JPH09157210A - Production of carboxylic acid ester or carboxylic acid - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject compound useful as a raw material for resins, perfumes, etc., in a high speed reaction rate and a high selectivity. SOLUTION: Palladium (e.g. palladium chloride), phosphine or arsine represented by formula I (M<1> and M<2> are each P or As; R is a 1-8C alkyl divalent organic crosslinkable group; R<1> , R<2> , R<3> and R<4> are each a 1-8C alkyl or a 6-12C aryl) and a metal halide represented by formula II (M<3> is Fe, Cu, Zn, etc.; X is a halogen; (n) is an integer of 1-4) and an N heterocyclic base (a pyridine compound or condensed N-heterocyclic compound) are added to an alcohol (e.g. methanol) or water, and an olefin (e.g. ethylene) is reacted with carbon monoxide and the alcohol or water containing the above substances to provide the objective carboxylic acid ester or carboxylic acid. The compound is obtained at high reaction speed in high selectivity by carrying out the reaction under low and mild pressure of carbon monoxide.

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 carboxylic acid ester or a carboxylic acid from an olefin at a high reaction rate and a high selectivity. Carboxylic acid esters and carboxylic acids are useful compounds as raw materials for resins, fragrances and the like.

[0002]

2. Description of the Related Art (1) Palladium, (2) phosphine or arsine, and (3) metal halide are added,
A method for producing a carboxylic acid ester or a carboxylic acid by reacting (a) an olefin with (b) carbon monoxide and (c) alcohol or water is described in JP-A-48-10350.
No. 8, US Pat. No. 3,906,015, and No. 42.
The method described in 57973 is known. However, in these methods, although a carboxylic acid ester or a carboxylic acid (particularly a normal form) can be obtained with a high selectivity, the reaction must be carried out under the condition that the carbon monoxide pressure is high, and the reaction rate is sufficient. There is no problem.

[0003]

The present invention provides a method for producing a carboxylic acid ester or carboxylic acid by reacting (a) an olefin with (b) carbon monoxide and (c) alcohol or water. It is an object of the present invention to provide a method capable of producing a carboxylic acid ester or a carboxylic acid (particularly a normal form) at a high reaction rate and a high selectivity under mild conditions where the pressure is low.

[0004]

The problems of the present invention are (1)
Palladium, (2) a compound represented by the general formula (I),

[0005]

Embedded image (Wherein, M ¹ and M ² represent P or As, and R has 1 carbon atom.
Represents a divalent organic bridging group of from ¹ to 8, R ¹ , R ² , R ³ , R
⁴ represents an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 12 carbon atoms. )

(3) A metal halide represented by the general formula (II), and

Embedded image (In the formula, M ³ is Fe, Cu, Sn, Zn, Mn, Al,
Mo, Ti or a lanthanoid atom is shown, X is a halogen atom, and n is an integer of 1 to 4. )

(4) A carboxylic acid characterized by adding N-heterocyclic base to alcohol or water to react (a) olefin with (b) carbon monoxide and (c) alcohol or water. This is achieved by a method for producing an ester or carboxylic acid.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.
As palladium, palladium metal and / or palladium compound is used. As the palladium metal, palladium-activated carbon, palladium-silica, palladium-
Examples include those in which a palladium metal such as alumina or palladium-zeolite is supported on a carrier. Further, as the palladium compound, palladium chloride, palladium nitrate,
Inorganic acid salts of palladium, such as palladium sulfate, organic acid salts of palladium, such as palladium acetate, bis (acetylacetonato) palladium, bis (triphenylphosphine) palladium dichloride, tetrakis (triphenylphosphine) palladium, etc. Examples thereof include coordination compounds. The amount of palladium used is olefin 1
It is usually 10 ^-5 to 1 mol, preferably 10 ^-4 to mol.
It is 1 mol.

The compound represented by the general formula (I) includes
M ¹ and M ² are P or As and R is a divalent organic cross-linking group having 1 to 8 carbon atoms (methylene group, ethylene group, trimethylene group, tetramethylene group or other alkylene group having 1 to 8 carbon atoms). Etc., and R ¹ , R ² , R ³ , and R ⁴ are alkyl groups having 1 to 8 carbon atoms (methyl group, ethyl group, propyl group, butyl group, etc.) or aryl groups having 6 to 12 carbon atoms ( A bidentate phosphine or arsine, which is a phenyl group, a tolyl group, etc.). Further, it is usually preferable that M ¹ and M ² are the same atom, and R ¹ , R ² and
R ³ and R ⁴ may be the same group or different groups.

Examples of the phosphine include bis (diphenylphosphino) methane, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane and 1,4-bis (diphenylphosphino) butane. Bis (diarylphosphino) alkanes such as 1,5-bis (diphenylphosphino) pentane and 1,2-
Specific examples include bis (dialkylphosphino) alkanes such as bis (dimethylphosphino) ethane, 1,3-bis (diisopropylphosphino) propane, and 1,3-bis (di-t-butylphosphino) propane. (However, the alkane has 1 to 8 carbon atoms). As arsine, 1,3-bis (diphenylarsino) propane,
Specific examples thereof include bis (diarylarsino) alkanes such as 1,4-bis (diphenylarsino) butane (provided that the alkane has 1 to 8 carbon atoms). Among the compounds represented by the general formula (I), phosphine is preferable, and among them, 1,3-bis (diphenylphosphino) propane, 1,4-bis (diphenylphosphino) butane and 1,5-bis (diphenylphosphine). Fino) pentane is preferred.

The amount of the compound represented by the general formula (I) used is usually 1 to 50 mol, preferably 1 to 20 mol, based on 1 mol of palladium. Further, these compounds may be used alone or in a mixture, and may be used in a mixture with a monodentate triarylphosphine such as triphenylphosphine.

In the metal halide represented by the general formula (II), M ³ is Fe, Cu, Sn, Zn, Mn or A.
a metal halide of 1, 1, Mo, Ti or a lanthanoid atom, wherein X is a halogen atom, that is, Fe, Cu, S
Examples thereof include halides of n, Zn, Mn, Al, Mo, Ti and lanthanoid elements. Specifically, ferric chloride, cupric chloride, stannous chloride, zinc chloride, manganese chloride, aluminum chloride, molybdenum chloride, titanium chloride, samarium chloride, ytterbium chloride, gadolinium chloride, samarium bromide, etc. Examples thereof include halides of the lanthanoid element, which may be anhydrous or may contain water of crystallization. Among these metal halides, halides of ferric chloride, cupric chloride, stannous chloride, aluminum chloride, titanium chloride and lanthanoid elements are particularly preferable. The amount of metal halide used is
It is usually 0.01 to 30 mol, preferably 0.1 to 15 mol, per mol of palladium.

In the present invention, an N-heterocyclic base is used as a reaction accelerator. The N-heterocyclic base can be used in a small amount or as a reaction solvent. The amount used is usually 0.1 to 10 ³ mol, preferably 0.5 to 10 ² mol, per 1 mol of metal halide.

Examples of the N-heterocyclic base include pyridine compounds and condensed N-heterocyclic compounds. Examples of the pyridine compound include pyridine, 2-picoline, 3-picoline, 4-picoline, 2,4-lutidine, 3,5-lutidine, 2,6-lutidine, 3,4-lutidine, and 4-cyclohexylpyridine. Alkyl-substituted pyridines having an alkyl group having 1 to 8 carbon atoms, alkoxy-substituted pyridines having an alkoxy group having 1 to 6 carbon atoms such as 2-methoxypyridine and 4-methoxypyridine, and carbon such as 4-phenylpyridine Examples thereof include aryl-substituted pyridines having an aryl group of the number 6 to 14, aryloxy-substituted pyridines having an aryloxy group of the carbon number 6 to 10 such as 4-phenoxypyridine, and 2,2′-dipyridyl. Examples of the condensed N-heterocyclic compound include quinolines such as quinoline and isoquinoline, and 1,10-phenanthroline. Among the N-heterocyclic bases, pyridine, alkyl-substituted pyridines and quinolines are preferable, and pyridine, lutidine and isoquinoline are particularly preferable. The N-heterocyclic base may be used alone or in combination of two or more.

As the olefin, ethylene, propylene, 1-butene, isobutene, 1-hexene, 2-hexene, 3-methyl-1-pentene, 3-pentenenitrile, 4-pentenenitrile, 3-pentenoic acid ester (3 3 such as methyl pentenoate and ethyl 3-pentenoate
-Ester of pentenoic acid and aliphatic alcohol having 1 to 8 carbon atoms), 4-pentenoic acid ester (methyl 4-pentenoate, ethyl 4-pentenoate, etc. 4-pentenoic acid and aliphatic having 1 to 8 carbon atoms) Ester with alcohol), chain monoene having 2 to 30 carbon atoms such as styrene, chain diene having 4 to 20 carbon atoms such as 1,5-hexadiene, and alicyclic group having 5 to 12 carbon atoms such as cyclohexene Monoene, 1,5-
Alicyclic dienes having 5 to 20 carbon atoms such as cyclooctadiene and 10 carbon atoms such as 1,5,9-cyclododecatriene.
.About.20 alicyclic triene, dicyclodiene such as 2,5-norbornadiene and dicyclopentadiene are used.

As the alcohol, an aliphatic group having 1 to 20 carbon atoms such as methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, t-butanol, n-hexanol, cyclohexanol and benzyl alcohol is used. Monohydric alcohols, aromatic monohydric alcohols having 6 to 14 carbon atoms such as phenol, and aliphatic dihydric alcohols having 2 to 20 carbon atoms such as ethylene glycol and butanediol are used. As the water, for example, ordinary distilled water is used. The amount of alcohol or water used is usually 0.05 to 10 with respect to 1 mol of olefin.
^{It is 4} mol, preferably 0.1 to 10 ³ mol.

In the present invention, alcohol, water, or N-heterocyclic base can be used as the reaction solvent, but other solvent inert to the reaction may be used.
Examples of the other reaction solvent include aromatic hydrocarbons such as benzene and toluene, aliphatic non-halogenated hydrocarbons such as tetralin and cyclohexane, ethers such as diethyl ether, tetrahydrofuran and dioxane, and acetone and methyl ethyl ketone. Ketone, methyl acetate, ε
-Esters such as caprolactone, aliphatic halogenated hydrocarbons such as dichloromethane, amides such as N, N-dimethylformamide and N-methylpyrrolidone, sulfones such as dimethylsulfone and sulfolane, sulfoxides such as dimethylsulfoxide, Examples thereof include nitriles such as acetonitrile and benzonitrile.

The reaction is carried out, for example, by putting alcohol or water in a pressure-resistant reactor, adding N-heterocyclic base, palladium, metal halide, phosphine or arsine, and olefin, and then pressurizing with carbon monoxide. It is performed under predetermined reaction conditions. The pressure of carbon monoxide is usually 0.5 to 300k
g / cm ² G, preferably 1 to 200 kg / cm ² G. Further, the ratio of carbon monoxide to olefin (C
The molar ratio of O: olefin) is usually 1 or more, and the amount of carbon monoxide in the reaction may be an amount sufficient to satisfy at least the stoichiometric amount. The reaction temperature is usually 20 to 3
The temperature is 00 ° C, preferably 50 to 200 ° C. After the reaction, the produced carboxylic acid ester or carboxylic acid is easily separated and purified by ordinary distillation.

[0019]

Next, the present invention will be described specifically with reference to examples and comparative examples. The olefin conversion rate and the carboxylic acid ester or carboxylic acid selectivity were determined by the following equations.

[0020]

(Equation 1)

[0021]

(Equation 2)

Example 1 12.00 g of methanol and 12.00 g of isoquinoline
0.584 mmol of palladium acetate and 2.336 mmol of samarium chloride hexahydrate are dissolved in 1, and 1,4
-Bis (diphenylphosphino) butane 2.920 mm
After ol was dissolved, 12.00 g of 1-hexene was added. This solution was placed in an autoclave having an internal volume of 100 ml equipped with a stirrer. After the inside of the autoclave was replaced with carbon monoxide, carbon monoxide was introduced at room temperature until the pressure became 40 kg / cm ² G. The reaction product was analyzed by gas chromatography after reacting at 145 ° C. for 1 hour under a constant pressure of 60 kg / cm ² G while additionally introducing consumed carbon monoxide with stirring. As a result, the conversion rate of 1-hexene was 74% and the selectivity of carboxylic acid ester was 90%.
The proportion of normal-form methyl heptanoate in the ester was 84%.

Example 2 In Example 1, pyridine 1 was used instead of isoquinoline.
The reaction and analysis were carried out in the same manner as in Example 1 except that 2.00 g was used. As a result, the conversion rate of 1-hexene is 70%,
Carboxylic acid ester selectivity is 88%, and the proportion of normal-form methyl heptanoate is 83%.
Met.

Example 3 Reaction and analysis were carried out in the same manner as in Example 1 except that 12.00 g of 2,6-lutidine was used in place of isoquinoline. As a result, the conversion rate of 1-hexene was 6
8%, the carboxylic acid ester selectivity is 88%, and the ratio of normal-form methyl heptanoate in the ester is 8%.
2%.

Comparative Example 1 In Example 1, benzene 1 was used in place of isoquinoline.
The reaction and analysis were carried out in the same manner as in Example 1 except that 2.00 g was used. As a result, almost no absorption of carbon monoxide was observed during the reaction, and the 1-hexene conversion rate was only 5%. The results of Examples 1 to 3 and Comparative Example 1 are shown in Table 1.

[0026]

[Table 1]

Example 4 In Example 1, except that 2.336 mmol of ferric chloride hexahydrate was used instead of samarium chloride hexahydrate,
The reaction and analysis were performed in the same manner as in Example 1. As a result, 1-
The conversion of hexene was 79%, the selectivity of carboxylic acid ester was 95%, and the ratio of methyl heptanoate, which is a normal form, of the ester was 82%.

Example 5 The reaction and analysis were carried out in the same manner as in Example 1 except that 2.336 mmol of stannous chloride dihydrate was used in place of samarium chloride hexahydrate. as a result,
The conversion rate of 1-hexene was 63%, the selectivity of carboxylic acid ester was 98%, and the proportion of methyl heptanoate as a normal form in the ester was 84%.

Example 6 In Example 1, except that cupric chloride dihydrate 2.336 mmol was used in place of samarium chloride hexahydrate,
The reaction and analysis were performed in the same manner as in Example 1. As a result, 1-
The hexene conversion was 65%, the carboxylic acid ester selectivity was 93%, and the proportion of methyl heptanoate, which is a normal form, in the ester was 80%.

Example 7 The reaction and analysis were performed in the same manner as in Example 1 except that 2.336 mmol of zinc chloride was used instead of samarium chloride hexahydrate. As a result, the conversion rate of 1-hexene was 60%, the selectivity of carboxylic acid ester was 90%,
The proportion of normal-form methyl heptanoate in the ester was 84%.

Example 8 The reaction and analysis were performed in the same manner as in Example 1 except that 2.336 mmol of aluminum chloride was used instead of samarium chloride hexahydrate. As a result, the 1-hexene conversion rate was 78% and the carboxylic acid ester selectivity was 9%.
At 2%, the proportion of normal-form methyl heptanoate in the ester was 80%.

Example 9 The reaction and analysis were performed in the same manner as in Example 1 except that 2.336 mmol of manganese chloride tetrahydrate was used instead of samarium chloride hexahydrate. as a result,
The conversion rate of 1-hexene was 66%, the selectivity of carboxylic acid ester was 93%, and the ratio of methyl heptanoate which is a normal form in the ester was 82%.

Example 10 The reaction and analysis were performed in the same manner as in Example 1 except that 2.336 mmol of molybdenum (V) chloride was used instead of samarium chloride hexahydrate. as a result,
The conversion rate of 1-hexene was 64%, the selectivity of carboxylic acid ester was 92%, and the ratio of methyl heptanoate which is a normal form in the ester was 82%.

Example 11 The reaction and analysis were carried out in the same manner as in Example 1 except that 2.336 mmol of titanium (IV) chloride was used instead of samarium chloride hexahydrate. As a result, the conversion rate of 1-hexene was 75% and the selectivity of carboxylic acid ester was 9%.
At 2%, the proportion of normal-form methyl heptanoate in the ester was 80%. Examples 1 and 4-11
Table 2 shows the results.

[0035]

[Table 2]

Example 12 The reaction and analysis were conducted in the same manner as in Example 1 except that 10.88 g of 2-hexene was used instead of 1-hexene. As a result, the conversion rate of 2-hexene was 65.
%, The carboxylic acid ester selectivity is 93%, and the ratio of normal-form methyl heptanoate is 75% in the ester.
%Met.

Comparative Example 2 In Example 12, benzene 1 was used in place of isoquinoline.
The reaction and analysis were carried out in the same manner as in Example 12 except that 2.00 g was used. As a result, almost no absorption of carbon monoxide was observed during the reaction, and the 2-hexene conversion rate was only 4%.

Example 13 In Example 1, styrene 1 was used instead of 1-hexene.
The reaction and analysis were carried out in the same manner as in Example 1 except that 4.87 g was used. As a result, the styrene conversion was 100%, the carboxylic acid ester selectivity was 67%, and among the esters,
The proportion of methyl 3-phenylpropionate, which is a normal body, was 80%.

Comparative Example 3 In Example 13, benzene 1 was used in place of isoquinoline.
The reaction and analysis were carried out in the same manner as in Example 13 except that 2.00 g was used. As a result, almost no absorption of carbon monoxide was observed during the reaction, and the styrene conversion rate was 8%.

Example 14 The reaction and analysis were performed in the same manner as in Example 1 except that 6.00 g of propylene was used instead of 1-hexene. It should be noted that propylene was introduced in a predetermined amount at room temperature after the inside of the autoclave was replaced with carbon monoxide. As a result, the propylene conversion was 90%, the carboxylic acid ester selectivity was 95%, and the proportion of methyl butyrate, which is a normal form, in the ester was 80%.

Example 15 The reaction and analysis were carried out in the same manner as in Example 1 except that 12.00 g of 4-pentenenitrile was used instead of 1-hexene. As a result, the 4-pentenenitrile conversion rate was 83%, and the carboxylic acid ester selectivity was 95%.
Then, the proportion of methyl 5-cyanovalerate, which is a normal form, in the ester was 91%.

Example 16 The reaction and analysis were carried out in the same manner as in Example 1 except that 12.00 g of methyl 4-pentenoate was used instead of 1-hexene. As a result, the 4-pentenenitrile conversion rate was 80%, and the carboxylic acid ester selectivity was 90%.
The proportion of normal-form methyl adipate in the ester was 91%.

Example 17 The reaction and analysis were carried out in the same manner as in Example 1 except that 12.00 g of cyclohexene was used instead of 1-hexene. As a result, the cyclohexene conversion rate was 8
4%, and the carboxylate selectivity was 88% (methyl cyclohexanecarboxylate yield: 74%).

Example 18 12.00 g of methanol and 12.00 g of isoquinoline
0.584 mmol of palladium acetate and 2.336 mmol of samarium chloride hexahydrate are dissolved in 1, and 1,4
-Bis (diphenylphosphino) butane 2.920 mm
ol was dissolved. This solution was placed in an autoclave with an internal volume of 100 ml equipped with a stirrer, and after replacing the inside of the autoclave with carbon monoxide, the pressure at room temperature was 33 kg /
Ethylene was introduced until the pressure reached cm ² G, and the pressure was increased to 40
Carbon monoxide was introduced until it reached kg / cm ² G. While stirring, while additionally introducing consumed carbon monoxide, 60 k
After reacting for 1 hour at 145 ° C. under a constant pressure of g / cm ² G, the reaction product was analyzed by gas chromatography.
As a result, the ethylene conversion was 97% and the carboxylic acid ester selectivity was 98% (methyl propionate yield:
95%). The results of Examples 1, 12 to 18 and Comparative Examples 2 and 3 are shown in Table 3.

[0045]

[Table 3]

Example 19 In Example 1, 8.00 g of water was used in place of methanol, and 12.00 g of tetrahydrofuran was used as a reaction solvent.
Reaction and analysis were carried out in the same manner as in Example 1 except that was used. As a result, the conversion rate of 1-hexene was 70%, the selectivity of carboxylic acid was 86%, and the ratio of heptanoic acid as a normal form in the carboxylic acid was 82%.

Example 20 Example 1 was repeated except that 10.00 g of water and 10.00 g of tetrahydrofuran were used and 10.00 g of 4-pentenenitrile was used instead of 1-hexene.
Reactions and analyzes were performed as in 4. As a result, the 4-pentenenitrile conversion rate was 81% and the carboxylic acid selectivity was 92%.
In the carboxylic acid, the ratio of normal-form 5-cyanovaleric acid was 92%. .

[0048]

INDUSTRIAL APPLICABILITY According to the present invention, (a) an olefin is reacted with (b) carbon monoxide and (c) an alcohol or water to give a carboxylic acid ester or a carboxylic acid under mild conditions where the pressure of carbon monoxide is low. (Especially normal body) can be produced with high reaction rate and high selectivity.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C07C 69/24 C07C 69/24 69/612 69/612 69/75 69/75 Z 253/30 8927 -4H 253/30 255/19 8927-4H 255/19 // C07B 61/00 300 C07B 61/00 300

Claims (2)

[Claims] (1) palladium, (2) a compound represented by the general formula (I), (Wherein, M ¹ and M ² represent P or As, and R has 1 carbon atom.
Represents a divalent organic bridging group of from ¹ to 8, R ¹ , R ² , R ³ , R
⁴ represents an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 12 carbon atoms. ) (3) A metal halide represented by the general formula (II), and (In the formula, M ³ is Fe, Cu, Sn, Zn, Mn, Al,
Mo, Ti or a lanthanoid atom is shown, X is a halogen atom, and n is an integer of 1 to 4. (4) Carboxylic acid ester characterized by adding N-heterocyclic base to alcohol or water to react (a) olefin with (b) carbon monoxide and (c) alcohol or water. Method for producing carboxylic acid. 2. The method for producing a carboxylic acid ester or a carboxylic acid according to claim 1, wherein the N-heterocyclic base is a pyridine compound or a condensed N-heterocyclic compound.