are the same or different and represent 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, an acyl group; R ¹
And R ² may combine with each other to form a double bond or an aromatic or non-aromatic ring. n is an integer of 1 to 3) is a method for regenerating the imide-based catalyst from the deactivated catalyst using an imide-based catalyst represented by the following formula:
A method for regenerating an imide-based catalyst, wherein the deactivated catalyst is treated with hydroxylamine or an acid. 2. The imide catalyst according to claim ^1, wherein R ¹ and R ² in the formula (1) are bonded to each other to form an aromatic or non-aromatic 5- to 12-membered ring. A method for regenerating an imide-based catalyst. 3. The following formula (2): [Wherein, R ¹ and R ² are the same or different and represent 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, an acyl group; R ¹
And R ² may combine with each other to form a double bond or an aromatic or non-aromatic ring. X represents a hydrogen atom or -OY (Y represents an organic group), and n represents an integer of 1 to 3], and the deactivated catalyst containing the compound represented by the formula (1) is treated with hydroxylamine. A method for regenerating an imide-based catalyst. 4. The following formula (3): (Wherein, R ¹ and R ² are the same or different and represent 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, an acyl group; R ¹
And R ² may combine with each other to form a double bond or an aromatic or non-aromatic ring. 2. The method for regenerating an imide catalyst according to claim 1, wherein the deactivated catalyst containing the compound represented by Y represents an organic group, and n represents an integer of 1 to 3). 5. The following formula (1) (Wherein, R ¹ and R ² are the same or different and represent 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, an acyl group; R ¹
And R ² may combine with each other to form a double bond or an aromatic or non-aromatic ring. n is an integer of 1 to 3) for regenerating the imide-based catalyst from the deactivated catalyst by using an imide-based catalyst represented by the following formula for the reaction, wherein the deactivated catalyst is hydroxylamine or An imide-based catalyst regeneration device including a treatment device for treating with an acid. 6. The following formula (2): [Wherein, R ¹ and R ² are the same or different and represent 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, an acyl group; R ¹
And R ² may combine with each other to form a double bond or an aromatic or non-aromatic ring. X represents a hydrogen atom or -OY (Y represents an organic group), and n represents an integer of 1 to 3], and a hydroxylamine is reacted with the compound represented by the following formula (1). ] (Wherein R ¹ , R ² and n are the same as those described above). 7. The following formula (3): (Wherein, R ¹ and R ² are the same or different and represent 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, an acyl group; R ¹
And R ² may combine with each other to form a double bond or an aromatic or non-aromatic ring. Y represents an organic group, n represents an integer of 1 to 3), and the compound represented by the following formula (1) is treated with an acid. (Wherein R ¹ , R ² and n are the same as those described above). 8. The following formula (1): (Wherein, R ¹ and R ² are the same or different and represent 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, an acyl group; R ¹
And R ² may combine with each other to form a double bond or an aromatic or non-aromatic ring. n represents an integer of 1 to 3) in the presence of an imide-based catalyst represented by the following formula: a reaction step of subjecting the organic substrate to a reaction, a separation step of separating a reaction product generated in the reaction step from the catalyst, and a reaction step. A process for producing an organic compound, comprising: a regeneration step of regenerating the imide catalyst by treating the deactivated catalyst with hydroxylamine or an acid; and a recycling step of recycling the regenerated imide catalyst to a reaction step. 9. The reaction includes an oxidation reaction in which the organic substrate is oxidized by molecular oxygen, a carboxylation reaction in which the organic substrate is carboxylated by reacting the organic substrate with carbon monoxide and oxygen, and a reaction in which the organic substrate is reacted with nitrogen oxide. 9. The production process according to claim 8, which is a reaction selected from nitration reactions in which nitration occurs. 10. An organic substrate comprising: (a) a compound having a methyl group or a methylene group at a site adjacent to an unsaturated bond, (b)
Allo- or heterocyclic compounds having a methylene group, (c) compounds having a methine carbon atom, (d) compounds having a methyl group or a methylene group adjacent to an aromatic ring, and (e) compounds adjacent to a carbonyl group. 9. The production process according to claim 8, wherein the production process is one selected from a compound having a methylene group and (f) a conjugated compound. 11. The production process according to claim 8, wherein a co-catalyst is used together with an imide-based catalyst as a catalyst in the reaction step. 12. The production process according to claim 11, wherein the cocatalyst is a compound containing at least one element selected from the group consisting of a group 2A element of the periodic table, a transition metal element, and a group 3B element of the periodic table. 13. The following formula (1): (Wherein, R ¹ and R ² are the same or different and represent 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, an acyl group; R ¹
And R ² may combine with each other to form a double bond or an aromatic or non-aromatic ring. n represents an integer of 1 to 3), a reaction device for subjecting an organic substrate to a reaction in the presence of an imide-based catalyst represented by the following formula, a separation device for separating a reaction product generated in the reaction from a catalyst, A regenerating apparatus for regenerating the imide-based catalyst by treating the deactivated catalyst with hydroxylamine or an acid, and an apparatus for producing an organic compound having a recycle unit for recycling the regenerated imide-based catalyst to the reactor.