JP2635519B2 - Telomerization catalyst and method for producing linear alkadienyl compound using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel telomerization catalyst comprising a phosphonium salt and a method for producing a linear alkadienyl compound using the same.

The phosphonium salt in the present invention is useful as a component of a telomerization catalyst for promoting a telomerization reaction between a conjugated diene and an active hydrogen compound. 2,7 obtained by the telomerization reaction
-Octadien-1-ol, 1-acetoxy-2,7
Linear alkadienyl compounds such as -octadiene and 1-methoxy-2,7-octadiene are useful as raw materials for producing polymers; synthetic raw materials for pharmaceuticals, flavors, agricultural chemicals and the like.

[0003]

2. Description of the Related Art Accounts of Chemical Res.
earch), Vol. 6, pp. 8-15 (1973) and R.E. F. Heck, "Palladium Regents in Organic Synthesis (Pallad)
ium Reagents in Organic S
325-334 [Academic Press, U.S.A., 1985] describes conjugated dienes such as butadiene and isoprene in the presence of palladium catalyst in water, alcohol, carboxylic acid, amine, ammonia. A 1-substituted-2,7-alkadiene is obtained by a telomerization reaction with an active hydrogen compound such as an enamine, active methyl, active methylene or active methine compound, azide, silane, and the like. It is described that favorable reaction results can be obtained by the presence of a ligand such as phosphine.

[0004]

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Wherein R represents a hydrogen atom or a methyl group, and Y represents a group obtained by removing one active hydrogen atom from an active hydrogen compound. As an example of a method for producing 7-alkadiene,
JP-B-48-43327, JP-B-50-1056
No. 5, JP-B-54-6270, and JP-A-56-270.
138129, JP-A-57-134427, and the like, and a method for producing 2,7-octadien-1-ol by subjecting butadiene to a telomerization reaction with water.

In the telomerization reaction between a conjugated diene and an active hydrogen compound in the presence of a palladium catalyst, a tertiary phosphorus compound such as trisubstituted phosphine and trisubstituted phosphite is used as a ligand. Is important not only in affecting the reaction rate and the selectivity of the reaction, but also in stabilizing the palladium catalyst. For this reason, as a telomerization catalyst, a low-valent palladium complex containing a ligand such as trisubstituted phosphine can be used as it is, or a palladium (II) compound can be used in the presence of a ligand such as trisubstituted phosphine. Has been used.

[0007]

The telomerization reaction using a palladium catalyst using the above tertiary phosphorus compound such as trisubstituted phosphine as a ligand has the following problems.

(1) The stability of a palladium catalyst is higher as the concentration of a ligand such as trisubstituted phosphine is higher or as the molar ratio of the ligand to palladium is higher. Drop extremely as the value of [Chemical Communications (Chemical Communications)
Communications) p. 330 (197)
1)), and a linear alkadienyl compound, ie, one of the active hydrogen atoms of the active hydrogen compound.
The selectivity to compounds in which one or more are substituted by 2,7-alkadienyl groups decreases as the molar ratio of ligand to palladium increases [Chemical Communications.
), p. 330 (1971), Japanese Patent Publication No. 50-10565, etc.]. Therefore, it is difficult to satisfy the demand for the property having such a contradictory tendency, that is, to achieve both the stabilization of the palladium catalyst, the high reaction rate, and the high selectivity to the linear alkadienyl compound.

(2) Trisubstituted phosphines used as ligands are easily oxidized in the presence of palladium [Angebande Chemie International Edition in English (Angewandte C)
hemie International Editi
on in English), Vol. 6, pp. 92-93 (1967)]. When this trisubstituted phosphine is cyclically used in a telomerization reaction over a long period of time, phosphine oxide, an oxidation product thereof, accumulates. ,
This phosphine oxide acts as a catalyst poison and adversely affects the telomerization reaction (JP-A-51-41).
No. 03). Moreover, it is difficult to separate and remove such phosphine oxide.

(3) According to the study of the present inventors, when a telomerization reaction is carried out using an excess amount of a trisubstituted phosphine with respect to palladium, for example, the palladium compound and the trisubstituted phosphine are not reacted with each other. It has been found that even when a low-valent palladium complex, which is used as a catalytically active species, is used for a telomerization reaction, the reaction involves a long induction period. In particular, when the telomerization reaction is continuously performed over a long period of time, the added palladium catalyst cannot exhibit sufficient activity immediately, which causes a situation in which a necessary amount of catalyst is added.

Since palladium is an expensive noble metal, when it is used industrially as a catalyst, it is required to increase the productivity per unit amount of palladium and to maintain the catalytic activity for a long period of time. . From this viewpoint, it is extremely important to solve the above problems (1) to (3).

Thus, one of the objects of the present invention is to produce a catalyst such as phosphine oxide without performing an induction period in performing a telomerization reaction using a conjugated diene and an active hydrogen compound. It is an object of the present invention to provide a telomerization catalyst containing a novel organophosphorus compound having high activity and capable of giving a linear alkadienyl compound at a high reaction rate and at a high selectivity without any problem. Another object of the present invention is to provide a method for producing a linear alkadienyl compound by reacting a conjugated diene with an active hydrogen compound using the telomerization catalyst.

[0013]

According to the present invention, the general formula

[0014]

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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 has a hydrogen atom or a substituent. represents an hydrocarbon group having 1 to 5 carbon atoms and, R ^4, R
⁵ and R ⁶ are each an optionally substituted hydrocarbon group having 1 to 8 carbon atoms , of which at least 1
Is a phenyl group which may have a substituent , and X represents a hydroxyl group, a hydroxycarbonyloxy group or a lower alkylcarbonyloxy group), and a palladium compound. A catalyst for stabilization is provided.

Further, according to the present invention, in producing a linear alkadienyl compound by reacting a conjugated diene with an active hydrogen compound in the presence of a catalyst, a phosphonium salt represented by the general formula (I) and palladium are used as catalysts. There is provided a method for producing a linear alkadienyl compound, which comprises using a catalyst for telomerization comprising the compound.

In the general formula (I), R ¹ , R ² , R ³ ,
R ⁴ , R ⁵ , R ⁶ and X are described in detail below . R
Examples of the hydrocarbon group having 1 to 12 carbon atoms represented by ¹ and R ² include alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, and n-octyl;
Aliphatic hydrocarbon groups such as alkenyl groups such as -propenyl, 3-butenyl and 4-pentenyl; alicyclic hydrocarbon groups such as cycloalkyl groups such as cyclohexyl; and aryl groups such as phenyl and tolyl, and aralkyl such as benzyl. An aromatic hydrocarbon group such as a group can be exemplified . Examples of the hydrocarbon group having 1 to 5 carbon atoms represented by R ³ include alkyl groups such as methyl, ethyl and propyl;
And aliphatic hydrocarbon groups such as alkenyl groups such as pentenyl . Examples of the hydrocarbon group having 1 to 8 carbon atoms representing R ^4, R ⁵ and R ⁶ are each methyl, ethyl, n- propyl, isopropyl pin le, n- butyl, t- butyl, n- pentyl, n- octyl An aliphatic hydrocarbon group such as an alkyl group; an alicyclic hydrocarbon group such as a cycloalkyl group such as cyclohexyl and methylcyclohexyl; and an aryl group such as phenyl and tolyl.
An aromatic hydrocarbon group such as an aralkyl group such as benzyl can be exemplified. These R ¹ , R ² , R ³ , R
Examples of the substituent which the hydrocarbon group represented by ⁴ , R ⁵ and R ⁶ may have include, for example, a di (lower alkyl) amino group such as a dimethylamino group; a cyano group;
O ₃ M or —COOM (M is lithium, sodium,
(Representing an alkali metal atom such as potassium). When the phosphonium salt represented by the general formula (I) is used as a component of a telomerization catalyst, at least one of R ⁴ , R ^5, and R ⁶ is selected from the viewpoint of the reaction results in the telomerization reaction. One is full Eniru Motoma other

[0018]

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And a group represented by the formula --SO ₃ M or --COOM (M is as defined above), a di (lower alkyl) amino group, etc.
It must be a phenyl group . The lower alkylcarbonyloxy group represented by X includes acetoxy.
Group , propionyloxy group , butyryloxy group , isobutyryloxy group , valeryloxy group and the like.

Next, the phosphonium salt represented by the general formula (I) can be converted to a compound represented by the general formula (I) in the presence or absence of water containing a carbonate ion and / or a bicarbonate ion in the presence of a palladium compound.

[0021]

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(Wherein R ⁴ , R ⁵ and R ⁶ are as defined above) represented by the following general formula:

[0023]

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(Wherein R ¹ , R ² and R ³ are as defined above, and R ⁷ represents a hydrogen atom or a lower alkylcarbonyl group). .

[0025] Specific examples of the trisubstituted phosphine represented by the general formula (II) used in preparing the phosphonium salt represented by the general formula (I), Application Benefits triphenylphosphine,
Tritolylphosphine, diphenyl isopropyl _{phosphine, (C 6 H 5) 2} PCH 2 CH 2 SO 3 Na, (C
_{6 H 5) 2 PCH 2 CH} (CH 3) COONa,

[0026]

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(C ₆ H ₅ ) ₂ PCH ₂ CH ₂ N (C
H _{3) 2,} and aromatic phosphines such as _{(C 6 H 5) 2 PCH} 2 COONa. Further, specific examples of the lower alkylcarbonyl group represented by R ⁷ in the general formula (III) include acetyl, propionyl, butyryl, isobutyryl, valeryl and the like. Examples of the allyl-type compound represented by the general formula (III) include allyl alcohol, 2-
Methyl-2-propen-1-ol, 2-buten-1-
All, 2,5-hexadien-1-ol, 2,7-
Octadien-1-ol, 1,4-pentadiene-3
Allylic alcohols such as -ol, 1,7-octadien-3-ol and 2-octen-1-ol; allyl acetate; 2-methyl-2-propenyl acetate;
General formula R ⁸ OH (IV) of an allyl alcohol such as 5-hexadienyl, 2,7-octadienyl acetate, 1-vinyl-5-hexenyl acetate, 1-vinyl-2-propenyl propionate and 2-octenyl propionate Wherein R ⁸ represents a lower alkylcarbonyl group). The amount of the allyl-type compound represented by the general formula (III) in producing the phosphonium salt represented by the general formula (I) is at least equimolar to the trisubstituted phosphine. General formula (II
The upper limit of the amount of the allyl-type compound represented by I) is not particularly limited. After the phosphonium salt represented by the general formula (I) is prepared, an excess amount of the allyl-type compound represented by the general formula (III) is removed. Considering ease of operation, it is preferable to use the allyl-type compound in an amount of about 1 to 10 moles per mole of the trisubstituted phosphine.

As the palladium compound to be present in the reaction system when producing the phosphonium salt represented by the general formula (I), a palladium compound that can be used in a usual telomerization reaction of a conjugated diene can be applied. Specific examples of such palladium compounds include palladium (II) compounds such as palladium acetylacetonate, π-allyl palladium acetate, palladium acetate, palladium carbonate, palladium chloride, bisbenzonitrile palladium chloride; and bis (1,5 Palladium (0) compounds such as -cyclooctadiene) palladium and tris (dibenzylideneacetone) dipalladium. When a palladium (II) compound is used, a reducing agent for reducing palladium (II) to palladium (0) can also be added. Examples of the reducing agent used for such a purpose include alkali metal hydroxides such as sodium hydroxide, formic acid, sodium phenolate, NaBH ₄ , hydrazine, zinc powder, magnesium and the like. The amount of the reducing agent to be used is usually preferably the stoichiometric amount required for reduction or an amount within 10 times the stoichiometric amount. It is desirable to use the palladium compound in such an amount as to give a concentration of 0.1 to 10 mg atom, preferably 0.5 to 5 mg atom as palladium atom per liter of the reaction mixture.

The formation reaction of the phosphonium salt represented by the general formula (I) is carried out in the presence of a palladium compound in the presence or absence of water containing carbonate ions and / or bicarbonate ions. When an allylic alcohol is used as the allylic compound represented by the general formula (III), the reaction is usually carried out in the presence of water containing a carbonate ion and / or a bicarbonate ion. )), A phosphonium salt in which X is a hydroxyl group or a hydroxycarbonyloxy group is formed. When an ester of an allyl alcohol with a carboxylic acid represented by the general formula (IV) is used as the allyl compound represented by the general formula (III), water containing carbonate ion and / or bicarbonate ion is used. Can be carried out in the absence of the compound, whereby a phosphonium salt of the formula (I) wherein X is a lower alkylcarbonyloxy group is formed. It is practical to derive the carbonate ion and / or bicarbonate ion from carbon dioxide, bicarbonate such as sodium bicarbonate, or carbonate such as sodium carbonate, which gives them in the reaction system. Is particularly preferred. 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 from normal pressure to 50 atm (gauge pressure), and in practical use, is preferably from normal pressure to 10 atm (gauge pressure).

The reaction for forming the phosphonium salt represented by the general formula (I) is inert to the reaction, and
The reaction may be carried out in the presence of an organic solvent capable of dissolving the trisubstituted phosphine represented by I) and the allylic compound represented by the general formula (III). Specific examples of such an organic solvent include diethyl ether, dibutyl ether, tetrahydrofuran, dioxane, dioxolan, ethylene glycol dimethyl ether, and an average molecular weight of 200 to 2,000.
Ethers such as polyethylene glycol dimethyl ether; and secondary alcohols such as t-butanol and isopropanol.
Grade or tertiary alcohols; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone; nitriles such as acetonitrile, benzonitrile, propiononitrile; acetamide, propionamide;
N, N- dimethylformamide, N, N-amides such as dimethylacetamide; sulfoxides such as dimethyl sulfoxide; sulfolane, sulfones, such as main Chirusuruhoran; phosphoric acid amides such as hexamethylphosphoric folder amide; acetate Esters such as methyl, ethyl acetate, methyl benzoate, and ethylene carbonate; aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; cyclic or acyclic such as butene, butane, hexane, cyclohexane, and methylcyclohexane. And aliphatic hydrocarbons. The organic solvent is usually used alone, but there is no problem even if it is used by mixing.

The reaction for forming the phosphonium salt represented by the general formula (I) is usually carried out at a temperature in the range of 10 ° C. to 80 ° C., but is conveniently carried out at room temperature . The reaction is usually completed in 0.5 to 24 hours, and the end point of the reaction can be easily known by a nuclear magnetic resonance spectrum of phosphorus, liquid chromatography, iodometric analysis or the like. As the atmosphere of the reaction system, it is desirable to use a gas that does not adversely affect the reaction, such as carbon dioxide and nitrogen, alone or as a mixture of two or more.

The phosphonium salt represented by the general formula (I) thus obtained can be separated and purified from the reaction mixture by, for example, the following method. If necessary, water, unreacted allyl-type compounds and the like are distilled off from the reaction mixture under reduced pressure, and the obtained residue is washed with a solvent such as methanol or diethyl ether to give the compound represented by the general formula (I). Crystals of phosphonium salts can be obtained.

The phosphonium salt represented by the general formula (I) provides a catalyst for a telomerization reaction between a conjugated diene and an active hydrogen compound when combined with a palladium compound. The amount of the phosphonium salt represented by the general formula (I) constituting the catalyst is usually an amount of 6 mol or more per 1 gram atom of palladium in the palladium compound, and is preferably in a range of 10 to 200 mol. And more preferably a ratio within the range of 30 to 100 mol. The palladium compound constituting the telomerization catalyst is a palladium (0) compound or a palladium (II) compound that can be used in the reaction for producing the phosphonium salt represented by the general formula (I). When a palladium (II) compound is used, a telomerization reaction may be performed by further adding a reducing agent. Examples of the reducing agent include those which can be used in the reaction for producing the phosphonium salt represented by the general formula (I). The amount of the reducing agent used is preferably a stoichiometric amount required for the reduction or an amount within 10 times the stoichiometric amount. As a method for adding the telomerization catalyst comprising the phosphonium salt represented by the general formula (I) and the palladium compound to the telomerization reaction system, the phosphonium salt and the palladium compound may be added separately. A mixture of a phosphonium salt and a palladium compound may be added. In one embodiment of the latter addition method, a reaction mixture containing the phosphonium salt and the palladium compound obtained by the reaction for producing the phosphonium salt represented by the general formula (I) was directly or appropriately subjected to a concentration or dilution operation. An embodiment used later for a telomerization reaction may be mentioned. The amount of the telomerization catalyst to be used is such that the amount of the palladium compound constituting the catalyst is usually 0.1 per liter of the telomerization reaction mixture in terms of palladium atom.
An amount that results in a concentration of 1-10 milligram atoms,
Preferably the amount is such that the concentration is between 0.5 and 5 milligram atoms.

Conjugated dienes which are reaction raw materials in a telomerization reaction to which a telomerization catalyst comprising a phosphonium salt represented by the general formula (I) and a palladium compound are applied include butadiene and isoprene. The active hydrogen compound is a compound having at least one active hydrogen atom in the molecule, for example, alcohol ; phenols; ammonia; amine; carboxylic acid; water; silane; Examples include active methyl, active methylene, or active methine compounds activated by a nitro group or the like. Specific examples of the alcohol include methanol, ethanol, butanol, allyl alcohol, 2-ethylhexanol, octadienol, stearyl alcohol, diethylene glycol, neopentyl glycol, pentaerythritol, trimethylolpropane, and polyethylene glycol. Specific examples of phenols include phenol and cresol. Examples of amines are methylamine, dimethyl Ji triethanolamine, ethylamine, diethylamine, butylamine, morpholine, piperazine and the like. Specific examples of carboxylic acids include formic acid, acetic acid,
And propionic acid, adipic acid, benzoic acid, phthalic acid and the like. Specific examples of silane include dimethylsilane,
Examples include diethylsilane and dimethoxysilane.
Specific examples of active methyl, active methylene, or active methine compounds include methyl acetoacetate, acetylacetone, nitromethane, methyl cyanoacetate, ethyl 2-formyl-2-phenylacetate, and 2-methyl-3-oxobutanenitrile.

In the telomerization reaction, additives can be used for increasing the reaction rate. Bases such as alkali metal hydroxides and aliphatic tertiary amines; salts of these bases with acids such as carbonic acid, phosphoric acid, acetic acid, boric acid and methanesulfonic acid; boric acid and phosphorous acid And weak acids such as phenol. As these additives, it is desirable to select and use suitable ones as appropriate according to the type of the starting compound used and the like.
For example, when a carboxylic acid is used as an active hydrogen compound, an aliphatic tertiary amine is used as an additive.When water is used as an active hydrogen compound, an aliphatic tertiary amine carbonate is used as an additive. The use of salts or bicarbonates can increase the reactivity of the active hydrogen compound.

The telomerization reaction can be performed by causing the active hydrogen compound to also serve as a solvent, but may be performed in the presence of an organic solvent that does not adversely affect the reaction. Such an organic solvent includes a compound represented by the general formula (I)
And organic solvents which can be present in the reaction system in the formation reaction of the phosphonium salt represented by

The telomerization reaction is usually carried out at 40 ° C.
It is carried out at a temperature in the range of 100 ° C, preferably in the range of 60 ° C to 80 ° C. The reaction pressure is not particularly limited, and pressure conditions under normal pressure, increased pressure, or reduced pressure can be appropriately selected and employed. The telomerization reaction can be carried out by a batch method or a continuous method, but is preferably carried out industrially by a continuous method.

In the telomerization reaction carried out using a telomerization catalyst comprising a phosphonium salt represented by the general formula (I) and a palladium compound, one or two of active hydrogen atoms of the active hydrogen compound are included. A linear alkadienyl compound in which at least one is substituted with a 2,7-alkadienyl group is obtained with high selectivity. And such linear reaction product represented by like alkadienyl compound and a catalyst component, a distillation method, JP 56-138129 and JP using a thin film evaporation apparatus 57-13
It is separated by applying an extraction method or the like as described in JP-B-4427, but employs an extraction method that reduces the risk of deterioration of the activity of the catalyst component and allows the catalyst component to be recycled for a longer period of time. It is desirable to do. The extraction method includes, for example, a di (lower alkyl) amino group as a phosphonium salt constituting a catalyst for telomerization, a formula -S
A hydrophilic phosphonium salt having a group represented by O ₃ M or —COOM (M is as defined above) is used, water is used as an active hydrogen compound, and sulfolane, ethylene carbonate, N, N
A telomerization reaction using an organic solvent having a high dielectric constant such as dimethylformamide, followed by subjecting the resulting reaction mixture to an extraction operation using a hydrocarbon such as hexane as an extractant; Thus, the product is obtained as an extraction component, and the catalyst component is obtained as a raffinate component.

[0039]

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.

Synthesis Example 1 (Synthesis of phosphonium salt) In an autoclave equipped with a stirrer, a carbon dioxide inlet tube and a purge tube, 30 ml of ion-exchanged water, 110 ml of dioxane, 0.1 ml of palladium acetate were added.
1 g, 35 g of lithium diphenylphosphinobenzene-m-sulfonate and 25 g of 2,7-octadien-1-ol were charged, the atmosphere in the system was sufficiently replaced with carbon dioxide, and then 5 kg / cm ² (gauge pressure) with carbon dioxide.
Pressurized. Next, the temperature of the reaction solution was raised to 60 ° C., and the reaction was performed for about 20 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, and the obtained solid was washed with 100 ml of ether.
The washed solid was vacuum dried at room temperature to obtain 35 g of a white powder.

This white powder was subjected to high performance liquid chromatography [eluent: 0.01 mole / l phosphoric acid aqueous solution / methanol = 1/4, column: YMC-Pack AM31]
2ODS (manufactured by Yamamura Chemical Laboratory Co., Ltd.)], no peak was observed at the position of the phosphine compound as the raw material, and a single peak was observed at another position. The empirical formula of the compound giving this peak was determined to be C ₂₇ H ₂₈ O ₆ SPLi based on the results of elemental analysis on C and H and colorimetric analysis on P and Li of the compound giving this peak. Further, 1N diluted sulfuric acid was poured into the obtained white powder, and the generated carbon dioxide gas was quantified by the barium hydroxide method. As a result, the molar ratio between the phosphorus atoms contained in the white powder and the generated carbon dioxide gas was 1: 1. It turned out to be. Further, ¹ H- and ³¹ P-NMR spectrum analysis and infrared absorption spectrum analysis were performed on the obtained white powder. From the above analysis results, the obtained white powder was determined to be a compound represented by the following structural formula.

[0042]

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The ¹ H-NMR spectrum, infrared absorption spectrum and ³¹ P-NMR spectrum data of the obtained compound are shown below.

¹ H-NMR spectrum (CDCl ₃ , HMDS standard, 90 MHz, ppm) δ 1.00 to 1.33 (m, 2H) 1.63 to 2.10 (m, 2H) 4.06 (dofd) , J = 15 and 6.9 Hz, 2H) 4.66 to 6.00 (m, 5H) 7.31 to 7.96 (m, 12H) 7.96 to 8.40 (m, 2H) Infrared absorption spectrum (KBr disk, cm ^-1 ) 690, 725, 755, 800, 970, 1040, 1110, 1210, 1230, 1400, 1440, 1485, 2940, 3410 ³¹ P-NMR spectrum (95% by weight aqueous solution of sulfolane, H ₃ PO ₄ standard, ppm) δ 21.55

[0045] Synthesis Example 2 (Synthesis of a phosphonium salt) stirrer, carbon dioxide inlet, sampling port, the autoclave equipped with a feed port <br/> and gas purge port, 85
100 g of a weight percent aqueous solution of tetrahydrofuran,
G of palladium acetate 50mg and triphenylphosphine 3.16 g, a pressure of 5 kg / cm ² (gauge pressure) with carbon dioxide and stirred for 30 minutes. Then, 3.
After feeding 5 g of allyl alcohol, the autoclave was heated to 60 ° C. and reacted for 4 hours. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain a solid. The obtained solid was washed with 100 ml of ether and then dried under vacuum to obtain 2.9 g of a white powder. This was analyzed by high-performance liquid chromatography under the same conditions as in Synthesis Example 1. As a result, no triphenylphosphine peak was observed, and a single peak was observed at another position. From the results of elemental analysis, colorimetric analysis, quantitative analysis of carbon dioxide gas, and ¹ H- and ³¹ P-NMR spectrum analysis, the obtained white powder was determined to be a compound represented by the following structural formula.

[0046]

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The ¹ H-NMR spectrum data of the compound is shown below. ¹ in H-NMR spectrum (DMSO-d _6, HMDS standard, 90 MHz, pp
m) δ 4.54 (dofd, J = 15.6 and 6.6H)
z, 2H) 5.13-6.03 (m, 3H) 7.53-8.03 (m, 15H)

Synthesis Example 3 (Synthesis of Phosphonium Salt) The same reaction and treatment as in Synthesis Example 1 were carried out except that 26 g of triphenylphosphine was used instead of 35 g of lithium diphenylphosphinobenzene-m-sulfonate.
7 g of a white powder were obtained. As a result of high performance liquid chromatography analysis, the white powder was found to be a single compound different from triphenylphosphine. Further, from the results of elemental analysis, colorimetric analysis, quantitative analysis of carbon dioxide gas, and ¹ H- and ³¹ P-NMR spectrum analysis, the structural formula of the compound was determined as follows.

[0049]

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The ¹ H-NMR spectrum data of the compound is shown below. ¹ H-NMR spectrum (CDCl ₃ , HMDS standard, 90 MHz, ppm) δ 1.05 to 1.48 (m, 2H) 1.63 to 2.08 (m, 4H) 4.05 (dofd, J = 15 and 6 Hz, 2H) 4.63 to 5.91 (m, 5H) 7.32 to 7.93 (m, 15H)

Synthesis Example 4 (Synthesis of phosphonium salt) Instead of 35 g of lithium diphenylphosphinobenzene-m-sulfonate, sodium diphenylphosphinobenzene-m-sulfonate 4 was used.
0 g and 2,7-octadien-1-ol 2
33 g of a white powder was obtained by performing the same reaction and processing operation as in Synthesis Example 1 except that 14 g of 2-buten-1-ol was used instead of 5 g. As a result of high performance liquid chromatography analysis, it was found that the white powder was a single compound different from the phosphine compound used as a raw material. Further, the structural formula of the product was determined as follows from the results of elemental analysis, colorimetric analysis, quantitative analysis of carbon dioxide gas, and ¹ H- and ³¹ P-NMR spectrum analysis.

[0052]

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The ¹ H-NMR spectrum data of the product is shown below. ¹ in H-NMR spectrum (DMSO-d _6, HMDS standard, 90 MHz, pp
m) [delta] 1.40-1.65 (m, 3H) 4.38 (dofd, J = 15.9 and 6.9 Hz,
2H) 5.00 to 5.93 (m, 2H) 7.47 to 8.10 (m, 14H)

Synthesis Example 5 (Synthesis of Phosphonium Salt) In a three-necked flask equipped with a magnetic stirrer, a carbon dioxide inlet tube and a purge tube, 14 g of ion-exchanged water was charged, and carbon dioxide was bubbled into the ion-exchanged water. Absorbed. Next, 6.7 mg of palladium acetate and 0.42 g of lithium diphenylphosphinobenzene-m-sulfonate were charged in a carbon dioxide atmosphere. After stirring for about 30 minutes, 0.55 g of allyl alcohol was charged with a syringe, and stirring was continued for about 4 hours while bubbling carbon dioxide at normal pressure and room temperature. The reaction was completed and a white precipitate formed. The precipitate was filtered through a glass filter and dried under reduced pressure to obtain 0.40 g of a white powder.

This white powder was subjected to high performance liquid chromatography [eluent: 0.01 mol / l phosphoric acid aqueous solution / methanol = 1/4 (flow rate: 1.2 ml / min); column: Y
MC-Pack AM312 ODS (manufactured by Yamamura Chemical Laboratory Co., Ltd.)], no peak was observed at the position of the raw material lithium diphenylphosphinobenzene-m-sulfonate, and a single peak was observed at another position. Was done. Furthermore, elemental analysis, colorimetric analysis, quantitative analysis of carbon dioxide gas, infrared absorption spectrum, ¹ H- and ³¹ P-
From the result of NMR spectrum analysis, the structural formula of the product was determined as follows.

[0056]

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The ¹ H-NMR spectrum, infrared absorption spectrum and ³¹ P-NMR spectrum data of this product are shown below.

[0058] ¹ in H-NMR spectrum (DMSO-d _6, HMDS standard, 90 MHz, pp
m) δ 4.58 (dofd, J = 16.5 and 7.1H)
z, 2H) 5.14 to 6.00 (m, 3H) 7.57 to 8.16 (m, 14H) Infrared absorption spectrum (KBr-Disk, cm ^-1 ) 690, 720, 760, 950, 1000, 104
0, 1110, 1200, 1240, 2940, 343
0 ³¹ P-NMR spectrum (in a 95% by weight aqueous solution of sulfolane, based on H ₃ PO ₄ , ppm) δ 21.35

Synthesis Example 6 (Synthesis of phosphonium salt) 6.9 mg (0.031 mmol) of palladium acetate, lithium diphenylphosphinobenzene-m were placed in a 300 ml three-necked flask equipped with a stirrer, a condenser and a thermometer. -Sulfonate 4.6
6 g (0.013 mol), 1-acetoxy-2,7-octadiene 3.5 g (0.021 mol) and acetic acid 13
7 g was charged in a nitrogen gas atmosphere and reacted under heating and reflux for 4 hours. After completion of the reaction, acetic acid was distilled off under reduced pressure using an evaporator, and the residue was washed with ether. When the obtained solid was dried, 7.15 g of powder was obtained. As a result of high performance liquid chromatography analysis, the powder was found to be a single compound different from the phosphine compound used as a raw material. Further, elemental analysis, colorimetric analysis, infrared absorption spectrum analysis and ¹ H- and ³¹ P-NM
From the results of the R spectrum analysis, the structural formula of the product was determined as follows.

[0060]

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The data of ³¹ P-NMR spectrum, ¹ H-NMR spectrum and infrared absorption spectrum of the product are shown below.

³¹ P-NMR spectrum (95% by weight sulfolane aqueous solution) δ 21 ppm ¹ H-NMR spectrum (CDCl ₃ , HMDS standard,
1.06-1.40 (m, 2H) 1.60-2.20 (m, 4H) 1.95 (s, 3H) 4.09 (dofd, J = 15.2 and 7.2 Hz) ,
2H) 4.66 to 5.93 (m, 5H) 7.46 to 7.83 (m, 2H) 8.08 to 8.37 (m, 2H) Infrared absorption spectrum (KBr-Disk, cm ^-1 ) 665,690,720 (cis-olefin), 75
0,800,995 (trans-olefin), 103
0, 1100, 1200 (—SO ₃ Li), 1400,
1570, 1710 (CH ₃ COO ⁽⁻⁾ ), 2850,
3010

Example 1 Tris (dibenzylideneacetone) was placed in a 300 ml stainless steel autoclave equipped with a magnetic stirrer, a carbon dioxide inlet, a sampling port, a charging port, a purge port and a temperature controller under a nitrogen gas atmosphere. 0.31 g (0.3 mmol) of palladium, formula

[0064]

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6.2 g of the phosphonium salt (12
Mmol), 66 g of sulfolane sufficiently degassed with nitrogen gas, 68 g of water and 16.5 g of triethylamine.
Was charged. Next, the inside of the system was set to a carbon dioxide atmosphere, and then pressurized to 5 kg / cm ² (gauge pressure) with carbon dioxide gas.
Stirred for 0 minutes. Reduce the partial pressure of carbon dioxide in the system to 5 kg / cm ²
(Gauge pressure) and then raise the temperature inside the system to 75 ° C.
The reaction was started by injecting 40 ml of butadiene all at once. After the start of the reaction, a small amount of a sample was taken out at regular intervals and analyzed by gas chromatography. As a result, it was confirmed that the telomerization reaction was proceeding without an induction period. Table 1 shows the results of these analyses.

[0066]

[Table 1]

When the catalyst solution after the reaction for 3 hours was analyzed, no formation of phosphine oxide was observed, and the palladium catalyst was uniformly dissolved without being metallized.

Example 2 As a phosphonium salt, a compound of the formula

[0069]

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4.37 g of a phosphonium salt represented by the following formula:
The reaction and analysis were carried out in the same manner as in Example 1 except that (12 mmol) was used. Table 2 shows the obtained results.

[0071]

[Table 2]

Examples 3 to 5 The reaction and analysis were carried out in the same manner as in Example 1 except that 12 mmol of each of the phosphonium salts shown in Table 3 was used as the phosphonium salt. Table 3 shows the obtained results.

[0073]

[Table 3]

Example 6 In the same reactor as used in Example 1, 60 g of acetic acid, 101 g of triethylamine and a compound of the formula

[0075]

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4.6 g of the phosphonium salt (1
(2.6 mmol) and 0.43 g (0.42 mmol) of tris (dibenzylideneacetone) palladium were charged in a nitrogen gas atmosphere, and then 50 ml of butadiene was charged and reacted at 75 ° C. for 3 hours. After 3 hours, the content liquid was taken out and analyzed by gas chromatography. As a result, 352 mmol and 60 mmol of 1-acetoxy-2,7-octadiene and 3-acetoxy-1,7-octadiene were formed, respectively.

Example 7 In the same reactor as used in Example 1, sulfolane 50 was used.
g, methanol 50 g, formula

[0078]

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2.16 g of the phosphonium salt (5
Mmol) and 0.2 g (0.2 mmol) of tris (dibenzylideneacetone) palladium were charged under a nitrogen gas atmosphere. Next, 20 g of butadiene was charged and reacted at 75 ° C. for 1.5 hours. After completion of the reaction, the reaction mixture was analyzed by gas chromatography to find that 1-
Methoxy-2,7-octadiene and 3-methoxy-
17.7 g and 4,7-octadiene respectively.
7 g had been produced.

[0080] distilling off the product from the reaction mixture 75 ° C. using a thin-film evaporation apparatus, a reduced pressure of 25 mmHg. The sulfolane solution containing the catalyst obtained as a residue was stirred at room temperature for 24 hours in an open system in contact with air. After completion of the stirring, the sulfolane solution was analyzed, but no formation of phosphine oxide was observed.

50 g of methanol and 20 g of butadiene were added to this sulfolane solution and reacted under the same conditions as in the first reaction. As a result, 1-methoxy-2,7-octadiene and 3-methoxy-1,7-octadiene were converted to 18 0.0 g and 4.6 g were produced.

From the above results, it can be seen that the catalyst has high stability against oxidation and maintains high activity even after being recovered from the reaction mixture.

Example 8 The same reactor as used in Example 1 was charged with 67.8 mg (0.3 mmol) of palladium acetate and a compound of the formula

[0084]

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6.2 g of the phosphonium salt (12
Mmol), 66 g of sulfolane, 68 g of water and trie
16.5 g of tylamine was charged. Then, diacid
6 kg / cm ² (gauge pressure)
The temperature was raised to 0 ° C. After stirring at 60 ° C for 1 hour,
Was heated to 75 ° C. Next, 40 ml of butadiene was added.
The reaction started immediately after the batch introduction.

After reacting for 2 hours, the reaction mixture was analyzed by gas chromatography. As a result, 149 mmol of 2,7-octadien-1-ol and 7.5 mmol of 1,7-octadien-3-ol were formed. I knew I was doing it.

Example 9 As a phosphonium salt, a compound represented by the formula

[0088]

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The reaction and analysis were carried out in the same manner as in Example 8 except that 12 mmol of the phosphonium salt represented by the following formula was used. As a result, 2,7-octadiene-
1-ol is 153 mmol, 1,7-octadiene-
3-ol is Rukoto have 9.1 mmol generated was found.

Example 10 17.8 mg (0.1 mmol) of palladium chloride was placed in the same reactor as used in Example 1

[0091]

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2.28 g of a phosphonium salt represented by the following formula:
(4.3 mmol), formic acid (5 mg, 0.11 mmol), triethylamine (25 ml) and acetic acid (25 ml), and the mixture was stirred at room temperature for 30 minutes under a nitrogen gas atmosphere.
Thereafter, 20 ml of butadiene was charged and reacted at 75 ° C. for 3 hours. As a result, 43 mmol of 1-acetoxy-2,7-octadiene and 13 mmol of 3-acetoxy-1,7-octadiene were produced.

Comparative Synthesis Example 1 95% by weight in the same reactor as used in Synthesis Example 1
70.0 g of an aqueous sulfolane solution, 63.0 ion-exchanged water
g, triethylamine 16.5 g, palladium acetate 0.1 g.
067 g and 4.22 g of lithium diphenylphosphinobenzene-m-sulfonate were charged, and the reaction system was heated at room temperature to an atmosphere of carbon dioxide [partial pressure of carbon dioxide: 5 kg / c.
m ² (gauge pressure)]. Next, the temperature was set to 75 ° C., and 40 ml of butadiene was charged to start the reaction. After the start of the reaction, the products in the reaction mixture were analyzed over time by gas chromatography, and it was found that there was an induction period of about 1 hour. After the reaction for 3 hours, the reaction mixture was analyzed by high performance liquid chromatography.

[0094]

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A peak was observed. Table 4 shows the results of quantitative analysis of the product.

[0096]

[Table 4]

Comparative Example 1 Acetic acid 10 was added to the same reactor as used in Example 1.
0 g, triethylamine 20 g, palladium acetate 0.0
67 g and sodium diphenylphosphinobenzene-m-sulfonate (4.8 g) were charged in a nitrogen gas atmosphere, and then butadiene (50 ml) was charged and reacted at 75 ° C. for 3 hours. After 3 hours, the contents were taken out and analyzed by gas chromatography, which revealed that 1-acetoxy-2,7-octadiene and 3-acetoxy-1,7-diene.
-Little formation of octadiene was observed. Thus, it can be seen that the reaction rate is extremely low when the concentration of the phosphine compound is high.

Comparative Example 2 Tetrakistriphenylphosphine palladium 0.23
g and 1.31 g of triphenylphosphine were dissolved in 100 ml of sulfolane. When the obtained sulfolane solution was stirred at room temperature for 24 hours in an open system capable of contacting with air, 1.33 g of phosphine oxide was generated, and precipitation of palladium metal was observed.

Comparative Example 3 As a phosphonium salt, a compound represented by the formula

[0100]

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The reaction and analysis were conducted in the same manner as in Example 8 except that 12 mmol of the phosphonium salt represented by the following formula was used, but it was found that the reaction did not proceed at all.

[0102] Total 30 times using a reactor and extraction apparatus as in Example 11 following
Repeated an experiment was conducted in.

(Reactor) A 300 ml stainless steel autoclave equipped with a thermometer, a stirrer, a butadiene quantitative feed pump, a carbon dioxide inlet, a liquid feed port and a liquid outlet was used as a reactor.

(Extractor) An 800 ml pressure-resistant glass autoclave equipped with a thermometer, a stirrer, a gas inlet, an n-hexane feed port and a liquid pressure inlet was used as the extractor. This extraction device is directly connected to the reactor.

(Experimental method) Sulfolane 41
g, distilled water 45 g, triethylamine 14 g, trisdibenzylideneacetone palladium 0.2 mg [corresponding to the concentration of 2 mmol / l (feed reaction liquid )] and the formula

[0106]

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After 4.1 g of the phosphonium salt shown in the above was charged and the inside of the system was sufficiently replaced with carbon dioxide, the mixture was heated with stirring until the internal temperature reached 70 ° C.
g / cm ² (gauge pressure). 600r
While stirring at a speed of pm, 15 ml of butadiene was charged in a liquid state, and then reacted at 75 ° C. for 60 minutes while continuously introducing the solution at a speed of 14 ml / hr. 6
After the reaction for 0 minutes, the introduction of butadiene was stopped, and the reaction mixture was sent to the extractor using a pressure difference while cooling. Next, the inside of the extraction device was pressurized with carbon dioxide to 3 kg / cm ² (gauge pressure), and then at 20 ° C., 100 m of n-hexane.
1 was added. After stirring for 15 minutes, the mixture was allowed to stand for 15 minutes to extract the product with n-hexane. The upper layer (n-hexane layer) was taken out of the system using a pressure difference. The remaining liquid was again charged with 100 ml of n-hexane, extracted similarly, and the upper layer was taken out of the system. The resulting n-hexane layers were combined, and the reaction product and sulfolane were each analyzed by gas chromatography, water was measured by the Karl Fischer method, triethylamine was measured by the titration method, and palladium and phosphorus (both in terms of atoms) were measured. Quantitative analysis was performed by an absorption method and a colorimetric method. With respect to the raffinate catalyst solution, the amount of water consumed in the reaction and the amount of water, triethylamine and sulfolane eluted in the n-hexane layer were added, and then sent to the reactor again using a pressure difference. Using the catalyst liquid, a series of operations including the steps of reaction, extraction, and catalyst circulation was repeated 30 times in total. Incidentally, a new additional palladium component and the phosphorus component was not performed throughout the repeated experiments. Table 5 shows the relationship between the number of repetitions, the reaction results, and the elution amounts of the palladium component and the phosphorus component into the n-hexane layer. Table 5 shows that the catalyst activity is maintained for a long time.

[0108]

[Table 5]

Example 12 In the same reactor as in Synthesis Example 5, 70.0 g of a 95% by weight aqueous solution of sulfolane, 63.0 g of ion-exchanged water, 16.5 g of triethylamine, 2.7 g of allyl alcohol,
67.4 mg of palladium acetate and 4.22 g of lithium diphenylphosphinobenzene-m-sulfonate were charged and stirred at room temperature for 5 hours under an atmosphere of carbon dioxide to prepare a catalyst solution. When the catalyst solution was analyzed by high performance liquid chromatography, the peak of the phosphine compound as a raw material disappeared, and it was confirmed that conversion was completed.

The entire amount of the catalyst solution was charged into an autoclave equipped with an electromagnetic stirrer, a carbon dioxide inlet pipe, a sampling pipe, a charging pipe, and a purge pipe. / Cm ² (gauge pressure)]. Next, the temperature was set to 75 ° C., and 40 ml of butadiene was charged to start a telomerization reaction. After the start of the reaction, when the products 2,7-octadien-1-ol and 1,7-octadien-3-ol, which are products in the reaction mixture, were analyzed with time by gas chromatography, it was found that there was an inducing period. No reaction was observed. Table 6 shows the results of the analysis by gas chromatography.

[0111]

[Table 6]

After the reaction for 3 hours, the catalyst solution was analyzed by high performance liquid chromatography, and no formation of phosphine oxide was observed.

Example 13 Using the same reactor as in Synthesis Example 5, 70.0 g of a 95% by weight aqueous solution of sulfolane, 20 g of ion-exchanged water,
8.0 g of 7-octadien-1-ol, 67.3 mg of palladium acetate and 3.7 g of sodium 2- (diphenylphosphino) ethanesulfonate were charged. This mixed solution was reacted at 50 ° C. for 10 hours in an atmosphere of carbon dioxide to prepare a catalyst solution. When the catalyst solution was analyzed by high performance liquid chromatography, the peak of the phosphine compound as the raw material disappeared, and it was confirmed that the conversion was completed.

In the same reactor as that used in carrying out the telomerization reaction in Example 12, 43 g of ion-exchanged water and 16.5 g of triethylamine were added, and carbon dioxide was further absorbed. Next, the entire amount of the catalyst solution was charged, and a telomerization reaction was carried out in the same manner as in Example 12. When the product in the reaction mixture was analyzed by gas chromatography over time, it was confirmed that the reaction was proceeding without an induction period. Table 7 shows the results of the analysis by gas chromatography.

[0115]

[Table 7]

After the reaction for 3 hours, the catalyst solution was analyzed by high performance liquid chromatography, and no formation of phosphine oxide was observed.

Example 14 Contents In a 50 ml three-necked flask, 20 g of a 95% by weight aqueous solution of sulfolane, 5 g of ion-exchanged water, and 0.1 g of palladium acetate were added.
067 g, sodium diphenylphosphinobenzene-
4.8 g of m-sulfonate and allyl alcohol 1.
Charge 4g and bubbling carbon dioxide 50
Stirred at C for 4 hours. When the obtained catalyst solution was analyzed by high performance liquid chromatography, the peak of the phosphine compound as the raw material disappeared, and it was confirmed that the conversion was completed.

In the same reactor as that used in conducting the telomerization reaction in Example 12, acetic acid 100
g, 20 g of triethylamine and the entire amount of the above catalyst solution were added under a nitrogen gas atmosphere. Next, 30 ml of butadiene was charged and reacted at 80 ° C. for 3 hours. After 3 hours reaction
The contents were taken out and analyzed by gas chromatography to find that 1-acetoxy-2,7-octadiene and 3
-Acetoxy-1,7-octadiene was produced in 52 mmol and 15 mmol, respectively. After the reaction for 3 hours, the catalyst solution was analyzed by high performance liquid chromatography, but no formation of phosphine oxide was observed.

Example 15 In the same reactor as used in Example 1, sulfolane 5 was added.
0 g, 1-acetoxy-2,7-octadiene 0.2
g, palladium acetate 28 mg and di (n-butyl)-
0.17 g of phenylphosphine was charged. The mixed solution was reacted at 50 ° C. for 2 hours to prepare a catalyst solution. When the obtained catalyst solution was analyzed by high performance liquid chromatography, the peak of the phosphine compound as the raw material disappeared, and it was recognized that the conversion was completed.

[0120] Formic acid 26 and triethylamine 57g were added to the catalyst solution in the above reactor and stirred for 15 minutes. Then, butadiene 60g was charged and reacted at 70 ° C for 2 hours. After completion of the reaction, the obtained reaction mixture was analyzed. As a result, 48 g of 1,7-octadiene and 7.2 g of 1,6-octadiene were formed.

[0121]

According to the present invention, as is apparent from the above Examples, the use of a novel telomerization catalyst comprising a phosphonium salt and a palladium compound makes it possible to obtain a catalyst without an induction period of the reaction. A linear alkadienyl compound can be obtained with high selectivity from a conjugated diene and an active hydrogen compound without generating phosphine oxide which is known to be a poison. Also,
Even when the phosphonium salt constituting the catalyst is used in a large excess with respect to the palladium compound in order to enhance the stability of the catalyst, a linear alkadienyl compound can be obtained at a high reaction rate.

Claims (2)

(57) [Claims] 1. A compound of the general formula (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, and represents R ⁴ , R ⁵ and R ⁶
Is a hydrocarbon group having 1 to 8 carbon atoms which may have a substituent , at least one of which is a substituent
A phenyl group which may be possessed , and X represents a hydroxyl group, a hydroxycarbonyloxy group or a lower alkylcarbonyloxy group), and a palladium compound; and a telomerization catalyst. 2. A method for producing a linear alkadienyl compound by reacting a conjugated diene and an active hydrogen compound in the presence of a catalyst, wherein the catalyst for telomerization according to claim 1 is used as the catalyst. A method for producing a linear alkadienyl compound.