JPH11279112A - Production of aromatic dicarboxylic acid - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for easily and efficiently producing the subject compound useful as a raw material for a synthetic resin, e.g. polyester resin in a moderate condition, by contacting a specific aromatic condensed cyclic compound with a molecular oxygen in the presence of an oxidation catalyst comprising a specific imide compound. SOLUTION: This compound (e.g. naphthalic acid) of formula III is obtained by contacting (B) an aromatic condensed cyclic compound (pref., acenaphthene) of formula II (R3 to R8 are each H or the like; and (m) is 0 or 1)with (C) an molecular oxygen in the presence of (A) an oxidation catalyst comprising an imide compound (e.g. N-hydroxyphthalimide) of formula I (R<1> and R<2> are each H or the like; X is oxygen or the like; and (n) is 1 to 3) pref. in the proportion of about 0.05 to 0.25 mol. of the component A and about 4 to 100 mol. of the component C based on 1 mol. of the component B, ordinarily in an inactive organic solvent e.g. acetic acid, pref. at 50 to 200 deg.C, under about 1 to 50 atmospheric condition, pref. for about 2 to 24 hrs.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a dicarboxylic acid having an aromatic fused ring.

[0002]

2. Description of the Related Art A dicarboxylic acid having an aromatic fused ring,
For example, as a method for producing naphthalic acid, a method for oxidizing a methylene group of acenaphthene is known. For example,
Beilstein EIV 9, p. 3534 (Karischin,
Fedorenko, Z. prikl. Chim. 29 [1956] 966), Berichte der Deutschen Hemichen Gesellschaft 25
Vol. 652, 1895 (Berichte der Deutschen C
hemischen Gesellschaft 25,652 (1895)), U.S. Pat.
No. 379,302 discloses a method for treating acenaphthene with chromic acid.
EII9, p. 651 (Casares, Ranedo, An. Soc. Espa
n. 20,524; C. 1924 I, 319) discloses a method of treating acenaphthene with hydrogen peroxide and permanganic acid. However, these methods require careful handling and use a large amount of chromic acid or permanganic acid, which is complicated in post-treatment.

In recent years, various studies have been made on mild oxidation reactions that can be replaced with chromic acid oxidation, permanganic acid oxidation, etc. as methylene group oxidation reactions. For example, Japanese Patent Application Laid-Open No. 9-3
No. 27626 discloses that adipic acid is produced by oxidation of cyclohexane in the presence of N-hydroxyphthalimide (catalyst) and a transition metal such as cobalt (cocatalyst). In addition, regarding the oxidation of an aromatic compound having a cyclic methylene, it is disclosed that fluorene is oxidized to generate fluorenone which is a ketone body. However, there is no mention of the production of aromatic dicarboxylic acids.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a method for easily and efficiently producing an aromatic carboxylic acid by oxygen oxidation. Another object of the present invention is to provide a method capable of oxidizing an aromatic fused ring compound under mild conditions.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that in an oxidation reaction using a catalyst composed of N-hydroxyphthalimide, a specific aromatic condensed ring compound is used. It has been found that when is used as a substrate, an aromatic dicarboxylic acid is efficiently produced, and the present invention has been completed.

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

[0007]

Embedded image (Wherein R ¹ and R ² are the same or different and each 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 an oxygen atom or a hydroxyl group, and n represents an integer of 1 to 3. ) In the presence of an oxidation catalyst composed of an imide compound represented by
The following equation (2)

[0008]

Embedded image(Where R^Three~ R⁸Are the same or different and are a hydrogen atom,
Halogen atom, alkyl group, aryl group, cycloalkyl
A hydroxyl group, an alkoxy group, ^Three~ R
⁸At least one pair of groups adjacent to each other is aromatic
It may form a ring. m represents 0 or 1. )
Aromatic fused ring compound (hereinafter referred to as compound (2)
) Is contacted with molecular oxygen to obtain the following formula (3)

[0009]

Embedded image (Wherein, R ^{3 to} R ⁸ are the same as above) to produce an aromatic dicarboxylic acid represented by the formula: The compound (2) may be composed of acenaphthene, acenathrene, acephenanthrene or cholanthrene. The oxidation catalyst may further include a promoter.

The method for oxidizing the compound (2) of the present invention can be carried out in the presence of an oxidation catalyst composed of the above imide compound and molecular oxygen. In the present specification, the term "carboxylic acid" is not limited to a compound having a free carboxyl group, but is substantially equivalent to a carboxylic acid, such as a salt generated under reaction conditions, an ester or an acid anhydride. It is used to include carboxylic acid derivatives.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION [Oxidation catalyst] In the imide compound represented by the above formula (1) constituting the oxidation catalyst used in the present invention, halogen atoms represented by R ¹ and R ² include iodine, It contains bromine, chlorine and fluorine atoms, and the alkyl group includes a C _1-10 alkyl group. The aryl group includes a phenyl group and the like, and the cycloalkyl group includes a C _1-10 cycloalkyl group. The alkoxy group includes a C _1-10 alkoxy group. The alkoxycarbonyl group includes a C _1-10 alkoxycarbonyl group, and the acyl group includes a C _1-6 acyl group.

The aromatic or non-aromatic ring formed by R ¹ and R ² bonded to each other includes a ring having about 5 to 12 members (such as a hydrocarbon ring, a heterocycle or a fused heterocycle). included.

Preferred imide compounds include the following formula (1)
Compounds represented by a) to (1f) are included.

[0014]

Embedded image(Where R⁹~ R¹²Are the same or different and are a hydrogen atom,
Halogen atom, alkyl group, hydroxyl group, alkoxy
Group, carboxyl group, alkoxycarbonyl group, reed
A nitro group, a nitro group, a cyano group, or an amino group. X is oxygen
Indicates an atom or a hydroxyl group. With the nitrogen atom "N"
The bond with “X” indicates a single bond or a double bond. R¹, R
^TwoAnd n are the same as above. ) R⁹~ R¹²A halogen atom, an alkyl group, or a hydride represented by
Roxyl group, alkoxy group, alkoxycarbonyl group,
As the acyl group, R 1 in the above formula (1)¹And R ^TwoAbout
And the same groups as those exemplified above. n is 1 to 3
Indicate an integer, preferably 1 or 2. Expression (1)
Can be used alone or in combination of two or more.
You.

Preferred imide compounds include, for example,
N-hydroxysuccinimide, N-hydroxymaleimide, N-hydroxyhexahydrophthalimide, N, N-dihydroxycyclohexanetetracarboxylic imide, N-hydroxyphthalimide, N-hydroxytetrabromophthalimide, N-hydroxyphthalimide -Hydroxyhetimide, N-hydroxyhymic imide, N
-Hydroxytrimellitic imide, N, N-dihydroxypyromellitic imide, N, N-dihydroxynaphthalenetetracarboxylic imide and the like.

The amount of the imide compound to be used per 1 mol of the compound (2) is, for example, 0.001 to 1 mol, preferably 0.01 to 0.5 mol, more preferably 0.05 to 0.5 mol.
It is about 0.30 mol, especially about 0.05 to 0.25 mol. The oxidation catalyst may include a cocatalyst, if necessary. As the co-catalyst, for example, groups 2A to 7A of the periodic table,
Compounds containing Group 8 and 1B-3B elements, preferably
4A group elements (titanium Ti, zirconium Zr, etc.), 5
Group A element (vanadium V, niobium Nb, etc.), group 6A element (chromium Co, molybdenum Mo, tungsten W, etc.), group 7A element (manganese Mn, technetium Tc,
Group 8 elements (iron Fe, ruthenium R, etc.)
u, osmium Os, cobalt Co, rhodium Rh, iridium Ir, nickel Ni, palladium Pd, platinum P
t) and a metal compound containing at least one element belonging to Group 1B elements (such as copper Cu).

Examples of the metal compound include simple metals, metal hydroxides, metal oxides (complex oxides or oxyacid salts), metal organic acid salts, metal inorganic acid salts, metal halides, and coordination compounds containing metal elements. (Complex), heteropoly acid (especially isopoly acid) or a salt thereof. Examples of the ligand forming the complex include an OH (hydroxo) group, an alkoxy group (e.g., methoxy, ethoxy, propoxy, butoxy group), an acyl group (e.g., acetyl, propionyl group), and an alkoxycarbonyl group (e.g., methoxycarbonyl (acetato)). , An ethoxycarbonyl group), an AA (acetylacetonato) group, a cyclopentadienyl group, a halogen atom (such as chlorine and bromine), CO, CN, an oxygen atom, a phosphorus compound, and a nitrogen-containing compound. These ligands can be used alone or in combination of two or more.

Preferred co-catalysts include, for example, acetyl
Ruacetonato complex (TiO (AA) _Two, ZrO (AA)
_Two, VO (AA)_Two, Mn (AA)_Two, Co (AA)_Two
Cyano complexes such as hexacyanomanganate (I) salt,
Xacyanoferrate (II), carbonyl complex (Fe
(CO)_Five, Fe_Two(CO)₉, Fe_Three(CO)₁₂What
), Cyclopentadienyl complexes (biscyclopentadi
Enenyl manganese (II), biscyclopentadienyl iron
(II)), thiocyanato complexes (manganese thiocyanate)
, Iron thiocyanate, cobalt thiocyanate, etc.)
Cetyl complexes (titanyl acetate, zirconium acetate,
Ngan, cobalt acetate, iron acetate, copper acetate, vanadyl acetate
Etc.). These cocatalysts may be used alone or in combination.
These can be used in combination.

The amount of the cocatalyst used per mole of the imide compound is, for example, 0.001 to 0.1 mol, preferably 0.005 to 0.08 mol, more preferably 0.01 to 0.1 mol.
About 0.07 mol. The amount of the cocatalyst to be used per 1 mol of the compound (2) is, for example, from 0.0001 to
It is about 0.01 mol, preferably about 0.0005 to 0.008 mol, and more preferably about 0.001 to 0.007 mol.

[Compound (2)] The compound (2) represented by the above formula (2) is selected from aromatic ortho-condensed rings and ortho-and peri-condensed rings.
Methylene groups are directly bonded to adjacent aromatic rings to form a 5- or 6-membered cyclic methylene. In the formula (2), m represents 0 or 1, and preferably represents 0 as shown in the following formula.

[0021]

Embedded image (Wherein, R ^{3 to} R ⁸ are the same as described above) In Formula (2), the halogen atoms represented by R ^{3 to} R ⁸ include iodine, bromine, chlorine, and fluorine atoms. Examples of the alkyl group include a linear or branched C _1-10 alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, t-butyl, pentyl, hexyl, and octyl groups. included.

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,
It includes C _1-10 (preferably C _1-6 , especially C _1-4 ) lower alkoxy groups such as propoxy, isopropoxy, butoxy, isobutoxy, t-butoxy and hexyloxy groups.

R^Three~ R⁸Of which are less adjacent to each other
Examples of the aromatic ring formed by a pair of groups include
Benzene ring, naphthalene ring, anthracene ring, phenanthate
1 to 6 6-membered hydrocarbons such as a
Preferably 1 to 3, especially 1 to 2) fused aromatic rings
No. These aromatic rings have two or more rings
Adjacent orthocondensation or orthoandperi condensation
Is also good. A naphthalene skeleton represented by the formula (2);
Examples of condensed rings formed together with an aromatic ring include
For example, phenanthrene ring, anthracene ring, pyrene ring,
Lysene ring, naphthacene ring, picene ring, pentaphene ring,
Examples include a pentacene ring and a coronene ring. these,
The aromatic ring fused to the naphthalene skeleton has the formula
R in (2) ^Three~ R⁸A halogen atom or an alkyl represented by
Group, aryl group, cycloalkyl group, hydroxyl group,
The alkoxy group may be substituted. Preferred compounds
As (2), for example, acenaphthene, acenatre
, Acephenanthrene, collanthrene, etc.
And these groups may have the substituents.

[Oxidation reaction] The oxygen used for oxidizing the compound (2) may be active oxygen, but it is economically advantageous to use molecular oxygen. As the molecular oxygen, pure oxygen may be used, oxygen diluted with an inert gas such as nitrogen, helium, argon, or carbon dioxide may be used, or air may be used. The amount of oxygen to be used is generally 2 mol or more (for example, 4 mol or more), preferably 2 to 200 mol, more preferably about 4 to 100 mol, per 1 mol of compound (2). 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.

The oxidation method of the present invention is usually carried out in an organic solvent inert to the reaction. As the organic solvent, for example,
Organic carboxylic acids (formic acid, acetic acid, propionic acid, etc.), nitriles (acetonitrile, benzonitrile, etc.), amides (dimethylformamide, etc.), alcohols (t-butanol, etc.), aliphatic hydrocarbons, aromatic hydrocarbons ( Benzene, etc., halogenated hydrocarbons (chloroform, trifluoromethylbenzene, etc.), nitro compounds, esters (ethyl acetate, etc.), ethers, and mixed solvents thereof. As the solvent, an organic acid solvent, a nitrile, or the like is often used.

In the reaction, a protonic acid may be used in combination, if necessary. In the presence of a protonic acid, the reaction proceeds more smoothly. Protic acids may be used as solvents as described above. Organic acids (formic acid, acetic acid,
Organic carboxylic acids such as propionic acid; oxycarboxylic acids such as oxalic acid, citric acid and acetic acid; methanesulfonic acid;
Alkylsulfonic acids such as ethanesulfonic acid; arylsulfonic acids such as benzenesulfonic acid and p-toluenesulfonic acid; and inorganic acids (hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, etc.).

The reaction temperature is usually about 0 to 300 ° C. (for example, 30 to 250 ° C.), preferably about 50 to 200 ° C. (for example, 70 to 150 ° C.). The reaction can be carried out under normal pressure or under pressure, for example, often at about 1 to 50 atm. The reaction time is, for example, about 30 minutes to 48 hours, preferably about 2 to 24 hours, depending on the reaction temperature and pressure. The reaction can be carried out by a conventional method such as a batch system, a semi-batch system, or a continuous system in the presence of molecular oxygen or in the flow of molecular oxygen.

[Aromatic dicarboxylic acid] By such an oxidation reaction, the aromatic dicarboxylic acid represented by the above formula (3) is efficiently produced. In addition, the aromatic dicarboxylic acid may be a salt, an ester, or an intramolecular or intermolecular acid anhydride.

The aromatic dicarboxylic acid can be easily isolated from the reaction mixture by a conventional method such as filtration, concentration, distillation, extraction, crystallization, recrystallization, or column chromatography. By isomerizing the aromatic dicarboxylic acid thus obtained, various aromatic dicarboxylic acids having different carboxyl group substitution positions can be produced. For example, when a salt of naphthalene-1,8-dicarboxylic acid (eg, sodium salt, potassium salt, etc.) is heated together with an isomerization catalyst (eg, cadmium chloride) in an inert gas (eg, carbon dioxide) atmosphere, naphthalene-2 is obtained. , 6-dicarboxylic acid (Beilstein EIII9, p. 4466 (Raecke, Schirp, Or
g.Synth. 40 [1960] 71)). The aromatic dicarboxylic acid obtained by the present invention can be used for various uses, for example, as a raw material of a synthetic resin such as polyester.

[0030]

According to the present invention, an aromatic condensed ring compound can be oxidized under mild conditions, and an aromatic dicarboxylic acid can be easily and efficiently produced.

[0031]

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 mixture of acenaphthene (2 mmol), N-hydroxyphthalimide (0.2 mmol), Mn (AA) ₂ (0.01 mmol), and acetic acid (5 ml) was treated under an oxygen atmosphere (1 atm) under an oxygen atmosphere (1 atm). After stirring at 6 ° C. for 6 hours, the conversion rate was 98%.
% And a yield of 65 mol% (based on acenaphthene) were obtained.

Example 2 Instead of 5 ml of acetic acid, 2 ml of acetic acid and 3 m of benzonitrile were used.
When the reaction was carried out in the same manner as in Example 1 except for using l, naphthalic acid was obtained with a conversion of 97% and a yield of 70 mol% (based on acenaphthene).

Example 3 The reaction was carried out in the same manner as in Example 1 except that 2 ml of acetic acid and 3 ml of trifluoromethylbenzene were used instead of 5 ml of acetic acid. The conversion was 95% and the yield was 30 mol% (based on acenaphthene). Gave naphthalic acid.

Example 4 A reaction was conducted in the same manner as in Example 1 except that Co (AA) ₂ was used instead of Mn (AA) _2.
Naphthalic acid was obtained in 9% at a yield of 50 mol% (based on acenaphthene).

Claims (4)

[Claims] [Claim 1] The following formula (1)(Where R¹And R^TwoAre the same or different
Atom, halogen atom, alkyl group, aryl group, cycloa
Alkyl group, hydroxyl group, alkoxy group, carboxy
R, alkoxycarbonyl, or acyl;¹
And R^TwoAre bonded to each other to form a double bond or an aromatic or
May form a non-aromatic ring. X is an oxygen atom or
A hydroxyl group is shown, and n shows the integer of 1-3. )so
In the presence of an oxidation catalyst composed of the imide compound represented,
The following formula (2)(Where R^Three~ R⁸Are the same or different and are a hydrogen atom,
Halogen atom, alkyl group, aryl group, cycloalkyl
A hydroxyl group, an alkoxy group, ^Three~ R
⁸At least one pair of groups adjacent to each other is aromatic
It may form a ring. m represents 0 or 1. )
Contacting the aromatic fused ring compound with molecular oxygen,
The following formula (3)(Where R^Three~ R⁸Is the same as defined above)
For producing a reactive dicarboxylic acid. 2. The method for producing an aromatic dicarboxylic acid according to claim 1, wherein the aromatic condensed ring compound comprises acenaphthene, acenathrene, acephenanthrene or cholanthrene. 3. The oxidation catalyst according to claim 1, further comprising a promoter.
A method for producing the aromatic dicarboxylic acid according to the above. 4. A method for oxidizing an aromatic fused ring compound according to claim 1, in the presence of the oxidation catalyst according to claim 1 and molecular oxygen.