JPH0639409B2 - Method for producing octane derivative - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing an octane derivative selected from n-octanol and 1-octene.

1-octene provided by the production method of the present invention is useful as a modifier for polyethylene, and n-octanol is useful as a synthetic intermediate for producing the 1-octene.

[Conventional technology]

Japanese Patent Publication No. 48-43327, Japanese Patent Publication No. 50-10565, Japanese Patent Publication No.
No. 57-134427 discloses a method for producing n-octanol by reacting butadiene with water in the presence of a palladium catalyst and hydrogenating the resulting octa-2,7-dien-1-ol. Has been done. In the reaction of butadiene and water as described above, using a tertiary phosphorus compound such as trisubstituted phosphine and trisubstituted phosphite as a ligand not only affects the reaction rate and the selectivity of the reaction, It is said to be important in stabilizing the palladium catalyst. Therefore, in the reaction between butadiene and water, a low-valence palladium complex containing a ligand such as trisubstituted phosphine is used as it is, or palladium is present in the presence of a ligand such as trisubstituted phosphine. (II) Species prepared by reducing compounds have been used.

In addition, Bulletin de la Societe Chimique de Franc (Bulletin de la Societe Chimique de Franc
e) Pages 1670 to 1674 (1963) and the like describe a method for producing 1-octene by subjecting n-octanol to a dehydration reaction.

[Problems to be Solved by the Invention]

There are the following problems in the reaction of butadiene and water which is carried out by using the above-mentioned tertiary phosphorus compound such as trisubstituted phosphine as a ligand in the palladium catalyst.

(1) The stability of the palladium catalyst increases as the concentration of the ligand such as trisubstituted phosphine increases or the molar ratio of the ligand to palladium increases, but the reaction rate increases with the concentration of the ligand. It has been extremely reduced in accordance with the [Chemical Communications] (Chemical Communications) No. 33
0 (1971), etc.], and the selectivity for octa-2,7-dien-1-ol decreases as the molar ratio of the ligand to palladium increases [Chemical Comunications ( Chemical Communications) Third
See page 30 (1971), Japanese Examined Patent Publication No. 50-10565, etc.].
Therefore, it is difficult to satisfy the requirements for properties having such contradictory tendencies, namely, stabilization of the palladium catalyst, high reaction rate, and high selectivity to octa-2,7-dien-1-ol. Is.

(2) Tri-substituted phosphines used as ligands are easily oxidized in the presence of palladium [Angewandte Chemie International Editio (Angewandte Chemie International Editio
n in English) Vol. 6, pp. 92-93 (1967)], when the trisubstituted phosphine is circulated for a long time in the reaction of butadiene and water, the oxidation product phosphine oxide is accumulated. However, this phosphine oxide acts as a catalyst poison and adversely affects the telomerization reaction between butadiene and a nucleophile (JP-A-51-4).
(See Japanese Patent No. 103). Moreover, it is difficult to separate the phosphine oxide from the trisubstituted phosphine and remove it from the reaction system.

(3) According to the studies by the present inventors, when the reaction of butadiene and water is carried out using an excess amount of trisubstituted phosphine with respect to palladium, even if the palladium compound and the trisubstituted phosphine are used. It was found that the reaction involves a long induction period even when the prepared low-valent palladium complex used as the catalytically active species is used in the reaction. In particular, when the reaction of butadiene and water is continuously carried out for a long period of time, the added palladium feel cannot immediately exhibit sufficient activity, which causes a situation in which an excessive amount of catalyst is added.

Palladium is an expensive precious metal, so
When it is used as a catalyst, it is required to enhance the productivity per unit amount of palladium and maintain the catalytic activity for a long period of time. In this respect, octa-2,7-diene-, which is useful as a synthetic intermediate for n-octanol and 1-octene, is to solve the problems (1) to (3).
It is extremely important for industrially producing 1-ol. However, such a problem has not been solved yet, and therefore, the industrially advantageous production method of n-octanol and 1-octene conveniently derived therefrom has not been established.

Therefore, one of the objects of the present invention is to obtain a reaction at a high reaction rate and a high selectivity by a reaction method which does not involve an induction period and does not generate a catalyst poison such as phosphine oxide. Another object of the present invention is to provide an industrially advantageous method for producing n-octanol by passing the obtained octa-2,7-dien-1-ol as a synthetic intermediate. Another object of the present invention is to provide an industrially advantageous method for producing 1-octene by passing the thus obtained n-octanol as a synthetic intermediate.

[Means for Solving the Problems]

According to the present invention, the above-mentioned object is to provide butadiene and water with a palladium compound and a general formula (In the formula, Represents an anion represented by R, wherein R represents a hydrocarbon group, Y represents an allyl group which may have a substituent, Represents a tri-substituted phosphonio group. ) Is carried out in the presence of a phosphonium salt, and the resulting octa-2,7-dien-1-ol is hydrogenated to provide a method for producing n-octanol. N-obtained by the above-mentioned production method
It is achieved by providing a process for the production of 1-octene characterized by dehydrating octanol.

In the general formula (I) showing the phosphonium salt used in the present invention, Y and Will be described in detail below.

Is an expression Anion expressed by Anion (bicarbonate ion) or formula Wherein R is an alkyl group having 1 to 6 carbon atoms such as methyl group, ethyl group, n-propyl group, and n-hexyl group; and 3 carbon atoms such as allyl group.
~ 6 alkenyl group; 1 to 6 carbon atoms such as phenyl group
Hydrocarbon groups of are preferred. The hydrocarbon group represented by R may be substituted with a substituent other than the hydrocarbon group as long as it does not adversely affect the reaction of butadiene and water according to the present invention. From the viewpoint of reaction results in the reaction between butadiene and water, As the formula The anion represented by is particularly preferable. The allyl group which may have a substituent represented by Y is represented by the general formula (In the formula, 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. And a group represented by a hydrocarbon group having 1 to 5 carbon atoms. Here, the hydrocarbon group having 1 to 12 carbon atoms represented by R ¹ and R ² is, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl or n-.
Aliphatic hydrocarbon groups such as alkyl groups such as octyl, alkenyl groups such as 2-propenyl, 3-butenyl, 4-pentenyl; alicyclic hydrocarbon groups such as cycloalkyl groups such as cyclohexyl; and phenyl, tolyl, etc. Examples thereof include aromatic hydrocarbon groups such as aryl groups and aralkyl groups such as benzyl. Further, the hydrocarbon group having 1 to 5 carbon atoms represented by R ³ includes methyl, ethyl,
Examples thereof include alkyl groups such as propyl; aliphatic hydrocarbon groups such as alkenyl groups such as allyl and 4-pentenyl. Examples of the substituent that the hydrocarbon group represented by R ¹ , R ² and R ³ may have include, for example, a di (lower alkyl) amino group such as a dimethylamino group; a cyano group; and a formula —SO ₃ Mention may be made of groups which do not adversely influence the reaction of butadiene with water according to the invention, such as those represented by M or --COOM (M represents an alkali metal atom such as lithium, sodium, potassium etc.). From the viewpoint of the reaction results in the reaction of butadiene and water, Y is an allyl group, octa-2,7-dienyl group, 1-vinyl-5.
-Hexenyl group and the like are preferable. Also The tri-substituted phosphonio group represented by (In the formula, R ⁴ , R ⁵ and R ⁶ each represent a hydrocarbon group having 1 to 8 carbon atoms which may have a substituent.) And the like. Here, the hydrocarbon group having 1 to 8 carbon atoms represented by R ⁴ , R ⁵ and R ⁶ is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-pentyl, n-. Aliphatic hydrocarbon groups such as alkyl groups such as octyl; alicyclic hydrocarbon groups such as cycloalkyl groups such as cyclohexyl and methylcyclohexyl; and aromatic carbon groups such as aryl groups such as phenyl and tolyl, aralkyl groups such as benzyl A hydrogen group can be exemplified. Examples of the substituent that the hydrocarbon group represented by R ⁴ , R ⁵ and R ⁶ may have include, for example, di (lower alkyl) amino group such as dimethylamino group; cyano group;
Examples thereof include a group represented by --SO ₃ M or --COOM (where M represents an alkali metal atom such as lithium, sodium, potassium, etc.) that does not adversely affect the reaction between butadiene and water according to the present invention. From the viewpoint of reaction results in the reaction with water, R ⁴ , R ⁵
And at least one of R ⁶ is an unsubstituted aryl group such as a phenyl group or a tolyl group; Or A group represented by the formula: —SO ₃ M or —COOM (where M is as defined above), an aryl group substituted with a di (lower alkyl) amino group or the like is preferable. .

The phosphonium salt represented by the general formula (I) is a trisubstituted phosphine in an equimolar amount to the trisubstituted phosphine in the presence of a palladium compound, in the presence or absence of water containing a carbonate ion and / or a bicarbonate ion. The above general formula R ⁷ OY (II) (wherein R ⁷ is a hydrogen atom or a formula Represents an acyl group represented by: wherein R is as defined above and Y is as defined above. ) It is manufactured by reacting with an allyl type compound. The tri-substituted phosphine has the general formula (In the formula, R ⁴ , R ⁵ and R ⁶ are as defined above.) And the like, and examples thereof include trisubstituted phosphines, and specific examples thereof include triisopropylphosphine, tri-n-butylphosphine, Tri-t-butylphosphine, tri-n-
Aliphatic phosphines such as octyl phosphines; cycloaliphatic phosphines such as tricyclohexyl phosphines; and triphenyl phosphines, tritolyl phosphines, diphenyl isopropyl phosphines, Aromatic phosphines such as In addition, the general formula (I
Examples of the allyl type compound represented by I) include allyl alcohol, 2-methyl-2-propen-1-ol, 2-buten-1-ol, 2,5-hexadiene-1-ol and 2,7.
-Octadien-1-ol, 1,4-pentadiene-3
-Ol, 1,7-octadien-3-ol, allyl alcohol such as 2-octen-1-ol and allyl acetate, 2-methyl-2-propenyl acetate, 2,5-acetic acid
Hexadienyl, acetic acid 2,7-octadienyl, acetic acid 1-
Vinyl-5-hexenyl, 1-vinyl-2 propionate
A general formula of an allyl alcohol such as -propenyl, 2-octenyl propionate R ⁸ OH (III) (wherein R ⁸ is Represents an acyl group represented by: wherein R is as defined above. ) And an ester with a carboxylic acid. When the phosphonium salt represented by the general formula (I) is produced, the amount of the allyl compound represented by the general formula (II) used is equimolar or more based on the trisubstituted phosphine. There is no particular limitation on the upper limit of the amount of the allyl compound represented by the general formula (II), but an excess of the allyl compound represented by the general formula (II) after preparing the phosphonium salt represented by the general formula (I) Considering the easiness of the operation for removing the compound, it is preferable to use the allylic compound in an amount of about 1 to 10 times the molar amount of the trisubstituted phosphine. The palladium compound to be present in the reaction system when producing the phosphonium salt represented by the general formula (I) can be used in the telomerization reaction of a usual conjugated diene represented by the dimerization hydration reaction of butadiene. A palladium compound can be applied.
Specific examples of such a palladium compound include palladium (II) compounds such as palladium acetylacetonate, π-allyl palladium acetate, palladium acetate, palladium carbonate, palladium chloride, and bisbenzonitrile palladium chloride; and bis (1,5 Examples include 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 be added. Examples of the reducing agent used for such purpose include alcal metal hydroxide such as sodium hydroxide, formic acid, sodium phenolate, sodium borohydride, hydrazine, sub-powder, magnesium and the like. The amount of the reducing agent used is usually the stoichiometric amount necessary for the reduction or an amount within 10 times the stoichiometric amount. The amount of the palladium compound used is 0.1 to 10 milligram atom as palladium atom, preferably 1 atom per reaction mixture.
It is desirable to use it in such an amount that the concentration becomes 0.5 to 5 mg atom. The reaction for producing 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 allyl alcohol is used as the allyl compound represented by the general formula (II), the reaction is usually carried out in the presence of water containing a carbonate ion and / or a bicarbonate ion. (I)
At Is the expression Or A phosphonium salt, which is an anion represented by, is produced.
When an ester of an allyl alcohol with a carboxylic acid represented by the general formula (III) is used as the allyl compound represented by the general formula (II), carbonate ion and / or
Alternatively, it is possible to carry out the reaction in the absence of water containing bicarbonate ions, which results in the general formula (I) Is the expression A phosphonium salt which is an anion represented by (R is as defined above) is formed. Carbonate ions and / or bicarbonate ions are practically derived from carbon dioxide which gives them in the reaction system, bicarbonate salts such as sodium bicarbonate; or carbonate salts such as sodium carbonate. It is particularly preferred to derive from When using carbon dioxide, a tertiary amine or quaternary ammonium hydroxide may be added for the purpose of increasing the carbonate ion concentration in the reaction system. When using carbon dioxide, the partial pressure of carbon dioxide is usually from atmospheric pressure to 50 atm (gauge pressure), and from atmospheric pressure to 10 atm (gauge pressure) is preferable for practical use. The formation reaction of the phosphonium salt represented by the general formula (I) is carried out in the presence of an organic solvent which is inactive to the reaction and which can dissolve the trisubstituted phosphine and the allyl type compound represented by the general formula (II). You can go. Specific examples of such an organic solvent include diethyl ether,
Dibutyl ether, tetrahydrofuran, dioxane,
Dioxolane, ethylene glycol dimethyl ether,
Ethers such as polyethylene glycol dimethyl ether having an average molecular weight of 200 to 2000; secondary or tertiary alcohols such as t-butanol and isopropanol; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; acetonitrile, benzonitrile, Nitriles such as propiononyltri; acetamide, propionamide, N, N-dimethylformamide,
Amides such as N, N-dimethylacetamide; sulfoxides such as dimethyl sulfoxide; sulfolane,
Sulfones such as methylsulfolane; Phosphoramides such as hexamethylphosphamide; Esters such as methyl acetate, ethyl acetate, methyl benzoate, ethylene carbonate; Aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene A cyclic or acyclic aliphatic hydrocarbon such as butene, butane, hexane, cyclohexane, methylcyclohexane, etc .; The organic solvent is usually used alone, but it may be used in a mixture. The formation reaction of the phosphonium salt represented by the general formula (I) is usually carried out at a temperature within the range of 10 ° C to 80 ° C, but it is convenient in operation to carry out the reaction 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 nuclear magnetic resonance spectrum of phosphorus, liquid, chromatography, iodometry analysis method and the like. As the atmosphere of the reaction system, it is desirable to use a gas such as carbon dioxide and nitrogen, which does not adversely affect the reaction, alone or in a mixture of two or more kinds. Separation / purification of the phosphonium salt represented by the general formula (I) thus obtained from the reaction mixture can be carried out, for example, by the following method. If necessary, water, unreacted allylic compound and the like are distilled off from the reaction mixture under reduced pressure, and the resulting residue is washed with a solvent such as methanol or diethyl ether to give the compound of the general formula (I). Crystals of the indicated phosphonium salt can be obtained.

General formula (I) in the reaction of butadiene with water according to the invention
The amount of the phosphonium salt represented by is usually 6 mol or more with respect to 1 gram atom of palladium in the palladium compound, and preferably 10 to 200 mol. More preferably 30 to 1
The amount is a ratio within the range of 00 mol. In the reaction of butadiene and water, 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) is used as the palladium compound. When a palladium (II) compound is used, a reducing agent may be further added to cause the reaction between butadiene and water. Examples of the reducing agent include reducing agents that can be used in the reaction for forming the phosphonium salt represented by the general formula (I). The amount of the reducing agent used is preferably a stoichiometric amount necessary for reduction or an amount within 10 times the stoichiometric amount. The amount of the palladium compound used is such that, in terms of palladium atom, the concentration is usually 0.1 to 10 mg atom per reaction mixture in the reaction of butadiene and water, and preferably 0.5 to 5 mg atom. It is such an amount.

As a method of adding the phosphonium salt represented by the general formula (I) and the palladium compound to the reaction system in the reaction of butadiene and water, the phosphonium salt and the palladium compound may be added separately, or the phosphonium salt and the palladium compound may be added separately. You may add the mixture with. As one aspect of the latter addition method, the reaction mixture containing the phosphonium salt and the palladium compound obtained by the production reaction of the phosphonium salt represented by the general formula (I) as it is or appropriately,
An example of the method is to use it for the reaction of butadiene and water after the operation of concentration or dilution.

In the reaction of porcine with water according to the present invention, the reaction rate can be further improved by adding a carbonate or bicarbonate of an aliphatic tertiary amine such as triethylamine to the reaction system. The reaction of butadiene and water may be carried out in the presence of an organic solvent that does not adversely influence the reaction. Examples of such an organic solvent include the above-mentioned organic solvents that can be present in the reaction system in the production reaction of the phosphonium salt represented by the general formula (I). The reaction is usually carried out at a temperature in the range of 40 ° C to 100 ° C, preferably in the range of 60 ° C to 80 ° C. The reaction pressure is not particularly limited,
Pressure conditions under normal pressure, increased pressure or reduced pressure can be appropriately selected and used. Further, the reaction of butadiene and water can be carried out by a batch method or a continuous method, but it is industrially preferable to carry out the reaction.

The octa-2,7-dien-1-ol contained in the reaction mixture obtained by reacting butadiene with water in this way and the contact component are distilled by using a thin film evaporator or the like. JP-A-56-138129 and JP-A-57-1344
Although they are separated from each other by applying the extraction method as described in Japanese Patent Publication No. 27, the catalyst component is less likely to deteriorate in activity, and the catalyst component can be circulated for a longer period of time. It is desirable to use the extraction method from the point. The extraction method includes, for example, a phosphonium salt represented by the general formula (I), a di (lower alkyl) amino group, a formula -SO ₃ M or -COOM.
An organic solvent having a high dielectric constant such as sulfolane, ethylene carbonate or N, N-dimethylformamide is used as a reaction solvent, using a hydrophilic phosphonium salt having a group represented by the formula (M is as defined above). After the reaction of butadiene with water using the above, the reaction mixture obtained was subjected to an extraction operation using a hydrocarbon such as hexane as an extractant to obtain an octane.
A product such as 2,7-dien-1-ol is obtained as an extraction component, and a catalyst component is obtained as a raffinate component. The mixture containing octa-2,7-dien-1-ol thus separated from the catalyst by a method such as a distillation method or an extraction method is recovered from unreacted butadiene after recovery from the mixture, if necessary. Although it can be directly subjected to the next hydrogenation reaction, a purified product of octa-2,7-dien-1-ol obtained by subjecting the mixture to a distillation operation may be subjected to the hydrogenation reaction.

The hydrogenation reaction of octa-2,7-dien-1-ol is usually carried out in the presence of hydrogen and a hydrogenation catalyst.

The hydrogenation catalyst can be used without particular limitation as long as it is known to have a catalytic ability for the hydrogenation reaction of olefin. As the hydrogenation catalyst,
Specifically, nickel-based catalysts such as Raney-Nickel catalysts, modified Raney-Nickel catalysts, supported Nickel-based catalysts; palladium-based catalysts such as supported palladium catalysts; ruthenium-based catalysts such as supported ruthenium catalysts; cobalt-based catalysts such as Raney cobalt catalysts; copper- Chromite catalyst, copper-chromium-
Examples include zinc oxide catalysts. As the modifying metal in the modified Raney-Nitzkel catalyst, chromium, rhenium,
Examples include molybdenum, tungsten, titanium, iron, manganese, lead and the like. Further, examples of the carrier in the supported catalyst include silica, alumina, diatomaceous earth, activated carbon and the like.

The hydrogenation reaction can be carried out in a stirring type reactor or a bubble column type reactor in a liquid phase system in which a hydrogenation catalyst is suspended, and in a column type reactor filled with a supported catalyst. It can also be carried out in the liquid phase or the gas phase. When the reaction is carried out in a liquid phase suspension, the concentration of the hydrogenation catalyst is usually within the range of 0.01 to 10% by weight, and preferably within the range of 0.1 to 5% by weight, based on the metal, of the reaction mixture. The hydrogenation reaction can be carried out by a batch method or a continuous method. The hydrogen pressure and reaction temperature employed depend on the type of hydrogenation catalyst used and cannot be unambiguously determined, but, for example, when using Raney-Nitzkel, Raney cobalt, supported palladium or supported ruthenium, it is desirable to use , Respectively in the range of 1 to 150 atm (absolute pressure) and 20 to 140 ° C. Further, when using supported nickel, copper-chromite or copper-chromium-zinc oxide as the hydrogenation catalyst, it is desirable that they be 1 to 150 atm (absolute pressure) and 100 to 100 atm, respectively.
It is selected within the range of 300 ° C.

As the hydrogenation reaction solvent, the raw material or the product can have the function thereof, but other solvents may be used. Solvents usable for this purpose include aliphatic hydrocarbons such as hexane, octane and decane, hydrocarbons such as aromatic hydrocarbons such as benzene, toluene and xylene; alcohols such as methanol, ethanol, butanol and decanol; Diisopropyl ether,
Dibutyl ether, anisole, tetrahydrofuran,
Examples thereof include ethers such as dioxane; esters such as isopropyl acetate and butyl acetate.

From the reaction mixture obtained by the hydrogenation reaction, after removing the hydrogenation catalyst by a usual operation, if necessary,
High-purity n-octanol is obtained by performing distillation purification.

The dehydration reaction from n-octanol to 1-octene is usually carried out at elevated temperature in the presence of a dehydration catalyst. As the dehydration catalyst, sulfuric acid, phosphoric acid, sodium hydrogen sulfate,
Inorganic acids such as boric acid; γ-alumina, thorium dioxide,
Lewis acids such as tungsten oxide, zinc chloride and tricalcium phosphate are used. The reaction is carried out in a liquid phase or a gas phase, and the reaction temperature is usually selected in the range of 150 to 500 ° C, preferably 250 to 450 ° C. Since 1-octene produced by dehydration of n-octanol may isomerize to internal olefin in the reaction system, it is desirable to suppress the isomerization in order to obtain 1-octene with high selectivity. As a method of suppressing the isomerization of 1-octene, the dehydration reaction time is made as short as possible and the produced 1-octene is rapidly distilled out of the reaction system, and the method is modified with a basic substance such as sodium hydroxide. And a method using a dehydration catalyst.

The reaction mixture thus obtained is optionally treated with a molecular sieve such as urea or molecular sieves and then subjected to a distillation operation to obtain 1-octene with high purity.

[Examples] Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples.

Reference Example 1 (Synthesis of phosphonium salt) 30 m of ion-exchanged water and dioxane 11 were placed in an autoclave equipped with a stirrer, a carbon dioxide introduction pipe and a purge pipe.
0 m, palladium acetate 0.1 g, lithium diphenylphosphinobenzene-m-sulfonate 35 g and octa-2,7-dien-1-ol 25 g were charged, the atmosphere in the system was sufficiently replaced with carbon dioxide, and then 5 carbon dioxide was added.
The pressure was increased to kg / cm ² (gauge pressure). Then, the temperature of the reaction solution was raised to 60 ° C. and the reaction was carried out for about 20 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, and the obtained solid was converted into ether 1
It was washed at 00m. The washed solid was vacuum dried at room temperature to obtain 35 g of white powder.

This white powder was applied to high performance liquid chromatography (eluent:
0.01mole / phosphoric acid aqueous solution / methanol = 1/4, column: YMC-Pack AM312 ODS (manufactured by Yamamura Chemical Laboratory Co., Ltd.)] No peak was observed at the position of the phosphine compound of the roller material, A single peak was observed at the position. Based on the results of elemental analysis of C and H of the compound giving this peak and colorimetric analysis of P, S and Li, the empirical formula of the compound was determined to be C ₂₇ H ₂₈ O ₆ SPLi. 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 of phosphorus atoms contained in the white powder to the generated carbon dioxide gas was 1: 1. It has been found. 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.

The data of ¹ H-NMR spectrum, infrared absorption spectrum and ³¹ P-NMR spectrum of the obtained compound are shown below. ¹ H-NMR spectrum (in CDC 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 6.9Hz, 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 in sulfolane aqueous solution, H
₃ PO ₄ standard, ppm) δ 21.55 Reference Example 2 (Synthesis of phosphonium salt) 85 in an autoclave equipped with a stirrer, carbon dioxide inlet, sampling port, charging port and gas purge port.
100% by weight of tetrahydrofuran in water,
50 mg of palladium acetate and triphenylphosphine 3.
16 g was charged, carbon dioxide was applied at a pressure of 5 kg / cm ² (gauge pressure), and the mixture was stirred for 30 minutes. Then, 3.5 g of allyl alcohol was fed, and 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 solid obtained is 100 m of ether
After washing with a white powder by vacuum drying
2.9 g was obtained. As a result of analyzing this by high performance liquid chromatography under the same conditions as in Reference Example 1, no peak of triphenylphosphine was observed and a single peak was observed at another position. From the results of elemental analysis, colorimetric analysis, quantitative analysis of carbon dioxide 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.

The data of ¹ H-NMR spectrum of the compound is shown below. ¹ H-NMR spectrum (in DMSO- _d6 , HMDS standard, 90 MHz, pp
m) δ 4.54 (dofd, J = 15.6 and 6.6Hz, 2H) 5.13 to 6.03 (m, 3H) 7.53 to 8.03 (m, 15H) Reference Example 3 (Synthesis of phosphonium salt) Lithium diphenylphosphinobenzene-m- 27 g of white powder was obtained by performing the same reaction and treatment operations as in Reference Example except that 26 g of triphenylphosphine was used instead of 35 g of sulfonate. As a result of high performance liquid chromatography analysis, the white powder was found to be a single compound different from triphenylphosphine. Furthermore, the structural formula of the compound was determined as follows from the results of elemental analysis, colorimetric analysis, quantitative analysis of carbon dioxide, and ¹ H- and ³¹ P-NMR spectral analysis.

The data of ¹ H-NMR spectrum of the compound is shown below. ¹ H-NMR spectrum (in CDC 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 6Hz, 2H) 4.63 to 5.91 (m, 5H) 7.32 to 7.93 (m, 15H) Reference Example 4 (Synthesis of phosphonium salt) Content 300m equipped with stirrer, cooler and thermometer
In a three-necked flask containing 6.9 mg (0.031 mmol) of palladium acetate, 4.66 g (0.013 mol) of lithium diphenylphosphinobenzene-m-sulfonate, 1-acetoxy-2,7.
-Octadiene 3.5 g (0.021 mol) and acetic acid 137 g
Was charged under a nitrogen gas atmosphere and reacted under heating under 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, it was found that the powder was a single compound different from the phosphine compound used as the raw material. Further, from the results of elemental analysis, colorimetric analysis, infrared absorption spectrum analysis and ¹ H- and ³¹ P-NMR spectrum analysis, the structural formula of the product was determined as follows.

About the product³¹P-NMR spectrum,¹H-NMR spectrum
And infrared absorption spectrum data are shown below.³¹ P-NMR spectrum (95 wt% sulfolane aqueous solution): δ 21ppm¹ H-NMR spectrum (CDC_ThreeMedium, HMDS standard, ppm) δ 1.06 to 1.40 (m, 2H) 1.60 to 2.20 (m, 4H) 1.95 (s, 3H) 4.09 (dofd, J = 15.2 and 7.2Hz, 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), 750,800,995 (trans-olefin), 1030,1100,1200 (-SO₃Li), 1400, 1570,1710 (CH_ThreeCOO ), 2850,3010 Reference Example 5 (Synthesis of phosphonium salt) Au equipped with stirrer, carbon dioxide introduction pipe and purge pipe
50m of deionized water and 10 of dioxane in the crepe
0m, palladium acetate 0.1g, sodium diphenyl
32.8 g of phosinobenzene-p-carboxylate and
Charge 11.7g of allyl alcohol, carbon dioxide is enough
After replacing the atmosphere inside, carbon dioxide is 7 kg / cm²(Game
(Pressurizing). Then, the mixture is heated at 80 ° C for 24 hours
It was stirred for a while. After the reaction is complete, the reaction mixture is concentrated under reduced pressure.
The resulting solid was washed with 100 m of ether. Wash
41 g of the purified solid was vacuum dried at room temperature.
As a white powder, the formulaI got some salt.

Reference Example 6 (Synthesis of Phosphonium Salt) 5 g of the phosphonium salt obtained in Reference Example 3 was dissolved in 200 m of a mixed solvent of methanol / water (volume ratio: 50/50), and 3.6 g of barium hydroxide octahydrate was added. 24 at room temperature
Stir for hours. The insoluble salt was filtered off, and methanol and water were distilled off from the filtrate to obtain a solid. The resulting solid was vacuum dried at room temperature to give the formula This yielded 4.2 g of the phosphonium salt.

Reference Example 7 (Production of Octa-2,7-dien-1-ol) In a stainless steel autoclave with a content of 300 m equipped with an electromagnetic stirrer, carbon dioxide inlet, sampling port, charging port, purge port and temperature controller. In a nitrogen gas atmosphere, tris (dibenzylideneacetone) palladium 0.31 g (0.3 mmol), formula 6.2 g (12 mmol) of the phosphonium salt represented by, 66 g of sulfolane sufficiently degassed with nitrogen gas, and water 6
8 g and 16.5 g triethylamine were charged. Then, the system was made into a carbon dioxide atmosphere, and then pressurized to 5 kg / cm ² (gauge pressure) with carbon dioxide and stirred for 30 minutes. The temperature of the system was raised to 75 ° C. while maintaining the carbon dioxide partial pressure in the system at 5 kg / cm ² (gauge pressure), and 40 m of butadiene was injected at once to start the reaction. After the reaction was started, a small amount of sample was taken out at regular intervals and analyzed by gas chromatography. As a result, it was confirmed that the reaction proceeded without an induction period. The results of these analyzes are shown in Table 1.

When the reaction mixture after the reaction for 3 hours was analyzed, the formation of phosphine oxide was not observed at all, and the palladium catalyst was uniformly dissolved without being metallized.

The obtained reaction mixture was taken out from the autoclave, and 5
After transferring to a separating funnel of 00 m, it was extracted with 150 m of n-hexane. N-Hexane was removed by evaporation from the taken-out n-hexane layer with an evaporator, and
0.9 g of concentrated liquid was obtained. This concentrated solution was distilled under a reduced pressure of 10 mmHg (absolute pressure) to obtain 19.9 g of octane.
2,7-Dien-1-ol (bp85 ℃ / 10mmHg) and 1.0g
Octa-1,7-dien-3-ol (bp 68 ℃ / 10mmH
g) was obtained.

Reference Example 8 (Production of octa-2,7-dien-1-ol) As a phosphonium salt, the formula The reaction and analysis were carried out in the same manner as in Reference Example 7 except that 4,37 g (12 mmol) of the phosphonium salt represented by was used. The results obtained are shown in Table 2.

The obtained reaction mixture was taken out from the autoclave, and 5
After transferring to a separating funnel of 00 m, it was extracted with 150 m of n-hexane. N-Hexane was removed by evaporation from the taken-out n-hexane layer by an evaporator, and 1
9 g of concentrated liquid was obtained. By distilling this concentrated solution under reduced pressure of 10 mmHg (absolute pressure), 16.3 g of octane was obtained.
2,7-Dien-1-ol (bp85 ℃ / 10mmHg) and 0.5g
Octa-1,7-dien-3-ol (bp 68 ℃ / 10mmH
g) was obtained.

Reference Examples 9 to 11 (Production of octa-2,7-dien-1-ol) Reaction and analysis in the same manner as in Reference Example 5 except that 12 mmol of each of the phosphonium salts shown in Table 3 was used as the phosphonium salt. Was done. The results obtained are shown in Table 3.

Each of the reaction mixtures thus obtained was subjected to the following operations to give the product octa-2,7-
Dien-1-ol and octa-1,7-dien-3-ol were isolated. Remove each reaction mixture from the autoclave and transfer to a 500 m separating funnel.
It was extracted with 50 m of n-hexane. N-Hexane was removed by evaporation from the taken-out n-hexane layer by an evaporator to obtain 16.7 g to 19.5 g of a concentrated liquid. By distilling this concentrated liquid under a reduced pressure of 10 mmHg (absolute pressure), the product octa-2,7-diene-
1-ol (bp 85 ° C / 10mmHg) and octa-1,7-dien-3-ol (bp 68 ° C / 10mmHg) were isolated. That is, in Reference Example 9, 13.6 g of octa-2,7-diene-1
-Ol and 0.88 g of octa-1,7-dien-3-ol were obtained, and in Reference Example 10 18.5 g of octa-2,7-dien-1-ol and 0.95 g of octa-1,7-diene were obtained. -3-
All was obtained, and in Reference Example 11, 15.6 g of octa-
2,7-Dien-1-ol and 0.88 g of octa-1,7-dien-3-ol were obtained.

Reference Example 12 (Production of octa-2,7-dien-1-ol) In the same reactor used in Reference Example 7, palladium acetate 67.5 mg (0.3 mmol), a compound of the formula 6.2 g (12 mmol) of the phosphonium salt represented by, 66 g of sulfolane, 68 g of water and 50 mg of formic acid were added, and 4
The mixture was stirred at 0 ° C for 1 hour. Then triethylamine 16.5g
After charging, the mixture was stirred at 60 ° C. for 30 minutes while maintaining the system at 5 kg / cm ² (gauge pressure) with carbon dioxide. 7 in the system
When the temperature was raised to 5 ° C. and 40 m of butadiene was introduced all at once, the reaction immediately started. After reacting for 3 hours, the reaction mixture was analyzed by gas chromatography. As a result, 172 mmol of octa-2,7-dien-1-ol and 10.6 mmol of octa-1,7-dien-3-ol were produced. It turned out. No formation of phosphine oxide was observed.

The reaction mixture thus obtained was taken out of the autoclave and transferred to a 500 m separating funnel, and then 1
It was extracted with 50 m of n-hexane. From the n-hexane layer taken out, n-hexane was removed by evaporation using an evaporator to obtain 21.8 g of a concentrated liquid. 1 of this concentrate
2 by distilling under reduced pressure of 0mmHg (absolute pressure)
0.5 g of octa-2,7-dien-1-ol (bp85 ° C /
10 mmHg) and 1.3 g of octa-1,7-dien-3-ol (bp 68 ° C / 10 mmHg) were obtained.

Reference Example 13 (Production of octa-2,7-dien-1-ol) A phosphonium salt of the formula Reaction and analysis were carried out in the same manner as in Reference Example 7 except that 12 mmol of the phosphonium salt represented by As a result, it was found that 165 mmol of octa-2,7-dien-1-ol and 10 mmol of octa-1,7-dien-3-ol were produced.

The obtained reaction mixture was taken out from the autoclave, and 5
After transferring to a separating funnel of 00 m, it was extracted with 150 m of n-hexane. N-Hexane was removed by evaporation from the taken-out n-hexane layer with an evaporator.
9.3 g of concentrated liquid was obtained. This concentrated solution was distilled under a reduced pressure of 10 mmHg (absolute pressure) to obtain 18.3 g of octane.
2,7-Dien-1-ol (bp85 ℃ / 10mmHg) and 1.0g
Octa-1,7-dien-3-ol (bp 68 ℃ / 10mmH
g) was obtained.

Reference Example 14 (Production of Octa-2,7-dien-1-ol) Using a reactor and an extractor as described below, 30 synthetic experiments were repeated.

(Reactor) A 300 m stainless 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) Content 800 m equipped with a thermometer, stirrer, gas inlet, n-hexane feed port and liquid pressure feed port
The pressure-resistant glass autoclave of was used as an extraction device. This extractor is directly connected to the reactor.

(Experimental method) 41 g of sulfolane and 45 distilled water in the reactor.
g, triethylamine 14 g, trisdibenzylideneacetone palladium 0.2 mg [corresponding to a concentration of 2 mmol / (charge reaction liquid)] and formula After charging 4.1 g of the phosphonium salt shown in (3) and thoroughly replacing the system with carbon dioxide, the system was heated with stirring until the internal temperature reached 70 ° C, and the internal pressure of carbon dioxide was changed to 8 kg / cm ² (gauge pressure). I introduced it until. While stirring at a speed of 600 rpm, 11 m of butadiene was charged in a liquid state, and then continuously introduced at a speed of 6.4 m / hr.
The reaction was carried out at 5 ° C for 60 minutes. After the reaction for 60 minutes, the introduction of butadiene was stopped, and the reaction liquid mixture was sent to the extraction device by utilizing the pressure difference while cooling. Next, pressurize the inside of the extractor with carbon dioxide to 3 kg / cm ² (gauge pressure) and then 40 ° C.
Then, 50 m of n-hexane 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 by utilizing the pressure difference. N-hexane 50m again in the residual liquid
Was charged and extracted in the same manner, and the upper layer was taken out of the system. The obtained n-hexane layers were combined and the reaction product and sulfolane were each analyzed by gas chromatography, water by the Karl Fisher method, triethylamine by the titration method, and palladium and phosphorus (either (Atomic equivalent) was quantitatively analyzed by an atomic absorption method and a colorimetric method. With respect to the residual catalyst liquid, water consumed in the reaction and water eluted in the n-hexane layer, triethylamine and sulfolane were added, and the mixture was sent again to the reactor by utilizing the pressure difference. Using this catalyst solution, a series of operations consisting of steps of reaction, extraction and catalyst circulation was repeated 30 times in total. It should be noted that no new addition of palladium component and phosphorus component was made through this repeated experiment. Table 4 shows the relationship between the number of repetitions, the reaction results, and the amounts of palladium component and phosphorus component eluted into the n-hexane layer. It can be seen from Table 4 that the catalytic activity is maintained for a long period of time.

The obtained extracts are combined and distilled to 100 mmHg (absolute pressure)
As a distillate at 137-138 ° C with a purity of 99.9%
238 g of 2,7-dien-1-ol was obtained.

Reference Example 15 (Production of Octa-2,7-dien-1-ol) The extraction catalyst solution obtained after 30 repeated experiments in Reference Example 14 was left at room temperature for 24 hours in an open system in which it was in contact with air. Stirred down. No formation of phosphine oxide was observed. Using this catalyst solution, the 31st repeating experiment was performed according to Reference Example 14. The amount of octadienol produced was 70 mmol, and octa-2,7-
The molar ratio of dien-1-ol to octa-1,7-dien-3-ol was 95: 5.

The obtained reaction mixture was taken out of the autoclave, and 3
The mixture was transferred to a separating funnel of 00 m and extracted with 70 m of n-hexane. N-Hexane was removed by evaporation from the taken-out n-hexane layer using an evaporator, and 8.
3 g of concentrated liquid was obtained. By distilling this concentrated solution under a reduced pressure of 10 mmHg, 8.0 g of octa-2,7-diene-1 was obtained.
-All (bp85 ℃ / 10mmHg) and 0.3g octa-1,7-
Dien-3-ol (bp 68 ° C / 10 mmHg) was obtained.

Example 1 (Production of octa-2,7-dien-1-ol) In the same manner as in Reference Example 14, octa-octane having a purity of 99.9%.
238 g of 2,7-dien-1-ol was obtained.

(Manufacture of n-octanol) A nickel-diatomaceous earth catalyst (Nissan Gardler G -69; Ni content: 52 wt%) 0.3 g and 2-ethylhexanol (solvent) 20 g were charged, the system was sufficiently replaced with hydrogen, and then the system was maintained at 9 kg / cm ² (gauge pressure) with hydrogen. . After raising the internal temperature to 150 ° C, while stirring vigorously,
2,7-Dien-1-ol was introduced at a rate of 7 g / hr for 5 hours. After the introduction was completed, the reaction was continued for another 10 minutes.
After cooling the autoclave, take out the reaction mixture,
It was analyzed by gas chromatography. The conversion of octa-2,7-dien-1-ol was 100%, and n-octanol was produced at a selectivity of 100%. The obtained reaction mixture is removed from the autoclave, the nickel-diatomaceous earth catalyst is removed by filtration, and the purity 9% is obtained by atmospheric distillation.
36 g of 9.9% n-octanol was obtained (bp 190-190).
198 ° C).

(Production of 1-octene) 1 g of tricalcium phosphate [Ca ₃ (PO ₄ ) ₂ ] and 0.07 g of sodium hydroxide were heated in 200 m of methanol under reflux for 1 hour, and then methanol was distilled off to obtain a product. The residue was dried under vacuum. 1 g of the dehydration catalyst thus prepared was mixed with 36 g of n-octanol to give a content of 100
m oak clave, and the mixture was reacted at 420 ° C. for 1.5 hours under a nitrogen gas atmosphere. After the reaction is complete, cool down,
When the reaction mixture was analyzed by gas chromatography, 28 g of 1-octene was produced, and the selectivity for 1-octene was 94%. As a result of rectifying this reaction mixture, a fraction with a purity of 99.6% was obtained as a fraction having a boiling point of 121 to 122 ° C.
22 g of octene were obtained.

Example 2 (Production of octa-2,7-dien-1-ol) In the same manner as in Reference Example 14, octane having a purity of 99.9%
232 g of 2,7-dien-1-ol was obtained.

(Production of n-octanol) A Raney nickel catalyst (manufactured by Kawaken Fine Chemicals Co., Ltd.) in the same reactor as used in the hydrogenation reaction in Example 1 was used.
NDT-65; water content: 50 wt%) 0.3 g and 2-ethylhexanol 20 g were charged, and the octane pressure was maintained while maintaining the hydrogen pressure at 9 kg / cm ² (gauge pressure) and the internal temperature at 80 ° C.
2,7-Dien-1-ol was introduced at a rate of 7 g / hr for 5 hours. After the introduction was completed, the reaction was continued for another 10 minutes.
After cooling the autoclave, take out the reaction mixture,
As a result of analysis by gas chromatography, octa-2,7
The conversion of -dien-1-ol is 100% and n-
The selectivity to octanol was 100%.

(Production of 1-octene) A U-shaped tube (inner diameter: 2 cm) was filled with 20 m of alumina (made by Norton; cylindrical shape having a diameter of 3 mm and a length of 3 mm). While maintaining the temperature of the alumina packed bed at 360 ° C., nitrogen gas was used as a carrier (nitrogen concentration: 50 mol%) under atmospheric pressure so that the contact time of the gasified n-octanol was 13 seconds. The gas that flowed and flowed out was condensed in a dry ice-acetone bath. As a result of analyzing the obtained condensate by gas chromatography, the conversion of n-octanol was 16% and the selectivity to 1-octene was 89%.

Examples 3 to 6 (Production of octa-2,7-dien-1-ol) In the same manner as in Reference Example 14, octane having a purity of 99.9% was used.
238 g of 2,7-dien-1-ol was obtained.

(Production of n-octanol) The octa-2,7-diene was produced in the same manner as in the production of n-octanol in Example 1 except that the catalyst, solvent, reaction temperature and hydrogen pressure shown in Table 5 were adopted. The hydrogenation reaction and analysis of the reaction mixture were carried out using 35 g each of -1-ol. The catalyst was used in an amount such that the amount of catalytic metal was 0.3 g. The amount of solvent used was 20 g.

Comparative Reference Example 1 (Production of Octa-2,7-dien-1-ol) 95 wt% in the same reactor used in Reference Example 7.
Aqueous sulfolane solution 70.0 g, ion-exchanged water 63.0 g, triethylamine 16.5 g, palladium acetate 0.067 g and lithium diphenylphosphinobenzene-m-sulfonate
4.22 g was charged, and the reaction system was kept at room temperature in an atmosphere of carbon dioxide [carbon dioxide partial pressure: 5 kg / cm ² (gauge pressure)].
Then the temperature is set to 75 ° C. and 40 m of butadiene
Was charged to start the reaction. After the reaction was started, the products in the reaction mixture were analyzed by gas chromatography over time, 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 to find that the retention time of 4.0 minutes Was observed. The results of the quantitative analysis of the products are shown in Table 6.

Comparative Reference Example 2 (Production of octa-2,7-dien-1-ol) Water 20 was added to the same reactor as used in Reference Example 7.
g, t-butanol 80 g, tetrakistriphenylphosphine palladium 0.34 g, triphenylphosphine 3.
1 g and 40 m of butadiene were charged and the pressure was increased to 5 kg / cm ² (gauge pressure) with carbon dioxide. The reaction mixture was heated to 75 ° C. with stirring and then reacted for 3 hours.

When the reaction mixture was analyzed by gas chromatography after the start of the reaction, almost no formation of octa-2,7-dien-1-ol and octa-1,7-dien-3-ol was observed. Thus, it can be seen that the reaction rate is extremely low when the phosphine compound is used at a high concentration.

Comparative Reference Example 3 (Stability confirmation test of palladium compound in the presence of triphenylphosphine) Tetrakistriphenylphosphine palladium (0.23 g) and triphenylphosphine (1.31 g) were added to sulfolane 100.
dissolved in m. When the obtained sulfolane solution was stirred in an open system capable of catalyzing air at room temperature for 24 hours, 1.33 g of phosphine oxide was produced and a large amount of palladium metal was observed.

〔The invention's effect〕

According to the present invention, as is clear from the above-mentioned examples, the reaction of butadiene with water does not involve an induction period of the reaction and produces phosphine oxide known to be a catalyst poison. , Octa-2,7-dien-1-ol, which is a synthetic intermediate, can be obtained with high selectivity. Even when the phosphonium salt constituting the catalyst is used in a large excess with respect to the palladium compound in order to increase the stability of the catalyst in the reaction, octa-2,7-dien-1-ol has a high reaction rate. can get. Therefore, according to the present invention, the octa-2,7-dien-1-ol, which is advantageously prepared as described above, is selected as the intermediate for the synthesis of n-octanol and 1-octene. The octane derivative can be produced industrially advantageously.

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Claims (2)

[Claims] 1. A butadiene and water containing a palladium compound and a general formula (In the formula, Represents an anion represented by R, wherein R represents a hydrocarbon group, Y represents an allyl group which may have a substituent, Represents a tri-substituted phosphonio group. ) In the presence of a phosphonium salt represented by the formula (4), the obtained octa-2,7-dien-1-ol is hydrogenated to produce n-octanol. 2. A butadiene and water containing a palladium compound and a general formula (In the formula, Y and Is as defined in claim 1. ) Is reacted in the presence of a phosphonium salt, and the resulting octa-2,7-dien-1-ol is hydrogenated to obtain n-octanol, and then the n-octanol is dehydrated. And a method for producing 1-octene.