JP2002105021A - Method for producing 1,4-disubstituted butene-2 or 3,4- disubstituted butene-1 - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a process for industrially advantageously producing a 3,4-disubstituted butene-1 or 1,4-disubstituted butene-2. SOLUTION: In the case of a 1,4-disubstituted butene-2, the 1,4-disubstituted butene-2 is obtained by (1) acyloxylation of butadiene in the presence of a carboxylic acid and oxygen, (2) separating a mixture composed mainly of a 3,4-disubstituted butene-1 by distillation from the reaction product obtained in the acyloxylation step, (3) isomerizing the mixture composed mainly of the 3,4-disubstituted butene-1 separated in the separation step to obtain the isomerization reaction product, containing the 1,4-disubstituted butene-2 as the main component as the corresponding isomerization reaction product, and (4) feeding the isomerization reaction product obtained in the isomerization reaction step into the separation step (2).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a 1,4-disubstituted butene-2 such as 1,4-diacyloxy-2-butene or a 3,4-disubstituted butene such as 3,4-diacyloxy-1-butene. Regarding the method for producing substituted butene-1, specifically, from the product obtained by the acyloxylation reaction of butadiene,
It relates to a series of processes for industrially producing 1,4-diacyloxy-2-butene or 3,4-diacyloxy-1-butene.

The 1,4-disubstituted butene-2 obtained by the method of the present invention is subjected to a hydrogenation reaction and a hydrolysis reaction to produce an important intermediate for producing 1,4-butanediol or tetrahydrofuran. Body. On the other hand, 3,4-disubstituted butene-1 is an important intermediate for producing terpentene compounds such as vitamin A acetate, as well as pharmaceuticals, agricultural chemicals, and various flavors.

[0003]

2. Description of the Related Art 1,4-Disubstituted butene-2 such as 1,4-diacetoxybutene-2 and 3,4-disubstituted butene-1 such as 3,4-diacetoxybutene-1 are used in acetic acid solvent. It is known that medium butadiene can be obtained by oxidizing it with molecular oxygen (for example, JP-A-48-72090, JP-A-48-96513). However, in this method,
Since the production ratio of 1,4-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.
It was very difficult to obtain diacetoxybutene-2. On the other hand, in order to selectively produce only 1,4-diacetoxybutene-2, a very special raw material such as 3,6-dihydro-1,2-dioxyin is required. Was virtually impossible.

Therefore, 3,4-diacetoxybutene-1
And / or 1,4-diacetoxybutene-2 isomerized using a specific catalyst, and the corresponding isomers, 1,4-diacetoxybutene-2 and / or 3,4-diacetoxybutene-, respectively. Various methods have heretofore been proposed as a method of manufacturing No. 1. For example, a method using a platinum chloride compound as a catalyst (German Patent No. 273)
6695, 2134115), a method using a palladium compound in the presence of hydrogen chloride or hydrogen bromide (JP-A-57-140744), PdCl
2 (PhCN) 2 A method using a compound having 6 to 20 carbon atoms (U.S. Pat. No. 4,095,030) is known. However, these methods have a problem in stability of the catalyst, and therefore have a problem that a large amount of a highly corrosive halogen compound must be used.

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.

[0007]

The products usually obtained by the acetoxylation reaction of butadiene include a monoacetoxy compound having a hydroxyl group, for example, 3-butene-1,2-diol monoacetoxylate and the diacetoxy compound described above. For example, 3,4-diacetoxy-1-butene is contained, and the former is known to generally have a remarkably slower isomerization reaction rate than the latter.

Therefore, in a conventional diacetoxy isomerization reaction method such as 3,4-diacetoxy-1-butene isomerization, a monoacetoxy compound such as 3-butene-1,2-diol monoacetoxylate is used. Since it is not sufficiently isomerized and accumulates in the reaction system, a recycling process cannot be constructed.
There is a problem that it is difficult to obtain a high yield,
This has been a very serious problem when the target isomerized compound is produced industrially.

As a method for solving such problems, industrially, a method of removing a monoacetoxy compound having a hydroxyl group which has not been isomerized and then performing an isomerization reaction can be considered. It has a boiling point close to that of the diacetoxy compound, and is difficult to separate by distillation. Furthermore, when the monoacetoxy form is removed by separation, since the monoacetoxy form does not participate in the isomerization reaction, there is a problem that the yield is reduced by the amount removed, and it is never satisfactory from an industrial viewpoint. I couldn't do it. Also, JP-A-47-
In Japanese Patent No. 30616, in a case where a monoacetoxy form in a mixture containing a diacetoxy form and a monoacetoxy form obtained by an acetoxylation reaction of butadiene is used as a raw material, when the isomerization reaction is performed using a sulfuric acid catalyst, the monoacetoxy form and A method is disclosed in which water is removed by reacting with acetic anhydride, followed by an isomerization reaction. However, this method requires an extremely expensive carboxylic anhydride for the target product, and is not industrially satisfactory.

An object of the present invention is to solve the above-mentioned problems and to provide a process for industrially and advantageously producing 1,4-disubstituted butene-2 or 3,4-disubstituted butene-1. is there.

[0011]

The inventors of the present invention have made intensive studies and as a result, have found that the isomerization reaction of a mixture containing a monoacetoxy form and a diacetoxy form is carried out by using a specific catalyst, whereby the reactivity is improved. It has been found that the isomerization reaction of a monoacetoxy compound containing a hydroxyl group, which was considered to be extremely low, proceeds as well as a highly reactive diacetoxy compound. It is not necessary to separate the body from the diacetoxy form or to pre-esterify the monoacetoxy form (diacetoxylation) to obtain a diacetoxy form,
The inventors have found that a recycling process can be constructed, and have completed the present invention.

That is, a first gist of the present invention is as follows:
A method for producing a 1,4-disubstituted butene-2 by a series of steps (1) to (4). (1) Butadiene is subjected to an acyloxylation reaction in the presence of a carboxylic acid and oxygen to give 3,4-diacyloxy-1-
Butene (3,4-diacyloxy) and 3-butene-1,
3,4-disubstituted butene-1 consisting of 2-diol monoacyloxylate (3,4-monoacyloxy), 1,4-diacyloxy-2-butene (1,4-diacyloxy) and 1 -Acyloxy-4-hydroxy-
1,4 consisting of 2-butene (1,4-monoacyloxy compound)
An acyloxylation reaction step for obtaining a reaction mixture containing the disubstituted butene-2, and (2) 3,4-distillation from the reaction mixture obtained in the acyloxylation reaction step by distillation.
A separation step of separating a mixture containing disubstituted butene-1 as a main component, and (3) isomerization of the mixture containing 3,4-disubstituted butene-1 as a main component separated in the above separation step to obtain a corresponding isomer. Reaction step for obtaining an isomerization reaction product containing 1,4-disubstituted butene-2 as a main component as an isomerization reaction product
(4) The recycling step includes supplying the isomerization reaction product obtained in the above isomerization reaction step to the separation step (2).

The second gist of the present invention is the following (1)
A method for producing 3,4-disubstituted butene-1 by a series of steps (1) to (4). (1) Butadiene is subjected to an acyloxylation reaction in the presence of a carboxylic acid and oxygen to give 3,4-diacyloxy-1-
Butene (3,4-diacyloxy) and 3-butene-1,
3,4-disubstituted butene-1 consisting of 2-diol monoacyloxylate (3,4-monoacyloxy), 1,4-diacyloxy-2-butene (1,4-diacyloxy) and 1 -Acyloxy-4-hydroxy-
1,4 consisting of 2-butene (1,4-monoacyloxy compound)
An acyloxylation reaction step for obtaining a reaction mixture containing -disubstituted butene-2, and (2) the reaction mixture obtained in the acyloxylation reaction step is subjected to distillation separation to obtain 1,4-disubstituted butene-2 as a main component. (3) isomerizing the mixture containing 1,4-disubstituted butene-2 as a main component, which is separated in the above-mentioned separation step, to obtain a corresponding isomerization reaction product, Reaction step for obtaining an isomerization reaction product containing 4,4-disubstituted butene-1 as a main component
(4) The recycling step includes supplying the isomerization reaction product obtained in the above isomerization reaction step to the separation step (2).

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention relates to a method for preparing a mixture (including a monoacyloxy compound and a diacyloxy compound) obtained by an acyloxylation reaction of butadiene (step (1)).
The mixture containing the 3,4-substituted or 1,4-substituted product is separated by distillation (step (2)), and then the separated mixture containing the 3,4-substituted or 1,4-substituted product is isomerized. To obtain the corresponding 1,4-substituted product or 3,4-substituted isomerized product (step (3)), and then the obtained isomerized product is recycled to the separation step (2) (step (3)). 4)).

In the acyloxylation step (1) of the present invention, butadiene is subjected to an acyloxylation reaction in the presence of a carboxylic acid and oxygen to give 3,4-diacyloxy-1-butene (3,4 -Diacyloxy) and 3
-Butene-1,2-diol monoacyloxylate (3,4-monoacyloxy form), 3,4-disubstituted butene-1, and 1,4-diacyloxy-2-butene (1,4-diene) Acyloxy body) and 1-acyloxy-4
-Hydroxy-2-butene (1,4-monoacyloxy compound)
Is a step of obtaining a reaction mixture containing 1,4-disubstituted butene-2.

Here, the carboxylic acid is a compound having 2 to 11 carbon atoms.
Fatty acids and aromatic carboxylic acids having 7 to 16 carbon atoms. Among them, acetic acid, propionic acid, butyric acid, etc. have 2 to 8 carbon atoms.
Are preferred. When this carboxylic acid is represented by R _A COOH, the reaction proceeds by replacing butadiene with an acyloxy group corresponding to the R _A (O) O— group. Examples of _RA include an alkyl group having 1 to 10 carbon atoms and an aryl group having 6 to 15 carbon atoms.
To 3 are preferred, and as R _A , a methyl group is particularly preferred.

The acyloxylation step can be performed by a known method,
For example, butadiene is carried out in the presence of a catalyst such as palladium at a temperature of usually 40 to 120 ° C., preferably 50 to 100 ° C., and a pressure of normal pressure to 20 MPa, preferably normal pressure to 10 MPa. Next, the reaction mixture obtained in the above acyloxylation reaction step is supplied to a separation step (step (2)), and is subjected to distillation separation to obtain a mixture or a mixture mainly containing 3,4-disubstituted butene-1. , 4-disubstituted butene-2 as a main component. When 1,4-diacyloxy-2-butene is obtained as the target product, in this separation step (2), a mixture containing 3,4-disubstituted butene-1 as a main component is separated, and this is separated into the following compound. Feed to the diacyloxylation step. On the other hand, when obtaining 3,4-diacyloxy-1-butene as the target product, in this separation step (2), a mixture containing 1,4-disubstituted butene-2 as a main component is separated, and this is separated. It is fed to the next diacyloxylation step.

The distillation conditions in this distillation separation step are generally such that a distillation column having 5 to 100 theoretical plates is used, and the distillation is carried out at a bottom temperature of 100 to 240 ° C. In addition, this distillation operation is, for example, to distill and separate a high-boiling product after distilling and separating a product having a lower boiling point than the target product.
A plurality of distillation columns may be combined. Further, a facility for separating unreacted butadiene may be provided before the separation step (2). 3, 4 obtained by the above separation step (2)
A mixture containing 1,2-disubstituted butene-1 or 1,4-
The mixture containing disubstituted butene-2 as a main component contains a monoacyloxy compound and a diacyloxy compound, respectively. For example, in the case of 3,4-disubstituted butene-1,
3,4-diacyloxy-1-butene (3,4-diacyloxy form) and 3-butene-1,2-diol monoacyloxylate (3,4-monoacyloxy form) are included. In the case of -disubstituted butene-2, 1,4-diacyloxy-2-butene (1,4-diacyloxy) and 1-acyloxy-4-hydroxy-2-butene (1,1
4-monoacyloxy).

The mixture obtained in the separation step (2) is
Then, it is subjected to an isomerization reaction step (step (3)),
Diacyloxy-1-butene (3,4-diacyloxy form)
And 3,4-disubstituted butene-2 containing 3-butene-1,2-diol monoacyloxylate (3,4-monoacyloxy) are the corresponding isomers, 1,4-diacyloxy-2- It isomerized to 1,4-disubstituted butene-2, including butene (1,4-diacyloxy) and 1-acyloxy-4-hydroxy-2-butene (1,4-monoacyloxy).

The above-mentioned isomerization reaction, for example, by isomerization of 3,4-diacyloxybutene-1 and 3-butene-1,2-diol monoacyloxylate, 1,4-diacetoxybutene-2 and 1-acyloxy- The reaction to obtain 4-hydroxy-2-butene is an equilibrium reaction, and the reaction ends when the equilibrium concentration is reached. This means that
When 1,4-diacetoxybutene-2 and 1-acyloxy-4-hydroxy-2-butene are used as raw materials, 3,4-diacetoxybutene-1 and 3-butene-1 are obtained by the same equilibrium reaction. , 2-diol monoacyloxylate can be produced.

For example, in the present invention, the reaction for obtaining 1,4-diacetoxybutene-2 by isomerization of 3,4-diacetoxybutene-1 is an equilibrium reaction. It contains ６５65 mol% of 1,4-diacetoxybutene-2 and 35-40 mol% of 3,4-diacetoxybutene-1. The molar ratio of 1,4-diacetoxybutene-2 to 3,4-diacetoxybutene-1 in the product obtained by the isomerization reaction is usually from 90:10 to 10:90, Within that range, 80:20, 70:30, 60:40, 50:50, 4
Products in any ratio, such as 0:60, 30:70, 20:80, can be produced. This ratio is not particularly limited, but can be adjusted according to the reaction conditions and the economics of the process.

In the present invention, the conversion rate Xm of the monoacetoxyl form is desirably not less than the conversion rate Xd of the diacetoxyl form. However, it is not always necessary that Xm> Xd, and if a certain Xm / Xd ratio can be achieved, accumulation in the system can be avoided by a technique such as distillation conditions or partial purging of the recycle liquid. This Xm /
The Xd ratio is 0.5 or more, preferably 0.8 or more, and more preferably 1.0 or more. The isomerization catalyst used in the isomerization reaction of the present invention is not particularly limited, but may be any of Groups 8 to 10 of the periodic table (IUPAC Inorganic Chemical Nomenclature Revised Edition (198
Those containing the metal compound and the organic phosphorus compound of 9)) are preferred. Examples of the metal compound include iron, cobalt,
Nickel, ruthenium, rhodium, platinum, iridium,
One or more compounds selected from the compounds of osmium and palladium may be mentioned, and among these, nickel, palladium and platinum compounds are more preferred, and palladium compounds are particularly preferred.

The metal compound may be, for example, an acetate,
Tilacetonate, halide, sulfate, nitrate, organic
Salt, inorganic salt, alkene compound, amine compound, pyridine
Compound, phosphine coordination compound, phosphite coordination compound
Objects and the like. As ruthenium compounds, RuC
l_Three, Ru (OAc)_Three, Ru (acac) _Three, RuCl_Two
(PPh_Three)_ThreeAnd the like, and as the osmium compound
Is OsCl _Three, Os (OAc)_ThreeAnd lojiu
Rh compounds include RhCl_Three, Rh (OAc)_Three, Logi
Um diacetate dimer, Rh (acac) (CO)_Two, [Rh
(OAc) (COD)]_Two, [RhCl (COD)]_Two,
Rh (COD) OAc and the like.

As the iridium compound, IrC
l_Three, Ir (OAc)_ThreeAnd the like, and a nickel compound
The NiCl_Two, NiBr_Two, Ni (NO_Three)_Two, Ni
SO _Four, Ni (COD)_Two, NiCl_Two(PPh_Three)_TwoEtc.
No. As the palladium compound, for example, Pd
(0) or PdCl_Two, PdBr_Two, PdCl_Two (CO
D), PdCl_Two (PPh_Three )_Two , Pd (PPh_Three)_Four,
Pd_Two(Dba)_Three・ CHCl_Three, K_TwoPdCl_Four, K_TwoPd
Cl₆(Potassium hexachloropalladate (IV)), PdC
l_Two(PhCN)_Two, PdCl_Two(CH_ThreeCN)_Two, Pd
(Dba)_Two, Pd_Two(Dba)_Three, Pd (NO_Three )_Two,
Pd (OAc)_Two , Pd (CF_ThreeCOO)_Two, PdS
O_Four, Pd (acac)_Two , A carboxylate compound,
Olefin-containing compound, Pd (PPh_Three)_FourOrganic phos such as
Fin-containing compound, allyl palladium chloride dimer
And Pd (OAc)
_Two , PdCl_TwoCarboxylate compound of palladium
Or halides are preferred. As a platinum compound,
Pt (acac)_Two, PtCl_Two(COD), PtCl_Two
(CH_ThreeCN)_Two, PtCl_Two(PhCN)_Two, Pt (PP
h_Three)_Four, K_TwoPtCl_Four, Na_TwoPtCl₆, H_TwoPtCl₆
And the like. (Where COD: cyclopentadie
, Dba: dibenzylideneacetone, acac: acetyl
Represents acetonate. In the present invention, in particular, the above-mentioned metal compound forms
Without limitation, active metal complex species are monomers, dimers and / or
Alternatively, it may be a multimer.

The amount of the metal compound used is not particularly limited, but from the viewpoint of catalytic activity and economic efficiency, it is 1 × 10 ⁻⁸ (0.01 mol ppm) to 1 × 10 ⁻⁸ (0.01 mol ppm) with respect to 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 organic phosphorus compound used in the isomerization reaction of the present invention is not particularly limited, but includes phosphines, phosphites, phosphonites, phosphinites, etc., and these are monodentate or polydentate. Although phosphites are preferable among them. Preferred phosphite compounds have the following general formulas (I), (II), (III),
It is at least one of the compounds represented by (IV), (V) and (VI).

[0027]

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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, and preferably 1 to 20; 1 to 14. Specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group,
t-butyl group, hexyl group, octyl group, decyl group and the like. Further, the alkyl group or the alkyl skeleton portion may further have a substituent, and the substituent may have 1 to 1 carbon atoms.
Examples thereof include an alkoxy group having 10 carbon atoms, 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 or a substituent having an aryl skeleton is used as R ^{10 to} R ²¹ , 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).

[0031]

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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. To 30 arylene groups or a diarylene group which may have a divalent linking group in the middle of -Ar ^1- (Q 1) n -Ar ^2-
r1 and Ar ² each independently represent an arylene group having 6 to 18 carbon atoms which may have a substituent. ). 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.

When Z ^{1 to} Z ⁴ or A ^{1 to} A ³ is an alkylene group, specific examples thereof include, for example, a tetramethylethylene group and a dimethylpropylene group. In the case of an alkylene group, the substituent may be an alkoxy group having 1 to 10 carbon atoms, 6 to 10 carbon atoms.
An aryl group, an amino group, a cyano group, an amide group, a nitro group, a trifluoromethyl group, a trimethylsilyl group, an ester group having 3 to 10 carbon atoms, a hydroxy group and a halogen atom.

When Z ^{1 to} Z ⁴ or A ^{1 to} A ³ is an arylene group which may have a substituent, specific examples thereof include a phenylene group and a naphthylene group. Examples of the substituent include an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an amino group, a cyano group, an ester group having 2 to 10 carbon atoms, an amide group, Examples include a nitro group, a trifluoromethyl group, a trimethylsilyl group, a hydroxy group, and a halogen atom.

Further, when Z ^{1 to} Z ⁴ or A ^{1 to} A ³ are —Ar ¹ —
In the case of a diarylene group which may have a divalent linking group in the middle of (Q) n -Ar ^2- , Ar ¹ and Ar ² are an arylene group which may have a substituent, and 6 ~
24, more preferably 6 to 16, and specific examples of preferred substituents include an alkyl group having 1 to 10 carbon atoms and 1 to 1 carbon atoms.
Examples include an alkoxy group having 10 carbon atoms, 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.

A¹~ A^ThreeAnd Z¹~ Z^FourAs a specific example of
Is-(CH_Two)_Two -,-(CH _Two )_Three -,-(CH
_Two)_Four -,-(CH_Two )_Five -,-(CH_Two )₆ -, -C
H (CH_Three ) -CH (CH_Three)-, -CH (CH_Three) C
H_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).
You. (A-47) is also a specific example of A1 to A3.
I can do it.

[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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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).

[0044]

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[0045]

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[0046]

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

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[0048]

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[0049]

Embedded image Specific examples of phosphines include triphenylphosphine, tri (n-butyl) phosphine, tri (t-butyl) phosphine, diphenylphosphinoethane, diphenylphosphinomethane, diphenylphosphinopropane, diphenylphosphinobutane, and the following: (13)-
(20) can be exemplified.

[0050]

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

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[0052]

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[0053]

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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.

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 an organic phosphorus, 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. The amount of acetic acid present is usually 5: 1 to 1: 1000, preferably 5: 1 to 1: 1000, in terms of catalytic activity, catalyst stability and economic efficiency, in terms of the total amount (weight ratio) of acetic acid: the allyl raw material compound as the raw material. , 4: 1
1: 100, more preferably within the range of 2: 1 to 1:10.

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, for example, carboxylic acids such as acetic acid, alcohols such as methanol, diglyme, diphenyl ether, dibenzyl ether, tetrahydrofuran (THF),
Ethers such as dioxane, N-methylpyrrolidone (NM
P), amides such as dimethylformamide (DMF) and dimethylacetamide, ketones such as cyclohexanone, esters such as butyl acetate, γ-butyrolactone, di (n-octyl) phthalate, and fragrances such as toluene, xylene and dodecylbenzene Examples include aromatic hydrocarbons, high-boiling substances generated as by-products in the isomerization reaction system, and allyl compounds themselves as raw materials. Among them, acetic acid is preferred in that it promotes the isomerization reaction.

The amount of these solvents used 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.
Weight times. 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-acetoxybutane-2-
On, 4-acetoxybutanal, 4-acetoxycyclotonaldehyde, diacetoxybutane, acetoxyhydroxybutane, butanediol, 1,4-butenediol,
One or more compounds (C) selected from 1,2-butenediol, 1-acetoxy-1,3-butadiene and diacetoxyoctadiene may be present.

In the isomerization reaction system, these compounds (C) are usually in a weight ratio of (compound (C): allyl compound) to the total amount of the allyl compound as a raw material in a ratio of 1: 1:
1-1: 10000, preferably 5: 1 to 1: 100
0, more preferably from 2: 1 to 1: 500, particularly preferably 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 rate is higher. Extremely large amounts of energy are required to completely exclude water from water. Therefore, industrially, the amount of water present in the isomerization reaction mixture is preferably 0.1 to 5% by weight, more preferably 0.5 to 2% by weight.
It is. Water can enter the reaction system from various routes,
Among them, a 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.

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 carried out in a batch system will be described. The catalyst component is dissolved in a solvent and, for example, 3,4-diacyloxybutene-1 is added thereto.
And a raw material containing 3-butene-1,2-diol monoacyloxylate are introduced and brought into contact with the catalyst under stirring for a sufficient conversion time.

In the case of performing the reaction continuously, a raw material containing, for example, 3,4-diacyloxybutene-1 and 3-butene-1,2-diol monoacyloxylate and a catalyst component are continuously supplied to a reaction vessel, A method in which a reaction solution containing the isomerized product as the target product is continuously extracted and then distilled, and a residual solution containing the catalyst component is continuously circulated to the reaction system and reused is considered.

The reaction temperature for the isomerization is usually 50 to 200.
C., preferably 80 to 160 ° C. In the present invention, in order to increase the isomerization efficiency of the monoacyloxy compound, the reaction temperature is set to 90 to 150 ° C., more preferably 100 to 140 ° C.
The temperature is preferably in the range of ° C. 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 product obtained in the isomerization reaction step (step (4)) is, if necessary, separated by distillation of acetic acid or acetic acid and water, and then recycled to the above-mentioned separation step (step (2)). As a result, the yield of the target product can be improved. Here, as a method of recycling the isomerization reaction product, it may be supplied to the reaction mixture stream obtained in the acyloxylation reaction step (1) supplied to the separation step (2),
The reaction mixture stream may be supplied to the separation step (2) independently. Above all, adopting a method of recycling the isomerization reaction product to the separation step (step (2)) can reduce the number of distillation columns and advantageously reduce the isomer abundance ratio in the isomerization reactor. It is preferable in that it can be performed.

FIG. 1 shows that following the acetoxylation reaction of butadiene, 3,4-disubstituted-1-butene isomerized to give 1,4
FIG. 1 illustrates a series of processes of the present invention, taking as an example the process of disubstituted-1-butene. The substance described in each flow represents a main component, and other substances may be mixed. FIG. 1 is a representative example, and the process described below may be used. 1) D1 and D2 may be a single distillation column or a combination of a plurality of separation columns. 2) In D2, (7) and (8) may be extracted as the same flow, and the 1,4-disubstituted-2-butene and the high-boiling component may be separated separately. 3) In D3, after extracting the reaction solution from (16) following (14), the disubstituted butenes, the high-boiling components and the catalyst are separated separately, and the disubstituted butenes are separated into (17) and / or (18). The disubstituted butenes may be recycled from (15) to (17) and / or (18) by separation at D3, and the high boiling components and catalyst may be withdrawn from (16) following (14). Is also good. 4) (14) may be recycled to (17) and / or (18). In that case, a part may be extracted from (16).

[0065]

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. Abbreviations used in the following examples are shown below. 3,4-DABE: 3,4-diacetoxybutene-1,3,4-HABE: 3-butene-1,2-diol monoacetoxylate 1,4-DABE: 1,4-diacetoxybutene-2 1, 4-HABE: 1-acyloxy-4-hydroxy-2-butene Further, as the phosphite compound used in the isomerization reaction step, the above-mentioned (P1) to (P21) are used, and all reactions using phosphite are used. Was performed under a nitrogen atmosphere.

Example Using the process shown in FIG. 1, 1,4-diacetoxy-2-butene and 3,4-diacetoxy-1-butene were produced from butadiene. (Acetoxylation reaction step (1) and separation step (2)) Pd-T
e, butadiene, acetic acid, 6% oxygen / 94 in the presence of a catalyst.
% Nitrogen mixed gas and acetoxylation reaction at 80 ° C. and 6 MPa to give 1,4-DABE 80 mol%, 3,4-DABE
A mixture containing 9 mol%, 3,4-HABE 3 mol% and acetic acid 7 mol% was obtained, and 5.0 kg of this mixture was distilled using a 30-stage distillation column. The pressure is maintained at 80 mmHg and the maximum temperature at the bottom is 170
° C. With a reflux ratio of 15, the top temperature is 130-140 ° C
In the temperature range of 450-500 g of distillate were obtained. The distillate contained 73 mol% of 3,4-DABE, 22 mol% of 3,4-HABE, and 5 mol% of other components. (Isomerization reaction step (3)) P 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 (P9) were dissolved at 120 ° C. Then, 5 μl of this solution was mixed with 78 mol% of 3,4-DABE and 3,4-HA
1 ml (6.5 mmol) of a solution consisting of 22 mol% BE and acetic acid (1 m
l) and the mixture was reacted at 120 ° C. for 1 hour. Analysis of the reaction product showed that 21 mol% of 1,4-isomer (1,4-DABE 18 mol% and 1,4-HABE 3 mol%)
And 79 mol% of the 3,4-isomer (64 mol% of 3,4-DABE and 3,4-
HABE 15 mol%), and the ratio of the conversion rate Xm of the monoacetoxy form to the conversion rate Xd of the diacetoxy form is Xm / Xd
= 1.78. No Pd metal was deposited in the reaction system.

(Recycling Step (4)) From the reaction product obtained in the isomerization reaction step, the number of theoretical plates is 5, the reflux ratio is 2, the top pressure is 100 mmHg, and the bottom temperature is 150 to 160.
The bottoms containing 3,4-DABE and 1,4-DABE obtained by distilling off water and acetic acid from the top of the column by distillation under the condition of ° C. were added to a part of the product of the acetoxylation reaction described above. The obtained mixture was subjected to distillation separation under the same conditions as in the above-mentioned separation step (2). As a result, a distillate containing the 3,4-isomer as a main component could be obtained in the same manner as in the separation step (2).

[0068]

By employing a series of steps of the present invention, 3,4-disubstituted butene-1 or 1,4-disubstituted butene-2 in a product solution obtained by the acyloxylation reaction of butadiene can be obtained. To produce 1,4-disubstituted butene-2 or 3,4-disubstituted butene-1 by industrially advantageous isomerization at a high conversion rate and high selectivity and while suppressing metal precipitation. Can be.

[Brief description of the drawings]

FIG. 1 is a diagram showing an example of a series of processes of the present invention.

[Explanation of symbols]

3,4-DABE 3,4-diacetoxy-1-butene 3,4-HABE 1-butene-3,4-diol monoacetate 1,4-DABE 1,4-diacetoxy-2-butene 1,4-HABE 1 -Acetoxy-4-hydroxy-2-butene BD 1,3-butadiene O ₂ oxygen AcOH acetic acid (AcO) ₂ O Acetic anhydride Cat Catalyst L. B. Low boiling point mixture H. B. High boiling component mixture (1) to (18) Number of each flow R1 Butadiene acetoxylation reactor (acyloxylation step (1)) R2 isomerization reactor (isomerization step (3)) D1 Low from acetoxylation reaction liquid Distillation column for separating boiling and high boiling components D2 Distillation column for separating 3,4-disubstituted-1-butene and 1,4-disubstituted-2-butene (separation step (2)) D3 From isomerization reaction solution Distillation tower for separating acetic acid and water

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C07C 43/10 C07C 43/10 69/16 69/16 C07D 307/08 C07D 307/08 // C07B 61 / 00 300 C07B 61/00 300 F term (reference) 4C037 BA04 4H006 AA02 AC27 AC29 AC41 AC43 AC48 AD11 BA21 BA23 BA24 BA25 BA26 BA50 BA53 BD32 BD53 BD70 FE11 FG28 GP01 KA12 KA30 4H039 CA66 CJ10

Claims (11)

[Claims] 1. A series of steps (1) to (4) described below,
A method for producing 4-disubstituted butene-2. (1) Butadiene is subjected to an acyloxylation reaction in the presence of a carboxylic acid and oxygen to give 3,4-diacyloxy-1-
Butene (3,4-diacyloxy) and 3-butene-1,
3,4-disubstituted butene-1 consisting of 2-diol monoacyloxylate (3,4-monoacyloxy), 1,4-diacyloxy-2-butene (1,4-diacyloxy) and 1 -Acyloxy-4-hydroxy-
1,4 consisting of 2-butene (1,4-monoacyloxy compound)
An acyloxylation reaction step for obtaining a reaction mixture containing the disubstituted butene-2, and (2) 3,4-distillation from the reaction mixture obtained in the acyloxylation reaction step by distillation.
A separation step of separating a mixture containing disubstituted butene-1 as a main component, and (3) isomerization of the mixture containing 3,4-disubstituted butene-1 as a main component separated in the above separation step to obtain a corresponding isomer. Reaction step for obtaining an isomerization reaction product containing 1,4-disubstituted butene-2 as a main component as an isomerization reaction product
(4) Recycling step of supplying the isomerization reaction product obtained in the above isomerization reaction step to the separation step (2) 2. A process according to the following steps (1) to (4):
A method for producing 4-disubstituted butene-1. (1) Butadiene is subjected to an acyloxylation reaction in the presence of a carboxylic acid and oxygen to give 3,4-diacyloxy-1-
Butene (3,4-diacyloxy) and 3-butene-1,
3,4-disubstituted butene-1 consisting of 2-diol monoacyloxylate (3,4-monoacyloxy), 1,4-diacyloxy-2-butene (1,4-diacyloxy) and 1 -Acyloxy-4-hydroxy-
1,4 consisting of 2-butene (1,4-monoacyloxy compound)
(2) an acyloxylation reaction step for obtaining a reaction mixture containing the disubstituted butene-2, and (2) the reaction mixture obtained in the acyloxylation reaction step is subjected to distillation separation to obtain 1,4-disubstituted butene-2 as a main component. And (3) isomerizing the mixture containing 1,4-disubstituted butene-2 as a main component, which is separated in the above separation step, to obtain a corresponding isomerization reaction product, Reaction step for obtaining an isomerization reaction product containing 4,4-disubstituted butene-1 as a main component
(4) Recycling step of supplying the isomerization reaction product obtained in the above isomerization reaction step to separation step (2) 3. In the isomerization reaction step, the eighth table in the synchronization table is used.
The production method according to claim 1, wherein the isomerization reaction is performed in the presence of a catalyst containing a metal compound belonging to Group 10 to 10 and an organic phosphorus compound. 4. The method according to claim 1, wherein acetic acid or a mixture obtained after separating acetic acid and water from the isomerization reaction product obtained in the isomerization reaction step is recycled to the separation step (step (2)). 3. The production method according to any one of 3. Wherein the carboxylic acid is represented by R _A COOH, an acyloxy group is represented by _{R A C (O) O-,} R A is an alkyl group or an aryl group having from 6 to 15 carbon atoms having 1 to 10 carbon atoms The method according to claim 1, wherein 6. The method according to claim 5, wherein the carboxylic acid is acetic acid and the acyloxy group is an acetoxy group. 7. The method according to claim 1, wherein the isomerization reaction is carried out in a temperature range of 80 to 140 ° C. 8. The process according to claim 1, wherein the isomerization reaction is carried out under the condition that the value obtained by dividing the conversion of the monoacyloxy compound by the conversion of the diacyloxy compound is 0.5 or more. 9. The 1,4-obtained by the method of claim 1
The disubstituted butene-2 is 1,4-diacetoxybutene-2, and the 1,4-diacetoxybutene-2 is further hydrogenated and hydrolyzed to produce 1,4-butanediol and / or tetrahydrofuran how to. 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 10.