JPH02172924A - Production of octane derivative - Google Patents

Abstract

PURPOSE:To obtain 1-octene in good selectivity by reacting butadiene with water in the presence of a Pd compound and phosphonium salt to give octa-2,7- diene-1-ol and hydrogenating octa-2,7-diene-1-ol to afford n-octanol and then dehydrating n-octanol. CONSTITUTION:Butadiene is reacted with water in the presence of a Pd compound (e.g. Pd acetylacetonato) and phosphonium salt expressed by the formula (X is OH, O-CO-OH or O-CO-R; R is hydrocarbon group; Y is allyl; Z is tri- substituted phosphonic group) at 60-80 deg.C to give octa-2,7-diene-1-ol, which is then hydrogenated in the presence of a hydrogenation catalyst to afford n- octanol or further n-octanol is dehydrated in the presence of an inorganic acid, etc., to provide 1-octene. In the reaction of the above-mentioned butadiene with water, induction period is not followed and toxicity of catalyst is not also brought out. 1-Octene is useful as a modifier for polyethylene.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing an octane derivative selected from n-octatool and 1-octene.

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

[Conventional technology]

Special Publication No. 48-43327, Publication No. 1056 of 1977
No. 5, Japanese Patent Application Laid-open No. 57-134427, etc.,
Reacting butadiene and water in the presence of a palladium catalyst,
A method for producing n-octatool by hydrogenating the obtained octa-2,7-dinin-1-ol is described. In the reaction of butadiene with water as described above, the use of tertiary phosphorus compounds such as trisubstituted phosphines and triIt-substituted phosphites as ligands only affects the reaction rate and reaction selectivity. It is said to be important in stabilizing palladium catalysts.

Therefore, in the reaction between butadiene and water, a low-valent palladium complex containing a ligand such as trisubstituted phosphine is used as a catalyst! Chemical species prepared by reduction of palladium(n) compounds in the presence of ligands such as trisubstituted phosphines have been conventionally used.

In addition, prechin de u nshiete kimikue day 7
U7 (Bulletin de la 5ocie)
te Cbimiquede FranCri No. 1670
- 1674 pages Cl 963] describes a method for producing 1-octene by subjecting n-octatool to a dehydration reaction.

[Problem to be solved by the invention]

The following problems occur in the reaction between butadiene and water, which is carried out using a tertiary phosphorus compound such as the above-mentioned trisubstituted phosphine as a ligand in a palladium catalyst.

(1) The stability of a palladium catalyst increases as the concentration of a ligand such as trisubstituted phosphine increases or as the molar ratio of ligand to palladium increases, but on the other hand, the reaction rate increases as the ligand concentration increases. [Chemical Communications]
cations), p. 330 (1971)], and the selectivity to octa-2,7-renin-1-ol decreases as the molar ratio of ligand to palladium increases [Chemical Communications (1971)].
Chemical
s) No. 330 (1971), Special Publication 1977-1056
See Publication No. 5, etc.]. Therefore, it is difficult to reconcile the demands for properties that tend to be contradictory, namely, the stabilization of palladium catalysts, the high reaction rate, and the high selectivity to octa-2゜7-renyn-l-ol. be.

(2) Trisubstituted phosphine, which is conveniently used as a ligand, is easily oxidized in the presence of palladium [Angevante et al.
Hemy International Edition 7-I7-I7G I) 7 Sea L (Angewandte Ch
emieInternational Edition
in English) Volume 6 No. 92-93 Tei (19
When this trisubstituted phosphine is circulated for a long period of time in the reaction between butadiene and water, its oxidation product, phosphine oxyto, accumulates, but this phosphine oxyto acts as a catalyst poison. and has a negative effect on the telomerization reaction between butadiene and the nucleophile (
(See Japanese Patent Application Laid-open No. 51-4103). Moreover, it is difficult to separate such phosphine oxyto from trisubstituted phosphine and remove it from the reaction system.

(8) According to the studies of the present inventors, when the reaction between butadiene and water is carried out using an excess amount of trisubstituted phosphine relative to palladium, even if a palladium compound and trisubstituted phosphine are used, It was found that even when a low-valent palladium complex, which is prepared as a catalytically active species, is conveniently used for the reaction, the reaction requires a long induction period. Particularly in the case where the reaction between butadiene and water is carried out in a delayed manner over a long period of time, the added palladium catalyst cannot exhibit sufficient activity immediately, leading to a situation in which more than the necessary amount of catalyst is added.

Palladium is an expensive precious metal, so it is used industrially.
When used as a catalyst, it is required to increase productivity per unit amount of palladium and maintain catalytic activity over a long period of time. From this point of view, the above (1) to (8)
) to solve the problems of n-octatool and 1
- Octa-2,7- useful as an intermediate for synthesis of octene
It is extremely important for industrially advantageous production of renin-1-ol. However, such problems have not yet been solved, and at present no industrially advantageous production method for tre-octatool and 1-octene easily derived therefrom has been established.

Therefore, one of the objects of the present invention is to obtain octane with high reaction rate and high selectivity by a reaction method that does not involve an induction period and does not generate catalyst poisons such as phosphine oxide. The object of the present invention is to provide an industrially advantageous method for producing n-octatool using -2,7-renin-1-ol as a synthetic intermediate. Another object of the present invention is to provide an industrially advantageous method for producing 1-octene by using the n-octatool thus obtained as a synthetic intermediate.

[Means to solve the problem]

According to the invention, said object represents an anion, purported to be butadiene, where R represents a hydrocarbon group, Y represents an optionally substituted allyl Φ group, and 2 represents a Represents a substituted phosphonio group. ) and hydrogenating the obtained octa-2,7-renin-1-ol. This is also achieved by providing a method for producing 1-octene, which is characterized in that the 1-octatool obtained by the method is dehydrated.

R represents the anion shown above, where R is a methyl group, an ethyl group, an n-propyl group, an alkyl group having 1 to 6 carbon atoms such as 11-hexyl group, and an alkyl group having 3 to 6 carbon atoms such as an allyl group. alkenyl group; a hydrocarbon group having 1 to 6 carbon atoms such as phenyl group is 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 between butadiene and water according to the present invention. From the viewpoint of the reaction result ee in the reaction between butadiene and water, an anion represented by 2-C-OH is particularly preferable as X. The allyl group which may have a substituent represented by Y is represented by the general formula (wherein R1 and R2 each represent a hydrogen atom or a hydrocarbon group having carbon formulas 1 to 12 which may have a substituent, and R3 represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms which may have a substituent.
Examples of the hydrocarbon group of 2 include alkyl i such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl, 2-7'Clbenyl, 3-7''tenyl%4-
Aliphatic hydrocarbon groups such as alkenyl groups such as pentenyl; alicyclic hydrocarbon groups such as cycloalkyl groups such as cyclohexyl; and aromatic hydrocarbon groups such as aryl groups such as phenyl and tolyl, and aralkyl groups such as benzyl. I can give an example. In addition, the number of carbon atoms represented by R3 is 1 to
Examples of the hydrocarbon group in 5 include alkyl groups such as methyl, ethyl, and propyl; aliphatic hydrocarbon groups such as an alknyl group such as allyl%4-pentenylnato. Examples of substituents that the hydrocarbon groups represented by R1, R2, and R3 may include, for example, di(lower alkyl)amino groups such as dimethylamino groups; cyano groups; formula -803M or -COOM( M represents an alkali metal atom such as lithium, sodium, potash, etc.) Examples include groups that do not adversely affect the reaction between butadiene and water according to the present invention. From the viewpoint of reaction results in the reaction between butadiene and water, Y may be an allyl group, an octa-2,7-genyl group, or a l-vinyl group.
5-hexenyl group Natka Φ Preferred. Examples of the trisubstituted phosphonio group represented by 2 include groups represented by the general formula (in the formula 14.Ha and R6 each represent a hydrocarbon group having 1 to 8 carbon atoms which may have a substituent), etc. can be mentioned. Here, the hydrocarbon groups having 1 to B carbon atoms represented by R4, R5 and R6 include methyl, ethyl, n-propyl, isopropyl,
Aliphatic hydrocarbon groups such as alkyl groups such as n-butyl, t-butyl, n-pentyl, and n-octyl; alicyclic hydrocarbon groups such as cycloalkyl groups such as cyclohexyl and methylcyclohexyl; and phenyl and tolyl Examples thereof include aryl groups such as , and aromatic hydrocarbon groups such as aralkyl groups such as benzyl. These R4゜R
Examples of substituents that the hydrocarbon groups represented by 5 and R6 may include, for example, a di(lower alkyl)amino group such as a dimethylamino group; a cyano group: Formula-803
Examples of M or 1000MCM include groups that do not adversely affect the reaction between butadiene and water according to the present invention, such as a group represented by an atom representing an alkali metal atom such as lithium, natritam, or potassium. From the viewpoint of reaction results in the reaction between butadiene and water, at least one of R4, R5 and R6 is a phenyl group,
Substituted or ()(H2N(C
H3) Formula -803M or -C such as a group represented by 2
A group represented by OOM (M is as defined above),
An aryl group substituted with a di(lower alkyl)amino group or the like is preferable.

The phosphonimium salt represented by the general formula (1) is prepared by converting a trisubstituted phosphine to the trisubstituted phosphine in the presence of a palladium compound and in the presence or absence of water containing carbonate ions and/or bicarbonate ions. Equimolar or more of the general formula % formula % () (wherein R7 represents a hydrogen atom or a so-acyl group represented by 2R-C-, where R is as defined above, and Y is as defined above It is produced by reacting with an allyl type compound shown in ). Examples of the trisubstituted phosphine include trisubstituted phosphine represented by Mongan (in the formula, R4, R5, and R6 are each as defined above), and specific examples thereof include triinglobylphosphine, trin -butylphosphine, tri-t-butylphosphine, tri-n-
Aliphatic phosphines such as octylphosphine; cycloaliphatic phosphines such as tricyclohexylphosphine; and triphenylphosphine, tritolylphosphine, diphenylinpropylphosphine, (Csds)2
PCMzCH2SO3Na 1PecOONa)3.
P+zN(CH:l)2)a.

(C6Hs)2Pcf(zcHzN(CH3)z,
Examples of aromatic phosphines include (CsHs)zPcHzcOONafl. In addition, allyl type compounds represented by -mona (n) include allyl alcohol, 2-methyl-2-propen-1-ol, 2-buten-1-ol, 2.5-hexadien-1-ol. , 2,7-octarenin-1-ol, 1,4-pentadiene-3-
Allyl type alcohols such as ol, 1,7-octarenin-3-ol, 2-octen-1-ol and acetic acid a+7/l'% 2-methyl-2-propenyl acetate, 2°5-hexagenyl acetate, acetic acid 2.7-octagenyl, 1-vinyl-5-hexenyl acetate, 1-propionic acid
General formula of allylic alcohols such as vinyl-2-propenyl and 2-octenyl propionate (% formula%) (wherein R8 represents an acyl group represented by the formula R-C-, where R is as defined above) Examples include esters with carboxylic acids shown in

- When producing the phosphonimium salt represented by Monka (1), the fecal amount of the allyl type compound represented by the general formula (■) is at least equimolar to the trisubstituted phosphine. - There is no particular restriction on the upper limit of the amount of the allylic compound represented by Mon'ena (II), but after preparing the phosphonium salt represented by - Mon'ena (II), excess Considering the ease of operation to remove the compound,
About 1 to 1 for the allyl compound trisubstituted phosphine
It is preferable to use it in an amount of 0 times the mole. - The palladium compound to be present in the reaction system during the production of the phosphonium salt shown by Monka (1) is palladium that can be used in the usual telomerization reaction of conjugated dienes, typified by the dimerization reaction of butadiene. compounds can be applied. Specific examples of such palladium compounds include palladium (II) compounds such as para9macetylacetonate, π-allylpalladium9macetate, acetate badge9m, palladium carbonate, palladium chloride, bisbenzonitrile palladium chloride; and Examples include palladium (0) compounds such as bis(1,5-cyclooctadiene)palladium and tris(nohenzylideneacetone)cybaladium. When using palladium (n) compounds, palladium (formerly known as palladium (
It is also possible to add a reducing agent for reducing to 0).

Reducing agents used for this purpose include alkali metal hydroxides such as sodium hydroxide, formic acid, sodium phenolate, sodium borohydride, hydrazine,
Examples include subpowder, magnesium, and the like.

The amount of reducing agent to be administered is preferably the stoichiometric amount required for reduction or within 10 times the stoichiometric amount. The amount of the palladium compound to be used is 0.0.0.0.
It is desirable to use an amount such that the concentration is between 1 and 10 milligram atoms, preferably between 0.5 and 5 milligram atoms.

-The reaction for producing the phosphonium salt shown by Monka (1) is as follows:
It is carried out in the presence or absence of water containing carbonate and/or bicarbonate ions in the presence of a palladium compound. -Usual when allyl type alcohol is used as the allyl type compound represented by the pattern (n).

The reaction is carried out in the presence of water containing carbonate and/or bicarbonate ions, thereby forming a phosphonium salt which is an anion of −υ.

In addition, when an ester of an allylic alcohol with a carboxylic acid represented by the general formula (III) is used as the allylic compound represented by -monna (II), it contains a carbonate ion and/or a bicarbonate ion. A phosphonium salt, an anion represented by R (R is as defined above), is produced. It is practical to derive carbonate ions and/or bicarbonate ions from carbon dioxide, bicarbonates such as sodium bicarbonate, or carbonates such as sodium carbonate, which provide them in the reaction system.
Among these, derivation from carbon dioxide is particularly preferred. When carbon dioxide is used, 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 between normal pressure and 50
It is an atmospheric pressure (gauge pressure), and in practice, normal pressure to 10 atmospheric pressure (gauge pressure is preferable.) - The reaction for producing a phosphonium salt represented by Monana (1) is inert to the reaction, and The reaction may be carried out in the presence of an organic solvent capable of dissolving the substituted phosphine and the allyl compound represented by the general formula (II). Specific examples of such organic solvents include diethyl ether, dibutyl ether, tetrahydrofuran, diochitin, Ethers such as dioquinrane, ethylene glycol dimethyl ether, and polyethylene glycol dimethyl ether with an average molecular weight of 200 to 2000 (7);
- Secondary or tertiary alcohols such as butanol, impropanol; acetone, methyl ethyl ketone,
Ketones such as methyl in butyl ketone; Nitriles such as acetonitrile, benzonitrile, and probiononitrile; Amides such as acetamide, propionamide, N,N-dimethylformamide, N,N-dimethylacetamide; dimethyl sulfoxide, etc. Sulfoxides: sulfolane, methylsulfolane! Phosphoric acid amides such as hexamethylphosphoramide; Esters such as methyl acetate, ethyl acetate, methyl benzoate, and ethylene carbonate; Aromatic hydrocarbon dibutenes such as benzene, toluene, xylene, and ethylbenzene , cyclic or acyclic aliphatic hydrocarbons such as butane, hexane, cyclohexipune, methylcyclohexipune, and the like. The organic solvents are usually used alone, but there is no problem in using them in combination. - The reaction for producing a phosphonium salt indicated by the pattern (1) is usually 1
The process is carried out at a temperature within the range of 0°C to 80°C, but it is convenient to carry out the process at room temperature. The reaction is usually completed in 0.5 to 24 hours, and the end point of the reaction is determined by the nuclear magnetic resonance spectrum of phosphorus.
It can be easily determined by liquid chromatography, iodometry analysis, etc. As the atmosphere for the reaction system 5, it is desirable to use gases such as carbon dioxide and nitrogen, which do not have an adverse effect on the reaction, either singly or in a mixture of two or more. The phosphonium salt represented by the general formula (1) thus obtained can be separated and purified from the reaction mixture, for example, by the following method. After water and unreacted allyl-type compounds are distilled off from the reaction mixture under reduced pressure as necessary, the resulting residue is washed with a solvent such as methanol or diethyl ether to obtain a phosphonium compound represented by the general formula ( Salt crystals can be obtained.

General formula (1) for the reaction of butadiene and water according to the present invention
) The amount of the phosphonium salt used is usually 6 moles or more per 1 gram atom of palladium in the palladium compound, preferably 10 to 200 moles. Yes, preferably 30~
The amount is such that the proportion is within the range of 100 moles. In such a reaction between butadiene and water, a palladium (0) compound or a palladium (n) compound that can be conveniently used in the reaction for producing the phosphonium salt shown in the above-mentioned -Momonen (1) is conveniently used as the palladium compound. . Palladium C
(2) When a compound is used, a reducing agent may be further added to carry out the reaction between butadiene and water. Examples of the reducing agent include those that can be used in the reaction for producing a phosphonium salt represented by the general formula (1) described above. The amount of the reducing agent in the stool is preferably the stoichiometric amount required for reduction or an amount within 10 times the stoichiometric amount. The amount of the palladium compound is usually such that the concentration of the reaction mixture 1 in the reaction of butadiene and water is 0.1 to 10 milligram atoms in terms of palladium atoms, preferably 0.1 to 10 milligram atoms.
The amount is such that the concentration is between 5 and 5 milligram atoms.

As a method for adding the phosphonium salt and palladium compound represented by general formula (1) to the reaction system in the reaction between 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 also add a mixture of As one embodiment of the latter addition method, the reaction mixture containing the phosphonium salt and the palladium compound obtained by the reaction for producing the phosphonium salt indicated by - is used as it is or as appropriate by am or dilution operation. Examples include embodiments in which it is later used in the reaction between butadiene and water.

Margin below In the reaction of butadiene and water according to the invention.

The reaction rate can be further improved by adding carbonate or bicarbonate of aliphatic tertiary amine such as triethylamine to the reaction system.The reaction of butadiene and water has no negative effect on the reaction. It may be carried out in the presence of an organic solvent.

Examples of such organic solvents include the aforementioned organic solvents that can be present in the reaction system in the reaction for producing the phosphonium salt represented by general formula (1). The reaction is generally carried out at a temperature within the range of 40°C to 100°C, preferably 60°C to 80°C. The reaction pressure is not particularly limited, and may be normal pressure,
Pressure conditions under increased pressure or reduced pressure can be appropriately selected and employed. Furthermore, although the reaction between butadiene and water can be carried out by a batch method or a continuous method, it is preferable to carry out the reaction by a continuous method from an industrial perspective.

The octa-2,7-renin-l-ol and the catalyst component contained in the reaction mixture obtained by reacting butadiene and water in this way are prepared by a distillation method using a thin film evaporator, etc. They can be separated from each other by applying extraction methods such as those described in Japanese Patent Application Laid-open No. 56-138129 and Japanese Patent Application Laid-Open No. 57-134427. It is desirable to employ an extraction method because the components can be reused for a longer period of time.For example, as a phosphonium salt represented by the general formula A hydrophilic phosphonium salt having a group represented by 1000M (M is as defined above) is used, and sulfolane, as a reaction solvent,
ethylene carbonate.

After reacting butadiene with water using an organic solvent with a high dielectric constant such as N,N-dimethylformamide, the resulting reaction mixture is subjected to an extraction operation using a hydrocarbon such as hexane as an extractant. A product such as octa-2,7-renin-1-ol is obtained as an extract component, and a catalyst component is obtained as a raffinate component. Octa-2,7-renine-1- separated from the catalyst by methods such as distillation and extraction
The mixture containing ol can be used as it is for the next hydrogenation reaction after recovering unreacted butadiene from it if necessary, but the mixture containing octa-2, A purified product of 7-renyn-1-ol may be subjected to a hydrogenation reaction.

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

As the hydrogenation catalyst, any catalyst known to have a catalytic ability for the hydrogenation reaction of olefins can be used without particular limitation. As the hydrogenation catalyst,
Specifically, nickel-based catalysts such as Raney nickel catalysts, modified Raney nickel catalysts, and supported nickel catalysts; Barak9-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-chromite catalyst
Examples include zinc oxide catalysts. Modifying metals in modified Raney nickel catalysts include chromium, rhenium,
Examples include molybdenum, tungsten, titanium, iron, manganese, and lead. Further, examples of the carrier in the supported catalyst include silica, alumina, diatomaceous earth, and activated carbon.

The hydrogenation reaction can be carried out in a liquid phase system with a hydrogenation catalyst suspended in a stirred reactor or a bubble column reactor, or in a basic reactor packed with a supported catalyst. It can also be carried out in the liquid or gas phase. When the reaction is carried out under liquid phase suspension, the concentration of the hydrogenation catalyst is usually 0.0% on a metal basis with respect to the reaction mixture. O is in the range of 1 to 10 weight percent, preferably in the range of 0.1 to 5 weight percent. The hydrogenation reaction can be carried out in a patch or continuous manner. The hydrogen pressure and reaction temperature to be employed vary depending on the type of hydrogenation catalyst used and cannot be determined unambiguously, but for example, Raney nickel,
When Raney cobalt, supported palladium or supported ruthenium is used, preferably 1 to 150
It is selected from the range of atmospheric pressure (absolute pressure) and 20 to 140°C. Further, when using supported nickel, copper-chromite or copper-chromium-zinc oxide as a hydrogenation catalyst, the temperature is preferably selected from the ranges of 1 to 150 atm (absolute pressure) and 100 to 300°C, respectively. O As the hydrogenation reaction solvent, the raw material or the product can serve the same function, but other solvents may also be used. Solvents that can be used for this purpose include hydrocarbons such as aliphatic hydrocarbons such as hexane, octane, and decane; aromatic hydrocarbons such as benzene, toluene, and xylene; alcohols such as methanol, ethanol, butanol, and tecanol; diimpropyl ether,
dibutyl ether, anisole, tetrahydrofuran,
Examples include ethers such as dioxane; esters such as inpropyl acetate and butyl acetate.

From the reaction mixture obtained by the hydrogenation reaction, after removing the hydrogenation catalyst by normal operations as necessary,
High purity n-octatool is obtained by distillation purification.

The dehydration reaction of n-octatool to 1-octene is usually carried out at elevated temperatures in the presence of a dehydration catalyst. As the dehydration catalyst, inorganic acids such as sulfuric acid, phosphoric acid, sodium hydrogen sulfate, and boric acid; Lewis acids such as γ-alumina, thorium dioxide, tungsten oxide, zinc chloride, and dicalcium phosphate are used. The reaction is carried out in a liquid phase or a gas phase, and the reaction temperature is usually selected within the range of 150 to 500"C, preferably within the range of 250 to 450"C.1-octene produced by dehydration of n-octatool may be isomerized to internal olefins in the reaction system, so it is desirable to suppress this isomerization in order to obtain 1-octene with high selectivity.As a method for suppressing the isomerization of 1-octene, , a method of reducing the dehydration reaction time as much as possible and quickly distilling the produced 1-octene out of the reaction system, and a method of using a dehydration catalyst modified with a basic substance such as sodium hydroxide. The reaction mixture thus obtained is optionally treated with a molecular sieve such as siurea or molecular sieves, and then subjected to a distillation operation to obtain 1-octene in high purity.

〔Example〕

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to these Examples.

Reference Example 1 (Synthesis of phosphonium salt) 30 ml of ion-exchanged water was placed in an autoclave equipped with a stirrer, a carbon dioxide inlet tube, and a purge tube. Dioxane 11
0 tul, palladium acetate 0.1f, lithium diphenylphosphinobenzene-m-sulfone) 3FM and octa-2,7-renin-1-ol 25F,
After the atmosphere in the system was sufficiently replaced with carbon dioxide, the pressure was increased to 5 Kp/m (gauge pressure) with carbon dioxide. Next, the temperature of one reaction solution was raised to 60°C, and the reaction was continued for about 20 hours.

After the reaction was completed, the solvent was distilled off under reduced pressure, and the resulting solid was washed with 100 m/ml of ether. The washed solid was vacuum dried at room temperature to obtain 352 as a white powder.

This white powder was subjected to high performance liquid chromatography [eluent:
0.01 mole /)' Phosphoric acid aqueous solution/methanol = 1/4. Column: YMC-Pack AM312
0DS (manufactured by Yamamura Kagaku Kenkyujo Co., Ltd.)], no peak was observed at the position of the raw material phosphine compound, and a single peak was observed at another position.C and H of the compound giving this peak Elemental analysis and P
, S and LiK, the empirical formula of the compound was determined to be C27H2sOsSPLi.

In addition, as a result of pouring IN dilute sulfuric acid into the obtained white powder and quantifying the generated carbon dioxide gas using the barium hydroxide method, the molar ratio of the phosphorus atoms contained in the white powder to the generated carbon dioxide gas was 1.
It turned out to be 1 to 1. Furthermore, the obtained white powder was subjected to 1H- and 31P-NMR spectrum analysis and infrared absorption spectrum analysis.

From the above analysis results, it was determined that the obtained white powder was a compound represented by the following structural formula.

CH2CH=CHCH2CH2CH2CH=CH2 Data on the IH-NMR spectrum, infrared absorption spectrum and 31P-NMR spectrum of the obtained compound are shown below.

IH-NMR spectrum (% HMDS standard in CDCI!3, 90 MHz, ppm) 61.00-1.33 (m, 2H) 1.63-2.10 (m, 2H) 4.06 (d
ofd, J'= 15 and 6.9) 1z,
2H) 4.66-6.00 (m, 5H) 7.31-7.96 (m, 12) 1) 7.96-8.
40 (m, 2H) Infrared absorption spectrum A/ (KBr disk, cy
*-”)690.725,755j800,970,1
040,1110°1210,1230.1400.1
440.1485.2940°31P-NMR spectrum (in 95% by weight sulfolane aqueous solution.

H3PO4 standard, ppm) 621.55 Reference Example 2 (Synthesis of phosphonium salt) 85
weight percent tetrahydrofuran aqueous solution 100f,
Palladium acetate 50q and hydriphenylphosphine 3
．． 16F was charged, a pressure of 5 K4/d (gauge pressure) was applied with carbon dioxide, and the mixture was stirred for 30 minutes. Next, 3.
5F allyl alcohol was fed, and the autoclave was heated to 60°C and reacted for 4 hours. After the reaction was completed, the solvent was distilled off under reduced pressure to obtain a solid. The obtained solid was washed with 100 ml of ether and then vacuum dried to obtain 2.92 ml of white powder. When this was analyzed by high performance liquid chromatography under the same conditions as Reference Example 1, no triphenylphosphine peak was observed, but a single peak was observed at a different position. From the results of elemental analysis, colorimetric analysis, quantitative analysis of carbon dioxide gas, and 1H- and P-NMR spectroscopy, it was determined that the obtained white powder was a compound represented by the following structural formula.

In addition, the data of the LH-NMR spectrum of this compound is shown below.

”H-NMRx (DMSO-da), HMD
S standard, 90MHz, ppm) δ4.54 (d of d, J=15.6 and
5.6Hz, 2H) 5.13~6.03 (m,
3H) 7.53-8.03 (m, 15H) Reference Example 3 (Synthesis of phosphonium salt) Triphenylphosphine 26f instead of lithium diphenylphosphinobenzene-m-sulfone) 35f
A white powder of 27f was obtained by carrying out the same reaction and treatment operations as in Reference Example 1 except that 27f was used. High performance liquid chromatography analysis revealed that the white powder was a single compound different from triphenylphosphine. Further, from the results of elemental analysis, colorimetric analysis, quantitative analysis of carbon dioxide gas, and 1H- and P-NMR spectroscopy, the structural formula of the compound was determined as follows.

(C6H5)3P-CH2CH=CHCH2CH2CH
2CH=CH2-HCO3 Note that 1H-NM of the compound
The R spectrum data is shown below.

'H-NMRx speckle (in CDαs, HMDS standard,
90MHz, ppm) 61.05-1.48 (m, 2H) 1.63-2.08 (m, 4H) 4.05 (d of d, J=15 and 6H
z, 2H) 4.63~5.91 (m, 5H) 7.32~? , 93 (m, 15H) Reference Example 4 (Synthesis of phosphonium salt) Contents 300 w equipped with a stirrer, cooler and thermometer
Palladium acetate 6.9” FCo in a three-necked flask,
031 mlJ mol), lithium diphenylphosphine benzene-m-sulfonate 4.669 (0,013 mol), 1-acetoxy-2,7-octadiene 3.5F (
0,021 mol] and acetic acid 1372 were charged in a nitrogen gas atmosphere, and the mixture was reacted under heating under reflux for 4 hours. After the reaction was completed, 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
．． A powder of 15 f 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 a raw material.

Further, from the results of elemental analysis, colorimetric analysis, infrared absorption spectrum analysis, and 1H- and "P-NMR spectrum analysis, the structural formula of the product was determined as follows. 31P-NMR spectrum IH-NM
The R spectrum and infrared absorption spectrum data are shown below.

31P-NMR spectrum (95% by weight sulfolane aqueous solution): 621 ppm I) l-NMR spectrum (CDα3.HMDS standard,
ppm) 61.06-1.40 (m, 2H) 1.60-2.20 (m, 4H) 1.95 (s, 3H) 4.09 (d
of d, J=15.2 and 7.2Hz,
2H) 4.66-5.93 (m, 5H) 7.46-7.83 (m, 2H) 8.08-8.
37 (m, 2H) infrared absorption spectrum (KBr
-Disk, ,, -1) 665.690,720 (cis-olefin).

750.800,995 (trans-olefin).

1030.1100.1200 (-3O3Li), 14
00°1570.1710 (CH3COOe), 285
0.3010 Reference Example 5 (Synthesis of phosphonium salt) In an autoclave equipped with a stirrer, a carbon dioxide inlet, and a purge pipe, ion-exchanged water 5Q/, dioxane 1Q
Qxl, palladium acetate 0.1, sodium diphenylphosphinobenzene-p-carboxylate 32.8
After charging f and allyl alcohol 11.72, and replacing the atmosphere in the system sufficiently with carbon dioxide,
The pressure was increased to 9/7A (gauge pressure).Then, the mixture was stirred at 80°C for 24 hours. After the reaction was completed, the reaction mixture was concentrated under reduced pressure, and the resulting solid was diluted with ether 100
Washed with ysl. The washed solid was vacuum-dried at room temperature to form a white powder of 412, and the phosphonium salt 52 obtained in Reference Example 3 was mixed with methanol/water (volume ratio: 50150). The mixture was dissolved in 200 ml of solvent, 3.62 ml of aqueous barium octahydrate was added, and the mixture was stirred at room temperature for 24 hours. Insoluble salts were filtered off, and methanol and water were distilled off from the filtrate to obtain a solid.

By vacuum drying the obtained solid at room temperature, one set of %formula%( 4.2F of phosphonium salt was obtained.

Reference Example 7 (Manufacture of octa-2,7-renin-1-ol) Contents 30: Equipped with an electromagnetic stirrer, carbon dioxide inlet, sampling port, charging port, Persil and temperature controller
Tris(dibenzylideneacetone)palladium 0.319 (0.3 mmol), phosphonium salt 6.2F (12 mmol) having the formula %,
66 ml of sulfolane, which had been thoroughly degassed using nitrogen gas, 682 ml of water, and 16.5 F of triethylamine were charged. Next, after creating a carbon dioxide atmosphere in the system, 5 kg/
Pressurize with carbon dioxide to d (cage pressure) and stir for 30 minutes. After raising the temperature in the system to 75°C while keeping the carbon dioxide partial pressure in the system at 5/- (gauge pressure), add 40 m of butadiene.
1 was injected all at once to start the reaction. After the reaction 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.

The n-hexane layer was removed by evaporation using a pn-hexane tube using an evaporator to obtain a concentrated liquid having a concentration of 20.99%.

This concentrate was distilled under reduced pressure of l Q mHf (absolute pressure) to obtain 19.9F octa-2,7-renin-1-ol (b, p, 85°C/l Q mHf).
) and 1.02 octa-1,7-renin-3-ol (b, p, 68°C/10■Hf) were obtained.

Reference Example 8 (Production of octa-2,7-renin-1-ol) As a phosphonium salt, the reaction mixture was analyzed for 3 hours, and no formation of phosphine oxyto was observed. In addition, the Padge 9m catalyst was uniformly dissolved without metalization.

The resulting reaction mixture was taken out of the autoclave and
After transferring to 00IIE# separatory funnel, 150-n-
Extracted using hexane. The reaction and analysis were carried out in the same manner as in Reference Example 7, except that 4.37 f (12 mmol) of the phosphonium salt taken out was used. The obtained results are shown in the second coat.

The resulting reaction mixture was taken out of the autoclave and
00ati? After transferring to a separating funnel of 150x10n
-Extracted with hexane. N-hexane was removed by evaporation from the taken out n-hexane layer using an evaporator to obtain a concentrated liquid of 19f. This concentrated liquid is 1 Q mHf
16. by distillation under reduced pressure (absolute pressure).
3F octa-2,7-cyen-1-ol (b, p
, 85℃/10■Hf) and 0.52 octa-1,7-
Renin-3-ol (b, p, 68°C/1O Hf) was obtained.

Reference Examples 9 to 11 (Production of octa-2,7-renin-1-ol) Reaction and analysis were carried out in the same manner as in Reference Example 5, except that 12 mmol of each of the phosphonium salts shown by Mr. 3 was used as the phosphonium salt. I did it. The analysis results obtained are shown in Table 3.

The following margins show that by subjecting the reaction mixture thus obtained to the following operations, the products octa-2,7
-renin-1-ol and octa-1゜7-renin-3-
All was isolated. Each reaction mixture was taken out from the autoclave, transferred to a 500-mm separating funnel, and then extracted using 150 mg of n-hexane. The taken out n-hexane layer was evaporated and removed using a color evaporator to obtain a concentrated liquid having a concentration of 16.7F to 19.5F. By distilling this concentrated liquid under reduced pressure of 10 H9 (absolute pressure), the respective products octa-
2,7,-dien-1-ol (b, p, 8°C/1
0■HQ and octa-1,7-renin-3-ol (b,
p, 68° C., 710 μH) was isolated. That is, in Reference Example 9, 13.6f octa-2,7-renin-1-ol and 0°882 octa-1,7-renin-3-ol were obtained, and in Reference Example 10, 18.5F octa-2,7-renin-3-ol was obtained. -2゜7-renin-1-ol and 0,95 octa-1゜7
-renin-3-ol was obtained, and in Reference Example 11, 1
5.6 f octa-2,7-renin-1-ol and 0
．． 88F octa-1,7-renin-3-ol was obtained.

Reference Example 12 (Production of octa-2,7-renin-1-ol) In the same reaction apparatus as that used in Reference Example 7.

Palladium acetate 67.5■ (0,
3 mmol)% phosphonium salt 6.2F (12 mmol).

Add 66 ri of sulfolane, 68 f of water and 50 cape of Giju,
The mixture was stirred at 40°C for 1 hour. Then triethylamine 16
．． After charging 5 F, add g/g to gold 5 in the system with carbon dioxide.
The mixture was stirred at 60° C. for 30 minutes while maintaining cIA (gauge pressure). When the temperature of the system was raised to 75° C. and 40 tons of phtadiene was introduced all at once, the reaction started immediately. After reacting for 3 hours, the reaction mixture was analyzed by gas chromatography, and it was found that octa-2,7-renin-1-ol was 17
2 mmol, 1 octa-1,7-renin-3-ol
It was found that 0.6 mmol was produced. Furthermore, no formation of phosphine oxyto was observed.

The reaction mixture obtained in this way was taken out from the autoclave and transferred to a 500 m/separating funnel.
50! Extraction was performed using n-hexane (R1). Pn-hexane was removed by evaporation from the taken out n-hexane layer using an evaporator to obtain a 21.8F concentrated liquid. This concentrated solution was distilled under reduced pressure of 1 QwiHf (absolute pressure) to obtain 20.5 F octa-2,7-renin-1-ol (b,p, 85°C 710 QHf) and 1
, 3 octa-1,7-renin-3-ol (b, p
, 68° C./10 μHf) was obtained.

Reference Example 13 (Production of octa-2,7-renin-1-ol) The 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 the formula % was used as the phosphonium salt. Ta. As a result, it was found that 165 mmol of octa-2,7-renin-1-ol and 10 mmol of octa-1,7-cyen-3-ol were produced.

The resulting reaction mixture was taken out of the autoclave and
The mixture was transferred to a 00-separatory funnel and extracted using 150d n-hexane. 19. Evaporate and remove n-hexane from the n-hexane layer taken out using an evaporator.
39(7) concentrate was obtained.

This concentrate was distilled under reduced pressure of 10 wHF (absolute pressure) to obtain 18.3f of octa-2,7-renin-1-ol (b,p, 85°C/10■HP) and 1.
02 octa-1,7-renin-3-ol (b, p,
68° C./10 μH9) was obtained.

Reference Example 14 (4 samples of octa-2,7-renin-1-ol) Synthesis experiments were repeated 30 times using the following reaction apparatus and extraction apparatus.

(Reaction apparatus a> A stainless steel autoclave with a capacity of 300 ate and equipped with a thermometer, a stirrer, a butadiene quantitative feed pump, a carbon dioxide inlet, a liquid feeder, and a liquid extraction port was used as the reaction apparatus.

(Extraction device) Contents 800 equipped with a thermometer, stirring device, gas inlet, n-hexane feeder and liquid pressure port
A tnl pressure glass autoclave was used as the extraction device. This extraction device is directly connected to the reaction device.

(Experimental method) Sulfolane 412, distilled water 4
5F,) ethylamine 14F,) ris dibenzylidene acetone 0.2q of palladium (corresponding to a concentration of 2 mmol/1 (prepared reaction solution)) and 4.1f of a phosphonium salt represented by the formula % were charged into the system. After sufficient substitution with gold and carbon dioxide, the internal temperature was heated to 70°C with stirring, and carbon dioxide was introduced until the internal pressure became 8 kg/i (gauge pressure).While stirring at a speed of 600 rprn, butadiene was charged in liquid form at 11 mC, and then reacted at 75°C for 60 minutes while continuously introducing it at a rate of 6.4 me/hr. After 60 minutes of reaction, the introduction of butadiene was stopped, and the reaction mixture was While cooling, the mixture was sent to the extractor using the pressure difference.The inside of the extractor was then pressurized to 3Kg/d (gauge pressure) with carbon dioxide, and then 5Qyxl of n-hexane was added at 40°C. Stirred for 15 minutes. After that, leave the product in a quiet place for 15 minutes.
-Extraction with hexane was carried out. The upper layer (n-hexane layer) was taken out of the system using a pressure difference. N-hexane 5Q*/ was charged again to the residual liquid, extracted in the same manner, and the upper layer was taken out of the system. For the resulting combined n-hexane layer, the reaction product and sulfolane were analyzed by gas chromatography, water was analyzed by the Karl Fischer method, triethylamine was analyzed by titration, and palladium and phosphorus (both on atomic basis) were analyzed by atomic amount. Quantitative analysis was performed by absorption method and colorimetric method, respectively. For the raffinate catalyst solution, the amount of water consumed in the reaction and the amount of water eluted into the 1 cn-hexane layer.

After adding triethylamine and sulfolane, the mixture was sent to the reactor again using the pressure difference. Using this catalyst liquid, a series of operations consisting of reaction, extraction, and catalyst circulation step 73λ was repeated 30 times in total. Note that throughout this repeated experiment, no new palladium component or phosphorus component was added. Table 4 shows the relationship between the number of repetitions, the reaction results, and the amounts of palladium and phosphorus components eluted into the n-hexane layer. It can be seen from Table 4 that the catalytic activity is maintained over a long period of time.

Table 4 0.6 0.07 0.6 0.06 0.5 0.06 o, so, os O150,05 (Note 1) 1.3 for products other than octadienol
7-octatriene and dioctagenyl ether were mentioned, the amount of the former produced was 1.2 to 1.3 mmol, and the amount of the latter produced was 0.4 to 0.6 mmol.

(Note 2') NOD is an abbreviation for "octa-2,7-thien-1-ol," and IOD is "octa-1゜7-ol."
It is an abbreviation for "renin-3-ol."

The obtained extracts were combined and distilled to obtain a fraction of 137-138°C at xoomHP (absolute pressure) with a purity of 99.
9% octa-2,7-renin-1-ol in 238f
Obtained.

Reference Example 15 (Production of octa-2,7-renin-1-ol) The raffinate catalyst solution obtained after 30 repeated experiments in Reference Example 14 was heated at room temperature for 24 hours in an open system where it was exposed to air. Stir under. No formation of phosphine oxyto was observed. 311 according to Reference Example 14 using this catalyst liquid.
00〈A reversal experiment was conducted. The amount of octadienol produced was 70 mmol, and the molar ratio of octa-2,7-cyen-1-ol to octa-1,7-cyen-3-ol was 95:5.

The obtained reaction mixture was taken out from the autoclave, and
After transferring to a separating funnel of 0 Q tut, 70ml of n
-Extracted with hexane. N-hexane was removed by evaporation from the n-hexane layer taken out using an evaporator to obtain a concentrated liquid of 8.3F. 1011J of this concentrate
H? 8.02 octa-2,7-cyen-1-ol (b, p.

85℃/10yHf') and 0,32 octa-
1,7-cyen-3-ol (b, p, 68°C/10
1131 Hy) was obtained.

Below is a blank Example 1 (Production of octa-2,7-cyen-1-ol) Oct-2 with a purity of 99.9% was prepared in the same manner as in Reference Example 14.
, 7-cyen-1-ol was obtained as 235F.

(Manufacturing of n-octatools) A nickel-Cain earth catalyst (Japan G-69 made by Girdler; N
i content: 52 wt%) 0.39 and 2-ethylhexanol (solvent) 2O2 were charged, the system was sufficiently replaced with hydrogen, and then maintained at 9 kf/era (gauge pressure) with hydrogen. After raising the internal temperature to 150°C, add 79% of octa-2°7-renin-1-ol while stirring vigorously.
/hr for 5 hours. 1 o more after the introduction
The reaction was allowed to continue for minutes. After cooling the autoclave,
The reaction mixture was taken out and analyzed by gas chromatography. The conversion rate of octa-2,7-cyen-1-ol was 100%, and n-octatool was produced with a selectivity of 100%. The resulting reaction mixture was removed from the autoclave, the Schinkel-Cain catalyst was removed by filtration, and the purity was 99.9% (Dn-octa/-) by atmospheric distillation.
Get 362 k&(b, p.

190-b (Production of 1-octene) Tricalcium phosphate (Ca3(PO4)) 211 t and sodium hydroxide 9m 0.07F are mixed with methanol 200ag
After heating and refluxing in / for 1 hour, methanol was distilled off, and the resulting residue was dried in vacuo. The dehydration catalyst 12 thus prepared was placed in an autoclave with a capacity of 10,011 tons together with an n-octatool 362,
The reaction was carried out at 420° C. for 1.5 hours under a nitrogen gas atmosphere.

After the reaction was completed, it was cooled and the reaction mixture was analyzed by gas chromatography, and it was found that 1-octene was 28? The selectivity to l-octene was 94. As a result of rectification of this reaction mixture, 222 1-octene with a purity of 99.6% was obtained as a fraction with a boiling point of 121 to 122°C.

Example 2 (Production of octa-2,7-renin-1-ol) Oct-2 with a purity of 99.9% was prepared in the same manner as in Reference Example 14.
, 2321 of 7-renin-1-ol were obtained.

(Manufacture of n-octatool) Raney nickel catalyst (ND-65 manufactured by Yoken Fine Chemical Co., Ltd.; water content: 50 wt%) 0.32 and 2 - Prepare ethylhexanol 20F and increase the hydrogen pressure to 9ky10+! (gauge pressure), while maintaining the internal temperature at 80°C,
It was introduced for 5 hours at a rate of y/hr. 1 more after installation
The reaction was continued for 0 minutes.

After cooling the autoclave, drain the reaction mixture and
As a result of gas chromatography analysis, octa-2,
The conversion rate of 7-renin-1-ol is 100%.
Selectivity to n-octatool was 100%.

(Manufacture of 1-octene) 20 txl of alumina (manufactured by Two-Tone; cylindrical shape with a diameter of 3 m and a length of 3 dragons) was filled into a 0-shaped tube (inner diameter: 2 m). While maintaining the temperature of the alumina packed bed at 360°C, the gasified n-octatool was circulated under normal pressure using nitrogen gas as a carrier (nitrogen gas concentration: 50 molt) so that the contact time was 13 seconds. The gas that flowed out was condensed in a dry ice bath.The resulting condensate was analyzed by gas chromatography, and the conversion rate of n-octatool was 16% to 1-octene. The selectivity was 89.

Examples 3 to 6 (Production of octa-2,7-renin-1-ol) Oct-2 with a purity of 99.9% was prepared in the same manner as in Reference Example 14.
, 2382 of 7-renin-1-ol were obtained.

(Production of n-octatool) The above octa-2,7 -renin-1
A hydrogenation reaction using 352 ols and an analysis of the reaction mixture were carried out.

Note that the catalyst was used in an amount such that the catalyst metal was 0.3F. Also, the amount of solvent in the box is 20? Met.

Figure 5 Solvent n-octatool n-butanol n-octatool hexane Reaction temperature (''C) Yield of n-octatool (H) (6) 99 or more 99 or more 99 or more and 99 or moreNote (1)
A catalyst prepared by developing an alloy of 3'% Mo-47% Ni-50% At according to a conventional method.

(2) 2.5% Re -47,5% Ni -5
A catalyst prepared by developing a 0% M alloy according to a conventional method.

(8) Commercially available product (manufactured by Nippon Engelhard).

Ru 5wt% supported.

(4) Commercial product (manufactured by Nippon Engelhard).

Carrying Pd2wt.

(5) Yield based on analysis value by gas chromatography.

Comparative Reference Example 1 (Production of octa-2,7-cyen-1-ol) Into the same reactor as used in Reference Example 7, a 95% by weight aqueous sulfolane solution 70. Of, ion exchange water 63. Of,) ethylamine 16°59. Balazicum acetate 0.067F
and lithium diphenylphosphinobenzene-m-sulfone (4.22F) were charged, and the reaction system was brought to a carbon dioxide atmosphere [partial pressure of carbon dioxide: 5 to 97 m (gauge pressure)] at room temperature. The temperature was then set at 75° C. and butadiene 4Qrxl was charged to start the reaction. After the reaction started, the product in the reaction mixture was analyzed over time by gas chromatography, and it was found that there was an induction period of about 1 hour. Furthermore, when the combined solution in one reactor was analyzed by high performance liquid chromatography after 3 hours of reaction, phosphine was removed at a retention time of 4.0 minutes. The results of quantitative analysis of the product are shown in Table 6.

Table 6 Comparative Reference Example 2 (Production of octa-2,7-renin-1-ol) Into the same reactor as used in Reference Example 7, 20% water was added. , t-
Butanol 80%, Tetrakistriphenylphosphine Halacium 0.34F, ) Liphenylphosphine 3.1
2 and butadiene 40ml, 5kf/crA
(gauge pressure) with carbon dioxide gas. The reaction mixture was heated to 75° C. while stirring, and then reacted for 3 hours.

After the reaction was completed, the reaction mixture was analyzed by gas chromatography, and almost no production of octa-2,7-renin-1-ol and octa-1,7-renin-3-ol was observed. Thus, it can be seen that when phosphine compounds are used at high concentrations, the reaction rate is extremely low.

Comparative Reference Example 3 (Stability confirmation test of palladium compound in the presence of triphenylphosphine) Tetrakistriphenylphosphine palladium 0.23
F and hydriphenylphosphine 1.31F were dissolved in sulfolane 1QQx/. When the obtained sulfolane solution was stirred at room temperature for 24 hours in an open system where it could come into contact with air, 1.33 f' of phosphine oxide was produced and a large amount of palladium metal was deposited.

〔Effect of the invention〕

According to the present invention, as is clear from the above examples, when butadiene and water are reacted, there is no induction period of the reaction, and phosphine oxide, which is known to be a catalyst poison, is produced. octa-2,7-renin-1-ol, which is a synthetic intermediate, can be obtained with high selectivity. In addition, even when the phosphonium salt constituting the catalyst is used in large excess with respect to the radicum compound in order to increase the stability of the catalyst, octa-2,7-renin-1-ol is high. Therefore, according to the present invention, n-octatool and 1 -Octane derivatives selected from octene can be advantageously produced industrially.

Applicant for permission: RiRashi Co., Ltd.

Claims (1)

[Claims] 1. Butadiene and water are combined into a palladium compound and the general formula [■-Y]■ (where ■ is the formula ■H, ▲ there is a mathematical formula, chemical formula, table, etc. ▼ or ▲ mathematical formula, chemical formula, table, etc.) ▼ represents an anion represented by , where R represents a hydrocarbon group, Y represents an allyl group that may have a substituent, and ■ represents a trisubstituted phosphonio group. A method for producing n-octanol, which comprises hydrogenating the obtained octa-2,7-dien-1-ol. 2. Reacting butadiene and water in the presence of a palladium compound and a phosphonium salt represented by the general formula [■-Y]■ (wherein, ■, Y and ■ are as defined in claim 1), A method for producing 1-octene, which comprises hydrogenating the obtained octa-2,7-dien-1-ol to obtain n-octanol, and then dehydrating the n-octanol.