JPH05345741A - Production of lower carboxylic acid - Google Patents

Abstract

PURPOSE:To easily produce a lower carboxylic acid from an inexpensive lower alkane and carbon monoxide in high efficiency. CONSTITUTION:A lower carboxylic acid is produced by reacting a lower alkane with carbon monoxide in the presence of a palladium and/or copper-based catalyst and a peroxy acid salt.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a lower carboxylic acid, and more specifically, reacting a lower alkane with carbon monoxide in the presence of a palladium and / or copper catalyst and a salt of peroxy acid. And to a method for producing a lower carboxylic acid.

[0002]

2. Description of the Related Art As a method for producing a lower carboxylic acid, a method of oxidizing a corresponding aldehyde, alkane, alkene, etc., a method of carbonylating methanol to produce acetic acid, etc. are known. There is. However, nothing is known about producing a lower carboxylic acid from a lower alkane and carbon monoxide.

The inventors of the present invention have conducted extensive studies on the reaction between alkane and carbon monoxide. As a result, if a palladium-based and / or copper-based catalyst and a salt of peroxy acid coexist,
It was found that the lower alkane reacts with carbon monoxide to form a lower carboxylic acid, and further various studies were conducted to complete the present invention.

[0004]

[Means for Solving the Problems] That is, the present invention provides a palladium-based and / or copper-based catalyst in the presence of a salt of a peroxy acid,
The present invention provides a method for producing a lower carboxylic acid, which comprises reacting a lower alkane with carbon monoxide.

The present invention will be described in detail below. Examples of the palladium-based catalyst include salts such as acetylacetonate salt, carboxylate, oxide, halide, ammonium salt, sulfate and nitrate of palladium and coordination compounds thereof.

Specific compounds include, for example, Pd (NH₃)₂(N
0₂)₂, Pd (NH₃)₂Br₂, Pd (NH₃)₂Cl₂, PdCl₂(CH₃CN), Pd
Cl₂(PhCN), PdCl₂(1,5-C₈H₁₂), Pd (O₂CCH₃)₂, Pd (O₂C
C₃H₇)₂, Pd (CH₃COCHCOCH₃)₂ , PdBr₂, PdCl₂ , PdI₂,
Pd (CN)₂ , Pd (NO₃)₂・ XH₂O, PdO, Pd (OCOC₂H_Five)₂, PdS
O_Four・ 2H₂O, Pd (O₂CCF₃)₂, [Pd (NH₃)_Four] (N0₃)₂, [Pd (NH₃)
_Four] [PdCl_Four], Pd (CH₃CN) (BF_Four)₂, PdCl₂[(Ph)₃P]₂, Pd
[(Ph)₃P]_FourEtc. are illustrated. Above all, Pd (O₂CCH₃)₂, Pd
(O₂CC₂H_Five)₂, Pd (O₂CC₃H₇)₂, (O₂CC₃H₇)₂, PdCl₂And so on
Used well.

As the copper-based catalyst, for example, copper oxide, halide, hydroxide, carboxylate, sulfate,
Examples thereof include nitrates and carbonates. Specific compounds include:
For example, cuprous oxide, cupric oxide, cuprous chloride, cupric chloride, cuprous bromide, cupric bromide, cuprous iodide, cupric iodide, copper hydroxide, acetic acid Examples include copper, copper oxalate, copper formate, copper naphthenate, copper stearate, copper sulfate, copper nitrate and copper carbonate. Of these, copper acetate, copper sulfate and the like are preferably used.

The palladium catalyst and the copper catalyst can be used in combination. The amount of the catalyst used is usually about 1 × 10 ⁻⁵ to 1 × 10 ⁻¹ mol times that of the alkane.

Examples of the salt of peroxy acid include salts of peroxysulfuric acid and salts of peroxyphosphoric acid. Examples of specific compounds include ammonium peroxydisulfate, sodium peroxydisulfate, potassium peroxydisulfate, potassium peroxydiphosphate, and the like. The amount used is usually 50 to 200 molar equivalents with respect to the catalyst.

Further, a trivalent phosphorus compound can be made to coexist, and when an alkane having 3 or more carbon atoms is used, the distribution of the product can be changed. For example, when propane is used, the production ratio of iso-form can be increased. Examples of such trivalent phosphorus compounds include compounds represented by the following formula. PR ¹ R ² R ³ [I], P (NR ⁴ ₂ ) ₃ [II], P (OR ⁵ )
₃ [III], PR ⁶ R ⁷ (CH ₂ ) _n PR ⁶ R [IV] (In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently alkyl. Represents a group, a cycloalkyl group, an aralkyl group, and an aryl group.)

More specific compounds include, for example, trimethylphosphine, triethylphosphine, tri-n-propylphosphine, triisopropylphosphine and triethylphosphine.
-n-butylphosphine, triisobutylphosphine, tri-t-butylphosphine, tri-sec-butylphosphine, tricyclopropylphosphine, tricyclohexylphosphine, triphenylphosphine, tri-p-tolylphosphine, tri-p-methoxyphenyl Phosphine,
Tri-2,4,6-trimethylphenylphosphine, phenyldiisopropylphosphine, diethylisopropylphosphine, ethyl-di-t-butylphosphine, diethyl-t-
Phosphines represented by the formula [I] such as butylphosphine, ethyldicyclohexylphosphine, methylphenylbenzylphosphine, diethylphenylphosphine, ethyldiphenylphosphine, dimethylphenylphosphine, and methyldiphenylphosphine, trisdimethylaminophosphine, trisdiethylaminophosphine, tris- Phosphines represented by formula [II] such as n-propylaminophosphine, trisdiisopropylaminophosphine, trisdi-n-butylaminophosphine, trisdiisobutylaminophosphine, trisdicyclohexylaminophosphine, trimethylphosphite, triethylphosphite, tri- n-propyl phosphite, triisopropyl phosphite, tri-n-butyl phosphite, triisobutyl phosphite Ito, tri -t- butyl phosphite, tri-cyclohexyl phosphite, triphenyl phosphite, tri -p- tolyl phosphite, tri
-p-Methoxyphenyl phosphite, phosphites represented by the formula [III], bisdiphenylphosphinomethane, 1,2-bisdiphenylphosphinoethane, 1,3-bisdiphenylphosphinopropane, 1,4 -Bisdiphenylphosphinobutane, 1,5-bisdiphenylphosphinopentane, 1,6-bisdiphenylphosphinohexane, 1,2-bisdimethylphosphinoethane, 1,2-bisdiethylphosphinoethane, 1,2 Examples include phosphines represented by the formula [IV] such as -bisdicyclohexylphosphinoethane and 1,2-bisdipentafluorophenylphosphinoethane.
Trivalent phosphorus compounds are usually used against palladium and copper metals.
It is used in an amount of 0.1 to 100 mole times, preferably 0.1 to 20 mole times.

Examples of the lower alkane include methane, ethane, propane, butane and the like. The reaction is carried out in the presence of a solvent. As such a solvent, for example, halogenated carboxylic acids such as trifluoroacetic acid, trichloroacetic acid, monochloroacetic acid and dichloroacetic acid, and halogenated hydrocarbons such as perfluorohexane are usually used.
The amount used is usually about 10 to 100 ml per mmol of the catalyst.

The reaction of the lower alkane with carbon monoxide is usually carried out under pressure, but the pressure of the lower alkane is usually about 1 to 50 atm. The pressure of carbon monoxide is usually about 1 to 50 atm. The reaction temperature is
It is usually 0 to 100 ° C., and the reaction time is usually about 1 to 50 hours.

Thus, methane is converted into acetic acid, ethane is converted to propionic acid, propane is converted to butanoic acid, and butane is converted to pentanoic acid. The lower carboxylic acid to be obtained can be taken out.

[0015]

According to the method of the present invention, a lower carboxylic acid can be easily and efficiently produced from an inexpensive lower alkane and carbon monoxide.

[0016]

EXAMPLES The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples. The yield was calculated by the following formula. Yield (%) = amount of produced carboxylic acid (mol) / amount of catalyst metal (mol) × 100

Example 1 Palladium propionate (Pd) was added to a 150 ml autoclave.
(OCOC ₂ H ₅ ) ₂ 0.05 mmol), copper sulfate (1 mmol), potassium peroxodisulfate (K ₂ S ₂ O ₄ 9 mmol), trifluoroacetic acid (5 m
l), n-perfluorohexane (2 ml), and then methane
(Purity of 99% or more) 40 atm and 20 atm of carbon monoxide were charged to a total of 60 atm. Then, raise the temperature to 80 ℃ and
After continuing stirring for an hour, the mixture was cooled to room temperature and the reaction mass was analyzed by gas chromatography. Acetic acid yield is 1300%
(Palladium metal standard). In addition, a small amount of propionic acid derived from the catalyst was detected, but no by-products were detected.

Example 2 The procedure of Example 1 was repeated except that n-perfluorohexane was not used. The yield of acetic acid is
It was 930% (based on palladium metal). In addition, a small amount of propionic acid derived from the catalyst was detected, but no by-products were detected.

Example 3 The procedure of Example 2 was repeated, except that propane was used instead of methane. The yield of butanoic acids was 660% (based on palladium metal), and the n-form / iso-
The body ratio was 5/6. In addition, a small amount of propionic acid derived from the catalyst was detected, but no by-products were detected.

Example 4 Example 1 was repeated except that copper sulfate was not used.
It was carried out in accordance with. The yield of acetic acid was 750% (based on palladium metal). In addition, a small amount of propionic acid derived from the catalyst was detected, but no by-products were detected.

Example 5 The procedure of Example 1 was repeated except that 0.05 mmol of copper sulfate was used and palladium propionate and n-perfluorohexane were not used. The acetic acid yield is 670.
% (Copper metal standard). No by-products were detected.

Example 6 In Example 1, without using palladium propionate and n-perfluorohexane, copper sulfate (0.05 mmol), potassium peroxodisulfate (18 mmol), trifluoroacetic acid (
5 ml) and the procedure was carried out in accordance with Example 1 except that stirring was continued for 45 hours. The acetic acid yield was 4000% (based on copper metal). No by-products were detected.

Example 7 Palladium acetate (Pd (OCOCH ₃ ) _{2 was} added to a 150 ml autoclave.
0.05 mmol), copper acetate (Cu (OCOCH ₃ ) ₂ 0.1 mmol), potassium peroxodisulfate (K ₂ S ₂ O ₄ 9 mmol), trifluoroacetic acid (
After adding 5 ml), 30 atm of ethane and 20 atm of carbon monoxide were charged to a total of 50 atm. Then, the temperature was raised to 80 ° C., the mixture was stirred at the same temperature for 30 hours, cooled to room temperature, and the reaction mass was analyzed by gas chromatography. The yield of propionic acid was 8000% (based on palladium metal). In addition, a small amount of acetic acid derived from the catalyst was detected, but no by-product was detected.

Example 8 Palladium acetate (0.05 mmol) in a 150 ml autoclave,
Copper acetate (0.05 mmol), potassium peroxodisulfate (9 mmo
l) and trifluoroacetic acid (5 ml) were added, and then 10 atm of propane and 20 atm of carbon monoxide were charged to a total of 30 atm. Then, the temperature was raised to 90 ° C., and after stirring at the same temperature for 20 hours,
After cooling to room temperature, the reaction mass was analyzed by gas chromatography. The yield of butanoic acids was 7100% (based on palladium metal), and the ratio of n-form / iso-form was 17/54. In addition, a small amount of acetic acid derived from the catalyst was detected, but no by-product was detected.

Example 9 The procedure of Example 8 was repeated except that the reaction was carried out at 70 ° C. Butanoic acid yield is 3800%
(Based on palladium metal), and the ratio of n-form / iso-form is
It was 3/16. In addition, a small amount of acetic acid derived from the catalyst was detected, but no by-product was detected.

Example 10 The procedure of Example 8 was repeated, except that the reaction was carried out at 60 ° C. Butanoic acid yield is 2240%
(Palladium metal standard), the ratio of n-form / iso-form is 1
It was 7/95. In addition, a small amount of acetic acid derived from the catalyst was detected, but no by-product was detected.

Example 11 The procedure of Example 8 was repeated except that triethylphosphite (0.15 m
mol) was added and the reaction was carried out in accordance with Example 8. The yield of butanoic acids was 5800% (based on palladium metal), and the ratio of n-form / iso-form was 11/47. In addition, a small amount of acetic acid derived from the catalyst was detected, but no by-product was detected.

Example 12 The procedure of Example 8 was repeated, except that 1,2-bisdiphenylphosphinoethane (0.075 mmol) was further added to carry out the reaction. The butanoic acid yield was 5500% (based on palladium metal), and the n-isomer / iso-isomer ratio was 2/13.
Met. In addition, a small amount of acetic acid derived from the catalyst was detected,
No by-products were detected.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display location C07C 53/124 7306-4H // C07B 61/00 300

Claims (1)

[Claims] 1. A method for producing a lower carboxylic acid, which comprises reacting a lower alkane with carbon monoxide in the presence of a palladium-based and / or copper-based catalyst and a salt of a peroxy acid.