JP2000355572A - Production of allyl compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain in high conversion and selectivity without causing metal deposition an allyl compound useful as an intermediate for producing tetrahydrofuran and medicaments and the like by isomerization of an allyl material compound through allyl rearrangement in the presence of a specific catalyst. SOLUTION: This allyl compound is obtained by incorporating a solvent (e.g. acetic acid) with a compound having at the allyl site an acyloxy group of the formula; RAC(O) (RA is a 1-10C alkyl or the like) or hydroxy group (e.g. 3,4-diacetoxybutene-1,3,4-dihydroxybutene-1), a group 8,9 or 10 metal compound (e.g. palladium acetate) and a phosphite compound followed by carrying out a reaction pref. at 50-200 deg.C; wherein the amount of the metal compound to be used is pref. 1×10-8 to 1 molar equivalent based on the raw material and the molar ratio of the phosphite compound to the metal compound is pref. 0.1-10,000.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for isomerizing a compound having an acyloxy group or a hydroxyl group at the allylic position by allylic rearrangement. More specifically, the present invention relates to a method for isomerizing a 3,4-disubstituted butene-1 and / or 1,4-diene. The present invention relates to a method for isomerizing disubstituted butene-2 using a specific catalyst to produce 1,4-disubstituted butene-2 and / or 3,4-disubstituted butene-1 which are the corresponding isomers. 1,4-diacetoxybutene-2 obtained by the method of the present invention is 1,4-diacetoxybutene-2.
It is an important intermediate for producing butanediol or tetrahydrofuran. On the other hand, 3,4-diacetoxybutene-1 is an important intermediate for producing terpentene compounds such as vitamin A acetate, as well as medicines, agricultural chemicals, and various flavors.

[0002]

2. Description of the Related Art It is known that 1,4-diacetoxybutene-2 and 3,4-diacetoxybutene-1 can be obtained by oxidizing butadiene with molecular oxygen in an acetic acid solvent (for example, see Japanese Patent Laid-Open Publication JP-A-48-72090, JP-A-48-9
No. 6513). However, in this method, 1,4
Since the production ratio of -diacetoxybutene-2 and 3,4-diacetoxybutene-1 mainly depends on the performance of the catalyst, it was extremely difficult to produce them at an arbitrary ratio.
Further, 3,4-diacetoxybutene-1 can be easily obtained by acetoxylation of 1,2-epoxybutene-3, but in this method, 1,4-diacetoxybutene-2 is obtained. It was extremely difficult. On the other hand, 1,
In order to selectively produce only 4-diacetoxybutene-2, a very special raw material such as 3,6-dihydro-1,2-dioxyin is required. Was impossible.

[0003] Therefore, 3,4-diacetoxybutene-1
And / or 1,4-diacetoxybutene-2 with specific contact
Isomerization using a medium, each isomer
1,4-diacetoxybutene-2 and / or 3,4-di
Conventional methods for producing acetoxybutene-1
Have proposed various methods. For example, with a catalyst
Using a platinum chloride compound (German Patent No. 273)
6695 and 2134115), pa
Using a radium compound in the presence of hydrogen chloride or hydrogen bromide
(JP-A-57-140744), PdCl
_Two (PhCN) _TwoMethod using compound having 6 to 20 carbon atoms
(U.S. Pat. No. 4,095,030) and the like are known.
ing. However, these methods do not improve the stability of the catalyst.
Problems, and therefore highly corrosive halogen compounds
It has a problem that it has to be used in large quantities.

On the other hand, as a method not using a halogen compound, a method using a catalyst comprising a palladium compound and an organic phosphine (JP-A-55-11555) or isomerization in the gas phase using an acid catalyst such as alumina or zeolite. (German Patent No. 3,326,668;
No. 0-126611) has also been proposed.

[0005]

SUMMARY OF THE INVENTION As described above, 1,4-
Since diacetoxybutene-2 and 3,4-diacetoxybutene-1 are intermediates of completely different product groups, the demand ratio varies depending on the region, the age, or the business background of the company that implements it. I have. Therefore, 3,4-diacetoxybutene-1 and / or 1,4-diacetoxybutene-2 is isomerized using a specific catalyst, and the corresponding isomers, 1,4-diacetoxybutene-2, are obtained. The significance of industrially producing and / or 3,4-diacetoxybutene-1 is extremely significant. However, in the above-mentioned conventional method, there is a problem that the activity of the catalyst is not at a satisfactory level or the selectivity is not sufficient, and it has never been satisfactory from an industrial viewpoint. Accordingly, an object of the present invention is to provide a high conversion rate by isomerizing an allyl compound such as 3,4-diacetoxybutene-1 and / or 1,4-diacetoxybutene-2.
Provided is a method for producing an allyl compound such as 1,4-diacetoxybutene-2 and / or 3,4-diacetoxybutene-1 having a high selectivity and without causing metal deposition. It is in.

[0006]

Means for Solving the Problems The present inventors have made intensive studies in view of such circumstances, and as a result, in the presence of a specific catalyst,
By isomerizing an allyl raw material compound such as 3,4-diacetoxybutene-1 and / or 1,4-diacetoxybutene-2 by allyl rearrangement, a high conversion rate and a high selectivity, and metal deposition It has been found that the desired isomer product can be obtained without causing the problem, and the present invention has been completed.

That is, the gist of the present invention is to provide a method for producing a corresponding allylic isomerization product by isomerizing an allylic starting compound having an acyloxy group or a hydroxyl group at the allylic position. Wherein the isomerization reaction is carried out in the presence of a catalyst containing the compound of formula (1) and a phosphite compound.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The raw material used in the isomerization reaction of the present invention may be any compound as long as it is an allyl compound having an acyloxy group or a hydroxyl group at the allyl position. Is a method for producing an allyl product which is the corresponding isomer by causing an allyl rearrangement.
Here, the acyloxy group, the general formula R _A C (O) O-
In expressed, the R _A, include an aryl group an alkyl group or a C6-15 having 1 to 10 carbon atoms, among them preferably an alkyl group having 1 to 3 carbon atoms, especially methyl as R _A Groups are preferred. Specifically, in the present invention, an allyl raw material compound selected from the following formulas (a) and (b) and a mixture thereof is subjected to an isomerization reaction, and the corresponding isomers of the formulas (b) and ( An allyl isomer product selected from a) and mixtures thereof can be produced.

Embedded imageIn the above formulas (a) and (b), R is an acetoxyl group
Or a hydroxyl group; ¹~ R^FiveEach independently of the water
Elemental atom, alkyl group having 1 to 20 carbon atoms, 1 to 20 carbon atoms
An alkoxy group, a cycloalkyl group having 3 to 20 carbon atoms,
Dialkylamino group having 2 to 40 carbon atoms, 6 to 20 carbon atoms
Aryl group, C 6-20 aryloxy group, carbon
An alkylaryl group having 6 to 20 carbon atoms;
Alkylaryloxy group, arylalkyl having 6 to 20 carbon atoms
Coxy group, cyano group, ester group having 2 to 20 carbon atoms,
A droxy group or a halogen atom, having a substituent
It is an optional group. R¹~ R^FiveMay have
Examples of the group include an alkoxy group having 1 to 10 carbon atoms and 1 carbon atom.
Carboxyl group, hydroxyl group, carbon number 6 to 10
And 10 aryl groups.

In the above equation (a), equation (a ′):
3,4-disubstituted butene-1 represented by CH ₂ ＣＨCH—CHR ⁶ —CH ₂ R ⁷ (where R ⁶ and R ⁷ are an acetoxyl group or a hydroxyl group) is preferable, and the above-described formula In (b), 1,4-disubstituted butene-2 represented by the formula (b ′): CH ₂ R ⁸ —CH ＝ CH—CH ₂ R ⁹ (where R ⁸ and R ⁹ are acetoxyl groups Or a hydroxyl group). Specific examples of the 3,4-disubstituted butene-1 of the formula (a ') include 3,4-diacetoxybutene-1, 3-butene-1,2-diol monoacetoxylate and 3,4-dihydroxy Butene-1
The 1,4-disubstituted butene-2 of the formula (b ′) includes 1,4-diacetoxybutene-2, 1-acetoxy-4-hydroxy-2-butene, and 1,4-dihydroxybutene-2. Is mentioned.

3,4-diacetoxybutene-1, an example of a raw material, can be prepared by a known method, for example, by reacting butadiene with acetic acid and oxygen in the presence of a catalyst such as palladium to give 1,4-diacetoxybutene. It is obtained as a by-product in the production of butene-2, for example, (JP-B-51-23)
008 or 59-28553). The raw material may be a pure product, or may be a mixture of a plurality of allyl compounds.In addition to the raw material allyl compound, other components that do not hinder this isomerization reaction as described below, for example, include acetic acid, water, and the like. It may be a mixture.

The isomerization catalyst used in the reaction of the present invention comprises:
It includes compounds of metals belonging to groups 8 to 10 of the periodic table (IUPAC revised edition of inorganic chemical nomenclature (1989)) and phosphite compounds. Examples of the metal compound include compounds selected from iron, cobalt, nickel, ruthenium, rhodium, platinum, iridium, osmium, and palladium compounds.
Among them, more than one kind of compounds are mentioned, and among these, nickel, palladium, and platinum compounds are more preferable, and palladium compounds are particularly preferable. The metal compound is
Examples include acetate, acetylacetonate, halide, sulfate, nitrate, organic salt, inorganic salt, alkene compound, amine compound, pyridine compound, phosphine coordination compound, phosphite coordination compound and the like.

Ruthenium compounds include RuCl_Three,
Ru (OAc)_Three, Ru (acac) _Three, RuCl_Two(P
Ph_Three)_ThreeOsmium compounds include O
sCl _Three, Os (OAc)_ThreeAnd the like, and rhodium compounds
The thing is RhCl_Three, Rh (OAc)_Three, Rhodium di
Acetate dimer, Rh (acac) (CO)_Two, [Rh (OA
c) (COD)]_Two, [RhCl (COD)]_Two, Rh
(COD) OAc and the like. Also, iridium
As the compound, IrCl_Three, Ir (OAc)_ThreeEtc.
And the nickel compound is NiCl_Two, NiB
r_Two, Ni (NO_Three)_Two, NiSO _Four, Ni (COD)_Two,
NiCl_Two(PPh_Three)_TwoAnd the like.

As the palladium compound, for example, Pd
(0), PdCl ₂ , PdBr ₂ , PdCl ₂ (CO
D), PdCl ₂ (PPh ₃ ) ₂ , Pd (PPh ₃ ) ₄ ,
Pd ₂ (dba) ₃ · CHCl ₃ , K ₂ PdCl ₄ , K ₂ P
dCl ₆ (potassium hexachloropalladate (IV)), Pd
Cl ₂ (PhCN) ₂ , PdCl ₂ (CH ₃ CN) ₂ , P
d (dba) ₂ , Pd ₂ (dba) ₃ , Pd (NO ₃ )
₂ , Pd (OAc) ₂ , Pd (CF ₃ COO) ₂ , PdS
O ₄ , Pd (acac) ₂ , carboxylate compound,
Examples include olefin-containing compounds, organic phosphine-containing compounds such as Pd (PPh ₃ ) ₄ , and allyl palladium chloride dimer. Among these, Pd (OA
c) _2, carboxylate compounds or halides of palladium PdCl ₂ and the like are preferable. Pt (acac) ₂ , PtCl ₂ (COD), PtC
l ₂ (CH ₃ CN) ₂ , PtCl ₂ (PhCN) ₂ , Pt
(PPh ₃ ) ₄ , K ₂ PtCl ₄ , Na ₂ PtCl ₆ , H ₂ P
tCl _{6 and the} like. (Where COD: cyclopentadiene, dba: dibenzylideneacetone, acac:
Represents acetylacetonate. In the present invention, the form of the above-mentioned metal compound is not particularly limited, and the active metal complex species may be a monomer, a dimer and / or a multimer.

The amount of the metal compound used is not particularly limited, but from the viewpoint of catalytic activity and economy, the amount is from 1 × 10 ⁻⁸ (0.01 mol ppm) to 1 × 10 ⁻⁸ (0.01 mol ppm) based on the allyl compound as a reaction raw material. Molar equivalent, preferably 1 × 10 ⁻⁷ (0.
It is used in the range of 1 mol ppm) to 0.001 molar equivalent, particularly preferably in the range of 10 ^{-6 to} 0.0001 molar equivalent. The phosphite compound used in the present invention is not particularly limited, but preferred phosphite compounds are represented by the following general formulas (I), (II), (III), (IV),
It is at least one of the compounds represented by (V) and (VI).

[0015]

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In the formulas (I) to (VI), R ^{10 to} R
²¹ is each independently an alkyl group, an alkoxy group,
Represents a cycloalkyl group, an aryloxy group, an alkylaryloxy group, an arylalkoxy group, or an aryl group, and may further have a substituent.

When an alkyl group is used as R ^{10 to} R ²¹ or when a substituent having an alkyl skeleton (such as an alkyl group in an alkyl aryloxy group) is used, the number of carbon atoms is usually 1 to 20. , Preferably 1-14. Specific examples thereof include, for example, a methyl group, an ethyl group,
n-propyl group, i-propyl group, n-butyl group, i-
Butyl, sec-butyl, t-butyl, hexyl, octyl, decyl and the like. Further, the alkyl group or the alkyl skeleton portion may further have a substituent, as the substituent, an alkoxy group having 1 to 10 carbon atoms,
Examples thereof include an aryl group having 6 to 10 carbon atoms, an amino group, a cyano group, an ester group having 2 to 10 carbon atoms, a hydroxy group, and a halogen atom.

When an aryl group is used as R ^{10 to} R ²¹ or when a substituent having an aryl skeleton is used, the number of carbon atoms is usually 6 to 20, preferably 6 to 20.
14. Specific examples include a phenyl group, a tolyl group,
Xylyl group, di-t-butylphenyl group, naphthyl group,
And a di-t-butylnaphthyl group. The aryl group or the aryl skeleton portion may further have a substituent. Examples of the substituent include a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and 3 to 2 carbon atoms.
A cycloalkyl group of 0, an aryl group having 6 to 20 carbon atoms,
A C6-C20 aryloxy group, a C6-C20 alkylaryl group, a C6-C20 alkylaryloxy group, a C6-C20 arylalkyl group, a C6-C20 arylalkoxy group, Cyano group, carbon number 2
To 20 ester groups, hydroxy groups and halogen atoms.

Specific examples of R ^{10 to} R ²¹ include a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 2,3-dimethylphenyl group, and a 2,4-dimethylphenyl group. 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 2-ethylphenyl group, 2-isopropylphenyl group, 2-t-butylphenyl group, 2,4-di-t-butylphenyl group, 2 -Chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2,3-dichlorophenyl group, 2,4-dichlorophenyl group, 2,5-dichlorophenyl group, 3,4-dichlorophenyl group, 3,5-dichlorophenyl group, 4 -Trifluoromethylphenyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 3,5-dimethoxyphenyl group, 4-cyanophenyl group, 4-nitrophenyl group,
Examples thereof include a trifluoromethyl group, a pentafluoroethyl group, a pentafluorophenyl group, and the following (C-1) to (C-8).

Embedded image Z ^{1 to} Z ⁴ and A ^{1 to} A ³ each independently represent an alkylene group having 1 to 20 carbon atoms which may have a substituent, or an alkylene group having 6 to 30 carbon atoms which may have a substituent. arylene group, or a ^{-Ar 1 - (Q 1) n} -Ar 2 - become middle bivalent which may Jiariren group having a linking group (wherein, Ar ¹ and Ar
² independently represents an arylene group having 6 to 18 carbon atoms which may have a substituent. ). T represents a carbon atom, an alkanetetrayl group, a benzenetetrayl group,
Or T ^2- (Q ² ) a tetravalent group which may have a substituent represented by n-T ² , wherein T ¹ and T ² each independently have 1 to 10 carbon atoms Alkantriyl group and carbon number 6
Represents a trivalent organic group which may have a substituent selected from benzenetriyl groups of 1 to 15. Q ¹ and Q ² are, each ^{independently, -CR 22 R 23 -, -} O -, - S- or -
Represents CO-, n is 0 or 1, R ²² and R ²³ are
Each is independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and may have a substituent.

Further, Z¹~ Z^FourOr A¹~ A^ThreeIs alkylene
In the case of a group, specific examples thereof include, for example, tetramethyl
A zylene group, a dimethylpropylene group or the like;
In the case of an alkylene group which may have a substituent,
A C 1-10 alkoxy group, a C 6-10
Aryl, amino, cyano, amide, nitro
Group, trifluoromethyl group, trimethylsilyl group, carbon
Ester groups, hydroxy groups and halogen atoms
Child. Also, Z¹~ Z^FourOr A¹~ A^ThreeIs a substituent
In the case of an arylene group which may have
Examples include phenylene and naphthylene groups.
And as the substituent, an alkyl group having 1 to 8 carbon atoms;
An alkoxy group having 1 to 10 carbon atoms, an ant having 6 to 10 carbon atoms
Group, amino group, cyano group, ester having 2 to 10 carbon atoms
Group, amide group, nitro group, trifluoromethyl group,
Limethylsilyl group, hydroxy group, halogen atom, etc.
No. Furthermore, Z¹~ Z^FourOr A¹~ A^ThreeIs -Ar¹−
(Q) n -Ar^Two-Even if it has a divalent linking group in the middle of
For good diarylene groups, Ar¹And Ar^TwoIs a substituent
Is an arylene group which may have a carbon number of 6 to
24, more preferably 6 to 16, and a preferred substituent group
Examples of the body include an alkyl group having 1 to 10 carbon atoms and 1 to 10 carbon atoms.
10 alkoxy groups, aryl groups having 6 to 10 carbon atoms,
Mino group, cyano group, ester group having 2 to 10 carbon atoms, hydr
And a roxy group and a halogen atom. Also, A¹
~ A^ThreeAnd Z¹~ Z^FourIs-(CH_Two )_Two 
-,-(CH _Two)_Three -,-(CH_Two)_Four -,-(C
H_Two)_Five -,-(CH_Two)₆ -, -CH (CH_Three) -C
H (CH_Three)-, -CH (CH_Three) CH_Two CH (C
H_Three)-, -C (CH_Three)_Two-C (CH_Three )_Two-, -C
(CH_Three)_Two -CH_Two-C (CH_Three)_Two-And below
(A-1) to (A-46). Also, A¹~
A^Three(A-47) is also a specific example.

[0021]

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Preferred examples of the compounds of the formulas (I) to (VI) include the following (1) to (11) and (P)
1) to (P21).

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Embedded image The ratio (molar ratio) of these phosphite compounds to the above metal compounds in the isomerization reaction system is usually 0.1.
It is used in the range of 1 to 10,000, preferably 0.5 to 500, particularly preferably 1.0 to 100. The metal compound and the phosphite compound may be added individually to the reaction system, or may be used in a state of being complexed in advance.

In the present invention, the presence of a carboxylic acid having 2 to 8 carbon atoms such as a fatty acid or an aromatic carboxylic acid in an isomerization reaction system using a catalyst containing a specific metal compound and a phosphite allows the isomerization reaction to be carried out. Has the advantage of accelerating the chemical reaction. Among them, fatty acids such as acetic acid, propionic acid and butyric acid are preferred, and acetic acid is most preferred. From the viewpoint of catalytic activity, catalyst stability and economy, the amount of acetic acid is determined based on the total amount (weight ratio) of acetic acid: allyl raw material compound as raw material.
And usually 5: 1 to 1: 1000, preferably
4: 1 to 1: 100, more preferably 2: 1 to 1:10
Is within the range.

The isomerization reaction is usually performed in a liquid phase, and may be performed in the presence or absence of a solvent. However, it is generally preferable to perform the isomerization reaction in a homogeneous system using a solvent. . The solvent can be used as long as it can dissolve the catalyst and the starting compound, and is not particularly limited.

Examples of the solvent include carboxylic acids such as acetic acid, alcohols such as methanol, ethers such as diglyme, diphenyl ether, dibenzyl ether, tetrahydrofuran (THF) and dioxane;
Methylpyrrolidone (NMP), dimethylformamide (DM
F), amides such as dimethylacetamide, ketones such as cyclohexanone, butyl acetate, γ-butyrolactone,
Esters such as di (n-octyl) phthalate; aromatic hydrocarbons such as toluene, xylene and dodecylbenzene; high-boiling substances produced as by-products in the isomerization reaction system; and allyl compounds themselves as raw materials. Can be Among them, acetic acid is preferred in that it promotes the isomerization reaction. The use amount of these solvents is not particularly limited, but is usually 0.1 to 20 times by weight, preferably 0.5 to 10 times by weight, based on the total amount of the allyl compound as the raw material.

In the present invention, the reaction for obtaining 1,4-diacetoxybutene-2 by isomerization of 3,4-diacetoxybutene-1 is an equilibrium reaction, and the equilibrium mixture at 120 ° C. It contains 65 mol% of 1,4-diacetoxybutene-2 and 35 to 40 mol% of 3,4-diacetoxybutene-1. This means that a reaction mixture containing 1,4-diacetoxybutene-2 as a main component is
The isomerization reaction means that a product containing 3,4-diacetoxybutene-1 as a main component can be obtained.

In the product obtained by the isomerization reaction,
The range of the molar ratio of 4-diacetoxybutene-2 to 3,4-diacetoxybutene-1 is usually 90:10 to 10: 9.
0, but within that range 80:20, 70:30,
60:40, 50:50, 40:60, 30:70, 2
Products in any ratio, such as 0:80, can be produced. This ratio is not particularly limited, but can be adjusted according to the reaction conditions and the economics of the process.

The isomerization reaction system of the present invention may contain reaction by-products other than raw materials and substrates, decomposition products of catalysts, and the like. Specifically, in the isomerization reaction system, butanediol monoacetoxylate, 1-acetoxybutan-2-one, 4-
Acetoxybutanal, 4-acetoxycyclotonaldehyde, diacetoxybutane, acetoxyhydroxybutane, butanediol, 1,4-butenediol, 1,2
-One or more compounds (C) selected from butenediol, 1-acetoxy-1,3-butadiene and diacetoxyoctadiene may be present. These compounds (C)
Is usually 1: 1 to 1: 10000, preferably 5: 1 by weight ratio to the total amount of the starting allyl compound (compound (C): allyl compound) in the isomerization reaction system.
1-1: 1000, more preferably 2: 1 to 1:50
0, particularly preferably in the range from 0.1: 1 to 1: 100.

In the present invention, when a large amount of water is present in the isomerization reaction system, the isomerization reaction is remarkably inhibited, so that a smaller amount of water is preferable in that the conversion is higher. Or, in order to completely exclude water from the reaction raw materials, extremely large energy is required. Therefore, industrially, the amount of water in the isomerization reaction mixture is
Preferably it is 0.1 to 5% by weight, more preferably 0.1 to 5% by weight.
5 to 2% by weight. Water can be introduced into the reaction system from various routes. Among them, the carboxylic acid used as a solvent or an accelerator for the isomerization reaction often accompanies water. In such a case, the weight ratio of water to carboxylic acid is preferably 1 or less.

According to the present invention, as described above, butadiene is
1,4-diacetoxy-2-butene and 3,4-diacetoxy-1- obtained by a diacetoxylation reaction in the presence of acetic acid and oxygen
From the reaction product containing butene, a reaction solution containing 3,4-diacetoxy-1-butene as a main component is separated, and then isomerized by the method of the present invention to give 1,4-diacetoxy-2.
-It is also effective when adopted as a process to obtain butene.

When a reaction product obtained by such a diacetoxylation reaction of butadiene is used as a raw material, 1,4-diacetoxy-2-butene or 3,4
In addition to diacetoxy compounds such as -diacetoxy-1-butene,
Since there is a compound similar to the compound (C) described above,
Further, by a method such as distillation, a mixture containing mainly either one of the 3,4-disubstituted-1-butene compound and the 1,4-disubstituted-2-butene compound is separated, and then the mixture Is preferably carried out.

As described above, it was separated by an operation such as distillation.
The mixture containing the 3,4-disubstituted-1-butene form and / or the 1,4-disubstituted-2-butene form contains the diacetoxy form and the monoacetoxy form. The isomerization reaction rate is much lower than that of the diacetoxy compound. Therefore, when performing an isomerization reaction of such a mixture of a diacetoxy compound and a monoacetoxy compound, 1) an acetoxylation reaction (esterification reaction) of the monoacetoxy compound is performed before the isomerization reaction, and It is preferable to adopt a method of performing an isomerization reaction of a mixture containing the obtained diacetoxy compound, or a method of simultaneously performing acetoxylation reaction (esterification reaction) of a monoacetoxy compound in an isomerization reaction system.

The acetoxylation reaction (esterification reaction) of the above-mentioned monoacetoxy compound, for example, 3-butene-1,2-diol monoacetoxylate and / or 1-acetoxy-4-hydroxy-2-butene is carried out by acetic anhydride. Proceed by the presence of The amount of acetic anhydride is not particularly limited, but may be about equimolar to the monoacetoxy compound. When acetic anhydride is used, the reaction temperature of the esterification reaction is as follows:
It is usually 40 to 200 ° C, preferably 100 to 160 ° C.
° C.

The acetoxylation reaction of the above-mentioned monoacetoxy compound also proceeds by the presence of an ion exchange resin and acetic acid. By using ion exchange resin,
There is an advantage that the acetoxylation reaction can be performed without using expensive acetic anhydride. The amount of acetic acid is not particularly limited, but since the reaction is an equilibrium reaction, the conversion of the acetoxylation reaction increases as the amount of acetic acid increases. Examples of the type of ion exchange resin that can be used include cation exchange resins such as styrene, methacrylic acid, and acrylic acid, and among them, styrene cation exchange resins are preferable.
The amount of the ion exchange resin used is not particularly limited, but from the viewpoint of catalytic activity and economy, in the case of the batch method, preferably from 0.01 to 1 kg of the allyl raw material compound.
5 kg, more preferably 0.05 to 1 kg, and in the case of the continuous method, the space velocity (space vol.
ume) is 1 liter of the allyl compound per hour,
It is preferably 0.05 to 10 liters, more preferably 0.2 to 2 liters. When an ion exchange resin is used, the esterification reaction temperature is usually 20 to 20.
0 ° C., preferably 30 to 120 ° C., and more preferably 40 to 100 ° C.

When the method 2) of simultaneously performing the acetoxylation reaction (esterification reaction) of the monoacetoxy compound in the isomerization reaction system as described above is employed, the above-mentioned acetic anhydride, ion exchange resin and acetic acid are used. By using this, it is possible to carry out the isomerization reaction and the esterification reaction under the same reaction conditions, that is, under the above-mentioned isomerization reaction conditions.

The isomerization method of the present invention can be carried out in either a batch system or a continuous system. More specifically, the case where the isomerization reaction is performed in a batch system will be described. A catalyst constituent component is dissolved in a solvent, and a raw material mainly containing, for example, 3,4-diacetoxybutene-1 is introduced thereinto, and the mixture is stirred. Contact with the catalyst for a sufficient conversion time. After completion of the reaction, the target component mainly composed of 1,4-diacetoxybutene-2 or the like can be separated and recovered from the reaction solution by means such as distillation. 1,4-
Separation of diacetoxybutene-2 and 3,4-diacetoxybutene-1 can be usually performed by a method such as distillation or extraction.

When the reaction is carried out in a continuous manner, for example, a raw material mainly composed of 3,4-diacetoxybutene-1 and a catalyst component are continuously supplied to a reaction tank, and a reaction solution containing an isomer, which is a target product, is supplied. Is continuously extracted and then distilled, and the residual liquid containing the catalyst component is continuously circulated to the reaction system and reused. The reaction temperature for the isomerization is usually 50 to 200.
° C, preferably 80 to 160 ° C. If the reaction temperature is too low, the activity will be low, and if it is too high, the stability of the catalyst will decrease, causing undesirable side reactions. The reaction pressure is not particularly limited, and is appropriately selected from the range from normal pressure to 3 MPa, preferably from the range from normal pressure to 2 MPa. The reaction time is also not particularly limited, and is appropriately selected in consideration of the reaction rate from factors such as the amount of the catalyst and the reaction temperature.

The reaction for obtaining the corresponding 1,4-disubstituted product by isomerization of the 3,4-disubstituted product is an equilibrium reaction, and the catalyst plays a role in bringing the composition of the reaction raw material closer to the equilibrium composition.
That is, the effect is the same regardless of whether the starting material is a mixture mainly composed of the 3,4-disubstituted product or the 1,4-disubstituted product. Therefore, regarding the isomerization reaction of a component mainly composed of 1,4-diacetoxybutene-2, 1,1 is used as a raw material.
Other than using 4-diacetoxybutene-2 or a mixture containing 4-diacetoxybutene-2, the reaction can be carried out according to the above-mentioned isomerization reaction of a raw material mainly composed of 3,4-diacetoxybutene-1.

According to the present invention, there is provided a catalyst comprising a 3,4-disubstituted butene-1 and / or a 1,4-disubstituted butene-2 containing a metal compound of an element of Groups 8 to 10 of the periodic table. When the isomerization is performed below, it becomes possible to obtain the isomerized product in a yield of 10 mol% or more while suppressing the precipitation of the metal compound.

[0040]

EXAMPLES The present invention will be described more specifically below, but the present invention is not limited to the following examples unless it exceeds the gist. The reaction results in the following examples were calculated from the results of analyzing the composition of the reaction solution by gas chromatography. 3,4-diacetoxybutene-1
(Hereinafter sometimes abbreviated as 3,4-DABE) as a raw material, other than 1,4-diacetoxybutene-2 (hereinafter sometimes abbreviated as 1,4-DABE) as a product is detected. Since it was not possible, the yield of 1,4-diacetoxybutene-2 was used as the reaction result. Further, as the phosphite compound, the above (P1) to (P21) were used, and all the reactions using phosphite were carried out under a nitrogen atmosphere.

Examples 1 to 8 3,4-diacetoxybutene-1 (0.633 mmol), Pd (OAc)
₂ (0.0221 mmol), the phosphite compound (0.041 mmol) and acetic acid (1 ml) to give 8
The reaction was performed at 0 ° C. for 1 hour. Table 1 shows the yields of 1,4-diacetoxybutene-2 (1,4-DABE). still,
No Pd metal was precipitated in any of the systems.

[0042]

[Table 1]

Example 9 A reaction was carried out in the same manner as in Example 3 except that 1 ml of diglyme was used in place of acetic acid used in Example 3 and the reaction temperature was changed to 120 ° C., and 1,4-DABE was collected. Rate is 5
6.5%. Also in this case, no precipitation of palladium metal was observed.

Example 10 Instead of (P3) used in Example 9, P (OPh) ₃
(0.082 mmol) and the same reaction as in Example 9 was carried out except that the reaction temperature was changed from 120 ° C to 100 ° C. As a result, the yield of 1,4-DABE was 10.9%.
No palladium deposition was observed.

Example 11 Pd (OAc) ₂ (0.633 mmol), (P3) (0.041 mmol) as a phosphite compound, acetic acid (0.037 ml), 1 ml of diglyme and 3,4-diacetoxybutene-1 ( 3,4-DABE) or 1,4
-Diacetoxybutene-2 (1,4-DABE) in 0.1.
FIG. 1 shows the results obtained by charging 633 mmol and reacting at 68 ° C. It was found that the isomerization reaction was completed in about 100 minutes for both raw materials, and reached an equilibrium concentration. Also in this case, no palladium deposition was recognized as long as the phosphite compound was present.

Examples 12 to 14 (Pd system, P19 to 21)
Example of use) 3,4-diacetoxybutene-1 1 ml (6.3 mm
ol) contained 21 μmol of Pd (OAc) ₂ (5 m
g) and the phosphite compounds (P19) to (P21)
After dissolving 12 mg of each, acetic acid (10 μl) was added and reacted at 120 ° C. for 30 minutes. The results are shown in Table 2 below. Note that no Pd metal was precipitated in any of the systems.

[Table 2] Table 2 -------------------------------------------------------- Ligands Molar balance (%) 1,4-DABE (% 5.) Trans / Cis P19 95 11 11.2 P20 95 38 7.7 P21 81 55 6. Trans / Cis ---------------- 0 -------------------------------------------

Example 15 (Pd-based, using P13) 3.7 mg (6.4 μmol) of Pd (dba) ₂ and 40 mg (51 μmo) of the phosphite compound (P13)
l) was treated with 3,4-diacetoxybutene-11 ml (6.
3 mmol) at 120 ° C.
0 μl was added to another Schlenk containing acetic acid (1 ml) and 11 ml of 3,4-diacetoxybutene-11 (6.3 mmol).
The reaction was performed at 120 ° C. for 3 hours in addition to the tube. The molar balance was 99% or more. When the reaction product solution was analyzed, 1,4-DABE was 62% and 3,4-DABE was 3%.
8% was included. In this reaction, no Pd metal was deposited.

Example 16 (Effect of Amount of Acetic Acid) Pd (OAc) ₂ and 3,4-D at the concentrations shown in Table 3 below
4 molar equivalents of bisphosphite (P4) based on ABE
With acetic acid in the amount shown in Table 3 and 1 ml of 3,4-DABE
(6.3 mmol) and reacted at 120 ° C. for 1 hour. The results are shown in Table 3. In this reaction, no Pd metal was deposited.

Table 3 Table 3 --- --- --- -------- Pd (OAc) ₂ (ppm) Acetic acid (ml) Conversion (%) mol Balance (%)--------------------------1500 * 0.01 52 72 35 0.1 59 98 17 0.1 49 100 7 0.1 29 98 2 1.0 29 In the case of ***, the reaction time was set to 15 minutes. From the results in Table 3, it can be seen that the molar balance is as high as 98% or more in the region where the concentration of acetic acid is high, that is, in the region where the concentration of the Pd compound is low.

Examples 17 to 28 (Additional Examples: Influence of Temperature and Time) 3,4-diacetoxybutene-1 ml (6.3 mmol)
1) Pd (OAc) ₂ 1.5 mg (6.7 μmo)
l) and the phosphite compounds 26.8 shown in Table 4 below.
μmol was dissolved at 120 ° C. Then 3μ of this solution
1 with acetic acid (1 ml) and 3,4-diacetoxybutene-
The mixture was added to another flask containing 1 ml (6.3 mmol) and reacted at 120 ° C. for 1 hour or at 140 ° C. for 3 hours.
The results are shown in Table 4 below. The molar balance was 98% or more, and only 1,4-DABE and unreacted 3,4-DABE were present in the reaction product solution. Note that no Pd metal was deposited in any of the systems.

[0050]

[Table 4] Table 4 --------------------------------------------- Ligands 1,4-DABE 1,4 -DABE (%; 120 ° C, 1h) (%; 140 ° C, 3h)-------------------------Examples 17 P15 1 Unmeasured Example 18 P16 1 Unmeasured Example 19 P17 2 Unmeasured Example 20 P18 2 Unmeasured Example 21 P11 7 Unmeasured Example 22 P5 8 Unmeasured Example 23 P4 19 35 Example 24 P1 23 Not measured Example 25 P10 25 46 Example 26 P12 25 46 Example 27 P13 25 44 Example 28 P9 31 55------------------------------------------------ −−−−− At the equilibrium point at 120 ° C., the reaction mixture contains 63% of 1,4-DABE and 37% of 3,4-DABEGA Had been.

Example 29 (additional example; Pt system, using phosphite P13) 3,4-diacetoxybutene-1 1 ml (6.3 mm
ol), 2.5 mg of Pt (acac) ₂ (6.21 μm).
mol) and 10 mg of the phosphite compound (P13)
(13 μmol) and then acetic acid (1 ml)
Was added and reacted at 120 ° C. for 1 hour. G
C analysis revealed that 1,4-DABE contained 17 mol% (trade
nc / cis = 4.5) and 83 mol% of 3,4-DABE. In this reaction, no Pt metal was deposited.

Example 30 (additional example; Rh system, using phosphite P13) 3,4-diacetoxybutene-1 1 ml (6.3 mm
ol), 1.8 mg of [Rh (COD) OAc] ₂
(3.5 μmol) and the phosphite compound (P1
3) 10 mg (13 μmol) was dissolved, and then acetic acid (1 ml) was added and reacted at 120 ° C. for 1 hour. GC analysis of the reaction product showed that 1,4-DABE was 6.
It contained 3% (tranc / cis = 4.3) and 92% 3,4-DABE. No Rh metal was precipitated in this reaction.

Example 31 (additional example; Ni-based, using phosphite P4) 3,4-diacetoxybutene-1 1 ml (6.3 mm
ol), 8 mg (29 μmol) of Ni (COD) ₂ and 62 mg (58 μmo) of the phosphite compound (P4)
l) was dissolved. Next, 10 μl of this solution was added to acetic acid (1 ml) and 3,4-diacetoxybutene-11 ml.
(6.3 mmol) was added to another Schlenk tube, and reacted at 120 ° C. for 1 hour. GC analysis of the reaction solution revealed that 1,4-DABE was 0.8% (tranc / ci
s = 8.8) and 99% of 3,4-DABE. In this reaction, no precipitation of Ni metal was observed.

Example 32 (Isomerization in the presence of water: H ₂ O
/ CH ₃ COOH = 0.02) 3,4- diacetoxybutene -1 1 ml (6.3 mm
ol), 3.7 mg (6.4 μmo) of Pd (dba) ₂
l) and 40 mg of the phosphite compound (P13) (5
1 μmmol) was dissolved at 120 ° C. Then, 3 μl of this solution was added to 1 ml of acetic acid and 20 μl of water (1.1 μmo
l) and 3,4-diacetoxybutene-11 ml (6.
4 mmol) in addition to another Schlenk tube containing
The reaction was performed at 0 ° C. for 1 hour. GC analysis of the reaction product showed that 20% of 1,4-DABE and 80% of 3,4-D
ABE was included, and the molar balance was 99% or more. In this reaction, no Pd metal was deposited.

Comparative Example 1 (Example in the absence of phosphite) 3,4-diacetoxybutene-1 (0.633 mmol), Pd (OAc)
₂ (0.06 mmol) and 1 ml of diglyme were reacted at a reaction temperature of 120 ° C. for 1 hour.
-The yield of DABE was 1.3%. However,
After the reaction, a metal mirror of palladium was observed on the flask surface.

Comparative Example 2 PdC was used instead of Pd (OAc) ₂ used in Comparative Example 1.
The same reaction as in Comparative Example 1 was carried out except that l2 (0.06 mmol) was used. As a result, the yield of 1,4-DABE was 58%. However, after the reaction was completed, a palladium metal mirror was observed on the flask surface.

Comparative Example 3 Instead of Pd (OAc) ₂ used in Comparative Example 1, PdC was used.
The same reaction as in Comparative Example 1 was performed except that l ₂ (PPh ₃ ) ₂ (0.06 mmol) was used. However, 1,
No generation of 4-DABE could be detected.

[0058]

According to the present invention, an allyl raw material compound such as 3,4-disubstituted butene-1 and / or 1,4-disubstituted butene-2 is used as a metal compound of Group 8 to 10 and a phosphite compound. By performing isomerization using a catalyst containing, at a high conversion, high selectivity, and while suppressing the precipitation of metal,
The corresponding isomers, 1,4-disubstituted butene-2 and / or
Alternatively, 3,4-disubstituted butene-1 or the like can be produced.

[Brief description of the drawings]

FIG. 1: 3,4-diacetoxybutene-1 and 1,4-
Isomerization reaction rate of diacetoxybutene-2.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) C07C 31/20 C07C 31/20 B 33/03 33/03 69/527 69/527 C07D 307/08 C07D 307 / 08 // C07B 61/00 300 C07B 61/00 300 C07F 9/145 C07F 9/145 9/6574 9/6574 Z (72) Inventor Naoto Urata 1000 Kamoshita-cho, Aoba-ku, Yokohama-shi, Kanagawa Prefecture Mitsubishi Chemical Corporation Inside Yokohama Research Institute (72) Inventor Hironobu Ohno 1000 Kamoshita-cho, Aoba-ku, Yokohama-shi, Kanagawa-ken Yokohama Research Institute, Mitsubishi Chemical Corporation

Claims (16)

[Claims] 1. A method for producing a corresponding allyl isomer product by isomerizing an allyl raw material compound having an acyloxy group or a hydroxyl group at the allylic position, comprising the steps of:
A process for producing an allyl compound, comprising performing an isomerization reaction in the presence of a catalyst containing a compound of a Group 0 metal and a phosphite compound. 2. An allyl raw material compound represented by the formula (a ′): CH
₂ = CH-CHR ⁶ -CH ₂ represented by R ⁷ 3,4-disubstituted butene-1, the formula _{(b '): CH 2 R} 8 -CH = CH-CH 2 R 9
The method for producing an allyl compound according to claim 1, wherein the method is selected from 1,4-disubstituted butene-2 represented by the formula: and mixtures thereof. (However, in the formulas (a ′) and (b ′), R ^{6 to} R ⁹ are groups selected from an acetoxyl group and a hydroxyl group, and may be the same or different.) 3. An allyl isomer product having the formula (b ′): C
^{_{H 2 R 8 -CH = CH-}} CH 2 represented by 1,4-disubstituted butene-2 with R ^9, wherein _{(a '): CH 2 =} CH-CHR 6 -CH 2 R
3. The method for producing an allyl compound according to claim 1, wherein the method is selected from 3,4-disubstituted butene-1 represented by ⁷ and a mixture thereof. (However, in the formulas (a ′) and (b ′), R ^{6 to} R ⁹ are groups selected from an acetoxyl group and a hydroxyl group, and may be the same or different.) 4. The process according to claim 1, wherein the allyl starting compound of the formula (a ′) is isomerized to the allyl isomer product of the formula (b ′).
4. The method for producing an allyl compound according to any one of 3. 5. The process according to claim 1, wherein the allyl starting compound of the formula (b ′) is isomerized to an allyl isomer product of the formula (a ′).
4. The method for producing an allyl compound according to any one of 3. 6. A method according to claim 1, wherein 3,4-diacetoxybutene-1 and 3-
A mixture mainly containing butene-1,2-diol monocarboxylate is isomerized to give 1,4-diacetoxybutene-
The method for producing an allyl compound according to any one of claims 1 to 5, wherein a reaction product containing 2 and 1-acetoxy-4-hydroxy-2-butene is obtained. 7. The method for producing an allyl compound according to claim 1, wherein the metal compound is at least one selected from the group consisting of a rhodium compound, a ruthenium compound, a nickel compound, a platinum compound, and a palladium compound. . 8. The phosphite compound represented by the following general formula (I)
The method for producing an allyl compound according to any one of claims 1 to 7, wherein the method is at least one selected from the group consisting of compounds represented by (VI) to (VI). Embedded image (In the formulas (I) to (VI), R ^{10 to} R ²¹ each independently represent an alkyl group, an alkoxy group, a cycloalkyl group, an aryloxy group, an alkylaryloxy group, an arylalkoxy group, or an aryl group. And a group which may further have a substituent, and Z ^{1 to} Z ⁴ and A ^{1 to} A ³
Are each independently an alkylene group which may have a substituent, an arylene group which may have a substituent, or-
^{Ar 1 - (Q 1) n} -Ar 2 - become middle bivalent which may Jiariren group having a linking group (wherein, Ar ¹ and Ar
² independently represents an arylene group having 6 to 18 carbon atoms which may have a substituent). T is a carbon atom, an alkanetetrayl group, a benzenetetrayl group, or a tetravalent group which may have a substituent represented by T ^1- (Q ² ) n-T ² , ¹ and T ² each independently represent a trivalent organic group which may have a substituent selected from an alkanetriyl group and a benzenetriyl group.
Q ¹ and Q ² are, each independently, -CR ²² R ²³ -,
Represents -O-, -S- or -CO-, n is 0 or 1, R ²² and R ²³ are each independently a hydrogen atom, an alkyl group or an aryl group, and have a substituent May be. ) 9. The method for producing an allyl compound according to claim 8, wherein the phosphite compound is a compound represented by the general formula (IV). 10. The method for producing an allyl compound according to claim 8, wherein the phosphite compound is a compound represented by the general formula (V). 11. The method for producing an allyl compound according to claim 8, wherein the phosphite compound is a compound represented by the general formula (VI). 12. In any one of the general formulas (VI) to (VI), R ^{16 to} R ²¹ have 6 carbon atoms which may have a substituent.
And Z ^{1 to} Z ⁴ each independently represent a diarylene group which may have a divalent linking group in the middle of —Ar ¹ — (Q ¹ ) n —Ar ² (however, Ar ¹ and Ar ² each independently represent an arylene group having 6 to 18 carbon atoms which may have a substituent group, Q ¹ is ^{independently, -CR 22 R 23 -, -} O-, -S- or -CO
Represents n, n is 0 or 1, and R ²² and R ²³ each independently represent a hydrogen atom, an alkyl group or an aryl group. And A ^{1 to} A ³ represent a bisarylene group having 12 to 20 carbon atoms which may have a substituent.
2. The method for producing an allyl compound according to any one of 1. 13. An allyl raw material compound having an acyloxy group or a hydroxyl group at the allylic position isomerized in the presence of a catalyst containing a metal compound of an element belonging to Groups 8 to 10 of the periodic table, and the corresponding allyl isomer is obtained. A method for producing an allyl compound, which comprises obtaining an isomerized product in a yield of 10% or more without substantially depositing the metal compound. 14. The 1,4-obtained by the method of claim 13.
A method for producing 1,4-butanediol and / or tetrahydrofuran by further hydrogenating and hydrolyzing diacetoxybutene-2. 15. The 1,4-obtained by the method of claim 14.
Polyester and / or polyurethane produced using butanediol as a raw material. 16. A polyalkylene ether glycol produced from tetrahydrofuran obtained by the method of claim 15.