JP3278925B2 - Process for producing octadienols and palladium complex - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to an octadienol which is a dimerized hydrate of butadiene by reacting 1,3-butadiene with water in the presence of a palladium compound, a phosphine compound and carbon dioxide. To an improved method of manufacturing the same.

[0002]

2. Description of the Related Art Among octadienols, octa-2,7-dien-1-ol is a compound important in the chemical industry as an intermediate for producing n-octanol and its esters. is there. A method of producing 1,3-butadiene and water by reacting 1,3-butadiene with water in the presence of a palladium compound, a phosphine compound and carbon dioxide is described in, for example, (Chemical Communications (Chemical Communications)).
cations) 330 (1971)) and Shoko 50
No. -10565. In this case, triphenylphosphine is known to be advantageous as a phosphine compound used as a ligand of the palladium catalyst, but the yield of octadienols and the desired octa-2,7-diene- The selectivity to 1-ol is not yet sufficient. It is also known that the use of triphenylphosphine in an excess of about 6 times the molar amount of palladium lowers the yield of octadienols (Chemical Communications, supra). There was also.

When a reaction for producing octadienols is carried out in a liquid phase system by this method, butadiene and water are simultaneously brought into contact with the catalyst component,
The operation of separating the generated octadienols from the catalyst by means such as distillation is performed continuously or batchwise. Then, at least the catalyst liquid containing the palladium compound and the phosphine is recycled to the reaction.

[0004] The applicant of the present invention first deposits a palladium complex from at least a part of a reaction solution of the above catalyst component in the production of alkadienols, and then supplies the complex to the reaction system again. Thus, a method of recirculating the catalyst in a form not containing by-products of a high-boiling substance that might hinder the reaction was proposed. (JP-A-2-174736)

[0005]

In the complex catalysis, the metal component used in the catalyst plays an important role, and the ligand used therewith also has a significant effect on the activity and selectivity of the catalysis. The present inventors have found that by using an optimal phosphine ligand for a dimerization hydration reaction of reacting 1,3-butadiene with water in the presence of a palladium compound, a phosphine compound and carbon dioxide, a desired 2,7- The present inventors have intensively studied to provide an industrially advantageous method for producing octadienols, which can provide -octadien-1-ol with high yield and high selectivity.

[0006] The catalyst reaction solution contains expensive substances such as palladium and phosphine, and the economical loss when these catalyst components are not effectively used is extremely large. Therefore, it is important for the industrially advantageous production of octadienol to take out only the catalyst component in a stable form by economic means without impairing the catalytic activity and to use it in the reaction in a cyclic manner. It is.

The method disclosed in the above-mentioned Japanese Patent Application Laid-Open No. 2-174736 discloses that the palladium complex used for precipitation circulation may have a problem in air stability depending on the kind of phosphine which is one of the catalyst components. Yes, it would be advantageous as a more industrial process if it could be handled with a more easily handled form of the palladium complex.

[0008]

The process for producing octadienols of the present invention comprises reacting 1,3-butadiene with water in the presence of a palladium compound, a phosphine compound and carbon dioxide to convert the octadienols. In the production method, the phosphine compound represented by the general formula (I)

[0009]

Embedded image

[0010] (wherein, R ^1, R ⁵ and R ⁹ represent respectively mutually different hydrocarbon group which may be substituted, also, R ^2,
At least one of R ³ , R ⁴ , R ⁶ , R ⁷ , R ⁸ , R ¹⁰ , R ¹¹ and R ¹² is an electron-donating substituent, and is hydrogen or a substituent which may be different from each other Represents a compound represented by the formula:
The novel bis (phosphine) palladium complex of the present invention is
It is characterized by comprising phosphine represented by the general formula (I) and palladium.

That is, the present inventors have proposed a palladium compound,
In a reaction for producing octadienols from 1,3-butadiene and water in the presence of a phosphine compound and carbon dioxide, the presence of a phosphine compound having the specific structure, which is not conventionally known, as a phosphine ligand. ,
Surprisingly, the high yield of octadienols, the high selectivity of 2,7-octadien-1-ol and the wide range of operating conditions can be selected, and also the reaction product obtained by the reaction. After depositing a catalyst containing a novel bis (phosphine) palladium complex which is stable even in air, has high thermal stability and is easy to handle, from at least a part of the liquid, the catalyst is again used in the reaction system. The present inventors have found that only the catalyst component can be recycled without losing its effectiveness as a catalyst, thereby completing the present invention.

Hereinafter, the present invention will be described in detail. Usually readily those available as butadiene feedstock for the preparation is reacted with water octadienols by the method of the present invention, C ₄ fraction of purified 1,3-butadiene and a so-called BBP That naphtha decomposition product And mixtures. In the case where BBP is used as a raw material mainly in consideration of economy, the raw material B
It is desirable to separate and remove acetylenes and allenes contained in the BP in advance. The method for reducing acetylenes and allenes is not particularly limited,
Known methods can be appropriately adopted. After removing or reducing acetylenes and allenes, the total concentration of acetylenes and allenes in the 1,3-butadiene raw material to be subjected to the dimerization hydration step for producing octadienols is possible. As low as possible is desirable, but usually 1.0% by weight or less based on 1,3-butadiene is a preferable amount.

As water as another raw material, water having a purity that does not affect the dimerization hydration reaction is appropriately used. The amount of water used is not particularly limited, but is usually selected from the range of 0.5 to 10 mol, preferably 1 to 5 mol, per mol of 1,3-butadiene. The form of the palladium compound used as the main catalyst in the present invention and its valence state are not necessarily limited.
In addition to a novel bis (phosphine) palladium complex having a phosphine structural formula of the general formula (I), for example, tetrakis (triphenylphosphine) palladium, tris (dibenzylideneacetone) dipalladium, (1,5
-Cyclooctadiene) (maleic anhydride) palladium complexes such as palladium, inorganic salts of palladium such as palladium nitrate, organic salts of palladium such as palladium acetate,
In addition to palladium chelate compounds such as bis (acetylacetone) palladium, divalent palladium complexes such as bis (tri-n-butylphosphine) palladium acetate and the like can be mentioned.

The amount of these palladium compounds used varies widely, but is usually 0.00001 to 1 gram atom, preferably 0.0001 to 0.1 gram atom of palladium per mole of 1,3-butadiene. Selected within the range. The phosphine compound used in the method of the present invention is a compound represented by the general formula (I).

R ¹ , R ⁵ and R ^{9 in the} general formula (I)
Represents a hydrocarbon group which may be different from each other, but is preferably a lower alkyl group having 1 to 4 carbon atoms,
Particularly, a methyl group is preferable. R ² , R ³ , R ⁴ , R ⁶ , R
⁷ , R ⁸ , R ¹⁰ , R ^11, and R ¹² are at least one of electron-donating substituents having a negative Hammett σ value and may be hydrogen or a substituent which may be different from each other, preferably Represents a donating substituent.

Examples of the electron donating substituent include an alkyl group, an alkylamino group, an amino group, an alkoxy group, a hydroxyl group and the like, and an electron-withdrawing halogen atom, a cyano group, a carbonyl group and a sulfonate group. Those having a substituent and having an electron donating property as a whole may be mentioned, and among them, an alkyl group and an alkoxy group are preferable. In particular, among these alkyl groups and alkoxy groups, those having 1 to 20 carbon atoms are preferable.

Specific examples of the phosphine compound include tris (2,4-dimethylphenyl) phosphine, tris (2,3-dimethylphenyl) phosphine, tris (2,5-dimethylphenyl) phosphine and tris (2,4,4). 5-trimethylphenyl) phosphine, tris (2,3,4-trimethylphenyl) phosphine, tris (2,3,4,5-tetramethylphenyl) phosphine, tris (2-methyl-4-ethylphenyl) phosphine, tris (2-methyl-4-octylphenyl)
Phosphine, tris (2-methyl-4- (2-sodium sulfonate) ethylphenyl) phosphine, tris (2-methyl-4- (2-lithium sulfonate) ethylphenyl) phosphine, bis (2,4-dimethylphenyl) ( 2-methylphenyl) phosphine, (2,4-
Dimethylphenyl) bis (2-methylphenyl) phosphine, bis (2,4-dimethylphenyl) (2-ethylphenyl) phosphine, tris (2-methyl-4-methoxyphenyl) phosphine, tris (2-methyl-4-
Ethoxyphenyl) phosphine, tris (2-methyl-
4-octoxyphenyl) phosphine, tris (2-methyl-4- (2-ethoxy) ethoxyphenyl) phosphine, tris (2-methyl-4- (2-sodium sulfonate) ethoxyphenyl) phosphine, tris (2
-Methyl-4- (2-lithium sulfonate) ethoxyphenyl) phosphine, bis (2-methyl-4-methoxyphenyl) (2-methylphenyl) phosphine, (2
-Methyl-4-methoxyphenyl) bis (2-methylphenyl) phosphine, tris (2-methyl-4-dimethylaminophenyl) phosphine, tris (2-methyl-
4-decoxyphenyl) phosphine, tris (2-methyl-4- (1-methyl-heptoxy) phenyl) phosphine, tris (2-methyl-4- (t-butyl) phenyl) phosphine and the like. However, the present invention is not limited to this.

The amount of the phosphine compound used is usually
It is selected from a wide range of about 0.1 to 100 mol per gram atom of palladium, preferably 3 to 50 mol, particularly preferably 4 to 20 mol, and a wide range of operating conditions can be selected. The carbon dioxide used in the method of the present invention may be any carbon dioxide that exists as carbon dioxide in the reaction system, and the supply form is not particularly limited.
For example, molecular carbon dioxide, carbonic acid, carbonate, bicarbonate, or an adduct of carbon dioxide or carbonic acid with an amine can be used. The upper limit of the amount of carbon dioxide used is determined for economic reasons, and its excessive use does not particularly hinder the reaction. Usually, carbon dioxide is present in an amount of at least 1 mole, preferably 1 mole, per gram atom of palladium.
0 mol or more is used.

In carrying out the method of the present invention, it is preferable to use a solvent in order to carry out the reaction more smoothly. Solvents that can be used include diethyl ether, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, ethers such as tetraethylene glycol dimethyl ether, acetone, methyl ethyl ketone,
Diethyl ketone, methyl isopropyl ketone, ethyl
ketones such as n-butyl ketone; nitriles such as acetonitrile, propionitrile and benzonitrile; aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; alkanes such as pentane, hexane and heptane; hexene and octene; Alkenes, sulfoxides such as dimethyl sulfoxide, nitrobenzene, nitro compounds such as nitromethane, pyridine, pyridine derivatives such as α-picoline, acetamide, propionamide,
Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide and the like can be mentioned. In addition, methanol, ethanol, n-
Examples thereof include alcohols such as propanol, isopropanol, n-butanol, isobutanol, t-butanol and n-octanol, and carboxylic acids such as formic acid, acetic acid, propionic acid and butyric acid. Of these, particularly when a lower alcohol is used, a by-product such as alkoxyoctadiene is not generated, and when a lower carboxylic acid is used, a by-product such as acyloxyoctadiene is not generated, which complicates the reaction system. Need to be careful together.

The use amount of the solvent is not necessarily limited, but usually, 1,3-butadiene 1 is used.
0.1 to 50 parts by weight, preferably 1 to 50 parts by weight,
It is arbitrarily selected from the range of 10 parts by weight. The reaction temperature for reacting 1,3-butadiene with water according to the present invention can be selected from a wide range from room temperature to about 180 ° C, but it is more general to select a temperature range of 50 to 130 ° C. It is. However, since a large amount of undesired by-products is generated in a high temperature range of 90 ° C. or higher, it is preferable to select a lower temperature range in order to obtain octadienols with good yield. In this case, the reaction rate is a problem, but by using the phosphine compound having the specific structure of the method of the present invention, octadienols can be produced with a sufficient rate and a high yield even in a lower temperature range. The reaction pressure is selected from a range from normal pressure to about 200 kg / cm ² .
At this time, in addition to carbon dioxide, an inert gas such as nitrogen, helium, argon or the like can coexist in the reaction.

In the present invention, 1,3-butadiene and water are reacted with each other under the above-described reaction raw materials and reaction conditions to produce octadienols. The reaction product solution obtained by this reaction contains a catalyst, 2,7-octadien-1-ol as a main product, and 1,7 as a by-product.
-Octadien-3-ol, octatrienes, dioctadienyl ethers, organic carboxylic acids and esters, and a solvent, unreacted 1,3-butadiene and water. The amount of by-products produced depends on the reaction conditions and is usually around a few mole percent on a 1,3-butadiene basis.

In the method of the present invention, as an additional step, a catalyst component containing a complex comprising palladium and phosphine is precipitated from a reaction product solution obtained by the reaction, and then the catalyst component is supplied to the reaction system again. However, the novel bis (phosphine) palladium complex comprising phosphine and palladium represented by the general formula (I) has high thermal stability, is easy to handle, and hardly causes a decrease in the activity of the catalyst accompanying circulation. It is advantageously used in circulation.

In order to form such a complex, the phosphine in the reaction product solution is in a free state capable of coordinating with palladium, and is at least twice, preferably at least 3 moles per gram atom of palladium. It is preferred to treat the reaction solution so that it is present at twice the molar amount. Specifically, the reaction solution or a part of the reaction solution containing the catalyst component is brought into contact with a basic substance, or with a reducing agent such as hydrogen, or the like, and is in a free state in which phosphine can be coordinated. Perform the operation described below. Naturally, supplying phosphine additionally to the reaction solution is also an effective means.

When the reaction solution or a part of the reaction solution containing the catalyst component is brought into contact with a basic substance, the basic substance may be a hydroxide formed of an alkali metal, an alkaline earth metal and ammonium ion, Oxides, alkoxides, carboxylates, carbonates and bicarbonates can be used. Specifically, lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium oxide,
Examples include calcium oxide, barium oxide, sodium ethoxide, sodium acetate, sodium carbonate, calcium carbonate, sodium bicarbonate and the like.

The basic substance is generally used in a form dissolved in a solvent such as water, but it can be used in a solid form. The concentration of the basic substance when used as a solution is not particularly limited, but is usually 0.05 to 5 mol / mol.
One solution is advantageously used. The amount of the basic substance used is not necessarily limited, but is preferably at least equimolar to phosphine.

The temperature at which the reaction product solution is contacted with a basic substance or a reducing agent such as hydrogen is preferably 0 to 150 ° C, particularly preferably 20 to 100 ° C. Further, in order to precipitate the catalyst efficiently, it is more preferable to cool the catalyst after the contact treatment. The catalyst precipitated from a part of the reaction solution containing the reaction product solution or the catalyst component can be easily separated and recovered by a known technique such as filtration or decantation. Part or all of the separated and recovered catalyst is subjected to a reaction of reacting 1,3-butadiene with water again to produce octadienols, if necessary.

The novel bis (phosphine) palladium complex whose phosphine is represented by the above general formula (I) is a known palladium zero-valent phosphine complex, for example, tetrakis (triphenylphosphine) palladium, tris ( It can also be synthesized by a method similar to that of triphenylphosphine) palladium. That is, D.
R. Coulson, Inorg. Synth. , 1
3,121 (1972), by reducing a divalent palladium complex such as palladium chloride with a reducing agent such as hydrazine hydrate in the presence of a predetermined phosphine ligand. can get.

The method of the present invention may be practiced using well-known techniques, including continuous, semi-continuous and batch operations. The main product, octadienols, can be recovered from the reaction product liquid or the filtrate from which the catalyst has been separated by the above operation, by various means, for example, distillation. A part or all of the catalyst and the remaining reaction mixture can be recirculated to the reaction system as it is or by separating and obtaining the catalyst by the above operation.

[0029]

EXAMPLES Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist.

Example 1 In a 300 ml stainless steel autoclave, under a nitrogen gas atmosphere, 0.36 mmol of palladium acetate, 1.44 mmol of tris (2,4-dimethylphenyl) phosphine, 61 g of acetone and 6 g of acetone were added. 0.5 g of water were charged, and 11 g of 1,3-butadiene and 11 g of carbon dioxide were further introduced. While stirring the reaction mixture at a speed of 800 rpm, the mixture was heated to an internal temperature of 80 ° C. over 20 minutes. After continuing the reaction at 80 ° C for another 2 hours,
The reaction products were analyzed by gas chromatography. Table 1 shows the results.

Examples 2 to 5 and Comparative Examples 1 and 2 The same procedures as in Example 1 were carried out except that the phosphine compounds shown in Table 1 were used instead of tris (2,4-dimethylphenyl) phosphine. Table 1 shows the results.

[0032]

[Table 1]

Example 6 Using 0.5 mmol of palladium acetate, 2 mmol of tris (2,4-dimethylphenyl) phosphine, 50 g of acetone, 18 g of water, 27 g of 1,3-butadiene and 15 g of carbon dioxide The reaction was carried out under the same operating conditions as in Example 1 except that the reaction was carried out for 4 hours. Table 2 shows the results.

Example 7 The same procedure as in Example 4 was carried out except that the reaction temperature was changed to 90 ° C. Table 2 shows the results.

Example 8 The procedure of Example 3 was repeated except that the amount of tris (2,4-dimethylphenyl) phosphine used was 8 mmol and the reaction time was 3 hours. Table 2 shows the results.

[0036]

[Table 2]

Example 9 Tris (2,3,4,5-tetramethylphenyl) was used instead of tris (2,4-dimethylphenyl) phosphine
Example 1 except that the reaction was carried out using phosphine for 4 hours.
The same was done. ΣHOD is 88.5%, 1-HOD /
ΣHOD is 93%, NOT is 1.6%, DODE is 2.
9%.

Example 10 (Synthesis of bis (tris (2,4-dimethylphenyl) phosphine) palladium complex) A stainless steel induction stirring autoclave having an inner volume of 300 ml was placed in a nitrogen gas atmosphere under a nitrogen gas atmosphere.
mmol palladium acetate, 17.5 mmol tris (2,4-dimethylphenyl) phosphine, 50 ml methanol were charged, and 25 ml 1,3-butadiene was further introduced. While stirring the reaction mixture at 800 rpm, the mixture was heated over 20 minutes until the internal temperature reached 80 ° C., and the reaction was continued at 80 ° C. for another 1.5 hours. After cooling to room temperature, the formed yellow palladium complex was filtered off, and methanol 40m
After washing with 1 l and further with 40 ml of n-hexane, 2.82 g of the obtained crystals were dried under reduced pressure at room temperature.

[0039]

Table 3 Elemental analysis results Pd 13.3% C 72.82% H 7.03% (same calculated value) (13.3) (72.13) (6.81)

From the result of elemental analysis, it was confirmed that the palladium complex obtained was a bis (tris (2,4-dimethylphenyl) phosphine) palladium complex. The thermal stability and the stability in air were examined by DSC (differential scanning calorimeter) and TG-DTA (differential thermogravimetry), respectively. The results are shown in Table 3, as shown in the known analogous complex (bis (tris (2
-Methylphenyl) phosphine) palladium).

Comparative Example 3 (Synthesis of bis (tris (2-methylphenyl) phosphine) palladium complex) In Example 10, tris (2-methylphenyl) phosphine was used in place of tris (2,4-dimethylphenyl) phosphine. The synthesis was carried out in exactly the same manner except for using. DSC, TG-DTA
Table 3 shows the results.

[0042]

[Table 4] * 1) Measurement conditions: 1 mg of sample, Ag pressure cell (enclosed in N ₂ ) 10 ° C./min, N ₂ 50 ml / min * 2) Measurement conditions: 5 mg of sample, Al pan 10 ° C./min, Air 200 ml / min

Example 11 0.75 mmol of bis (tris (2,4-dimethylphenyl) phosphine) palladium and tris (2,4-
1.5 mmol of dimethylphenyl) phosphine, 55
g of acetone and 10 g of water.
g of 1,3-butadiene and 11 g of carbon dioxide,
The reaction was carried out for 1.5 hours in the same manner as in Example 1. After distilling off acetone as a solvent under reduced pressure at room temperature, tris (2,4-dimethylphenyl) phosphine was added to 1.5 mm
1 mol / l sodium hydroxide aqueous solution 1
After adding 00 ml and reacting at 60 ° C. for 1 hour, the mixture was ice-cooled. After separating the aqueous phase, the organic phase containing the yellow precipitated complex was washed twice with 50 ml of water, and the solid component was filtered off. 55% of the obtained solid component (containing bis (tris (2,4-dimethylphenyl) phosphine) palladium)
Using 1.5 g of acetone, 10 g of water, 20.2 g of 1,3-butadiene, and 11 g of carbon dioxide, the reaction was carried out for 1.5 hours in the same manner as the first time. Table 4 shows the analysis results of the respective reaction products.

[0044]

[Table 5]

Example 12 0.377 mmol of palladium acetate and 1.5 mm of tris (2-methyl-4-methoxyphenyl) phosphine were added.
ol, 55 g of acetone and 10 g of water, and further reacted for 5 hours in the same manner as in Example 1 using 20.2 g of 1,3-butadiene and 11 g of carbon dioxide. After distilling off the solvent acetone under reduced pressure at room temperature, 0.75 mmol of tris (2-methyl-4-methoxyphenyl) phosphine was added, and 100 ml of a 1 mol / l sodium hydroxide aqueous solution was added. After reacting at 1 ° C. for 1 hour, the mixture was cooled with ice. After separating the aqueous phase, the organic phase containing the yellow precipitated complex was washed twice with 50 ml of water, and the solid component was filtered off. The obtained solid component (bis (tris (2-
Containing methyl-4-methoxyphenyl) phosphine) palladium), 55 g acetone, 10 g water, 20.
Using 1 g of 1,3-butadiene and 11 g of carbon dioxide, the reaction was carried out for 5 hours in the same manner as the first time. Table 5 shows the analysis results of the respective reaction products.

[0046]

[Table 6]

[0047]

According to the method of the present invention, 1,3-butadiene is reacted with water in the presence of a palladium compound, a phosphine compound having a specific structure and carbon dioxide to give octadienols in high yield. Also, 2,7-octadiene-1
The present invention provides an industrially advantageous method for producing octadienols, which enables highly selective production of all.

The novel bis (phosphine) of the present invention
The palladium complex has excellent thermal stability and is easy to handle. In the above-mentioned method for producing octadienols, even if it is precipitated from the reaction product liquid and supplied to the reaction system again, there is almost no decrease in the activity of the catalyst, which is advantageous. Used for circulation.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-3-232831 (JP, A) JP-A-2-174736 (JP, A) JP-A 64-25739 (JP, A) JP-A 54-1979 144307 (JP, A) JP-A-54-32411 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07C 33/02 C07C 29/44 CA (STN) REGISTRY (STN)

Claims (4)

(57) [Claims] 1. A method for producing octadienols by reacting 1,3-butadiene with water in the presence of a palladium compound, a phosphine compound and carbon dioxide,
As the phosphine compound, a compound represented by the general formula (I): (Wherein, R ¹ , R ⁵ and R ⁹ each represent a hydrocarbon group which may be different from each other, and R ² , R ³ , R ⁴ ,
At least one of R ⁶ , R ⁷ , R ⁸ , R ¹⁰ , R ¹¹ and R ¹² is an electron-donating substituent, and represents hydrogen or a substituent which may be different from each other) A process for producing octadienols, characterized by the presence of a compound. 2. The method for producing octadienols according to claim 1, wherein a catalyst component containing a complex composed of palladium and phosphine is precipitated from a reaction product liquid obtained by reacting 1,3-butadiene with water. A process for supplying the catalyst component to the reaction system again after the reaction. 3. The method for producing octadienols according to claim 2, wherein the complex comprising palladium and phosphine is a bis (phosphine) palladium complex comprising phosphine and palladium represented by the general formula (I). A method characterized by: 4. A bis (phosphine) palladium complex comprising phosphine and palladium represented by the general formula (I).