JP2000086574A - Production of carboxylic acids - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce carboxylic acids in excellent yield and selectivity even if the hydrogen peroxide solution as an oxidant is in a low concentration by carrying out an oxidation reaction of an olefin by using a specific catalyst. SOLUTION: (A) An olefin is reacted with (B) hydrogen peroxide in the coexistence of (C) tungstic acids (preferably an alkali tungstate) and a quarternary ammonium hydrogen sulfate to provide the objective carboxylic acids. The component A is preferably a cyclic olefin. For example, the carboxylic acid of formula II (R5 is carboxyl, a 1-4C alkyl, a 1-4C carbonyl or the like) is obtained from the olefin of formula I [(n) is 0-3; R1 to R5 are each H, a halogen, carboxyl, a 1-4C alkyl or the like], and the carboxylic acid of formula III is obtained from the olefin of formula I in which R5 is H or a halogen. The obtained carboxylic acids are preferably adipic acid meso-1,2,3,4- butanetetracarboxylic acid or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for oxidizing olefins, and more particularly to a method for producing carboxylic acids having excellent yield and excellent selectivity using hydrogen peroxide as an oxidizing agent.

[0002]

2. Description of the Related Art As a method for producing a carboxylic acid by oxidizing olefins, there are a method of oxidizing with a metal compound such as permanganates, dichromates and ruthenium tetroxide, and a method of producing hypochlorous acid in the presence of a catalyst. A method using salts or periodates as an oxidizing agent is known. However,
These methods impose a large burden on the environment in terms of toxicity, corrosiveness, and the like of the oxidizing agent, and cannot be said to be industrially excellent methods. Hydrogen peroxide is an inexpensive, non-corrosive, harmless water after the reaction, has a low environmental load, and is an excellent oxidizing agent for industrial use. Conventionally, methods for producing carboxylic acids by oxidizing olefins using hydrogen peroxide include a method using a tungsten compound and a nitrogen-containing aromatic carboxylic acid as a catalyst (JP-A-08-295649). A method using an acid as a catalyst (JP-A-63
-93746) and the like. However, these production methods have a problem that the yield of the target carboxylic acid is reduced when a low-concentration aqueous hydrogen peroxide solution that can be operated more safely is used as an oxidizing agent.

[0003]

SUMMARY OF THE INVENTION In view of such circumstances, the present inventors provide an olefin oxidation method capable of producing a carboxylic acid with excellent yield even when using a low concentration of aqueous hydrogen peroxide. As a result of intensive studies for the purpose, they have found that the object can be achieved by reacting tungstic acids with quaternary ammonium hydrogensulfate, and have completed the present invention.

[0004]

That is, the present invention provides a process for producing a carboxylic acid, which comprises reacting an olefin with hydrogen peroxide in the presence of a tungstic acid and a quaternary ammonium hydrogen sulfate. To provide.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The olefins of the substrate in the present invention include, for example, those represented by the general formula (1)

Embedded image (In the formula, n represents an integer of 0 to 3, R ¹ , R ² , R ³ , R ⁴ , and R ⁵ are the same or different, and are a hydrogen atom, a halogen atom, a carboxyl group, and an alkyl having 1 to 4 carbons. A group, an alkoxy group having 1 to 4 carbon atoms, a carbonyl group having 2 to 5 carbon atoms, or a cycloalkyl group having 5 to 7 carbon atoms formed together by adjacent ones, an aryl group, an acid anhydride, Or,
R ¹ and R ⁴ , R ¹ and R ³ , or R ² and R ³ are those which are cross-linked by a carbon chain having 1 to 3 carbon atoms, each of which independently has 1 to 4 carbon atoms.
An alkyl group, an alkoxy group having 1 to 4 carbon atoms, and 5 carbon atoms
To 7 cycloalkyl groups, aryl groups, aralkyl groups,
It may be substituted with a carboxyl group, a carbonyl group having 2 to 5 carbon atoms, or a halogen atom. ), Specifically, for example, cyclopentene, cyclohexene, cycloheptene, cyclooctene, 1-methylcyclopentene, 3-methylcyclopentene, 4-methylcyclopentene, 1,3-dimethylcyclopentene, 1,4 -Dimethylcyclopentene, 1,5-dimethylcyclopentene,
3,4-dimethylcyclopentene, 3,5-dimethylcyclopentene, 1,3,4-trimethylcyclopentene, 1,3,5-trimethylcyclopentene, 1,4,5-trimethylcyclopentene, 3,4,5-trimethylcyclopentene, 1,3,4,5-tetramethylcyclopentene, 1-methylcyclohexene, 3-methylcyclohexene, 4-methylcyclohexene, 1,3-dimethylcyclohexene, 1,4-dimethylcyclohexene,
1,5-dimethylcyclohexene, 1,6-dimethylcyclohexene, 3,4-dimethylcyclohexene, 4,5-dimethylcyclohexene, 3,5-dimethylcyclohexene, 1,3,4-trimethylcyclohexene, 1,3,5- Trimethylcyclohexene, 1,3,6-trimethylcyclohexene, 1,4,5-trimethylcyclohexene, 1,4,6-trimethylcyclohexene,
1,5,6-trimethylcyclohexene, 3,4,5-trimethylcyclohexene, 3,4,6-trimethylcyclohexene, 1,3,
4,5-tetramethylcyclohexene, 1,3,4,6-tetramethylcyclohexene, 1,3,5,6-tetramethylcyclohexene, 1,4,5,6-tetramethylcyclohexene, 3,4,5, 6-tetramethylcyclohexene, 1,3,4,5,6-pentamethylcyclohexene, 1-methylcycloheptene, 1-methylcyclooctene, 1-chlorocyclopentene, 1-bromocyclopentene, 1-chlorocyclohexene, 1- Bromocyclohexene, cyclopentene-1-carboxylic acid, cyclohexene-1-carboxylic acid, 1-acetylcyclopentene, 1-acetylcyclohexene, norbornene, bicyclo (2.2.1)
Hept-5-ene-2,3-endo-dicarboxylic anhydride, cyclohexene-4,5-dicarboxylic anhydride, cyclohexene-
Cis-4,5-dicarboxylic acid, phenanthrene, 2-methylphenanthrene and the like. Preferably, cyclohexene, cyclopentene, cyclohexene-4,5-dicarboxylic acid, cyclohexene-4,5-dicarboxylic anhydride and the like are mentioned.

[0006] The amount of hydrogen peroxide used is usually in the range of 2 to 20 moles, preferably 3 to 8 moles, more preferably 4 to 6 moles per mole of the olefin. There is no limitation, and a commercially available 30% aqueous solution is sufficient.
It may be used after dilution.

[0007] The tungstic acids are compounds that generate a tungstate anion in water, for example, alkali tungstates such as sodium tungstate dihydrate and potassium tungstate dihydrate, ammonium tungstate, and tungsten trioxide. , Tungsten trisulfide,
Tungsten hexachloride, phosphotungstic acid and the like are mentioned, and alkali tungstates such as sodium tungstate dihydrate and potassium tungstate dihydrate are preferred. Tungstic acids may be used alone or in combination of two or more. The amount used is usually in the range of 0.0001 to 5 mol%, preferably 0.0005 to 3 mol%, based on the olefins of the substrate.

Examples of the quaternary ammonium hydrogen sulfate include tetramethyl ammonium hydrogen sulfate, tetraethyl ammonium hydrogen sulfate, tetrapropyl ammonium hydrogen sulfate, tetrabutyl ammonium hydrogen sulfate, benzyl trimethyl ammonium hydrogen sulfate, benzyl triethyl ammonium hydrogen sulfate, lauryl. Trimethyl ammonium hydrogen sulfate, stearyl trimethyl ammonium hydrogen sulfate, dilauryl dimethyl ammonium hydrogen sulfate, methyl trioctyl ammonium hydrogen sulfate, ethyl trioctyl ammonium hydrogen sulfate, methyl tricaprylammonium hydrogen sulfate, N-lauryl pyridinium hydrogen sulfate, N
-Cetylpyridinium hydrogen sulfate, N-lauryl picolinium hydrogen sulfate, N-cetyl picolinium hydrogen sulfate, N-
Examples thereof include lauryl quinolium hydrogen sulfate and N-cetyl quinolium hydrogen sulfate, and methyl trioctyl ammonium hydrogen sulfate is more preferably used. The amount used is usually 0.0001 to 5 mol% based on the olefins of the substrate,
Preferably it is in the range of 0.0005 to 3 mol%.

[0009] The reaction is usually carried out at a temperature in the range of 30 to 130 ° C, and does not require an organic solvent, but may be carried out by adding a solvent. Such organic solvents include, for example, toluene,
Examples thereof include aromatic hydrocarbon solvents such as xylene and ethylbenzene, aliphatic hydrocarbon solvents such as heptane, and halogenated hydrocarbon solvents such as dichloroethane and chlorobenzene. Each of these solvents is used alone or in combination of two or more. The amount of the solvent used is usually 0.1 to 20 times by weight, preferably 0.1 to 20 times by weight, based on the olefins.
The range is 5 to 10 times by weight.

As the carboxylic acid thus obtained, when R ⁵ of the olefin (1) is other than a hydrogen atom or a halogen atom, a compound represented by the general formula (2)

Embedded image ^{(Wherein, n, R 1, R 2} , R 3, R 4 are each as defined above, R ⁵
Is a carboxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a carbonyl group having 2 to 5 carbon atoms, or 5 to 7 carbon atoms formed by adjoining ones. Cycloalkyl group, aryl group, acid anhydride, or, R ¹ and R ⁴ , R ¹ and R ³ , or R ² and R ³ show those cross-linked by a carbon chain of 1 to 3 carbon, these Is independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, an aryl group,
It may be substituted by an aralkyl group, a carboxyl group, a carbonyl group having 2 to 5 carbon atoms, or a halogen atom. Wherein R ⁵ of the olefin (1) is a hydrogen atom or a halogen atom,

Embedded image (In the formula, n, R ¹ , R ² , R ³ and R ⁴ represent the same meaning as described above.)
It is a compound represented by these. Specifically, for example, glutaric acid, adipic acid, pimelic acid, suberic acid, 5-oxohexanoic acid, 2-methylglutaric acid, 3-methylglutaric acid, 2-methyl-5-oxohexanoic acid, 3-methyl -5-oxohexanoic acid, 4-methyl-5-oxohexanoic acid, 2,3-dimethylglutaric acid, 2,4-dimethylglutaric acid, 2,3-dimethyl-5-oxohexanoic acid, 3,4-dimethyl -5-oxohexanoic acid, 2,4-dimethyl-5-oxohexanoic acid, 2,3,4-trimethylglutaric acid, 2,3,4-trimethyl-5-oxohexanoic acid, 5-oxoheptanoic acid, 2 -Methyladipic acid, 3-methyladipic acid, 2-methyl-6-oxoheptenoic acid, 3-methyl-6-oxoheptanoic acid, 4-methyl-6-oxoheptanoic acid, 5-methyl-6-oxoheptanoic acid, 2,3-dimethyladipic acid, 3,4-dimethyladipic acid, 2,4-dimethyladipic acid, 2,3-dimethyl-6-oxohepta Acid, 2,4-dimethyl-6-oxoheptanoic acid, 2,5-dimethyl-6-oxoheptanoic acid, 3,4-dimethyl-6-oxoheptanoic acid, 3,5-dimethyl-6-oxoheptanoic acid, 4,5-dimethyl-6-oxoheptanoic acid, 2,3,4-trimethyladipic acid, 2,3,5-trimethyladipic acid, 2,3,4-trimethyl-6-oxoheptanoic acid,
2,3,5-trimethyl-6-oxoheptanoic acid, 2,4,5-trimethyl-6-oxoheptanoic acid, 3,4,5-trimethyl-6-oxoheptanoic acid, 2,3,4,5- Tetramethyladipic acid, 2,3,4,
5-tetramethyl-6-oxoheptanoic acid, 7-oxooctanoic acid, 7-oxononanoic acid, 2-oxoadipic acid, 2-oxopimelic acid, 5,6-dioxoheptanoic acid, 6,7-dioxooctanoic acid , 1,3-cyclohexanedicarboxylic acid, 1,2,3,
4-cyclohexanetetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, 2,2′-biphenyldicarboxylic acid, 4-methyl-2,2′-biphenyldicarboxylic acid and the like. Preferred results include adipic acid, meso
-1,2,3,4-butanetetracarboxylic acid, glutaric acid and the like.

[0011] The target carboxylic acid thus produced can be extracted by a usual method such as recrystallization, distillation, sublimation or the like after concentrating the mixed solution after the reaction.

[0012]

According to the production method of the present invention, the hydrogen peroxide oxidation of olefins can be carried out safely with excellent selectivity without using a high-concentration aqueous hydrogen peroxide solution. It can be manufactured efficiently. In addition, the present production method does not necessarily require an organic solvent, and thus has an effect of reducing the load on the environment.

[0013]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. (Example 1) A magnetic stirrer and a reflux condenser were attached to a 1 L four-necked flask, and 4.01 g (12.2.
Na ₂ WO ₄ · 2H ₂ O in mmol), 5.67g (1
2.2 mmol) of _{[CH 3 (n-C 8} H 17) 3 N] HS
O ₄ and 607 g (5.355 mol) of 30% aqueous hydrogen peroxide are charged. The mixture is stirred vigorously for 10 minutes at room temperature. Then, 100 g (1.217 mol) of cyclohexene are added. The two-phase mixture was gradually heated and stirred at 75 ° C. for 30 minutes, at 80 ° C. for 30 minutes, at 85 ° C. for 30 minutes, and finally at 90 ° C. for 6.5 hours at 1000 rpm.
Stir at m. After completion of the reaction, the homogeneous solution is cooled to 0 ° C and kept at 0 ° C for 12 hours. The generated crystals were separated by filtration, washed with 20 ml of cold water, and dried under reduced pressure to obtain adipic acid (138 g, yield 78%). The filtrate was concentrated and analyzed by GC. As a result, the total yield was 93%. White crystal mp: 151.0-152.0 ° C

(Example 2) A magnetic stirrer and a reflux condenser were attached to a 1 L four-necked flask, and the aqueous layer of Example 1 (having a tungsten catalyst), 5.67 g (12.
2 mmol) of [CH ₃ (nC ₈ H ₁₇ ) ₃ N] HSO ₄ and 552 g (4.868 mol) of 30% hydrogen peroxide are charged. The mixture is stirred vigorously for 10 minutes at room temperature.
Then, 100 g (1.217 mol) of cyclohexene are added. The two-phase mixture is heated at 75 ° C. for 30 minutes at 80 ° C.
The mixture was gradually heated and stirred at 30 ° C. for 30 minutes and at 85 ° C. for 30 minutes, and finally stirred at 90 ° C. for 46.5 hours at 1000 rpm. After completion of the reaction, the homogeneous solution is cooled to 0 ° C and kept at 0 ° C for 12 hours. The generated crystals are separated by filtration,
After washing with cold water, it was dried under reduced pressure to obtain 138 g of adipic acid (78% yield).

Example 3 Glutaric acid was obtained at a yield of 90% in the same manner as in Example 1 except that cyclopentene was used instead of cyclohexene.

Example 4 Meso-1,2,3,4-butane was prepared in the same manner as in Example 1 except that cyclohexene-4,5-dicarboxylic anhydride was used instead of cyclohexene. Tetracarboxylic acid was obtained with a yield of 91%.

Example 5 Meso-1,2,3,4-butane was prepared in the same manner as in Example 1 except that cyclohexene-cis-4,5-dicarboxylic acid was used instead of cyclohexene. Tetracarboxylic acid was obtained with a yield of 96%.

Example 6 6-oxoheptanoic acid was obtained in a yield of 59% in the same manner as in Example 1 except that 1-methylcyclohexene was used instead of cyclohexene.

(Example 7) 2,2'-biphenyldicarboxylic acid was obtained in a yield of 41% in the same manner as in Example 1 except that phenanthrene was used instead of cyclohexene.
I got it.

Example 8 Suberic acid was obtained at a yield of 9% in the same manner as in Example 1 except that cyclooctene was used instead of cyclohexene.

(Comparative Example 1) (in the method described in JP-A-63-93746), the concentration of the hydrogen peroxide solution used was adjusted to 3
Example) A 200 mL four-necked flask was equipped with a magnetic stirrer and a reflux condenser, and 0.74 g of tungstic acid and 100 g of 30% aqueous hydrogen peroxide (0.88 g) were added.
mol), cyclohexene 16.8 g (0.2 mol)
Prepare. The mixture was heated to reflux with vigorous stirring. After reacting for 3 hours, the reaction solution was analyzed by GC.
The amount of adipic acid obtained was trace.

Claims (5)

[Claims] 1. A process for producing carboxylic acids, which comprises reacting an olefin with hydrogen peroxide in the presence of tungstic acids and quaternary ammonium hydrogen sulfate. 2. The method according to claim 1, wherein the olefin is a cyclic olefin. 3. An olefin represented by the general formula (1): ## STR1 ## (In the formula, n represents an integer of 0 to 3, R ¹ , R ² , R ³ , R ⁴ , and R ⁵ are the same or different, and are a hydrogen atom, a halogen atom, a carboxyl group, and an alkyl having 1 to 4 carbons. A group, an alkoxy group having 1 to 4 carbon atoms, a carbonyl group having 2 to 5 carbon atoms, or a cycloalkyl group having 5 to 7 carbon atoms formed together by adjacent ones, an aryl group, an acid anhydride, Or,
R ¹ and R ⁴ , R ¹ and R ³ , or R ² and R ³ are those which are cross-linked by a carbon chain having 1 to 3 carbon atoms, each of which independently has 1 to 4 carbon atoms.
An alkyl group, an alkoxy group having 1 to 4 carbon atoms, and 5 carbon atoms
To 7 cycloalkyl groups, aryl groups, aralkyl groups,
It may be substituted with a carboxyl group, a carbonyl group having 2 to 5 carbon atoms, or a halogen atom. Wherein R ^{5 of} the olefin is other than a hydrogen atom or a halogen atom, the resulting carboxylic acid is represented by the general formula (2): ^{(Wherein, n, R 1, R 2} , R 3, R 4 are each as defined above, R ⁵
Is a carboxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a carbonyl group having 2 to 5 carbon atoms, or 5 to 7 carbon atoms formed by adjoining ones. Cycloalkyl group, aryl group, acid anhydride, or, R ¹ and R ⁴ , R ¹ and R ³ , or R ² and R ³ show those cross-linked by a carbon chain of 1 to 3 carbon, these Is independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, an aryl group,
It may be substituted by an aralkyl group, a carboxyl group, a carbonyl group having 2 to 5 carbon atoms, or a halogen atom. Wherein R ^{5 of} the olefin is a hydrogen atom or a halogen atom, the resulting carboxylic acid is represented by the general formula (3): (In the formula, n, R ¹ , R ² , R ³ and R ⁴ represent the same meaning as described above.)
The method according to claim 1, wherein 4. The method according to claim 1, wherein the tungstic acid is an alkali tungstate. 5. The carboxylic acid is adipic acid, meso-1,2,3,4
1-butanetetracarboxylic acid or glutaric acid
4. The production method according to any one of 4.