JPH0930993A - Production of alkatrienes - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce the subject compound, especially an octatriene, in high yield and selectivity by dimerizing a conjugated alkadiene in the presence of a new catalyst system composed of a palladium compound and a specific phosphorus compound. SOLUTION: A conjugated alkadiene is dimerized in the presence of (A) a palladium compound (e.g. palladium acetate) and (B) a phosphorus compound having trivalent phosphorus-oxygen single bond [preferably a phosphonite compound of formula (A<1> is a (substituted)aryl; A<2> and A<3> are each a (substituted) arylene; (x) and (y) are each 0 or 1; Q is O, S, etc.; (n1 ) is 0 or 1). The reaction is preferably carried out in a solvent. The reaction temperature is usually 50-130 deg.C and the reaction pressure is atmospheric pressure to 200kg/cm<2> . A compound of formula I wherein A<1> is α-naphthyl, e.g. α-naphthyl(2,2'- methylenebis(6-t-butyl-4-methylphenoxy))phosphine is a new compound.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing alkatrienes. More specifically, the present invention relates to a method for producing alkatrienes by subjecting a conjugated alkadiene to a dimerization reaction.

[0002]

2. Description of the Related Art Alkatrienes are compounds useful as raw materials for synthesizing various general-purpose or special-purpose organic compounds. In particular, straight-chain octatrienes such as 1,3,7-octatriene can be chemically synthesized by, for example, a method of carbonylating an olefin moiety and then hydrogenating, or a method of hydrating an olefin moiety. Industrially important compounds, octanol, nonanol,
Octanediol, nonanediol or esters thereof can be produced. As a method for producing such alkatrienes, a method of producing alkatrienes by dimerizing a conjugated alkadiene using a palladium compound and a phosphine compound as a catalyst has been known (Japanese Patent Publication No. 46-24003). .

[0003]

In the above conventional method,
Triphenylphosphine is known to be advantageous as a phosphine compound used as a ligand of a palladium catalyst. However, the yield and selectivity of the alkatrienes obtained by such conventional techniques are not yet sufficient. The metal component used as a catalyst plays an important role in the complex catalyzed reaction, and the selection of the kind of the ligand used with it has a significant influence on the activity and selectivity of the catalytic reaction. The present inventors have found that industrially advantageous alkatrienes capable of obtaining desired alkatrienes in a high yield and a high selectivity in a dimerization reaction of a conjugated alkadiene using a palladium compound and a phosphorus compound as a catalyst. Earnestly studied in order to provide the manufacturing method of.

[0004]

The present invention provides a method for producing alkatrienes by dimerizing a conjugated alkadiene using a novel catalyst system. The present inventors have used a catalyst in which a palladium compound and a specific phosphorus compound are combined, instead of a combination of a palladium compound and a phosphine compound, which is conventionally known to be used as a catalyst, and a conjugated alkadiene is subjected to a dimerization reaction. By doing so, the catalyst component can be effectively and efficiently utilized even at a low palladium concentration, and in the case of using 1,3-butadiene as the alkatriene, especially the conjugated alkadiene, the straight-chain octatrienes, particularly The present invention has been reached by finding that 1,3,7-octatriene can be obtained in high yield and high selectivity.

That is, the first gist of the present invention is to produce alkatrienes by dimerizing a conjugated alkadiene in the presence of a palladium compound and a phosphorus compound having one or more trivalent phosphorus-oxygen single bonds. A method for producing alkatrienes, which is characterized by the above. The second aspect of the present invention
The gist of the present invention resides in a phosphonite compound represented by the following general formula (2).

[0006]

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(In the formula (2), A ⁴ represents a phenyl group in which at least one of the two ortho positions is substituted with an alkyl group having 1 to 4 carbon atoms, and A ⁵ is independently substituted. Represents an optionally substituted arylene group, k and l are independently
0 or 1 represents an integer, Q ^{is, -CR 11 R 12 -, -} O
-, - S -, - SO 2 -, - NR 13 -, - SiR 14 R 15
Represents a divalent bridging group represented by -or -CO-, and R ¹¹
And R ¹² independently represents hydrogen, an alkyl group having 1 to 12 carbon atoms, a phenyl group, a tolyl group, or an anisyl group,
R ¹³ , R ¹⁴ and R ¹⁵ independently represent hydrogen or a methyl group, and n ₂ represents an integer of 0 or 1. Further, the third gist of the present invention resides in a phosphonite compound represented by the following general formula (3).

[0008]

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(In the formula (3), A ⁶ represents an optionally substituted α-naphthyl group, A ⁷ independently represents an optionally substituted arylene group, and m and n independently. , 0
Or 1 represents an integer, Q is ^{-CR 21 R 22 -, - O-} ,
_{-S -, - SO 2 -,} - NR 23 -, - SiR 24 R 25 - or -CO- represents a divalent bridging group represented by the R ²¹ and R ²² are independently, hydrogen, 1 to carbon atoms 12 represents an alkyl group, a phenyl group, a tolyl group, or an anisyl group represented by R ²³ , R
²⁴ and R ²⁵ independently represent hydrogen or a methyl group, and n ₃ represents an integer of 0 or 1. )

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. Examples of the conjugated alkadiene that is a raw material for producing alkatrienes by the method of the present invention include 1,3-butadiene, 2-ethyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, isoprene, 1,3-pentadiene, chloroprene, 1,3-octadiene and the like can be mentioned. When the raw material is 1,3-butadiene, those which are usually available include purified 1,3-butadiene and so-called BB fraction (BBP), that is, a C ₄ fraction mixture in a naphtha decomposition product.

When BBP is used as a raw material mainly in consideration of economy, it is desirable to separate and remove acetylenes and allenes contained in the raw material BBP in advance. The method for reducing acetylenes and allenes is not particularly limited, and various known methods can be appropriately adopted. When octatrienes are produced by the dimerization reaction of 1,3-butadiene, 1,3-butadiene after removing or reducing acetylenes and allenes in BBP is produced.
It is desirable that the total concentration of acetylenes and allenes in the butadiene raw material is as low as possible.
About 1.0% by weight or less with respect to butadiene is desirable.

In the present invention, a palladium compound is used as the main catalyst. The form of the palladium compound used and its valence state are not limited, and for example, a bis (phosphonite) palladium complex which is a palladium compound having a specific phosphorus compound used as a cocatalyst as a ligand as described later. , Tris (phosphonite) palladium complex, tetrakis (phosphonite) palladium complex, (bis) phosphinite) palladium complex, tris (phosphinite) palladium complex, tetrakis (phosphinite) palladium complex, bis (phosphite) palladium complex, tris (phosphite) Examples thereof include a palladium complex and a tetrakis (phosphite) palladium complex. Further, for example, tetrakis (triphenylphosphine) palladium, tris (dibenzylideneacetone) dipalladium, (1,5-cycloalkadiene) (maleic anhydride) palladium and other zero-valent palladium complexes; palladium nitrate and other inorganic acid salts A palladium organic acid salt such as palladium acetate; a divalent palladium complex such as bis (acetylacetonato) palladium or bis (tributylphosphine) palladium acetate. The amount of these palladium compounds used can be varied over a wide range, but usually 2 × 10 ⁻⁶ or more, preferably 2 × 10 ⁻⁵ as palladium per mol of the conjugated alkadiene.
Above, it is selected in the range of 1 mol or less, preferably 0.1 mol or less.

The present invention is characterized in that a phosphorus compound having at least one trivalent phosphorus-oxygen single bond is used as a cocatalyst. A phosphorus compound having one or more trivalent phosphorus-oxygen single bonds is a phosphinite (trivalent phosphorus atom has one oxygen atom and two carbon atoms depending on the number of trivalent phosphorus atom-oxygen atom single bonds). Is also a phosphorus compound having a structure bonded by a single bond), phosphonite (a phosphorus compound having a structure in which two oxygen atoms and one carbon atom are both bonded to a trivalent phosphorus atom by a single bond), and phosphite (3 A phosphorus compound having a structure in which all three oxygen atoms are bonded to a valence phosphorus atom by a single bond) can be classified into three types. Among these phosphorus compounds, the phosphonite compound represented by the following general formula (1) is preferable.

[0014]

[Chemical 6]

(In the formula (1), A¹Is replaced
Represents a good aryl group, A^TwoAnd A ^ThreeAre independently replaced
Represents an optionally substituted arylene group, x and y are independent
Represents an integer of 0 or 1 and Q is -CR.¹R^Two−,
-O-, -S-, -SO_Two-, -NR^Three-,-SiR^Four
R^FiveRepresents a divalent crosslinking group represented by -or -CO-,
R¹And R^TwoAre independently hydrogen and an alkyl group having 1 to 12 carbon atoms.
Represents an optionally substituted aryl group,
R^Three, R^FourAnd R^FiveIndependently represent hydrogen or a methyl group.
Then n₁Represents an integer of 0 or 1. )

Examples of the aryl group represented by A ¹ in the formula (1) include aryl groups having 6 to 30 carbon atoms such as phenyl group, naphthyl group, tolyl group, xylyl group and alkyl-substituted naphthyl group. The aryl group (A ¹ ) is an alkyl group having 1 to 12 carbon atoms, an aryl group, a methoxy group,
Ethoxy group, a hexyloxy group, an alkoxy group having 1 to 20 carbon atoms such as decyloxy group, dimethylamino group, total dialkylamino group having a carbon number of 2 to 30, such as di-octyl amino group, -SO ₃ Na, -COONa, -COOCH _It may be substituted with a group such as ₃ . Examples of the arylene group represented by A ² and A ³ include an arylene group having 6 to 30 carbon atoms such as a phenylene group, an alkyl-substituted phenylene group, an aryl-substituted phenylene group, a naphthylene group, an alkyl-substituted naphthylene group, and an aryl-substituted naphthylene group. These arylene groups are methoxy group, ethoxy group,
1 to 20 carbon atoms such as hexyloxy group and decyloxy group
Alkoxy group, dimethylamino group, dioctylamino group and the like, dialkylamino group having 2 to 30 carbon atoms, -SO
_{3 It} may be substituted with a group such as Na, —COONa, —COOCH ₃ . Examples of the alkyl group having 1 to 12 carbon atoms represented by R ¹ and R ² include a methyl group, an ethyl group,
Examples thereof include a butyl group, a hexyl group, an octyl group and a decyl group. Examples of such phosphonite compounds include the following compounds.

[0017]

[Chemical 7]

[0018]

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[0019]

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[0020]

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[0021]

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[0022]

[Chemical 12]

Among the phosphonite compounds represented by the above formula (1), the following compounds are preferable. That is, A ¹ is an aryl group having 1 to 12 carbon atoms, an aryl group, an alkoxy group, a dialkylamino group, or an optionally substituted SO ₃ Na group, having 6 to 30 carbon atoms, and particularly, a phosphorus atom. A monocyclic aryl group having the above-mentioned substituent in at least one of the two ortho-positions, or an α-naphthyl group optionally having the above-mentioned substituent, and a bicyclic ring having a branch in the ortho-position to the phosphorus atom. More preferred is an aryl group. Further, Q is preferably —CR ¹ R ² —, and R ¹ and R ² are independently substituted with hydrogen, an alkyl group having 1 to 12 carbon atoms, a phenyl group, a tolyl group, an anisyl group or the like. Is an aryl group having 6 to 30 carbon atoms, and the arylene group represented by A ² and A ³ is preferably an optionally substituted 1,2-arylene group, and A ² and A 3 More preferably, ³ are the same arylene group. In particular, it has a substituent such as an alkyl group having 1 to 20 carbon atoms and an alkoxy group having 1 to 20 carbon atoms at the 6-position of the arylene group, and has 1 to 20 carbon atoms at one or more positions of the 3-position, 4-position and 5-position. It is preferably a 1,2-phenylene group which may have a substituent such as an alkyl group. However,
Here, the 1-position of the 1,2-phenylene group is a position where it is bonded to an oxygen atom which is bonded to a phosphorus atom.

In the present invention, the general formula (1)
Among the phosphonite compounds represented by, the phosphonite compound represented by the following general formula (2) or (3) is a novel phosphonite compound. High yields and high selectivities to can be achieved.

[0025]

Embedded image (In the formula (2), A ⁴ represents a phenyl group in which at least one of the two ortho positions is substituted with an alkyl group having 1 to 4 carbon atoms, and A ⁵ may be independently substituted. It represents an arylene group, two arylene groups A ⁵ are preferably the same, k and l each independently represent an integer of 0 or 1, and Q is —CR ¹¹ R ¹² —, —O—, —S. -,
^{_{-SO 2 -, - NR 13 -}} , - SiR 14 R 15 - or -CO
Represents a divalent bridging group represented by-, R ¹¹ and R ¹² independently represent hydrogen, an alkyl group having 1 to 12 carbon atoms, a phenyl group, a tolyl group or an anisyl group, and R ¹³ , R ¹⁴ and R
¹⁵ independently represents hydrogen or a methyl group, and n ₂ represents an integer of 0 or 1. )

[0026]

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(In the formula (3), A ⁶ represents an optionally substituted α-naphthyl group, A ⁷ independently represents an optionally substituted arylene group, and two arylene groups A are shown.
⁷ is preferably the same, m and n are independently 0
Or 1 represents an integer, Q is ^{-CR 21 R 22 -, - O-} ,
R ²¹ and R represent a divalent bridging group represented by —S—, —SO ₂ —, —NR—, —SiR ²⁴ R ²⁵ — or —CO—.
²² independently represents hydrogen, an alkyl group having 1 to 12 carbon atoms, a phenyl group, a tolyl group, or an anisyl group, and R ²³ and R ²⁴
And R ²⁵ independently represent hydrogen or a methyl group, and n ₃ is 0
Or represents an integer of 1. )

The phosphonite compound represented by the general formula (2) or (3) can be produced, for example, by the following method. Although the general formulas (2) and (3) have the same synthetic route for the phosphonite compound, there are two synthetic routes, and the P-O bond is formed after the P-C bond is formed first. Either case or vice versa is possible. The P—C bond is formed by preparing a Grignard compound from an aryl bromide as a raw material and reacting it with phosphorus trichloride or bisphenoxyphosphine chloride. The P—O bond is formed by reacting bisphenol with phosphorus trichloride or arylphosphine dichloride using a basic compound such as a tertiary amine compound. As the phosphinite compound used as a cocatalyst in the present invention,
The following compounds are exemplified.

[0029]

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[0030]

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[0031]

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[0032]

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Examples of the phosphite compound used as a cocatalyst in the present invention include the following compounds.

[0034]

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[0035]

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[0036]

[Chemical 21] Among the above-mentioned phosphorus compounds having one or more trivalent phosphorus-oxygen single bonds, it is particularly preferable to use a phosphonite compound in that the target compound can be obtained in high yield and high selectivity. The amount of the above-mentioned specific phosphorus compound used is usually selected from 0.1 or more, preferably about 2 or more moles in terms of phosphorus atom per 1 mole of palladium,
The amount is 250 mol or less, preferably 150 mol or less, more preferably 100 mol or less, and is preferably within the above range so that the compound can be dissolved in the reaction solution under the reaction conditions.

In the present invention, the palladium compound and 1
A catalyst composed of a phosphorus compound having three or more trivalent phosphorus-oxygen single bonds, particularly a phosphonite compound, can be separated from the reaction product solution after the reaction and recycled to the dimerization reaction step. In the present invention, an active hydrogen compound may be allowed to be present in the reaction solution for the purpose of, for example, increasing the reactivity or selectivity for alkatrienes. As the active hydrogen compound to be used, a compound containing an -OH group, -N
Compound containing H group, sandwiched between electron-withdrawing groups-
Examples thereof include compounds containing a CH group, compounds containing a -COOH group, and the like. Specific examples of the active hydrogen compound include water, methanol, ethanol, phenol, ethylamine, diethylamine, octylamine, acetylacetone, acetic acid, benzoic acid and the like.

In the present invention, an amine compound is allowed to exist in the reaction solution for the purpose of stabilizing the palladium compound or phosphorus compound in the reaction solution, or enhancing the reactivity and selectivity to alkatrienes. You can also The amine compound used is most preferably a tertiary amine compound. Specific examples of amine compounds include trialkylamines represented by trimethylamine, triethylamine, tripropylamine, tributylamine, trioctylamine, and 1- (N, N-dimethylamino).
-2-Propanol, 1- (N, N-dimethylamino)
Amino alcohols such as -3-butanol, pyridine, heteroaromatic amines such as 2,6-dimethylpyridine, and N, N-dimethyl-2-methoxyethylamine, N, N-dimethyl-3-ethoxyprolylamine, N
-Methylpyrrolidine, N-methylpiperidine, N-methylmorpholine, N, N'-dimethylpiperazine, N-methylpipecoline, N, N, N ', N'-tetramethyl-
1,3-butanediamine, N, N, N ′, N′-tetramethylhexamethylenediamine and the like can be mentioned. The amount of the amine compound used is usually 0.01 parts by weight or more, preferably 0.1 parts by weight or more, and 20 parts by weight or less, preferably 5 parts by weight or less, with respect to 1 part by weight of the conjugated alkadiene. Is arbitrarily selected from the range.

In carrying out the above-mentioned dimerization reaction of the conjugated alkadiene, it is preferable to use a solvent in order to carry out the reaction more smoothly. Examples of usable solvents include ethers such as diethyl ether, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether, ketones such as acetone, methyl ethyl ketone, diethyl ketone, methyl isopropyl ketone, ethyl-n-butyl ketone, acetonitrile, and propylene. Nitriles such as pionitrile and benzonitrile, aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, alkanes such as pentane, hexane and heptane, alkenes such as hexene and octene, sulfoxides such as dimethyl sulfoxide, sulfolane , Nitro compounds such as nitrobenzene and nitromethane, pyridine, pyridine derivatives such as α-picoline, acetamide, propionamide N, N- dimethylformamide, N, N- dimethylacetamide,
Amides such as N, N-diethylacetamide, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, n-alkanol, formic acid, acetic acid,
Examples thereof include carboxylic acids such as propionic acid and butyric acid. When using such a solvent, these are used alone,
Alternatively, any of them may be used as a mixed solvent.

Although the amount of the solvent used is not limited, it is usually
0.1 parts by weight or more based on 1 part by weight of the conjugated alkadiene,
The amount is preferably 1 part by weight or more and 50 parts by weight or less, preferably 10 parts by weight or less. The reaction temperature for reacting the conjugated alkadiene is from room temperature to 1
It can be selected from the range of about 80 ° C, but usually
It is more general to select a temperature range of about 50 to 130 ° C. The reaction pressure is selected from a range from normal pressure to about 200 kg / cm ² . At this time, an inert gas such as nitrogen, helium, argon, carbon dioxide can be allowed to coexist in the reaction.

In the present invention, the conjugated alkadiene is subjected to a dimerization reaction according to the above-mentioned reaction raw materials, reaction conditions, and recycling method of the catalyst component to produce alkatrienes. In the reaction product solution obtained by this reaction, in addition to the catalyst and the main product, alkatriene, unsaturated hydrocarbons having a higher molecular weight as a by-product, and the compound having active hydrogen are used in the reaction system. It contains a telomerization reaction product with a conjugated alkadiene that is generated when it coexists with the solvent, a solvent, an unreacted conjugated alkadiene, and the like.
The amount of by-products produced depends on the reaction conditions. Alkatrienes can be recovered by a known means such as distillation, if desired. The method of the present invention can be carried out using well-known techniques including continuous operation, semi-continuous operation, and batch operation, and the effect of the present invention can be sufficiently achieved even in the continuous method.

[0042]

EXAMPLES Specific examples of the present invention will now be described in more detail with reference to Examples, but the present invention is not limited to the following Examples without departing from the gist thereof. Example 1 In a stainless steel autoclave having an internal volume of 200 ml, 0.0062 mmol of palladium acetate and 1.99 mmol of o-tolyl (2,2'-methylenebis (6-t-butyl-4-methyl) were added under a nitrogen gas atmosphere. Phenoxy)) phosphine, 47 ml of acetone, 6.7 ml of water, and 1.5 ml of o-xylene as an internal standard for gas chromatographic analysis were charged, and 13.9 g of 1,3-butadiene and 8 g of carbon dioxide were introduced. did. 8 reaction mixture
The internal temperature was 9 over 20 minutes while stirring at a speed of 00 rpm.
Warm up to 0 ° C. After continuing the reaction at 90 ° C. for 5 hours, the reaction liquid was analyzed by gas chromatography. As a result, the yield per charged 1,3-butadiene was 68.
2% of n-octatrienes (hereinafter referred to as NOTs) (yield of 1,3,7-octatriene 53.6
%), 4.4% of octadienol (hereinafter referred to as HOD) was obtained.

Example 2 In Example 1, the amount of palladium acetate used was 0.07.
The amount of the phosphonite compound used was 0.1 mM.
773 mmol, without using water and carbon dioxide,
The amount of 1,3-butadiene was 14.3 g and the reaction time was 17
The reaction was performed in the same manner as in Example 1 except that the time was set.
As a result, the charged 1,3-butadiene was 100% converted,
97% N based on the yield of 1,3-butadiene charged.
OTs, 94% of 1,3,7-NOT were obtained.

Example 3 In Example 1, the amount of palladium acetate used was 0.12.
Mmol, changing the phosphonite compound to o-ethylphenyl (2,2'-methylenebis (6-t-butyl-4-methylphenoxy)) phosphine and setting the reaction temperature to 75
As a result of carrying out the reaction in the same manner as in Example 1 except that the temperature was 7.5 ° C. and the reaction time was 7.5 hours, the yield based on 1,3-butadiene charged was 42.9% NOTs, 10.3%. H
ODs were obtained.

Example 4 The reaction was carried out in the same manner as in Example 3 except that the reaction temperature was 90 ° C. and the reaction time was 5 hours. , 88.
5% NOTs and 8.8% HODs were obtained.

Example 5 In Example 1, the amount of palladium acetate used was 0.13.
Mmol, phosphonite compound to α-naphthyl (2,
The reaction was performed in the same manner as in Example 1 except that 2′-methylenebis (6-t-butyl-4-methylphenoxy)) phosphine was used instead of the reaction temperature of 75 ° C. and the reaction time was 6.5 hours. As a result, 24.8% NOTs and 10.2% HODs were obtained as the yield per charged 1,3-butadiene.

Example 6 In Example 1, the amount of palladium acetate used was 0.13.
Mmol, except that the phosphonite compound was changed to o-phenylphenyl (2,2'-methylenebis (6-t-butyl-4-methylphenoxy)) phosphine, 3 ml of triethylamine was allowed to coexist, and the reaction temperature was 75 ° C. As a result of carrying out the reaction in the same manner as in Example 1, the yield based on 1,3-butadiene charged was 24.2% NOTs, 1
7.1% HODs were obtained. In the ³¹ PNMR analysis after the reaction, no decomposed phosphorus compound was found.

Example 7 The reaction was carried out in the same manner as in Example 6 except that triethylamine was not allowed to coexist.
19.5% NOT as a yield per 3-butadiene
, 13.1% HODs were obtained. ³¹ PN after reaction
In the MR analysis, the decomposed phosphorus compound was 4 based on phosphoric acid.
Observed at 3.7 ppm.

Comparative Example 1 In Examples 1 to 7, the results were obtained using phosphonite, but using phosphine compounds instead of phosphonite compounds. In Example 2, triphenylphosphine was used in place of o-tolyl (2,2′-methylenebis (6-t-butyl-4-methylphenoxy)) phosphine, and the reaction time was 5 hours, except that The reaction was carried out in the same manner as in Example 2. As a result,
3-Butadiene is converted by 6.3% and the NOT selectivity is 92.
%, And as the yield per charged 1,3-butadiene,
5.80% NOTs were obtained. From the results of Examples 1 to 7 and Comparative Example 1, by using a phosphorus compound having one or more trivalent phosphorus-oxygen single bonds as a cocatalyst, the yield of alkatrienes per charged conjugated alkadiene was increased. You can see that it will improve.

Reference Example 1 Synthesis of (2,2'-methylenebis (4-methyl-6-t-butylphenoxy)) phosphino chloride In a two-necked flask having an internal volume of 1 L, under nitrogen atmosphere, 14.76 g of phosphorus trichloride. (107.5 mmol), toluene 10
Charge 0 ml and stir with a magnetic stir bar.
Under a nitrogen atmosphere, 2,2'-methylenebis (4-methyl-
6-t-butylphenol) 36.6 g (107.5 m)
mol) and 25 ml of triethylamine in 180 toluene
The solution dissolved in ml was added dropwise in 15 minutes. After the addition was complete, the reaction mixture was heated to 60 ° C. and stirred at this temperature for 1 hour. The reaction mixture was cooled to room temperature, the precipitated inorganic salt was filtered off, the solvent was distilled off from the obtained filtrate, and the residue was dried under reduced pressure to obtain 43.07 g (106.3 mmol) of white powder. ^{As a result of 31} PNMR and ¹ HNMR analysis, the results were as follows, and it was confirmed that the product was the desired product.

³¹ PNMR (CDCl ₃ , triphenyl phosphate: -18 ppm standard) δ 154.6 ppm ¹ HNMR (CDCl ₃ , (CH ₃ ) ₄ Si standard) δ / ppm 1.39 (s, 18H, -C ( _{CH 3) 3) 2.30 (s} , 6H, -CH 3) 3.71 (d, J = 12.0Hz, 1H, ArCH 2 A
r) 3.99 (d, J = 12.0 Hz, 1H, ArCH ₂ A
r) 7.03 (s, 2H, -OArH) 7.09 (s, 2H, -OArH)

Example 8 Synthesis of o-ethylphenyl (2,2'-methylenebis (4-methyl-6-t-butylphenoxy)) phosphine In a 2-necked flask having an internal volume of 200 ml, nitrogen-containing magnesium was added under a nitrogen atmosphere. .385 g (15.8 mmol) and 20 ml of tetrahydrofuran (THF) were charged and stirred with a magnetic stirrer, and under nitrogen atmosphere, 2.92 g (15.8 mmol) of o-bromoethylbenzene was added to T.
The solution dissolved in 20 ml of HF was added dropwise over 30 minutes. After the addition was completed, the reaction mixture was stirred under heating under reflux for 1 hour to prepare a Grignard reagent. After cooling this solution,
It was synthesized in Reference Example 1 while cooling in an ice bath (2,2 ').
-Methylenebis (4-methyl-6-t-butylphenoxy)) phosphino chloride 6.33 g (15.6 mmo)
What melt | dissolved l) in 30 ml THF was dripped in 20 minutes. After the addition was completed, the reaction mixture was stirred under heating and reflux conditions for 1 hour, then the solvent THF was distilled off under normal pressure, the residue was dissolved in 100 ml of toluene, and the insoluble inorganic salt was removed by filtration. Toluene was distilled off from this toluene solution under reduced pressure to obtain a crude phosphonite compound. Recrystallization with acetonitrile gave 3.75 g of white crystals. ^{As a result of 31} PNMR and ¹ HNMR analysis, the results were as follows, and it was confirmed that the product was the desired product.

³¹ PNMR (CDCl ₃ , triphenyl phosphate: −18 ppm standard) δ 182.1 ppm and 161.1 ppm (both are broad peaks, which are peaks of two structural isomers in the solution) ¹ HNMR (CDCl ₃ , (CH ₃ ) ₄ Si standard) δ / ppm 1.20 (s, 18H, -C (CH ₃ ) ₃ ) 1.32 (t, 3H, J = 7.5Hz, -CH ₂ C
_{H 3) 2.30 (s, 6H} , -CH 3) 3.23 (broad, 2H, -CH 2 CH 3) 3.44 (d, J = 12.9Hz, 1H, ArCH 2 A
r) 4.52 (dd, J = 3.2 Hz, 12.8 Hz, 1
_{H, ArCH 2 Ar) 6.99 (} s, 2H, -OArH) 7.17 (s, 2H, -OArH) 7.36 (t, 1H, -ArH, m -position) 7.39 (s, 1H, -ArH, m position) 7.48 (t, 1H, -ArH, p position) 8.04 (broad, 1H, -ArH, o position)

Example 9 α-naphthyl (2,2'-methylenebis (4-methyl-)
Synthesis of 6-t-butylphenoxy)) phosphine In a two-necked flask having an internal volume of 200 ml, under nitrogen atmosphere, 0.378 g (15.5 mmol) of scraped magnesium, T
HF (20 ml) was charged and stirred with a magnetic stirrer, and under nitrogen atmosphere, α-bromonaphthalene (3.11 g) was added.
A solution prepared by dissolving (15.0 mmol) in 20 ml of THF was added dropwise over 30 minutes. After the addition was completed, the reaction mixture was stirred under heating under reflux for 1 hour to prepare a Grignard reagent. After cooling this solution, while cooling in an ice bath, 6.03 g (14.9 mmol) of (2,2′-methylenebis (4-methyl-6-t-butylphenoxy)) phosphinochloride synthesized in Reference Example 1 was obtained. What was melt | dissolved in THF of 30 ml was dripped in 20 minutes. After the addition was completed, the reaction mixture was stirred under heating and reflux conditions for 1 hour, then the solvent THF was distilled off under normal pressure, and the residue was added with toluene (100 m).
It was dissolved in 1 and the insoluble inorganic salt was filtered off. Toluene was distilled off from this toluene solution under reduced pressure to obtain a crude phosphonite compound. Recrystallize with acetonitrile,
4.79 g of white powder was obtained. ³¹ PNMR and ¹ HNMR
The results of the analysis were as follows, and it was confirmed that the product was the target.

³¹ PNMR (CDCl ₃ , triphenyl phosphate: −18 ppm standard) δ 183 ppm and 164 ppm (both are broad peaks and peaks of two structural isomers in solution) ¹ HNMR (CDCl ₃ , (CH ₃ ) ₄ Si) δ / ppm 1.12 (s, 18H, —C (CH ₃ ) ₃ ) 2.31 (s, 6H, —CH ₃ ) 3.54 (d, J = 12. 75Hz, 1H, ArCH ₂
Ar) 4.69 (d, J = 12.3 Hz, 1H, ArCH ₂ A
r) 6.99 (s, 2H, -OArH) 7.21 (s, 2H, -OArH) 7.56 (m, 2H, -ArH) 7.61 (s, 1H, -ArH) 7.94 ( d, 1H, -ArH) 8.03 (d, 1H, -ArH) 8.23 (broad, 1H, -ArH) 9.01 (broad, 1H, -ArH)

[0056]

According to the method of the present invention, a conjugated alkadiene,
In particular, by dimerizing 1,3-butadiene,
Octatrienes can be produced in high yield and high selectivity, and decomposition of phosphorus compounds can be suppressed, so that they have high industrial utility value.

Claims (11)

[Claims] 1. An alkatriene is produced by dimerizing a conjugated alkadiene in the presence of a palladium compound and a phosphorus compound having one or more trivalent phosphorus-oxygen single bonds. Production method. 2. The phosphorus compound having at least one trivalent phosphorus-oxygen single bond is selected from the group consisting of phosphonite, phosphinite and phosphite.
The method described in. 3. The method according to claim 2, wherein the phosphorus compound is a phosphonite compound. 4. The phosphonite compound has the following general formula:
A phosphonite compound represented by (1).
The method described in. [Chemical 1](In the formula (1), A¹Is an optionally substituted aryl
Represents a group, A^TwoAnd A^ThreeMay be independently replaced
Represents an arylene group, and x and y are independently 0 or 1.
Represents an integer, and Q is -CR¹R^Two-, -O-, -S
−, −SO_Two-, -NR^Three-,-SiR^FourR^Five-Or-
R represents a divalent crosslinking group represented by CO- ¹And R^Two
Are independently hydrogen, an alkyl group having 1 to 12 carbon atoms or a substituent.
Represents an optionally substituted aryl group, R^Three, R^FourAnd R
^FiveEach independently represents hydrogen or a methyl group, and n₁Is 0 or
Represents an integer of 1. ) 5. The aryl group A ¹ has at least one of two ortho positions which is an alkyl group having 1 to 12 carbon atoms, an aryl group, an alkoxy group, a dialkylamino group and SO.
The method according to claim 4, which has a substituent selected from the group consisting of ₃ Na groups. 6. The method according to claim 4, wherein the aryl group A ¹ is an optionally substituted α-naphthyl group. 7. The method according to claim 1, wherein the dimerization reaction is carried out in the presence of an active hydrogen compound. 8. The method according to claim 1, wherein the dimerization reaction is carried out in the presence of an amine compound. 9. The method according to claim 1, wherein the conjugated alkadiene is 1,3-butadiene and the alkatriene is a linear octatriene. 10. A phospho represented by the following general formula (2):
Knight compound. Embedded image(In formula (2), A^FourIs at least one of the two ortho positions
One of which is substituted with an alkyl group having 1 to 4 carbon atoms
Represents a phenyl group, A^FiveMay independently be substituted
Represents an arylene group, and k and l independently represent 0 or 1.
Represents an integer, Q is -CR¹¹R¹², -O-, -S-,-
SO_Two-, -NR¹³-,-SiR¹⁴R^Fifteen-Or-CO-
Represents a divalent cross-linking group represented by¹¹And R¹²Is independent
To hydrogen, an alkyl group having 1 to 12 carbon atoms, a phenyl group,
Represents a tolyl group or anisyl group, R ¹³, R¹⁴And R^FifteenIs
Independently represent hydrogen or a methyl group, and_TwoIs 0 or 1
Represents an integer. ) 11. A phosphonite compound represented by the following general formula (3). Embedded image (In formula (3), A ⁶ represents an optionally substituted α-naphthyl group, A ⁷ independently represents an optionally substituted arylene group, and m and n independently represent 0 or represents the integer 1, Q is ^{-CR 21 R 22 -, - O} -, - S -, - S
O ₂ −, —NR ²³ —, —SiR ²⁴ R ²⁵ — or a divalent bridging group represented by —CO—, wherein R ²¹ and R ²² are independently hydrogen, an alkyl group having 1 to 12 carbon atoms, Phenyl group,
Represents a tolyl group or an anisyl group, and represents R ²³ , R ²⁴ and R ²⁵
Each independently represent hydrogen or a methyl group, and n ₃ is 0 or 1.
Represents the integer. )