JP2002105026A - Method for producing allyl compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing the corresponding isomer in high conversion and selectivity without causing metal deposition by isomerizing an allyl compound such as 3,4-diacetoxybutene-1 or 1,4-diacetoxybutene-2. SOLUTION: This method for producing the corresponding allyl isomer product comprises isomerizing an allyl stock compound having an acyloxy group and/or hydroxy group in the presence of a carboxylic acid on the allyl site; wherein this method is characterized by involving the following practice: the carboxylic acid is separated from the isomerization reaction product and then fed to the isomerization reaction system; in this case; the content of the water accompanying the carboxylic acid fed to the reaction system is adjusted to <=8 wt.% based on the carboxylic acid.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for isomerizing a compound having an acyloxy group and / or a hydroxyl group at the allylic position by allylic rearrangement. More particularly, 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 4-disubstituted butene-2 to produce 1,4-disubstituted butene-2 and / or 3,4-disubstituted butene-1, which are the corresponding isomers, in high yield. 1,4-diacetoxybutene-2 obtained by the method of the present invention is an important intermediate for producing 1,4-butanediol, tetrahydrofuran or the like. 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)
No. 6695, No. 2134115),
Using a radium compound in the presence of hydrogen chloride or hydrogen bromide
(JP-A-57-140744), PdCl
_Two (PhCN) _Two Method using compound having 6 to 20 carbon atoms
(U.S. Pat. No. 4,095,030) and the like are known.
ing. However, these methods are not suitable for catalyst stability.
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]

In the case of conducting an isomerization reaction of an allyl raw material compound in the presence of a carboxylic acid, the carboxylic acid often has a boiling point lower than that of the desired allyl isomer product. Separated from the subsequent reaction solution by distillation,
It can be re-supplied to the isomerization reaction system. However, when the carboxylic acid is separated by distillation, water in the reaction solution often accompanies. Water is mixed in from the isomerization reaction raw material,
Since it is produced when the allyl raw material compound having a hydroxyl group is esterified, water accumulates in the isomerization reaction system, making it difficult to industrially construct a process, and inhibiting the isomerization reaction by increasing the water concentration, Conversion may be reduced. The present inventors have conducted intensive studies in view of such circumstances, and as a result, have found that 3,4-diacetoxybutene-1 and / or 1,
Allyl raw material compounds such as 4-diacetoxybutene-2,
When isomerizing by allylic rearrangement in the presence of a carboxylic acid, by controlling the amount of water in the carboxylic acid recycled to the isomerization reaction system, the above problems can be avoided, high conversion, high selectivity, and It has been found that the desired isomer product can be obtained without causing metal precipitation.
The present invention has been completed.

That is, the gist of the present invention is to provide a method for isomerizing an allyl raw material compound having an acyloxy group and / or a hydroxyl group at the allyl position in the presence of a carboxylic acid to produce a corresponding allyl isomer product. When the carboxylic acid is separated from the reaction product after the isomerization reaction, and then the separated carboxylic acid is supplied to the isomerization reaction system, the content of water accompanying the carboxylic acid supplied to the isomerization reaction system is reduced to the carboxylic acid. To 8 wt% or less.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Used in the isomerization reaction of the present invention
The raw material has an acyloxy group and / or a hydroxyl group at the allyl position.
What kind of allyl compound is
In the present invention, the starting material may undergo allylic rearrangement.
To produce the corresponding isomer, the allyl product
is there. Here, the acyloxy group is represented by the general formula R_AC
(O) O-, R_AMay have 1 to 10 carbon atoms
And an aryl group having 6 to 15 carbon atoms.
And among them, an alkyl group having 1 to 3 carbon atoms is preferable, and in particular,
Is R _AIs preferably a methyl group. Specifically,
In the light, the following formulas (a), (b) and mixtures thereof
Allyl starting compound selected from the isomerization reaction
Formula (b), formula (a) and its corresponding isomers
Producing an allyl isomer product selected from these mixtures
Can be

[0009]

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In the above formulas (a) and (b), R is
A ethoxy group or a hydroxyl group; ¹~ R^FiveRespectively
Independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms,
An alkoxy group having 1 to 20 carbon atoms, a cyclo group having 3 to 20 carbon atoms
Alkyl group, dialkylamino group having 2 to 40 carbon atoms, charcoal
Aryl group having 6 to 20 prime numbers, arylo having 6 to 20 carbon atoms
Xy group, alkylaryl group having 6 to 20 carbon atoms, carbon number
6-20 alkyl aryloxy groups, 6-20 carbon atoms
Arylalkoxy group, cyano group,
Represents a stele group, a hydroxy group, or a halogen atom;
It is a group which may have a substituent. R¹~ R^FiveHas
The substituent which may be used is an alkoxy group having 1 to 10 carbon atoms.
Group, carboxyl group having 1 to 10 carbon atoms, hydroxyl
And aryl groups having 6 to 10 carbon atoms.

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.

Further, 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.

In the present invention, the above allyl raw material compound is isomerized in the presence of a carboxylic acid, the carboxylic acid is separated from the reaction product after the isomerization reaction, and the separated carboxylic acid is then isomerized. Recycle to reaction system. Examples of the carboxylic acid include carboxylic acids having 2 to 8 carbon atoms, such as fatty acids and aromatic carboxylic acids. The presence of the carboxylic acid has the advantage of promoting the isomerization 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.

In the present invention, when the carboxylic acid is separated by distillation, water in the reaction solution often accompanies. This entrained water is mixed in from the isomerization reaction raw material or is generated when the allyl raw material compound having a hydroxyl group is esterified, so that water accumulates in the isomerization reaction system, making it difficult to industrially construct a process. At the same time, the present inventors have paid attention to the possibility that the isomerization reaction may be inhibited by an increase in the water concentration and the conversion may be reduced. As a result, if a large amount of water is present in the isomerization reaction system, the isomerization reaction is significantly inhibited, and it has been found that a smaller amount of water results in a higher conversion rate. Extremely large amounts of energy are required to completely exclude water from water. Therefore, in the present invention, by controlling the amount of water accompanying the carboxylic acid recycled to the isomerization reaction system to 8 wt% or less, preferably 5 wt% or less, more preferably 3 wt% or less based on the carboxylic acid, It is characterized by simply reducing the amount of water in the isomerization reaction system, and has the advantage that a decrease in the conversion of the isomerization reaction can be suppressed. In the present invention, a method for controlling the amount of water accompanying the carboxylic acid can be performed by separating the carboxylic acid from the reaction product after the isomerization reaction, and then purifying the carboxylic acid by distillation. Specifically, the number of theoretical plates is 5 to 40, the top pressure is 200 mmH
g-2MPa, tower top temperature 60-120 ° C, tower bottom temperature 80
The conditions can be selected from a range of up to 150 ° C. and a reflux ratio of 0.01 to 5. Further, when the carboxylic acid is separated in the distillation column after the isomerization reaction, the amount of water in the carboxylic acid may be adjusted by adjusting the distillation conditions.

As the isomerization catalyst used in the reaction of the present invention, for example, a catalyst containing a metal compound of Group 8 to 10 of the periodic table (IUPAC revised edition of inorganic chemical nomenclature (1989)) and an organic phosphorus compound can be used. Can be used. Examples of the metal compound include iron, cobalt, nickel, ruthenium,
One or more compounds selected from the compounds of rhodium, platinum, iridium, osmium and palladium are mentioned, and among these, nickel, palladium and platinum compounds are more preferred, and furthermore palladium compounds are particularly preferred. The metal compound is, for example, acetate, acetylacetonate, halide, sulfate, nitrate, organic salt, inorganic salt, alkene compound, amine compound, pyridine compound,
Examples include phosphine coordination compounds and phosphite coordination compounds.

As the ruthenium compound, RuCl_Three,
Ru (OAc)_Three, Ru (acac) _Three, RuCl_Two(P
Ph_Three)_ThreeOsmium compounds include O 2
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 Pd
Cl ₆ (potassium hexachloropalladate (IV)), PdC
l ₂ (PhCN) ₂ , PdCl ₂ (CH ₃ CN) ₂ , Pd
(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 (OAc)
₂ , palladium carboxylate compounds or halides such as PdCl ₂ are preferred. As a platinum compound,
Pt (acac) ₂ , PtCl ₂ (COD), PtCl ₂
(CH ₃ CN) ₂ , PtCl ₂ (PhCN) ₂ , Pt (PP
_{h 3) 4, K 2 PtCl} 4, Na 2 PtCl 6, H 2 PtCl 6
And the like. (Here, COD: cyclopentadiene, dba: dibenzylideneacetone, acac: acetylacetonate.) In the present invention, the form of the above-mentioned metal compound is not particularly limited, and the active metal complex species is a single compound. Body, dimer and / or
Alternatively, it may be a multimer.

The amount of these metal compounds used is not particularly limited, but from the viewpoint of catalytic activity and economy, 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. Examples of the organic phosphorus compound used in the present invention include phosphines, phosphites, phosphonites, phosphinites and the like, and these may be monodentate or polydentate,
Among them, phosphite compounds are preferred. The phosphite compound is not particularly limited, but preferred phosphite compounds are represented by the following general formulas (I), (II), (III),
It is at least one of the compounds represented by (IV), (V) and (VI).

[0019]

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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).

[0024]

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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 6 carbon atoms which may have a substituent. 30 arylene group, or a ^{-Ar 1 - (Q 1) n} -Ar 2 - become middle bivalent which may Jiariren group having a linking group (wherein, a
r ¹ and Ar ² each independently represent an optionally substituted arylene group having 6 to 18 carbon atoms. ). T is a carbon atom, alkanetetrayl groups, benzenetetraol yl group, or T ² - a (Q ²⁾ n-T may have a substituent represented by ² tetravalent radical, T ¹ And T ²
Each independently represents a trivalent organic group which may have a substituent selected from an alkanetriyl group having 1 to 10 carbon atoms and a benzenetriyl group having 6 to 15 carbon atoms. Q ¹
And Q ² are each ^{independently, -CR 22 R 23 -, -} O
-, -S- or -CO-, wherein n is 0 or 1,
R ²² and R ²³ each independently represent a hydrogen atom, a carbon atom of 1;
An alkyl group having 10 to 10 or an aryl group having 6 to 10 carbon atoms, which may have a substituent.

Also, 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
3 to 10 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 the substituent is 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, Ar¹ And Ar^Two Is a substituent
Is an arylene group which may have a carbon number of 6 to
24, more preferably 6 to 16, and the preferred substituents
Examples of the body include an alkyl group having 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 -,-(CH
_Two )_Five -,-(CH_Two )₆ -, -CH (CH_Three ) -CH
(CH_Three )-, -CH (CH_Three ) CH_Two CH (CH_Three )
-, -C (CH_Three )_Two -C (CH_Three )_Two -, -C (CH
_Three )_Two -CH_Two-C (CH_Three )_Two-And the following (A-
1) to (A-46). Also, A₁~ A_ThreeUtensils
Examples of the body include (A-47).

[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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As preferred specific examples of the compounds of the formulas (I) to (VI), the following (1) to (11) and (P)
1) to (P21).

[0034]

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[0035]

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[0036]

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Further, the following compound (12) can also be used.

[0038]

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[0039]

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[0040]

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[0041]

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Specific examples of the phosphines include triphenylphosphine, tri (n-butyl) phosphine,
Examples thereof include tri (t-butyl) phosphine, diphenylphosphinoethane, diphenylphosphinomethane, diphenylphosphinopropane, and diphenylphosphinobutan, and the following (13) to (20).

[0043]

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Examples of the phosphonites and phosphinites include the following (21) to (35).

[0045]

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[0046]

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[0047]

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The ratio (molar ratio) of these organic phosphorus compounds to the above-mentioned metal compounds in the isomerization reaction system is as follows:
Usually 0.1 to 10000, preferably 0.5 to 5
00, particularly preferably in the range of 1.0 to 100. The metal compound and the organic phosphorus compound may be added alone to the reaction system, or may be used in a state of being complexed in advance.

The isomerization reaction is usually carried out in a liquid phase, and may be carried out in the presence or absence of a solvent. However, it is usually preferable to carry out 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.

Specific 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.

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 derivative and / or the 1,4-disubstituted-2-butene derivative contains a diacetoxy derivative and a monoacetoxy derivative (hydroxyl-containing compound). The isomerization reaction rate of the monoacetoxy form is much lower than that of the diacetoxy form. 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.

Here, the hydroxyl group-containing compound is, for example, the above-mentioned allyl raw material compound, a 3,4-disubstituted butene-1 in which either R ⁶ or R ^{7 in} the formula (a ′) is a hydroxyl group. Or a hydroxyl group-containing allyl compound consisting of 1,4-disubstituted butene-2 in which either R ⁸ or R ^{9 in} the formula (b ′) is a hydroxyl group. When such an esterification reaction of a hydroxyl group-containing compound is performed, water is produced as a by-product, so that water may accumulate in the reaction system and the conversion of isomerization may decrease. Therefore, the method for controlling water of the present invention is more effective when applied to a process for performing an esterification reaction.

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 above-mentioned acetoxylation reaction of the 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 either in 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.

[0064]

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 1-4 and Comparative Example 1 In 1 ml (6.3 mmol) of 3,4-DABE,
3.7 mg (6.4 μmol) of d (dba) 2 and 28 mg (26.1 μmol) of the phosphite compound (P) were dissolved at 120 ° C. Next, 5 μl of this solution was added to 1 ml of acetic acid, water and 1 ml of 3,4-DABE (6.3 mm).
ol), and at 120 ° C for 1
The reaction was allowed to proceed with stirring for an hour. Table 1 shows the amount of water relative to acetic acid added to the isomerization reaction and the results of GC analysis of the reaction product liquid. In each case, the molar balance was 99% or more. In this reaction, no Pd metal was deposited.

[0066]

[Table 1]

[0067]

According to the present invention, when the allyl raw material compound such as 3,4-disubstituted butene-1 and / or 1,4-disubstituted butene-2 is isomerized, the water content in the recycled carboxylic acid is reduced. By controlling the amount, high conversion, high selectivity,
In addition, it is possible to produce the corresponding isomers such as 1,4-disubstituted butene-2 and / or 3,4-disubstituted butene-1 while suppressing the precipitation of metal.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C07C 43/11 C07C 43/11 69/16 69/16 C07D 307/08 C07D 307/08 C08G 65/20 C08G 65/20 // C07B 61/00 300 C07B 61/00 300 F term (reference) 4C037 BA04 4H006 AA02 AC27 AC29 AC41 AC43 AC48 BA21 BA23 BA24 BA25 BA26 BA50 BA53 BA83 BD36 BD52 FE11 FG28 GN08 GP01 KA30 4H039 CA66 CJ10 4J005 AA08

Claims (11)

[Claims] In a method for producing an allyl isomer product by isomerizing an allyl raw material compound having an acyloxy group and / or a hydroxyl group at the allyl position in the presence of a carboxylic acid, the reaction product after the isomerization reaction is obtained. When the carboxylic acid is separated from the product, and then the separated carboxylic acid is supplied to the isomerization reaction system, the content of water accompanying the carboxylic acid supplied to the isomerization reaction system is reduced to 8% by weight or less based on the carboxylic acid. A method for producing an allyl compound, which comprises adjusting the concentration. 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. An allyl raw material compound represented by the formula (a ′):
3,4-disubstituted butene-1 wherein either one of ⁶ and R ⁷ is a hydroxyl group, or 1,4-disubstituted butene wherein one of R ⁸ and R ^{9 in} the formula (b ′) is a hydroxyl group 3. The isomerization reaction according to claim 2, which comprises a hydroxyl group-containing allyl compound consisting of butene-2, and the esterification reaction of the hydroxyl group-containing allyl compound to obtain a compound having a corresponding acyloxy group, followed by an isomerization reaction. A method for producing an allyl compound. (Because we consider separate applications that combine esterification and isomerization,
The subclaims do not provide any details. (There is description in the text) 7. The method according to claim 1, wherein the 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 6, wherein a reaction product containing 2 and 1-acetoxy-4-hydroxy-2-butene is obtained. 8. The process for producing an allyl compound according to claim 1, wherein the isomerization reaction is carried out in the presence of a catalyst containing a compound of a metal belonging to Groups 8 to 10 of the periodic table and an organic phosphorus compound. . 9. The 1,4-diacetoxybutene-2 obtained by the method of claim 7, which is further hydrogenated and hydrolyzed.
A method for producing 4-butanediol and / or tetrahydrofuran. 10. Polyester and / or polyurethane produced from 1,4-butanediol obtained by the method according to claim 9. 11. A polyalkylene ether glycol produced from tetrahydrofuran obtained by the method of claim 9.