KR20100019430A - Method for isomerizing allyl compound - Google Patents

Abstract

Disclosed is a commercially advantageous method for isomerizing an allyl compound using a catalyst, which enables to obtain an isomer with high yield with use of a small amount of catalyst by suppressing deterioration of the catalyst. Specifically disclosed is a method for isomerizing a raw material allyl compound into a corresponding allyl compound in the presence of a catalyst. This isomerization method is characterized in that a liquid containing the raw material allyl compound is brought into contact with an organophosphorus compound before isomerization by the catalyst.

Description

Isomerization method of allyl compound {METHOD FOR ISOMERIZING ALLYL COMPOUND}

The present invention relates to a method for isomerizing an allyl compound, and more particularly, to generate a 1,4-diacetoxy allyl compound, which is a corresponding compound, from a 3,4-diacetoxy allyl compound by isomerization. It relates to an isomerization method.

Allyl compounds are important starting materials for organic synthetic chemistry, and are converted into the desired products by various reactions. In particular, diacetoxy allyl compounds are not only compounds that can be converted into various substances because of their characteristic skeleton, but also hydrolysis. It is an important intermediate capable of producing diols. Therefore, the manufacturing process of various diacetoxy allyl compounds has been developed. For example, the manufacturing method of the diacetoxy allyl compound by the diacetoxylation reaction of butadiene using a rhodium solid catalyst is reported (patent document 1). Although the diacetoxylation reaction of conjugated dienes for producing a diacetoxy allyl compound often proceeds in a good yield in the presence of a solid catalyst, it is a present situation that the position given by an acetoxy group cannot be fully controlled. In 1, 4- diacetoxy 2-butene reaction which becomes a raw material of 1, 4- butanediol especially, 3, 4- diacetoxy 1-butene which cannot be converted into 1, 4- butanediol will by-produce. . Therefore, in the 1,4-butanediol manufacturing process, the cost of butadiene which is a raw material was raised.

Therefore, the method of isomerizing this by-product 3, 4- diacetoxy 1-butene and producing 1, 4- diacetoxy allyl compounds, such as 1, 4- diacetoxy 2-butene, has been developed. For example, isomerization of 3,4-diacetoxy-1-butene to 1,4-diacetoxy-2-butene has been reported using a palladium complex catalyst having a phosphite ligand (Patent Document 2). ). In addition, in addition to the palladium complex catalyst and the phosphite ligand, a more active isomerization catalyst has been reported by adding a phosphonium compound (Patent Document 3). However, in the isomerization method of these diacetoxy allyl compounds, catalyst deterioration was remarkable and it was necessary to use a large amount of catalyst.

As a cause of this catalyst deterioration, the catalyst deterioration component contained in a diacetoxy allyl compound can be considered, and the method of removing this catalyst deterioration component using a solid base is reported (patent document 4). However, in this method, since the solid base adsorbs several acidic components in addition to the catalyst deterioration component, a large amount of solid base is required, which is industrially advantageous and can efficiently remove or harm the catalyst deterioration component. There has been a demand.

Patent Document 1: Japanese Patent Application Laid-Open No. 11-71327

Patent Document 2: Japanese Unexamined Patent Publication No. 2002-105025

Patent Document 3: Japanese Unexamined Patent Publication No. 2004-115506

Patent Document 4: Japanese Unexamined Patent Publication No. 2006-282564

Disclosure of Invention

Problems to be Solved by the Invention

SUMMARY OF THE INVENTION An object of the present invention is to provide an isomerization method of an allyl compound which is industrially advantageous in the method for isomerizing an allyl compound using a catalyst, thereby suppressing catalyst deterioration and obtaining an isomer in a high yield with a small amount of catalyst. .

Means to solve the problem

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, the present inventors discovered that the component which remarkably accelerates the deterioration of the isomerization catalyst contained in the diacetoxy allyl compound liquid can be removed by the phosphorus compound, and completed this invention. I came to let it. That is, the summary of this invention exists in the following [1]-[13].

[1] An isomerization method characterized by isomerizing the allyl compound in the presence of a catalyst after contacting a liquid containing an allyl compound as a raw material with a phosphorus compound.

[2] The isomerization method according to the above [1], wherein the phosphorus compound is an organic phosphorus compound.

[3] The isomerization method according to the above [2], wherein the organophosphorus compound is an organic phosphine.

[4] The isomerization method according to the above [3], wherein the organic phosphines have two or more aryl groups.

[5] The isomerization method according to the above [3] or [4], wherein the organic phosphines are triphenylphosphine.

[6] The isomerization method according to any one of the above [1] to [5], wherein the amount of the phosphorus compound to be brought into contact with the containing liquid of the allyl compound is in the range of 0.0001 to 10% by weight relative to the allyl compound.

[7] The isomerization method according to any one of [1] to [6], in which the contact between the liquid containing the allyl compound and the phosphorus compound is performed at 60 ° C or higher.

[8] The isomerization method according to any one of the above [1] to [7], further comprising the step of obtaining a liquid containing the allyl compound by a diacetoxylation reaction of conjugated dienes.

[9] The isomerization method according to any one of [1] to [8], wherein the catalyst is a liquid homogeneous palladium catalyst and contains a phosphorus ligand having at least one P-O bond.

[10] The isomerization method according to the above [9], wherein the phosphorus ligand having a P-O bond is a bidentate phosphite.

[11] The isomerization method according to the above [9], wherein the phosphorus ligand having a P-O bond is a bidentate phosphoramidite.

[12] The above-mentioned [1]-, wherein the allyl compound is a 3,4-diacetoxyallyl compound, and isomerization produces a 1,4-diacetoxyallyl compound that is a compound corresponding to the allyl compound. Isomerization method in any one of [11].

[13] A method for producing an allyl compound, wherein the corresponding isomerized allyl compound is produced from the allyl compound using the isomerization method according to any one of the above [1] to [12].

Effects of the Invention

According to the present invention, in the isomerization of a diacetoxy allyl compound using a catalyst, an isomer can be obtained in a high yield by using a small amount of the catalyst.

Best Mode for Carrying Out the Invention

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail. Description of the component requirements described below is an example of embodiment of this invention, and is not specified in these content.

In addition, the allyl compound in this invention is a compound produced | generated by isomerization using a catalyst from the compound which has an allyl group, and the compound which has an allyl group, and an allyl position, such as an acetoxy group, a halogen, a carboxylic acid, is carried out at the allyl position in the substance. All of them having a leaving group are targeted and are not particularly limited. For example, the compound obtained by isomerizing a 3, 4- diacetoxy allyl compound is made into a 1, 4- diacetoxy allyl compound in this invention.

Moreover, the isomerization method in this invention also includes the method of converting the compound which the compound which has an allyl group produces | generates by isomerization into the compound which has an allyl group.

In the following embodiment, the case where the 1, 4- diacetoxy allyl compound which is a corresponding allyl compound is produced by isomerizing the 3, 4- diacetoxy allyl compound which is an allyl compound is demonstrated to an example.

As for "the method of isomerizing a 3, 4- diacetoxy allyl compound with a 1, 4- diacetoxy allyl compound" of this invention, a 1, 4- diacetoxy allyl compound which is a raw material by a catalyst is used. In the method of isomerizing with a cethoxyallyl compound, after contacting the liquid containing a 3, 4- diacetoxy allyl compound of a raw material (henceforth a 3, 4- diacetoxy allyl compound containing liquid) with a phosphorus compound, And isomerizing the 3,4-diacetoxyallyl compound as a raw material in the presence of a catalyst.

By contacting a phosphorus compound with a 3, 4- diacetoxy allyl compound containing liquid, the component which remarkably accelerates deterioration of an isomerization catalyst can be removed by a phosphorus compound. Compared with the solid base, the phosphorus compound is easy to change the amount of addition during the operation of the process, and thus the catalyst deterioration can be suppressed at the minimum necessary amount while monitoring the amount of 1,4-diacetoxyallyl compound produced by isomerization. Can be. In addition, like the solid base, it is not necessary to charge a predetermined amount of the solid base before the start of the process operation, so that the amount to be used is also minimal.

As a "method of isomerizing a 3,4-diacetoxy allyl compound to a 1,4- diacetoxy allyl compound with a catalyst", for example, "a 3,4- diacetoxy allyl compound is brought into contact with a catalyst, Isomerization with a, 4-diacetoxy allyl compound to obtain a 1,4-diacetoxy allyl compound "," A mixture of a 3, 4- diacetoxy allyl compound and a 1, 4- diacetoxy allyl compound is catalyzed And isomerizing the 3,4-diacetoxyallyl compound in the mixture to a 1,4-diacetoxyallyl compound to increase the concentration of the 1,4-diacetoxyallyl compound ”, or“ 3,4- A mixture of a diacetoxy allyl compound and a 1,4-diacetoxy allyl compound is contacted with a catalyst to isomerize the 1,4-diacetoxy allyl compound in the mixture to a 3,4-diacetoxy allyl compound, and 3,4 -The method of raising the density | concentration of a diacetoxy allyl compound. "

The 3,4-diacetoxy allyl compound (including a "mixture of a 3,4-diacetoxy allyl compound and a 1,4-diacetoxy allyl compound") in the present invention is not particularly limited, but a catalyst It can be manufactured by diacetization reaction of conjugated dienes, etc. in the presence of.

The diacetoxyation reaction of conjugated dienes to prepare a diacetoxy allyl compound can be carried out by various methods. Most commonly, butadiene, acetic acid and oxygen are reacted in the presence of a palladium-based catalyst to obtain diacetoxy allyl compounds 1,4-diacetoxy-2-butene and 3,4-diacetoxy-1-butene Can be. Furthermore, 1-hydroxy-4-acetoxy-2-butene, 3-hydroxy-4-acetoxy-1-butene and 4-hydroxy-3-acetoxy- which are hydrolyzates of these diacetoxy allyl compounds 1-butene and the like are also produced.

As conjugated dienes which can be used in the present invention, for example, butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-cyclohexadiene, 1,3-cyclopentadiene, 1,3- Cycloheptadiene, 1,3-cyclooctadiene, 1,3-pentadiene, 1,3-hexadiene, 2,4-hexadiene, etc. are mentioned, Preferably butadiene, isoprene, 1, 3-cyclo Hexadiene, 1,3-cyclopentadiene, and particularly preferably butadiene and isoprene. This is why it is preferable that conjugated dienes having a low carbon number such as butadiene and isoprene exhibit the highest reaction activity.

As a catalyst used for the deacetization reaction of conjugated dienes, any catalyst having a capability of converting conjugated dienes into a diacetoxy allyl compound can be used, but preferably contains a Group 8 to 10 transition metal. It is a solid catalyst, Especially preferably, it is a palladium solid catalyst. The palladium solid catalyst is composed of a palladium metal or a salt thereof, and the use of a metal such as bismuth, selenium, antimony, tellurium, copper, or a salt thereof as the promoter is preferred, and particularly preferably tellurium. The combination of palladium and tellurium is preferred because of its high catalytic activity and the high selectivity of the diacetoxyallyl compound obtained. Therefore, it is preferable that it is a solid catalyst which carries palladium and tellurium as an active component. Although the palladium solid catalyst is not specifically limited, It is preferable to use it, being supported by support | carriers, such as a silica, alumina, titania, zirconia, activated carbon, and graphite, Especially preferably, it is a silica excellent in strength. As a physical property of a support | carrier, a porous is preferable, The porous which especially the average pore diameter is 1-100 nm is preferable, and the porous which is 5-80 nm is more preferable. In the case of the catalyst supported on the carrier, the ratio of the catalyst metal to the whole catalyst is usually 0.1 to 20% by weight, preferably 1 to 10% by weight, and the ratio of other promoter metal to the catalyst as a whole is 0.01 to 30% by weight. More preferably, it is selected in the range of 0.1-10 weight%. When this value is too small, the cost competitiveness by the fall of catalyst activity will fall, and when this value is too large, the competitiveness by deepening of catalyst cost will fall.

The diacetoxylation reaction is preferably carried out in air, oxygen-enriched air, air diluted with an inert gas such as nitrogen or oxygen, or in an oxygen atmosphere, and the oxygen concentration is in the range of 1 to 100 vol%. More preferably, it is 2-50 vol%, Especially preferably, it is 3-40 vol%. The higher the oxygen concentration, the faster the reaction rate, so that the product can be efficiently obtained. On the other hand, the lower the oxygen concentration, the lower the risk of processes such as explosion and fire.

The diacetoxyation reaction can be carried out either in the gas phase or in the liquid phase. Reaction temperature is the range of 0-300 degreeC, Preferably it is 10-250 degreeC, More preferably, it is the range of 30-200 degreeC. The higher the reaction temperature, the faster the reaction rate, and the product can be efficiently obtained. On the other hand, the lower the reaction temperature, the lower the risk of processes such as explosion and fire. The reaction pressure is preferably in the range of atmospheric pressure to 50 MPa, more preferably atmospheric pressure to 30 MPa, particularly preferably 1 to 20 MPa.

In the case of carrying out the diacetoxylation reaction in a liquid phase, the solvent used for the reaction is not particularly limited as long as it dissolves the reaction raw materials, but conjugated dienes per se that are used as reaction raw materials such as water or acetic acid, or butadiene Or the diacetoxy allyl compound itself which is a product is preferable. Moreover, as a solvent, Hydrocarbons, such as hexane, heptane, an octane; Ethers such as tetrahydrofuran, diethyl ether and triglyme; Esters such as ethyl acetate and butyl butyrate; Ketones such as acetone and methyl isobutyl ketone; Alcohol, such as 1, 4- butanediol, can also be used.

The weight ratio of the conjugated dienes to be a raw material and the catalyst is preferably in the range of 1 to 100,000,000, more preferably in the range of 10 to 50,000,000, and particularly preferably 100 to 20,000,000. The smaller the weight ratio, the faster the reaction rate, and the reaction is likely to proceed in a short time. Further, the larger the weight ratio, the lower the catalyst cost.

In addition, as a "3, 4- diacetoxy allyl compound containing liquid" in this invention, a 3, 4- diacetoxy allyl compound or a 3, 4- diacetoxy allyl compound and a 1, 4- diace It will not specifically limit, if it is a liquid containing the mixture of a methoxyallyl compound. For example, (1) before contacting a 3, 4- diacetoxy allyl compound containing liquid with a phosphorus compound, the process of carrying out the diacetoxy reaction of the conjugated dienes by the said catalyst is formed, and the reaction products obtained therefrom (2) Compounds having a light boiling point than diacetoxy allyl compounds produced as by-products from the reaction products thereof (hereinafter, compounds having a boiling point more than diacetoxy allyl compounds are abbreviated as nascent point compounds) Part or all of which is removed by distillation or the like, (3) a compound having a higher boiling point than the 3,4-diacetoxy allyl compound produced as a by-product from the reaction products (hereinafter, 3,4-diacetoxy allyl A part or whole amount of a compound having a higher boiling point than the compound is abbreviated as a high boiling point compound) by distillation or the like; (4) a high-boiling point compound and a high boiling point compound which are by-products from the reaction products; Which of the two sides of the distribution will be removed by the part or total amount of distillation or the like is preferably set to "3, 4-diacetoxy-allyl-compound-containing liquid". Especially, (1) It is especially preferable to make the reaction products themselves obtained by the diacetization reaction of the conjugated diene by the catalyst as "3, 4- diacetoxy allyl compound containing liquid". When the "3,4-diacetoxy allyl compound containing liquid" is derived from the reaction products obtained by the diacetoxylation reaction of the conjugated dienes by the said catalyst, the corresponding 1, 4- in the containing liquid Diacetoxyallyl compound exists. In addition, "3, 4- diacetoxy allyl compound containing liquid" is a 3, 4- hydroxyacetoxy allyl compound and / or 3, 4- dihydroxy allyl which are the hydrolyzate of a 3, 4- diacetoxy allyl compound. The compound may be contained and may further contain the 1, 4-hydroxyacetoxy allyl compound and / or the 1, 4- dihydroxy allyl compound which are the hydrolyzate of a 1, 4- diacetoxy allyl compound.

"3, 4- diacetoxy allyl compound containing liquid" used by this invention contains a 3, 4- diacetoxy allyl compound, a 1, 4- diacetoxy allyl compound, a low boiling point compound, and a high boiling point compound. The liquid to be introduced is introduced into a distillation column, and the liquid containing the high boiling point compounds and the 1,4-diacetoxy allyl compound is extracted from the column bottom, and the liquid containing the 3,4-diacetoxy allyl compound is obtained from the top of the column. Can be. At this time, the 3,4-diacetoxy allyl compound-containing liquid may be extracted from the column top together with the nasal point compounds, and the 3,4-diacetoxy allyl compound-containing solution is extracted from the side stream, and the nasal point is separated from the column top. You may flow out a compound. At this time, almost all of the high-boiling compounds are extracted from the column bottom, but a small amount of the high-boiling compounds are extracted from the top or side stream together with the 3,4-diacetoxy allyl compound-containing liquid.

In addition, although the pressure of the distillation column can be arbitrarily set, it is preferable to set the tower pressure to 1-760 mmHg from a viewpoint of the energy cost used for the reboiler of a distillation column, in order to lower tower bottom temperature. More preferably, the top pressure is 5-200 mmHg, Especially preferably, it is the range of 10-100 mmHg. If the column pressure is too low, a great cost is required to maintain the pressure, and the distillation column itself is enlarged, thereby increasing the construction cost of the process. In addition, when the tower pressure is too high, the column bottom temperature of the distillation column becomes high, and steam cost increases. The top temperature is 0-200 degreeC normally, Preferably it is 20-160 degreeC, More preferably, it is the range of 40-140 degreeC. If the tower temperature is too low, special equipment, such as a cooler, is required and the cost is worsened. If the temperature is too high, the cost of the steam is increased because the bottom temperature is also higher. Reflux ratio is 1-100, and there is no problem, Preferably it is 1-10. If the reflux ratio is too small, the resolution is deteriorated. If the reflux ratio is too high, the amount of heat required is increased, which causes cost deterioration. The flow rate of the column top is 3,4-diacetoxy allyl compound, 3,4- diacetoxy allyl compound, 1,4- diacetoxy allyl compound, low boiling point compounds, high boiling point compounds in a liquid containing 3,4-diacetoxy allyl introduced into the distillation column It is preferable to flow out the total amount of a compound and a non-point compound. In addition, when a 3, 4- diacetoxy allyl compound containing liquid is made to flow out from a side stream, and a non-point compound is sent out from a tower top, the content of the 3, 4- diacetoxy allyl compound in an introduction liquid is added to the introduction liquid from side flow. It is preferable to flow out content content of non-point compound each from a column top. Distillation column material resin (3) extracts the liquid containing a high boiling point compound and a 1, 4- diacetoxy allyl compound from the column bottom of a distillation column, and contains 3, 4- diace containing a nap point compound from a tower top. In the case where the oxyallyl compound is allowed to flow out, when the weight of the introduction flow rate per unit time is 100, the top discharge flow rate per unit time is 1 to 50, preferably 5 to 30. 50-99 are preferable and, as for the extraction amount of the liquid containing the high boiling point compounds and the 1, 4- diacetoxy allyl compound per unit time from the tower bottom at that time, More preferably, it is 70-95. Furthermore, the liquid containing high boiling point compounds and a 1, 4- diacetoxy allyl compound is taken out from the bottom of a distillation column, the nasal point compound is flowed out from a tower top, and the 3, 4- diacetoxy allyl compound containing liquid is obtained from the side stream. In the case of distilling off, when the weight of the introduction flow rate per unit time is 100, the top discharge flow rate per unit time is 0.1 to 30, and preferably 1 to 20. Moreover, as for the outflow amount of the 3, 4- diacetoxy allyl compound containing liquid from side stream, 0.9-50 are preferable, More preferably, it is 2-30. Moreover, 20-99 are preferable, and, as for the extraction amount per unit time of the liquid containing the high boiling point compounds and the 1, 4- diacetoxy allyl compound from a tower bottom, 50-97 are more preferable.

The 3,4-diacetoxy allyl compound-containing liquid containing the boiling point compounds obtained in the above-described column top may be supplied to an isomerization reaction after removing the boiling point compounds by distillation. In this case, the guard point compounds may be discharged from the column top in the separation distillation column of the guard point compounds, and the 3,4-diacetoxy allyl compound-containing liquid can be extracted from the column bottom including the side stream.

In addition, although the pressure of the distillation column can be arbitrarily set, it is preferable to set the tower pressure to 1-760 mmHg from a viewpoint of the energy cost used for the reboiler of a distillation column, in order to lower tower bottom temperature. More preferably, the column head pressure is 5-400 mmHg, and particularly preferably it is in the range of 10-200 mmHg. If the column pressure is too low, a great cost is required to maintain the pressure, and the distillation column itself is enlarged, thereby increasing the construction cost of the process. In addition, when the tower pressure is too high, the column bottom temperature of the distillation column becomes high, and steam cost increases.

The top temperature is 0-200 degreeC normally, Preferably it is 20-160 degreeC, More preferably, it is the range of 40-140 degreeC. If the tower temperature is too low, special equipment, such as a cooler, is required and the cost is worsened. If the temperature is too high, the cost of the steam is increased because the bottom temperature is also higher. Reflux ratio is 1-100, and there is no problem, Preferably it is 1-10. If the reflux ratio is too small, the resolution is deteriorated. If the reflux ratio is too high, the amount of heat required is increased, which causes cost deterioration. It is preferable to flow out the total amount of nasal point compounds in the liquid containing 3, 4- diacetoxy allyl compound and low boiling point compounds which were introduce | transduced into the distillation column. The distillation column material resin extracts a liquid containing a 3,4-diacetoxy allyl compound from the bottom of the column including the side stream of the distillation column, and when the distillation column compound flows out of the column top, When it is set at 100, the top discharge flow volume per unit time is 1 to 50, preferably 5 to 45. 50-99 are preferable, and, as for the extraction amount of the liquid containing a 3, 4- diacetoxy allyl compound per unit time from the tower bottom containing side flow in that case, 55-95 are more preferable.

The present invention is characterized in that the 3,4-diacetoxyallyl compound-containing liquid is brought into contact with a phosphorus compound. Methoxyallyl compound-containing liquid ”, the reaction products may be contacted with phosphine before the reaction products are subjected to distillation separation, and the reaction products after the acetoxylation reaction of the conjugated diene are distilled off, and then distilled off from the column top. The 3, 4- diacetoxy allyl compound containing liquid may be contacted, and the 3, 4- diacetoxy allyl compound containing liquid which flowed out from side flow may be contacted. Since the amount of the liquid to be contacted is small and the effect can be exerted with a small amount of the phosphorus compound, it is preferable to bring the phosphorus compound into contact with the liquid flowing out of the column top or the liquid flowing out from the side stream.

As a kind of distillation column which can be used, a packed tower, a borandane tower, etc. are mentioned, A borandane tower is preferable. In order to separate a 3, 4- diacetoxy allyl compound containing liquid and a 1, 4- diacetoxy allyl compound containing liquid, it is preferable to make a distillation tower theoretical stage into three or more stages especially 10-50 stage. Distillation towers with more than 50 stages are undesirable for the economics, difficulty of operation and safety management of the construction of the distillation column. If the number is too small, separation becomes difficult.

Specifically as a 3, 4- diacetoxy allyl compound used for the isomerization reaction of this invention, 3, 4- diacetoxy 1-butene and 3, 4- diacetoxy 2-methyl-1- butene , 3,4-diacetoxy-3-methyl-1-butene, 3,4-diacetoxy-2,3-dimethyl-1-butene, 3,4-diacetoxy-1-cyclohexene, 3, 4-diacetoxy-1-cyclopentene, 3,4-diacetoxy-1-cycloheptene, and 3,4-diacetoxy-1-cyclooctene are preferred, and more preferably 3,4-diacet Methoxy-1-butene, 3,4-diacetoxy-2-methyl-1-butene, 3,4-diacetoxy-3-methyl-1-butene, 3,4-diacetoxy-1-cyclohexene , 3,4-diacetoxy-1-cyclopentene, particularly preferably 3,4-diacetoxy, which can be converted to 1,4-diacetoxy-2-butene, an intermediate of 1,4-butanediol -1-butene.

Also in isomerization reactions such as 3-hydroxy-4-acetoxy-1-butene and 4-hydroxy-3-acetoxy-1-butene which are hydrolyzates of 3,4-diacetoxy-1-butene The isomerization method of the present invention can be applied.

In addition, in this invention, the 1, 4- diacetoxy allyl compound obtained by the isomerization of a 3, 4- diacetoxy allyl compound is an isomer corresponding to the 3, 4- diacetoxy allyl compound before isomerization. Specifically as a 1, 4- diacetoxy allyl compound which is an isomer, 1, 4- diacetoxy 2-butene, 1, 4- diacetoxy 2-methyl- 2-butene, and 1, 4- dia Cetoxy-2,3-dimethyl-2-butene, 1,4-diacetoxy-2-cyclohexene, 1,4-diacetoxy-2-cyclopentene, 1,4-diacetoxy-2-cyclo Preferred are heptene, 1,4-diacetoxy-2-cyclooctene, 1,4-diacetoxy-1-butene, 1,4-diacetoxy-2-methyl-1-butene, 1,4- Diacetoxy-3-methyl-1-butene, 1,4-diacetoxy-1-cyclohexene, 1,4-diacetoxy-1-cyclopentene, particularly preferably an intermediate of 1,4-butanediol Phosphorus 1,4-diacetoxy-1-butene.

In the present invention, various solvents can be used when isomerizing the 3,4-diacetoxyallyl compound. The solvent is not particularly limited, but specifically, carboxylic acids such as formic acid, acetic acid, propionic acid and butyric acid; Alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol and octanol; Ethers such as diethyl ether, tetrahydrofuran, dioxane and triglymedimethyl ether; Aromatic hydrocarbons such as benzene, toluene and xylene; Organic solvents such as hexane, heptane, octane, nonane, decane, dodecane, cyclohexane, cycloheptane and cyclooctane can be used. Preferably they are carboxylic acids, such as formic acid, acetic acid, propionic acid, butyric acid, Especially preferably, acetic acid which improves the isomerization rate of an acetoxy group. Acetic acid is preferable as the solvent because the acetoxy group concentration in the reaction solution, that is, the acetic acid concentration, which contributes to the improvement of the isomerization rate is increased.

The amount of the solvent added is preferably 0 to 10,000 wt%, more preferably 0.05 to 500 wt%, particularly preferably 1 to 200 wt%, based on the weight of the diacetoxy allyl compound. The smaller the amount of the solvent added, the smaller the capacity of the reactor, and the higher the amount of the solvent, the slower the rate of catalyst degradation tends to be.

In the present invention, the catalyst used for isomerization of the 3,4-diacetoxyallyl compound is not particularly limited as long as it has the ability to isomerize the 3,4-diacetoxyallyl compound to the 1,4-diacetoxyallyl compound. It is a liquid homogeneous complex catalyst, Preferably it is a homogeneous complex catalyst of group 8-10 transition metals, Especially preferably, it is a liquid homogeneous palladium complex catalyst which shows especially high activity with an acetoxy isomerization rate.

The liquid homogeneous complex catalyst can be prepared with various transition metals, specifically, acetate, acetylacetonate compound, chloride, bromide, iodide, sulfate, nitrate, organic salt, inorganic salt, olefin coordination compound, Carbon monoxide coordination compounds, phosphine coordination compounds, phosphite coordination compounds and the like.

The liquid homogeneous complex catalyst is preferably palladium metal, palladium acetate, palladium chloride, dichlorocyclooctadiene palladium, tetrakis (triphenylphosphine) palladium, bis (dibenzylideneacetone) palladium, palladium trifluoroacetate And palladium acetylacetonate, nickel acetate, dicyclooctadiene nickel, platinum acetate, dicyclooctadiene platina, and the like, and particularly preferably, palladium acetate, palladium chloride, and palladium trifluoroacetate which are inexpensive palladium sources. In the present invention, the form of the metal compound described above is not particularly limited, and the active complex catalyst may be a monomer, a dimer and / or a multimer.

In the present invention, a phosphorus compound can be used as the ligand of the liquid homogeneous complex catalyst. For example, as long as it is a phosphorus ligand, such as phosphine, phosphite, phosphonite, phosphinite, and phosphoramidite, it can use without particular limitation. These ligands may be single seated or multiple seated. The ligand is preferably a phosphorus compound having a P-O bond, particularly phosphites and phosphoramidites, and particularly preferred are bisulfite and phosphoramidites. As a reason, in the isomerization reaction via π-allyl intermediate, a phosphorus compound having a P-O bond having a low electron density is preferable because a ligand having a low electron density promotes an improvement in reaction rate. In the present invention, one type of ligand is usually used, but two or more phosphorus ligands may be used in combination. Moreover, you may use another ligand together in the range which does not significantly inhibit the effect of this invention as needed.

When using the phosphorus compound which has a P-O bond in this invention as a ligand, the compound represented by following General formula (1)-(5) and Formula (6-1)-(6-7) is mentioned. In the present invention, one type of ligand is usually used, but two or more phosphorus ligands may be used in combination. Moreover, you may use another ligand together in the range which does not significantly inhibit the effect of this invention as needed.

[Formula 1]

In the formulas (1) to (5), X to X '' 'are selected from any of (X1) to (X5), and Y to Y' '' is optionally selected from any of (Y1) to (Y5). You can choose.

In the above (X1) ~ (X5), (Y1) ~ (Y5) and the equation (6-1) ~ (6-7), R, R ' and R ¹ ~ R ⁵⁴ are each independently an alkyl group, an alkoxy A group, a cycloalkyl group, an aryloxy group, an alkylaryloxy group, an amino group, or an aryl group may be shown, and may have a substituent further. If the R, R 'and R ¹ ~ R when the ⁵⁴ is an alkyl group, or a substituent having an alkyl backbone (the alkyl group of the alkyl, aryloxy, etc.), the carbon number is usually from 1 to 20, preferably from 1 to 14 . As a specific example, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, octyl group , Decylating, etc. In addition, the alkyl group or the alkyl skeleton portion may further have a substituent, and examples of the substituent include 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, and a hydroxyl group. And halogen atoms.

In addition, if the R, R 'and R ¹ ~ R ^54, which is the substituent having a case an aryl group, or an aryl group skeleton is, the carbon number is usually from 6-20, preferably 6-14. The aryl group or the aryl skeleton portion may further have a substituent. As said substituent, a hydrogen atom, a C1-C20 alkyl group, a C1-C10 alkoxy group, a C3-C20 cycloalkyl group, a C6-C20 aryl group, a C6-C20 aryloxy group, C6 An alkylaryl group of 20, a C6-C20 alkylaryloxy group, a C6-C20 arylalkyl group, a C6-C20 arylalkoxy group, a cyano group, an ester group, a hydroxyl group, and a halogen atom are mentioned.

R, R 'and R ¹ ~ R ⁵⁴ is a phenyl group as a specific example in which an aryl group, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,3-dimethylphenyl group, 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-chloro Phenyl 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, trifluoromethyl group, pentafluoroethyl group, pentafluoro A phenyl group and the following group (C-1)-(C-8) are mentioned.

[Formula 2]

In Formulas (1) to (5) and (Y1) to (Y5), A to A ″ and A ¹ to A ⁵ each independently have an alkylene group having 1 to 20 carbon atoms and a substituent which may have a substituent. An arylene group having 6 to 30 carbon atoms or a diarylene group which may have a divalent linking group in the middle of Ar ^1- (Q ¹ ) _n -Ar ² (wherein Ar ¹ and Ar ² each independently have a substituent) To an arylene group having 6 to 18 carbon atoms).

In Formulas (6-1) to (6-7), T ¹ to T ⁷ are each independently represented by a carbon atom, an alkane tetrayl group, a benzene tetrayl group, or T ^8- (Q ² ) _n -T ⁹ It is a tetravalent group which may have a substituent, T <^8> and T <^9> respectively independently represent the trivalent group which may have a substituent chosen from a C1-C10 alkane triyl group and a C6-C15 benzene triyl group. Q ¹ and Q ² each independently represent —CR ⁵⁵ R ⁵⁶ —, —O—, —S—, —CO—, n is 0 or 1, and R ⁵⁵ and R ⁵⁶ are each independently a hydrogen atom, It is a C1-C10 alkyl group or a C6-C20 aryl group, and may have a substituent.

In addition, "and the like, and A ¹ ~ A case ⁵ is an alkylene group, e.g., tetramethyl-ethylene group, a dimethyl propylene group. Further, A ~ A 'A ~ A and A ¹ ~ A ⁵ is a substituent In the case of an alkylene group which may be used, a C1-C10 alkoxy group, a C6-C20 aryl group, an amino group, a cyano group, an amide group, a trifluoromethyl group etc. are mentioned as a substituent. Further, A ~ A ", and A ¹ ~ A case ⁵ is an arylene group which may have a substituent, such as a phenylene group or naphthyl group can be exemplified by groups such as an alkoxy group having 1 to 10 carbon atoms as a substituent, the number of carbon atoms 6-20 aryl group, amino group, cyano group, amide group, trifluoromethyl group, etc. are mentioned.

Further, A ~ A ", and A ¹ ~ A ⁵ is _{^{Ar 1 - (Q 1) n}} -Ar case dia tolylene group which may have a bivalent linking group in the middle ^two, Ar ¹ and Ar ² are, each independently, a substituent It is a C6-C18 arylene group which may have, The carbon number of this arylene group is 6-24, Furthermore, 6-16 are preferable. As a specific example of a preferable substituent, a C1-C10 alkyl group and C1-C10 are preferable. An alkoxy group, a C6-C20 aryl group, an amino group, a cyano group, an amide group, a trifluoromethyl group, etc. are mentioned.

Further, specific examples of A to A ″ and A ¹ to A ⁵ include-(CH ₂ ) ₂ -,-(CH ₂ ) ₃ -,-(CH ₂ ) _4- , and-(CH ₂ ) ₅ -,-( CH ₂ ) _6- , -CH (CH ₃ ) -CH (CH ₃ )-, -CH (CH ₃ ) CH ₂ CH (CH ₃ )-, -C (CH ₃ ) ₂ -C (CH ₃ ) _2- And -C (CH ₃ ) ₂ -CH ₂ -C (CH ₃ ) ₂ -and the following groups (A-1) to (A-48).

[Formula 3]

[Formula 4]

[Chemical Formula 5]

[Formula 6]

As a preferable specific example of a compound of Formula (1)-(5) which shows the ligand of this invention, and Formula (6-1)-(6-7), following single seat ligand (L-1)-(L-16) And multidentate ligands (L-17) to (L-44), and (L-17) to (L-36) can be illustrated as particularly preferred examples.

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[Formula 13]

In the specific example of phosphites and phosphoramidites, Preferably they are L20-L44, Especially preferably, they are L21-L30. The reason why these are preferable is that the thermal stability of the ligand is relatively high and the loss due to deactivation of the catalytically active species is relatively small.

In the present invention, the amount of the homogeneous complex catalyst used for the isomerization of the diacetoxy allyl compound is converted into the amount of metal in the 3,4-diacetoxy allyl compound-containing liquid and is added to the 3,4-diacetoxy allyl compound-containing liquid. 0.001-1000 wtppm are preferable, More preferably, it is 0.01-100 wtppm, Especially preferably, it is 0.1-10 wtppm. As the amount of the catalyst increases, the reaction rate increases, and the size of the reactor can be reduced, thereby reducing the equipment cost. In addition, as the amount of the catalyst decreases, the ligand cost can be reduced.

The molar ratio of phosphorus atoms in the ligand is preferably 0.1 to 1000 with respect to the transition metal in the complex catalyst, more preferably 1 to 100, and particularly preferably 1 to 10 for the amount of the ligand. As the amount of ligand increases, the reaction rate increases. On the other hand, the lower the amount of ligand, the lower the catalyst cost can be.

40-200 degreeC is preferable, as for the reaction temperature at the time of implementing this isomerization reaction, More preferably, it is 80-180 degreeC, Especially preferably, it is 100-160 degreeC. The higher the reaction temperature, the higher the reaction rate, and the smaller the reactor may be, so that the equipment cost can be reduced. On the other hand, the lower the reaction temperature, the slower the progress of catalyst deterioration, so that the catalyst cost can be reduced.

In addition to the catalyst ligand, the stability of the catalyst or the reaction rate can be improved by using another phosphorus compound as a cocatalyst in the reactor. The phosphorus compound used here is not specifically limited as long as three substituents couple | bonded with the phosphorus atom. For example, triphenylphosphine, tri (2-methylphenyl) phosphine, tri (4-methylphenyl) phosphine, tri (2-methoxyphenyl) phosphine, tri (4-methoxyphenyl) phosphine, etc. Aryl phosphines; Diaryl alkyl phosphines, such as diphenyl methyl phosphine, diphenyl ethyl phosphine, and diphenyl propyl phosphine; Dialkyl aryl phosphines such as dimethyl phenyl phosphine and diethyl phenyl phosphine; Trialkyl phosphines, such as trioctyl phosphine and tributyl phosphine, are preferable, More preferably, triphenyl phosphine, tri (2-methylphenyl) phosphine, tri (4-methylphenyl) phosphine, and tri (2- Triaryl phosphines, such as a methoxyphenyl) phosphine and a tri (4-methoxyphenyl) phosphine, are especially a triphenyl phosphine.

As for the quantity of the other phosphorus compounds which are promoters other than these ligands, the molar ratio of the phosphorus atom in the phosphorus compound is 1-10,000 with respect to the amount of the transition metal in a complex catalyst, More preferably, it is 10-2000, Especially preferably, Is 50 to 500. When the amount of the phosphorus compound is too small, the reaction rate is lowered, and when too large, the cost is increased. If it is these ranges, even if it uses together the phosphorus compound used together or mixes several phosphorus compounds, it does not interfere.

If the reactor used for the isomerization reaction in this invention is a type used for a normal liquid phase reaction, it will not interfere. Preferably, they are a tubular reactor and a tank reactor, and these can be used in single or multiple stages. In particular, a molding reactor and a multistage molding reactor are preferable, and a multistage molding reactor in which an opening tray is provided is preferable.

In the present invention, the above-mentioned 3,4-diacetoxy allyl compound-containing liquid is contacted with a phosphorus compound before isomerizing the 3,4-diacetoxy allyl compound to the 1,4-diacetoxy allyl compound by a catalyst. It is necessary to let. Also in a phosphorus compound, Preferably it is an organic phosphorus compound, Among these organic phosphorus compounds, More preferably, they are organic phosphites, organic phosphoramidites, organic phosphines, Especially preferably, they are organic phosphines. As these organic phosphines, single dents, two dents, three dents or more of organic phosphines can be used, and preferably single sequential organic phosphines containing two or more aryl groups. These are not specifically limited, A commercial item can be used. Specifically, trimethyl phosphine, triethyl phosphine, tripropyl phosphine, tributyl phosphine, tripentyl phosphine, trihexyl phosphine, triheptyl phosphine, trioctyl phosphine, tricyclopentyl phosphine Alkyl phosphines such as tricyclohexyl phosphine and tricycloheptyl phosphine; Or triphenylphosphine, diphenylmethylphosphine, diphenylethylphosphine, diphenylbutylphosphine, dimethylphenylphosphine, diethylphenylphosphine, dibutylphenylphosphine, tris (tolyl) phosphine, 1, Phenyl phosphine, such as 2-bis (diphenyl phosphino) ethane, More preferably, it is phenyl phosphine, Especially preferably, triphenyl phosphine, diphenyl methyl phosphine, diphenyl ethyl phosphine, and di Phenylbutylphosphine and tris (tolyl) phosphine, most preferably triphenylphosphine. In the present invention, one kind of phosphorus compound is usually used, but two or more kinds of phosphorus compounds may be used in combination. Moreover, you may use another compound together as needed in the range which does not significantly inhibit the effect of this invention.

Before isomerizing the 3,4-diacetoxyallyl compound to the 1,4-diacetoxyallyl compound by the catalyst, the temperature at the time of contacting with the above-mentioned phosphorus compound is usually 60 ° C or higher, preferably 80 ° C or higher. , And particularly preferably 100 ° C. or higher, on the other hand, the temperature usually brought into contact with the phosphorus compound is 200 ° C. or lower, preferably 180 ° C. or lower, and particularly preferably 160 ° C. or lower. The higher the temperature, the higher the inhibitory effect of the catalyst deterioration component by the phosphorus compound. In addition, the lower the temperature, the lower the energy cost for heating the phosphorus compound.

Moreover, 1 minute-100 hours are preferable, as for a contact time, More preferably, they are 10 minutes-10 hours, Especially preferably, they are 30 minutes-5 hours. The longer the contact time, the more sufficient the catalyst deterioration component can be removed. In addition, the shorter the contact time, the higher the operational efficiency of the process.

The phosphorus compound may be used in the range of 0.00001 to 10% by weight, more preferably 0.0001 to 1% by weight, particularly preferably 0.001 to 1% by weight, based on 3,4-diacetoxyallyl compound-containing liquid. 0.1 wt%. The larger the amount of phosphorus compound used, the more sufficient the effect of removing the catalyst deterioration component can be obtained. On the other hand, when the usage-amount of a phosphorus compound is small, the cost of a phosphorus compound can be reduced.

In the present invention, the method of contacting the 3,4-diacetoxyallyl compound and the phosphorus compound before isomerizing the 3,4-diacetoxyallyl compound to the 1,4-diacetoxyallyl compound by the catalyst, Although it does not specifically limit, Usually, (1) the method of stirring and mixing a 3, 4- diacetoxy allyl compound and a phosphorus compound in a container, (2) the 3, 4- diacetoxy allyl compound solution containing a phosphorus compound It is prepared separately, the method of stirring and mixing a 3, 4- diacetoxy allyl compound and the 3, 4- diacetoxy allyl compound solution containing a phosphorus compound in the container, or (3) 3, 4- diace And a method in which the oxyallyl compound and the solution of the 3,4-diacetoxy allyl compound containing the phosphorus compound are integrated into one piping and contacted and mixed as a flow. Moreover, it can also heat after contact and mix with the above-mentioned desired temperature and time. Since a continuous process is preferable from a productivity viewpoint, as a method of contacting, the said (3) 3, 4- diacetoxy allyl compound and the 3, 4- diacetoxy allyl compound solution containing a phosphorus compound are flowed. It is advisable to integrate, contact and mix each line (piping) as one line (piping).

Although the contact method of a phosphorus compound and a 3, 4- diacetoxy allyl compound does not interfere with any of ash and continuous, a continuous flow type is especially preferable since operation is easy. The phosphorus compound may be separated and recycled by distillation prior to the isomerization reaction, but from the viewpoint of energy efficiency, after completion of the isomerization reaction, distillation or the like is produced from the 1,4-diacetoxyallyl compound produced in the same manner as the catalyst component. It is preferable to separate. The phosphorus compound separated here may be recycled, but is usually discharged out of the process system as a waste liquid.

In the present invention, an unreacted 3,4-diacetoxy allyl compound exists in addition to the 1,4-diacetoxy allyl compound that is a reaction product in the reaction solution obtained by the isomerization reaction, and distillation or the like is performed from the reaction solution. 3, 4- diacetoxy allyl compound containing liquid can be isolate | separated. Although the pressure of the distillation column at that time can be arbitrarily set, it is preferable to make column top pressure into 1-760 mmHg in order to lower tower bottom temperature. More preferably, the top pressure is 5-200 mmHg, Especially preferably, it is the range of 10-100 mmHg. If the column pressure is too low, a great cost is required to maintain the pressure, and the distillation column itself is enlarged, thereby increasing the construction cost of the process. In addition, when the tower pressure is too high, the column bottom temperature of the distillation column becomes high, and steam cost increases. The top temperature is 0-200 degreeC normally, Preferably it is 20-160 degreeC, More preferably, it is the range of 40-140 degreeC. If the tower temperature is too low, special equipment, such as a cooler, is required and the cost is worsened. If the temperature is too high, the cost of the steam is increased because the bottom temperature is also higher. Reflux ratio is 1-100, and there is no problem, Preferably it is 1-10. If the reflux ratio is too small, the resolution is deteriorated. If the reflux ratio is too high, the amount of heat required is increased, which causes cost deterioration. The flow rate of the column top is 3,4-diacetoxy allyl compound, 3,4- diacetoxy allyl compound, 1,4- diacetoxy allyl compound, low boiling point compounds, high boiling point compounds in a liquid containing 3,4-diacetoxy allyl introduced into the distillation column It is preferable to flow out the total amount of a compound and a non-point compound. In addition, when a 3, 4- diacetoxy allyl compound containing liquid is made to flow out from a side stream, and a non-point compound is sent out from a tower top, the content of the 3, 4- diacetoxy allyl compound in an introduction liquid is added to the introduction liquid from side flow. It is preferable to flow out content content of non-point compound each from a column top.

The unreacted 3,4-diacetoxy allyl compound can be isomerized to a 1,4-diacetoxy allyl compound by introducing the 3,4-diacetoxy allyl compound-containing liquid obtained by distillation separation into an isomerization reactor. . The 3,4-diacetoxyallyl compound-containing liquid to be recycled to this reactor is preferably maintained at the temperature at the point of time obtained by distillation or in the isomerization reactor, but isomerized regardless of temperature, pressure, etc. at the time of recycling. Isomerization with a 1, 4- diacetoxy allyl compound can be carried out on condition. In addition, the isomerization reaction conditions at this time may be the same conditions as the above-mentioned.

The 1,4-diacetoxy allyl compound obtained by the isomerization reaction is purified as it is or after further distillation, and then, as a 1,4-diacetoxybutane compound which may be hydrogenated in the presence of a transition metal catalyst to have a substituent. Is converted. Although the transition metal catalyst used here is a commercially available hydrogenation catalyst, it does not interfere, but it is a catalyst or nickel catalyst containing noble metals, such as palladium or ruthenium, preferably. In the presence of these hydrogenation catalysts, hydrogen and a 1,4-diacetoxy allyl compound-containing liquid are brought into contact with each other at a temperature in the range of 40 to 180 ° C, and hydrogenation can be carried out under conditions of a pressure range of normal pressure to 15 MPa. If the reaction temperature is too high, the catalyst deterioration proceeds quickly. If the reaction temperature is too low, the reaction rate is lowered. If the pressure is too low, the reaction rate is lowered. If the pressure is too high, an expensive reactor is required.

The 1,4-diacetoxybutane compound obtained by the hydrogenation reaction is hydrolyzed in presence of water with an acid catalyst or a basic substance, and is converted into diols, such as 1, 4- butanediol. The catalyst is preferably a solid acid catalyst, and in particular, the use of a cation exchange resin is preferable because of its high hydrolysis rate and fewer by-products such as tetrahydrofuran. Specifically, sulfonic acid type strongly acidic cation exchange resins having a copolymer of styrene and divinylbenzene as a mother, which is either a gel type or a porous type, have no problem. The reaction is usually carried out at a temperature of 30 to 110 ° C, preferably 40 to 90 ° C. If the temperature is too low, the rate of hydrolysis decreases, and an expensive and grand reactor is required. When the temperature is too high, by-products such as tetrahydrofuran increase, and the yield of 1,4-butanediol decreases. The amount of water is usually 2 to 100 moles, preferably 4 to 50 moles per 1 mole of 1,4-diacetoxybutane. If the amount of water is too small, the reaction rate is lowered, and an expensive and grand reactor is required. If the amount of water is too large, a large amount of energy is required to remove water from 1,4-butanediol after hydrolysis, thereby increasing the energy cost.

Example

Hereinafter, although an Example demonstrates this invention still in detail, it is not limited to a following example, unless the summary of this invention is made.

In the following examples, 3,4-diacetoxy-1-butene and 1,4-diacetoxy-2-butene were analyzed by gas chromatography using an internal standard method. Dodecane was used as internal standard.

Reference Example 1 Butadiene Acetoxylation Process

In the presence of 1 kg of Pd-Te catalyst, 0.21 kg / hr of butadiene, 2.94 kg / hr of acetic acid, 0.34 kg / hr of 6 vol% oxygen / 94 vol% nitrogen mixed gas were passed through the reactor, and the conditions were 80 ° C. and 6 MPa. To 1,4-diacetoxy-2-butene, 9% by weight of 3,4-diacetoxy-1-butene, and 3-hydroxy-4-acetoxy-1. -A mixed liquid containing 2% by weight of butene, 3% by weight of acetic acid, 3% by weight of other non-point compounds, and 2% by weight of high-boiling compounds.

Reference Example 2: Separation of 3,4-diacetoxy-1-butene-containing liquid

The 3,4-diacetoxy-1-butene containing liquid was isolate | separated from 11 L of the liquid mixture obtained by the reference example 1 by continuous distillation. In addition, a 20-stage Aldershaw distillation column was used for distillation. The top pressure is 20 mmHg, the reflux ratio is 3, the top temperature is 95 ° C, and the bottom temperature is 151 ° C. The top pressure is continuously introduced into the 10-stage position from the top bottom at a flow rate of 150 cc / hr. Continuous outflow was performed at cc / hr, and continuous extraction was performed at 123 cc / hr from the bottom. By this continuous distillation, a liquid containing 1,4-diacetoxy-2-butene is obtained as a effluent from the column bottom, and a 3,4-diacetoxy-1-butene-containing liquid is obtained from the column top. Obtained as an effluent. The obtained 3,4-diacetoxy-1-butene containing liquid has 45 weight% of 3, 4- diacetoxy-1-butenes, 11 weight% of 3-hydroxy-4- acetoxy-1- butenes, 22% by weight of acetic acid, 20% by weight of other components having a lower boiling point than 3,4-diacetoxy-1-butene, and 2% by weight of components having a higher boiling point than 3,4-diacetoxy-1-butene It was a mixed liquid. In addition, content of 1, 4- diacetoxy 2-butene of this 3, 4- diacetoxy 1-butene containing liquid was 1 weight% or less.

Reference Example 3: Purified Distillation of 3,4-Diacetoxy-1-butene Containing Liquid

From 1 L of the 3,4-diacetoxy-1-butene-containing liquid obtained in Reference Example 2, most of the nasal point compounds were separated by continuous distillation. In addition, a 40-stage Aldersho distillation column was used for distillation. The column top pressure is 100 mmHg, the reflux ratio is 1, the column top temperature is 95 ° C., the tower bottom temperature is 148 ° C., and it is continuously introduced into the 20-stage position from the tower bottom at a flow rate of 100 cc / hr. Continuous discharge was performed at / hr, and continuous extraction was performed at 59 cc / hr from the bottom. By this continuous distillation, nasal point compounds were obtained as an outflow liquid from the tower top. The effluent contained 59% by weight of acetic acid, 1.6% by weight of 3,4-diacetoxy-1-butene (corresponding to 1.5% by weight of the amount of 3,4-diacetoxyallyl compound introduced into the distillation column), 3, 39.4 weight% of components containing a boiling point lower than 4-diacetoxy-1-butene were contained. Also, the liquid extracted from the column bottom contained 72% by weight of 3,4-diacetoxy-1-butene, 18% by weight of 3-hydroxy-4-acetoxy-1-butene, and 6% by weight of other non-point compounds. And the 3, 4- diacetoxy-1-butene containing liquid containing 4 weight% of high boiling point compounds.

Reference Example 4 Catalyst Preparation

3,4-diacetoxy-1-butene-containing liquid obtained in the reference example 3 which obtained 10.5 mg of palladium acetate, 96.3 mg of phosphite ligands represented by said L21, and 49.8 mg of triphenylphosphines in glass Schlenk under nitrogen gas atmosphere. It was added in 41.3 g. This liquid mixture was heated at 80 degreeC for 1 hour, and it melt | dissolved completely, and obtained the catalyst liquid.

Reference Example 5 Catalyst Preparation

Under a nitrogen gas atmosphere, 5.9 mg of palladium acetate, 56.9 mg of the ligand represented by L29 and 30.3 mg of triphenylphosphine were added in 13.99 g of toluene in a glass Schlenk. This liquid mixture was heated at 120 degreeC for 20 minutes, and it melt | dissolved completely and obtained the catalyst liquid.

Reference Example 6 Catalyst Preparation

Under a nitrogen gas atmosphere, 5.5 mg of palladium acetate, 43.0 mg of ligand represented by the above L30 and 25.8 mg of triphenylphosphine were added in 12.19 g of toluene in a glass Schlenk. This liquid mixture was heated at 120 degreeC for 20 minutes, and it melt | dissolved completely and obtained the catalyst liquid.

Example 1

3,4-diacetoxy-1-butene-containing liquid (3,4-diacetoxy-1-butene obtained by the above-mentioned reference example 3 "purification distillation of a 3, 4- diacetoxy-1-butene containing liquid" 72% by weight, 18% by weight of 3-hydroxy-4-acetoxy-1-butene, 6% by weight of other components having a lower boiling point than 3,4-diacetoxy-1-butene, 3,4-diacene 0.166 mg (3,4-diacetoxy-1) of triphenylphosphine to 1.5 cc of tablets 3,4-diacetoxy-1-butene) containing 4 weight% of components having a higher boiling point than oxy-1-butene 0.0073% by weight relative to -butene) was added as 18 µl of an acetic acid solution having a triphenylphosphine concentration of 0.86%, followed by stirring at a temperature of 150 캜 for 3 hours.

Next, 1.5 cc of acetic acid was added to the Schlenk and mixed, and the temperature was raised to 130 ° C in an oil bath. 26 µL of the catalyst solution prepared in Reference Example 4 was added thereto under a nitrogen atmosphere, followed by heating and stirring at 130 ° C for 3 hours (1.0 wtppm of palladium concentration in the reaction solution). As a result of analyzing the liquid after isomerization by gas chromatography, the weight ratio of 1, 4- diacetoxy 2-butene (cis body and a trans body total) and 3, 4- diacetoxy 1-butene was 45 : 55. Dodecane was also used as internal standard. The results are shown in Table 1.

Example 2

In Example 1, it carried out similarly to Example 1 except having changed the addition amount of triphenylphosphine into 0.332 mg (0.01 47 weight% with respect to 3, 4- diacetoxy 1-butene). As a result of analyzing the liquid after isomerization by gas chromatography, the weight ratio of 1, 4- diacetoxy 2-butene (the total of cis body and a trans body) and 3, 4- diacetoxy-1-butene was 44 : 56 was. Dodecane was also used as internal standard. The results are shown in Table 1.

Example 3

In Example 1, it carried out similarly to Example 1 except having performed stirring after adding triphenyl phosphine at the temperature of 150 degreeC for 1 hour. As a result of analyzing the liquid after isomerization by gas chromatography, the weight ratio of 1, 4- diacetoxy 2-butene (the total of cis body and a trans body) and 3, 4- diacetoxy-1-butene was 44 : 56 was. Dodecane was also used as internal standard. The results are shown in Table 1.

Example 4

In Example 1, after adding 0.166 mg (0.0073 weight% with respect to 3, 4- diacetoxy 1-butene) triphenylphosphine, it stirred Example 5 at the temperature of 30 degreeC except Example 1. The same procedure was followed. As a result of analyzing the liquid after reaction by gas chromatography, the weight ratio of 1, 4- diacetoxy 2-butene (the total of cis body and a trans body) and 3, 4- diacetoxy 1-butene was 40: It was 60. Dodecane was also used as internal standard. The results are shown in Table 1.

Example 5

In Example 1, triphenyl phosphine was used as triphenyl phosphite, and the addition amount of triphenyl phosphite was changed to 0.166 mg (0.0073 weight% with respect to 3, 4- diacetoxy-1-butene). , It carried out similarly to Example 1. As a result of analyzing the liquid after isomerization by gas chromatography, the weight ratio of 1, 4- diacetoxy 2-butene (cis body and trans body total) and 3, 4- diacetoxy-1-butene was 36 : 64. Dodecane was also used as internal standard. The results are shown in Table 1.

Example 6

3,4-diacetoxy-1-butene-containing liquid (3,4-diacetoxy-1-butene obtained by the above-mentioned reference example 3 "purification distillation of a 3, 4- diacetoxy-1-butene containing liquid" 72% by weight, 18% by weight of 3-hydroxy-4-acetoxy-1-butene, 6% by weight of other components having a lower boiling point than 3,4-diacetoxy-1-butene, 3,4-diacene 0.15 mg (3,4-diacetoxy-1) of triphenylphosphine to 2.94 cc of purified 3,4-diacetoxy-1-butene) containing 4 wt% of a component having a higher boiling point than oxy-1-butene 0.0050% by weight relative to -butene) was added as 8 µl of an acetic acid solution having a triphenylphosphine concentration of 0.86%, followed by stirring at a temperature of 150 캜 for 3 hours.

Next, 0.06 cc of acetic acid was added and mixed in Schlenk, and the temperature was raised to 130 ° C in an oil bath. 18 µl of the catalyst solution prepared in Reference Example 5 was added thereto under a nitrogen atmosphere, followed by heating and stirring at 130 ° C for 3 hours (1.0 wtppm of palladium concentration in the reaction solution). As a result of analyzing the liquid after an isomerization reaction by gas chromatography, the weight ratio of 1, 4- diacetoxy 2-butene (cis body and a trans body total) and 3, 4- diacetoxy 1-butene was 49 : 53 was. Dodecane was also used as internal standard. The results are shown in Table 2.

Example 7

3,4-diacetoxy-1-butene-containing liquid (3,4-diacetoxy-1-butene obtained by the above-mentioned reference example 3 "purification distillation of a 3, 4- diacetoxy-1-butene containing liquid" 72% by weight, 18% by weight of 3-hydroxy-4-acetoxy-1-butene, 6% by weight of other components having a lower boiling point than 3,4-diacetoxy-1-butene, 3,4-diacene 0.15 mg (3,4-diacetoxy-1) of triphenylphosphine to 2.94 cc of purified 3,4-diacetoxy-1-butene) containing 4 wt% of a component having a higher boiling point than oxy-1-butene 0.0050% by weight relative to -butene) was added as 8 µl of an acetic acid solution having a triphenylphosphine concentration of 0.86%, followed by stirring at a temperature of 150 캜 for 3 hours.

Next, 0.06 cc of acetic acid was added and mixed in Schlenk, and the temperature was raised to 130 ° C in an oil bath. 18 µl of the catalyst solution prepared in Reference Example 6 was added thereto under a nitrogen atmosphere, followed by heating and stirring at 130 ° C for 4 hours (1.0 wtppm of palladium concentration in the reaction solution). As a result of analyzing the liquid after isomerization by gas chromatography, the weight ratio of 1, 4- diacetoxy 2-butene (cis body and trans body total) and 3, 4- diacetoxy 1-butene was 52 : 48 was. Dodecane was also used as internal standard. The results are shown in Table 2.

Comparative Example 1

In Example 1, instead of triphenylphosphine, anion exchange resin (Diion, WA20) was equivalent to 7.8 mg (0.50% by weight based on 3,4-diacetoxy-1-butene and 0.02% by weight of triphenylphosphine) Amine exchange capacity) was added, and the same operation was conducted except that the mixture was stirred at a temperature of 30 ° C for 1 hour. As a result of analyzing the liquid after reaction by gas chromatography, the weight ratio of 1, 4- diacetoxy 2-butene (the total of cis body and a trans body) and 3, 4- diacetoxy 1-butene was 30: It was 70. Dodecane was also used as internal standard. The results are shown in Table 1.

Comparative Example 2

In Example 1, 38.9 mg of anion exchange resin (Diion, WA20) instead of triphenylphosphine (2.5% by weight based on 3,4-diacetoxy-1-butene, equivalent to 0.1% by weight of triphenylphosphine) Amine exchange capacity) was added, and the same operation was conducted except that the mixture was stirred at a temperature of 30 ° C for 1 hour. As a result of analyzing the liquid after reaction by gas chromatography, the weight ratio of 1, 4- diacetoxy-2-butene (cis body and trans body total) and 3, 4- diacetoxy-1-butene was 33: 67. Dodecane was also used as internal standard. The results are shown in Table 1.

Comparative Example 3

3,4-diacetoxy-1-butene-containing liquid (3,4-diacetoxy-1-butene obtained by the above-mentioned reference example 3 "purification distillation of a 3, 4- diacetoxy-1-butene containing liquid" 72% by weight, 18% by weight of 3-hydroxy-4-acetoxy-1-butene, 6% by weight of other components having a lower boiling point than 3,4-diacetoxy-1-butene, 3,4-diacene To 3.0 cc of purified 3,4-diacetoxy-1-butene) containing 4% by weight of a component having a higher boiling point than oxy-1-butene, 0.06 cc of acetic acid is added to the Schlenk and mixed, and 130 ° C in an oil bath. The temperature was raised to. 18 µl of the catalyst solution prepared in Reference Example 5 was added thereto under a nitrogen atmosphere, followed by heating and stirring at 130 ° C for 3 hours (1.0 wtppm of palladium concentration in the reaction solution). As a result of analyzing the liquid after isomerization by gas chromatography, the weight ratio of 1, 4- diacetoxy 2-butene (the total of cis body and a trans body) and 3, 4- diacetoxy-1-butene was 44 : 56 was. Dodecane was also used as internal standard. The results are shown in Table 2.

Comparative Example 4

3,4-diacetoxy-1-butene-containing liquid (3,4-diacetoxy-1-butene obtained by the above-mentioned reference example 3 "purification distillation of a 3, 4- diacetoxy-1-butene containing liquid" 72% by weight, 18% by weight of 3-hydroxy-4-acetoxy-1-butene, 6% by weight of other components having a lower boiling point than 3,4-diacetoxy-1-butene, 3,4-diacene To 3.0 cc of purified 3,4-diacetoxy-1-butene) containing 4% by weight of a component having a higher boiling point than oxy-1-butene, 0.06 cc of acetic acid is added to the Schlenk and mixed, and 130 ° C in an oil bath. The temperature was raised to. 18 µl of the catalyst solution prepared in Reference Example 6 was added thereto under a nitrogen atmosphere, and heated and stirred at 130 ° C for 3 hours (1.0 wtppm of palladium concentration in the reaction solution). As a result of analyzing the liquid after isomerization by gas chromatography, the weight ratio of 1, 4- diacetoxy 2-butene (cis body and a trans body total) and 3, 4- diacetoxy 1-butene was 40 : 60. Dodecane was also used as internal standard. The results are shown in Table 2.

(* 1) 3,4-DABE: 3,4-diacetoxy-1-butene

(* 2) 1,4-DABE: 1,4-diacetoxy-2-butene (cis body, trans body total)

(* 1) 3,4-DABE: 3,4-diacetoxy-1-butene

(* 2) 1,4-DABE: 1,4-diacetoxy-2-butene (cis body, trans body total)

From the above result, compared with an Example and a comparative example, it turns out that the isomerization reaction result in an Example improves with respect to the actual addition weight of an additive, and also about the exchange capacity of phosphorus and nitrogen atoms.

INDUSTRIAL APPLICABILITY The present invention is industrially useful as an isomerization method of an allyl compound that suppresses catalyst deterioration and enables the isomer to be obtained in high yield with a small amount of catalyst usage.

In addition, the JP Patent application 2007-132184, the claim, and all the content of the abstract for which it applied on May 17, 2007 are referred here, and it introduces as an indication of the specification of this invention.

Claims (13)

An isomerization method characterized by isomerizing the allyl compound in the presence of a catalyst after contacting a liquid containing a raw allyl compound with a phosphorus compound. The method of claim 1, Isomerization method, characterized in that the phosphorus compound is an organic phosphorus compound. The method of claim 2, Isomerization method characterized by the said organic phosphorus compound being organic phosphines. The method of claim 3, wherein Isomerization method characterized in that the said organic phosphines have 2 or more aryl groups. The method according to claim 3 or 4, Isomerization method characterized in that the said organic phosphines are triphenylphosphine. The method according to any one of claims 1 to 5, The isomerization method in which the quantity of the phosphorus compound brought into contact with the containing liquid of the said allyl compound exists in the range of 0.0001-10 weight% with respect to an allyl compound. 7. The method according to any one of claims 1 to 6, The isomerization method in which contact of the allyl compound-containing liquid and a phosphorus compound is performed at 60 degreeC or more. The method according to any one of claims 1 to 7, Furthermore, the isomerization method characterized by having the process of obtaining the content liquid of the said allyl compound by the diacetization reaction of conjugated dienes. The method according to any one of claims 1 to 8, And the catalyst is a liquid homogeneous palladium catalyst and a catalyst containing a phosphorus ligand having at least one P-O bond. The method of claim 9, The phosphorus ligand which has the said P-O bond is a bidentate phosphite, The isomerization method characterized by the above-mentioned. The method of claim 9, The phosphorus ligand having a P-O bond is a bidentate phosphoramidite. The method according to any one of claims 1 to 11, An isomerization method wherein said allyl compound is a 3,4-diacetoxy allyl compound and isomerized to produce a 1,4-diacetoxy allyl compound corresponding to the allyl compound. The manufacturing method of the allyl compound which produces | generates the corresponding isomerized allyl compound from an allyl compound using the isomerization method in any one of Claims 1-12.