JP2002371089A - Phosphonium salt, its production method and its use - Google Patents

Abstract

(57) [Problem] Even when conducting a telomerization reaction between a conjugated diene compound and an active hydrogen compound on an industrial scale continuously for a long period of time, precipitates such as inorganic salts are completely precipitated in the reaction system. The present invention provides a phosphonium salt which is a component of a telomerization catalyst. SOLUTION: General formula (I) (Wherein, R ¹ and R ² each represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, and R ³ may have a hydrogen atom or a substituent. Represents a hydrocarbon group having 1 to 5 carbon atoms, R ⁴ and R ⁵ each represent a phenyl group optionally substituted with a lower alkyl group, and R ⁶ represents a phenylene group optionally substituted with a lower alkyl group; A phosphonium salt represented by the following formula:

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a phosphonium salt,
The present invention relates to a method for producing the same and uses of the phosphonium salt.
The phosphonium salt provided by the present invention is useful as a component of a catalyst for promoting a telomerization reaction between a conjugated diene compound and an active hydrogen compound. Accordingly, the above-mentioned applications include telomerization catalysts comprising the phosphonium salt provided by the present invention as a component, and also include methods for producing alkadienyl compounds using the telomerization catalyst. Alkadienyl compounds such as 2,7-octadien-1-ol, 1,7-octadien-3-ol, 1-acetoxy-2,7-octadiene, 1-amino-2,7-octadiene obtained by a telomerization reaction Is used as a raw material for various polymer compounds, medicines, agricultural chemicals and the like.

[0002]

2. Description of the Related Art Japanese Patent Publication No. 54-6270 reports a method for telomerizing diene in the presence of a catalyst comprising a water-soluble phosphine and a palladium compound. As the above-mentioned water-soluble phosphine, a quaternary ammonium salt of (sulfophenyl) diphenylphosphine, di (sulfophenyl) phenylphosphine or tri (sulfophenyl) phosphine is known, and among these, phosphorus (trivalent) is actually used. The tetraethylammonium salt of tri (3-sulfophenyl) phosphine containing 60% is used for the telomerization reaction of butadiene. Such a tetraethylammonium salt of tri (3-sulfophenyl) phosphine has phosphorus (5
Value). According to the findings of the present inventors, when phosphine containing a large amount of phosphorus (pentavalent) as an impurity is used as a component of the telomerization catalyst, the impurity accumulates in the reaction system and the solubility of the reaction substrate changes. Has been found to adversely affect the reaction.

[0003] Applied Catalysis A: Gen
eral), 131, pp. 167-178 (1995)
Year), the dimethyldodecylamine salt of diphenylphosphinobenzene-3-monosulfonic acid (water-insoluble) is
Utilizing its surface activity, it is used in the telomerization reaction of butadiene. However, its reaction rate is low.

JP-A-63-88150 discloses that as a ligand for a hydroformylation catalyst, higher amine salts such as trioctyl ammonium salt, dimethyl octyl ammonium salt and dimethyl dodecyl ammonium salt of diphenylphosphinobenzene-3-sulfonic acid are used. Is described. JP-A-8-176168 describes a sulfonated phosphine as a component of a water-soluble catalyst system for a CC bond-forming reaction such as a hydroformylation reaction. ,Boric acid,
Sulfonate in a mixture of concentrated sulfuric acid, treat with a solution of triisooctylamine in toluene to introduce the triisooctylamine salt of the sulfonated phosphine into the organic phase, and then wash the organic phase with sodium hydroxide solution. Extraction gives the sodium salt of the sulfonated phosphine. The higher amine salts, which are ligands or synthetic intermediates of these hydroformylation catalysts, are insoluble in water, and no industrially advantageous telomerization catalyst can be obtained.

In general, in a catalyst comprising phosphine and a transition metal, if the amount of phosphine is large, the stability of the catalyst is good, but the catalytic activity cannot be sufficiently exhibited, and if the amount of phosphine is small, the stability of the catalyst is insufficient. Rather, it cannot exhibit sustained catalytic activity. As described above, the activity and stability of the catalyst are contradictory, and when a catalyst containing phosphine as a component is used, an alkadienyl compound cannot be industrially advantageously produced.

As the above-mentioned improvement technique, Japanese Patent Application Laid-Open No.
No. 988 (Japanese Patent No. 2635519) reports a method of performing a telomerization reaction using a catalyst comprising a phosphonium salt and a palladium compound.
For example, a telomerization reaction between a conjugated alkadiene and water is carried out using a water-soluble compound containing a group represented by the formula —SO ₃ M or —COOM (where M represents an alkali metal atom such as lithium, sodium, or potassium). The reaction is carried out under pressure of carbon dioxide in the presence of a mixed solvent of sulfolane and water using a catalyst comprising a phosphonium salt and a palladium compound.

[0007]

DISCLOSURE OF THE INVENTION The present inventors have developed butadiene using a telomerization catalyst comprising a phosphonium salt derived from an alkali metal salt of diphenylphosphinobenzene-3-monosulfonic acid and a palladium compound. When the dimerization reaction with water was performed continuously for a long period of time, it was found that precipitates might be precipitated in the reaction system, and such precipitation caused clogging of pipes and reduction in heat transfer efficiency of the reactor. Admitted to cause.

As a result of the present inventors' efforts to investigate the cause of the generation of precipitates, when the dimerization reaction of butadiene and water is continuously performed for a long period of time, the alkali contained as a component of the phosphonium salt in the reaction solution is considered. That the concentration of metal ions unexpectedly increases, or that such alkali metal ions react with bicarbonate ions or carbonate ions as reaction accelerators to form alkali metal bicarbonates and / or alkali metal carbonates; It has been clarified that metal salts precipitate as precipitates. Originally, under the conditions of the dimerization reaction between butadiene and water, the above phenomenon was extremely surprising since the alkali metal bicarbonate and the alkali metal carbonate kept in a dissolved state.

An object of the present invention is to provide a telomerization method in which no precipitate is deposited in a reaction system even when a telomerization reaction between a conjugated diene compound and an active hydrogen compound is continuously performed for a long period on an industrial scale. An object of the present invention is to provide a phosphonium salt which is a component of a catalyst and a method for producing the same.
Another object of the present invention is to provide a telomerization catalyst comprising the above phosphonium salt as a constituent.
Still another object of the present invention is to provide a method for producing an alkadienyl compound from a conjugated diene compound and an active hydrogen compound using the telomerization catalyst.

[0010]

According to the present invention, the above objects have been achieved by the general formula (I)

[0011]

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(Wherein, R ¹ and R ² each represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, and R ³ represents a hydrogen atom or a substituent. Represents a hydrocarbon group having 1 to 5 carbon atoms which may be substituted, R ⁴ and R ⁵ each represent a phenyl group which may be substituted with a lower alkyl group, and R ⁶ may be substituted with a lower alkyl group (Which represents a phenylene group) [hereinafter, this is abbreviated as phosphonium salt (I)], a general formula (II)

[0013]

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(Wherein R ¹ , R ² and R ³ are as defined above, and X is a hydroxyl group, an alkoxyl group, an alkenyloxy group, an acyloxy group, a carbonate group or a phenoxy optionally having a substituent. Alkenyl compound represented by the general formula (III):

[0015]

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(Wherein R^Four , R^Five And R⁶ Is the definition above
And R⁷ , R⁸ And R ⁹ Is low
Represents an alkyl group. The phosphine compound represented by
This is abbreviated as phosphine compound (III) below]
Characterized by reacting in the presence of a palladium compound
For producing phosphonium salt (I), which comprises:
Characterized by containing no alkali metal compound
Telomerization catalyst [hereinafter referred to as telomerization catalyst
Abbreviated as catalyst (I)), and the presence of a catalyst comprising a conjugated diene compound and an active hydrogen compound.
When producing an alkadienyl compound by reacting
And a telomerization catalyst (I) is used as the catalyst.
For producing an alkadienyl compound
Is achieved by providing

[0017]

DETAILED DESCRIPTION OF THE INVENTION The phosphonium salt (I) has extremely high solubility in a telomerization reaction system, gives excellent reaction results as a component of a telomerization catalyst, and does not contain an alkali metal. The alkali metal salt does not precipitate in the reaction system.

In the above formula, the hydrocarbon group having 1 to 12 carbon atoms represented by R ¹ and R ² includes, for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-butyl group.
Aliphatic hydrocarbon groups such as alkyl groups such as pentyl group and n-octyl group, alkenyl groups such as 2-propenyl group, 3-butenyl group and 4-pentenyl group; alicyclic groups such as cycloalkyl groups such as cyclohexyl group A hydrocarbon group; an aryl group such as a phenyl group and a tolyl group; and an aromatic hydrocarbon group such as an aralkyl group such as a benzyl group.
Examples of the hydrocarbon group having 1 to 5 carbon atoms represented by R ³ include an alkyl group such as a methyl group, an ethyl group and a propyl group; and an aliphatic hydrocarbon group such as an alkenyl group such as an allyl group and a 4-pentenyl group. No. Examples of the lower alkyl group of the phenyl group represented by R ⁴ and R ⁵ and the lower alkyl group of the phenylene group represented by R ⁶ include those having 1 to 4 carbon atoms such as methyl, ethyl, propyl, and butyl. An alkyl group is mentioned, and among them, a methyl group and an ethyl group are preferable.

As the phosphonium salt (I), R ¹ and R ² in the general formula (I) are each a hydrogen atom or an aliphatic hydrocarbon group having 1 to 12 carbon atoms, and
^A phosphonium salt in which ³ is a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms is preferable, and R ⁴ and R ⁵ in the general formula (I) are each a phenyl group or a phenyl group having a methyl group or an ethyl group. And a phosphonium salt wherein R ⁶ is a 1,3-phenylene group or a 1,3-phenylene group having a methyl group or an ethyl group is preferred. Among them, R ⁴ and R ⁵ are each a phenyl group or a 2-methylphenyl group, and R ⁶ is a 1,3-phenylene group or a 4-methyl-
Phosphonium salts which are 1,3-phenylene groups are particularly preferred.

The alkoxyl group represented by X includes, for example, methoxy, ethoxy, propoxy, butoxy and the like. The alkenyloxy includes, for example, propenyloxy, butenyloxy, allyloxy, 2,7-octa! And a dienyloxy group.
Examples of the acyloxy group include a formyloxy group, an acetyloxy group, and a propionyloxy group. Examples of the substituent of the phenoxy group represented by X include an alkyl group such as a methyl group and an ethyl group, and an alkyloxy group such as a methoxy group and an ethoxy group. Examples of the lower alkyl group represented by R ⁷ , R ⁸ and R ⁹ include, for example, a methyl group, an ethyl group, a propyl group,
An alkyl group having 1 to 4 carbon atoms such as a butyl group;
Of these, a methyl group and an ethyl group are preferred.

Next, a method for producing the phosphonium salt (I) will be described. As the alkenyl compound (II),
For example, allyl alcohol, 1-methyl-2-propene-
1-ol, 2-buten-1-ol, 2,5-hexadien-1-ol, 2,7-octadien-1-ol, 1,4-pentadien-3-ol, 1,7-octadien-3- Allyl alcohols such as all; allyl ethyl ether, diallyl ether, methyl-2,7
-Allyl ethers such as octadienyl ether, di (2,7-octadienyl) ether and allyl phenyl ether; allyl acetate, 2,5-hexadienyl acetate,
Allyl-type esters such as 2,7-octadienyl acetate, 1-vinyl-5-hexenyl acetate, and 2-octenyl propionate are used. Examples of the phosphine compound (III) include triethylammonium
3- (diphenylphosphino) benzenesulfonate,
Trimethylammonium 3- (diphenylphosphino) benzenesulfonate, triethylammonium
3- (bis (2-methylphenyl) phosphino) -4-
Methylbenzenesulfonate or the like is used.

The palladium compound used for producing the phosphonium salt (I) includes, for example, palladium such as palladium acetylacetonate, π-allyl palladium acetate, palladium acetate, palladium carbonate, palladium chloride and bisbenzonitrile palladium chloride. Divalent) compounds; and palladium (zero-valent) compounds such as bis (1,5-cyclooctadiene) palladium and tris (dibenzylideneacetone) dipalladium. When a palladium (divalent) compound is used, a reducing agent for reducing palladium (divalent) to palladium (zero valent) can be used in combination. Examples of the reducing agent include alkali metal hydroxides such as sodium hydroxide, formic acid, sodium phenolate, sodium borohydride, hydrazine, zinc powder, and magnesium. The amount of the reducing agent used is preferably 10 times or less the stoichiometric amount required for the reduction. The amount of the palladium compound to be used is preferably such that the concentration becomes 0.1 to 10 mg atom as palladium atom per liter of the reaction mixture, and more preferably the amount becomes 0.5 to 5 mg atom. .

In preparing the phosphonium salt (I),
For the purpose of accelerating the reaction, carbonate ions and / or
Alternatively, water containing bicarbonate ions can be present. The carbonate ion and / or bicarbonate ion is practically derived from carbon dioxide, bicarbonate such as sodium bicarbonate or carbonate such as sodium carbonate, which gives them in the reaction system. It is particularly preferable to derive from the viewpoint that alkali metal salts are not mixed. When carbon dioxide is used, a tertiary amine or quaternary ammonium hydroxide can be added for the purpose of increasing the carbonate ion concentration in the reaction system.
When carbon dioxide is used, the partial pressure of carbon dioxide is usually 0 to 4.9 MPa (normal pressure to 50 atm) (gauge pressure), and practically 0 to 0.98 MPa (normal pressure to 10 atm) ( Gauge pressure).

When a tertiary amine or quaternary ammonium ion is present in the reaction system, the phosphonium salt (I) is estimated to be in equilibrium with the phosphonium salt represented by the general formula (IV).

[0025]

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(Wherein R ¹ , R ² , R ³ , R ⁴ , R
⁵ and R ⁶ are as defined above, R ¹⁰ represents a hydrogen atom or a hydrocarbon group, R ¹¹ , R ¹² and R ¹³ each represent a hydrocarbon group, Y represents a hydroxyl group, an alkoxyl group, an alkenyloxy group , An acyloxy group, a hydroxycarbonyloxy group, an alkoxycarbonyloxy group, and a phenoxy group which may have a substituent. )

The preparation of the phosphonium salt (I) can be carried out in the presence of an organic solvent which is inert to the reaction and can dissolve the alkenyl compound (II) and the phosphine compound (III). Examples of the organic solvent include ethers such as diethyl ether, tetrahydrofuran, dioxane, and ethylene glycol dimethyl ether;
Secondary or tertiary alcohols such as butyl alcohol and isopropyl alcohol; ketones such as acetone and methyl isobutyl ketone; nitriles such as acetonitrile and benzonitrile; amides such as acetamide and N, N-dimethylformamide; Sulfoxides such as dimethyl sulfoxide; sulfones such as sulfolane; carboxylic acids such as acetic acid and propionic acid; esters such as ethyl acetate and methyl benzoate; aromatic hydrocarbons such as benzene and toluene; Or acyclic aliphatic hydrocarbons. The organic solvent is usually used alone, but may be used in combination.

The preparation of the phosphonium salt (I) is usually carried out in 10
It is performed at a temperature in the range of 〜80 ° C. Further, the atmosphere of the reaction system is preferably a gas atmosphere that does not adversely affect the reaction of carbon dioxide and nitrogen, and such a gas is used alone or in a mixture of two or more.

The phosphonium salt (I) thus obtained can be separated and purified from the reaction mixture by, for example, the following method. Reaction solvent from the reaction mixture,
After the unreacted alkenyl compound (II) and the like are distilled off under reduced pressure, the obtained residue is washed with a solvent in which the phosphonium salt (I) is not dissolved, and the phosphonium salt (I) is obtained by removing the palladium compound. can do.

The phosphonium salt (I) provides the telomerization catalyst (I) of the present invention when combined with the above-mentioned palladium compound. Telomerization catalyst (I)
Contains no alkali metal compound, and even when bicarbonate ions or carbonate ions are present in the telomerization reaction system, the above-mentioned alkali bicarbonate and / or alkali carbonate as precipitates are formed. Never. Further, the mixture obtained by reacting the alkenyl compound (II) and the phosphine compound (III) in the presence of a palladium compound contains the phosphonium salt (I) and the palladium compound. It can be used as a lysis catalyst (I). Further, a reaction solvent, unreacted alkenyl compound (II) and the like are distilled off from the above reaction mixture under reduced pressure, and the resulting mixture can be used as a telomerization catalyst (I).

The concentration of the phosphonium salt (I) in the telomerization catalyst (I) can vary over a wide range but is usually 2 per gram atom of palladium in the palladium compound.
It is preferably at least mol, and more preferably from 4 to 50 mol. As a method of adding the telomerization catalyst (I) to the telomerization reaction system, the phosphonium salt (I) and the palladium compound may be separately added, or a mixture of the phosphonium salt (I) and the palladium compound May be added.

Next, a method for producing an alkadienyl compound by reacting a conjugated diene compound with an active hydrogen compound in the presence of a telomerization catalyst (I) will be described.

Examples of the conjugated diene compound include butadiene and isoprene. The active hydrogen compound is a compound having at least one active hydrogen atom in a molecule, such as water, alcohol, phenol, and the like.
Ammonia, amine, carboxylic acid and the like can be mentioned. Specific examples of alcohol include methanol, ethanol,
Examples thereof include butanol, allyl alcohol, 2-ethylhexanol, octadienol, stearyl alcohol, diethylene glycol, neopentyl glycol, pentaerythritol, trimethylolpropane, and polyethylene glycol. Specific examples of phenol include phenol, cresol, t-butylphenol, and the like. Specific examples of the amine include methylamine, dimethylamine, ethylamine, diethylamine,
Butylamine, morpholine, piperazine and the like. Specific examples of the carboxylic acid include formic acid, acetic acid, propionic acid, adipic acid, benzoic acid, and phthalic acid. The amount of the conjugated diene compound and the active hydrogen compound used varies depending on the type of the compound used and the target product, but the ratio of the active hydrogen compound to the conjugated diene compound is preferably 0.3 to 20 mol per 1 mol. preferable.

In the telomerization reaction, additives can be used for the purpose of increasing the reaction rate. Additives include bases such as aliphatic tertiary amines such as trimethylamine and triethylamine; such bases and carbonic acid;
Salts with acids such as phosphoric acid, acetic acid, boric acid and methanesulfonic acid; weak acids such as boric acid, phosphorous acid and phenol are used. When water is used as the active hydrogen compound, it is preferable to use a carbonate or bicarbonate of an aliphatic tertiary amine as an additive.

When no tertiary amine or quaternary ammonium ion is present in the reaction system, the phosphonium salt (I) constituting the telomerization catalyst (I) exists as it is. On the other hand, when a tertiary amine or quaternary ammonium ion exists in the reaction system, the phosphonium salt (I) is estimated to be in equilibrium with the phosphonium salt represented by the general formula (V).

[0036]

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(Wherein R ¹ , R ² , R ³ , R ⁴ , R
⁵ and R ⁶ are as defined above, R ¹⁴ represents a hydrogen atom or a hydrocarbon group, R ¹⁵ , R ¹⁶ and R ¹⁷ each represent a hydrocarbon group, Z is a hydroxyl group, an alkoxyl group, an alkenyloxy group , An acyloxy group, a hydroxycarbonyloxy group, an alkoxycarbonyloxy group, and a phenoxy group which may have a substituent. )

The telomerization reaction can be carried out with the active hydrogen compound also serving as a solvent, but is preferably carried out in the presence of an organic solvent which does not adversely affect the reaction. When water is used as the active hydrogen compound, it is preferable to use sulfolane, dimethyl sulfoxide, or the like as the organic solvent, and it is more preferable to use sulfolane from the viewpoint of the reaction rate.

The telomerization reaction is 40 to 100
C., and more preferably at a temperature of 60 to 80.degree. In the hydration dimerization reaction using water as the active hydrogen compound, it is desirable to carry out the reaction in the presence of carbon dioxide. Carbon dioxide may be present as carbon dioxide in the reaction system, and is supplied, for example, as molecular carbon dioxide, carbonic acid, carbonate, or bicarbonate. When molecular carbon dioxide is used, the reaction can be performed under carbon dioxide pressure in order to increase the solubility of molecular carbon dioxide in the reaction system. The reaction pressure is 0 to 9.8 MPa (normal pressure to 100 kg / cm ²⁾ , including the vapor pressure of the conjugated diene compound, the reaction product and the solvent at the reaction temperature.
) (Gauge pressure). On this occasion,
An inert gas such as nitrogen or argon can coexist in the reaction. The reaction can be carried out by a batch method or a continuous method, but is preferably carried out industrially by a continuous method.

The telomerization catalyst (I) comprising the phosphonium salt (I) and the palladium compound is separated and recovered from the reaction mixture after the telomerization reaction by a distillation method or an extraction method. It is desirable to recover the catalyst component by an extraction method which has a lower risk of activity degradation and can be recycled for a longer period of time. The extraction method is performed, for example, by performing a telomerization reaction and then subjecting the reaction mixture to an extraction operation using a solvent that does not mix with the reaction solvent as an extractant. Since the telomerization catalyst (I) of the present invention has high water solubility, it is possible to separate the catalyst component as a raffinate component by using a solvent containing water as a reaction solvent. By returning the separated catalyst component to the reaction system as it is, the catalyst component can be recycled while suppressing the loss of the catalyst component.

[0041]

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 Synthesis of Phosphonium Salt In a 100 ml stainless steel autoclave equipped with a stirrer, 0.048 g (0.214 mmol) of palladium acetate and 20 g (45 mmol) of triethylammonium 3- (diphenylphosphino) benzenesulfonate were used. , Water 15 g, 2,7-octadien-1-ol 14 g and 1,4-dioxane 55 ml, and the inside of the system was replaced with carbon dioxide gas.
cm ² ) (gauge pressure), and the temperature was raised to 80 ° C. After continuing to heat and stir for 13 hours, the reaction mixture was taken out by cooling and the solvent was distilled off by an evaporator. The precipitated solid was washed with diethyl ether and dried to obtain 11 g of a white powder. This white powder was subjected to high performance liquid chromatography [eluent: 0.01 mol / liter phosphoric acid aqueous solution / methanol = 35/65 (volume),
Column: L-column ODS (4.6 × 150 m
m, manufactured by The Chemicals Evaluation and Research Institute)]], no peak was observed at the position of the phosphine compound as the raw material. From the results of ¹ H-NMR spectrum analysis, the obtained white powder was determined to be a phosphonium salt represented by the structural formula (VI).

[0043]

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¹ H-NMR (270 MHz, CD ₃ O
D, TMS standard, ppm) δ: 1.27 to 1.36
(M, 2H), 1.80 to 1.90 (m, 2H), 1.
95 to 2.08 (m, 2H), 4.30 (dd, J =
6.9 and 15 Hz, 2H), 4.88-4.9
8 (m, 2H), 5.31 to 5.48 (m, 1H),
5.64 to 5.90 (m, 2H), 7.20 to 7.90
(M, 12H) 8.10 to 8.30 (m, 2H)

Example 2 A telomerization reaction between butadiene and water was carried out by the following method. In a 1 liter glass autoclave,
123.8 g of water, 121.7 g of sulfolane, 41.2 g of triethylamine, 0.128 g of palladium acetate and 6.4 g of the phosphonium salt obtained in Example 1 were added, and the system was replaced with carbon dioxide. Pressure to 0.39MPa (4kg / cm ² ) (gauge pressure)
And After the temperature was raised to 70 ° C., 75 ml of 1,3-butadiene was introduced into the glass autoclave, and the internal pressure was adjusted to 1.37 MPa (14 kg / cm ² ) (gauge pressure) with carbon dioxide to start the reaction. 30 minutes later 1,3-
The reaction was stopped 1 hour after the start of the reaction by adding 45 ml of butadiene. The reaction solution was extracted with 450 ml of hexane, the upper hexane layer was taken out and analyzed, and the lower catalyst liquid layer was returned to the reactor again and the reaction was repeated four times.
Table 1 shows the analysis results of the upper layer. As is clear from Table 1, it was confirmed that the catalyst was not deactivated and the telomerization reaction was in progress.

[0046]

[Table 1]

Example 3 Preparation of Catalyst Solution 0.068 g (0.304 mmol) of palladium acetate and 2.7 g (6) of triethylammonium 3- (diphenylphosphino) benzenesulfonate were placed in a 100 ml stainless steel autoclave equipped with a stirrer. 0.08 mmol), water 16 g, 2,7-octadien-1-ol 4.28 g (34 mmol), triethylamine 5.5
1 g (54.6 mmol) and sulfolane 17.1 g
After replacing the inside of the system with carbon dioxide, 0.69MP
a (7 kg / cm ² ) (gauge pressure)
The temperature was raised to 0 ° C. After continuing heating and stirring for 13 hours as it was, it was cooled to obtain a catalyst liquid. This catalyst solution was analyzed by high performance liquid chromatography, and triethyl ammonium 3
It was confirmed that all of-(diphenylphosphino) benzenesulfonate was converted to a phosphonium salt in the system.

Example 4 A telomerization reaction between butadiene and water was continuously performed by the following method. That is, 1,3-butadiene, water, sulfolane, triethylamine and the catalyst solution obtained in Example 3 were continuously supplied into the system so as to have the following composition, and the reaction pressure was increased by pressurizing with carbon dioxide. 37MP
a (14 kg / cm ² ) (gauge pressure), reaction temperature 72
The reaction was carried out at a temperature of 1 ° C. and a residence time of 1 hour.

1,3-butadiene: 6% by weight Water: 24% by weight Sulfolane: 40% by weight Triethylamine: 7% by weight Palladium: 200 ppm Phosphonium salt: 20 mole times with respect to palladium

The above reaction was carried out continuously for three months.
No precipitation of a solid such as an inorganic salt was observed.

Comparative Example 1 A catalyst solution was prepared in the same manner as in Example 3, except that lithium 3- (diphenylphosphino) benzenesulfonate was used instead of triethylammonium 3- (diphenylphosphino) benzenesulfonate. This catalyst solution was analyzed by high performance liquid chromatography, and lithium 3
It was confirmed that all of-(diphenylphosphino) benzenesulfonate was converted to a phosphonium salt in the system. In Example 4, when the same reaction was continuously performed for three months by continuously supplying the above-mentioned catalyst solution instead of the catalyst solution obtained in Example 3, lithium (bi) carbonate was deposited. Was allowed to do so.

[0052]

According to the present invention, even when the telomerization reaction between a conjugated diene compound and an active hydrogen compound is carried out continuously on an industrial scale for a long time, precipitates such as inorganic salts are formed in the reaction system. A telomerization catalyst that does not precipitate at all is provided, and a phosphonium salt that is a component of the catalyst and a method for producing the same are provided. Further, by using such a telomerization catalyst, without accompanying precipitation of a precipitate such as a catalyst component or an inorganic salt derived from the component,
An alkadienyl compound can be obtained from a conjugated diene compound and an active hydrogen compound at a high reaction rate and a high selectivity.

 ────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Fujishi 36-family Towada, Kamisu-cho, Kashima-gun, Ibaraki Prefecture F-term in Kuraray Co., Ltd. 4H050 AA01 AA02 AB40 BB25 BB31 WA16 WB11 WB21

Claims (4)

[Claims] 1. A compound of the general formula (I) (Wherein, R ¹ and R ² each represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, and R ³ may have a hydrogen atom or a substituent. Represents a hydrocarbon group having 1 to 5 carbon atoms, R ⁴ and R ⁵ each represent a phenyl group optionally substituted with a lower alkyl group, and R ⁶ represents a phenylene group optionally substituted with a lower alkyl group; A phosphonium salt represented by the following formula: 2. A compound of the general formula (II) (Wherein, R ¹ and R ² each represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, and R ³ may have a hydrogen atom or a substituent. X represents a hydrocarbon group having 1 to 5 carbon atoms, and X represents a hydroxyl group, an alkoxyl group, an alkenyloxy group, an acyloxy group, a carbonate group, or a phenoxy group which may have a substituent. General formula (II
I) (Wherein, R ⁴ and R ⁵ each represent a phenyl group optionally substituted with a lower alkyl group, R ⁶ represents a phenylene group optionally substituted with a lower alkyl group,
⁷ , R ⁸ and R ⁹ each represent a lower alkyl group. The method for producing a phosphonium salt according to claim 1, wherein the phosphine compound represented by the formula (1) is reacted in the presence of a palladium compound. 3. A telomerization catalyst comprising the phosphonium salt according to claim 1 and a palladium compound, wherein the telomerization catalyst does not contain an alkali metal compound. 4. An alkadenyl compound which is produced by reacting a conjugated diene compound with an active hydrogen compound in the presence of a catalyst, wherein the telomerization catalyst according to claim 3 is used as said catalyst. A method for producing a compound.