TWI423956B - Allyl compound isomerization method and manufacturing method thereof - Google Patents

Description

Isomerization method of allyl compound and preparation method thereof

The present invention relates to an isomerization process for allyl compounds, and more particularly to an isomerization process characterized by isomerization from 3,4-diethyloxyallyl compounds A 1,4-diethoxymethoxyallyl compound of the corresponding compound is produced.

The allyl compound is an important starting material for organic synthetic chemistry, and is converted into a target product by various reactions. In particular, the diethyl ethoxyallyl compound has a characteristic skeleton, so it can be converted into various types. The compound of the substance is also an important intermediate for the production of glycols by hydrolysis. Therefore, development of various manufacturing processes for diethoxymethoxyallyl compounds has been carried out. For example, a method for producing a diethoxymethoxyallyl compound by a diethylation reaction of butadiene using a solid catalyst is disclosed (Patent Document 1). The diethyl oximation reaction of the conjugated diene used for the production of the diethyl ethoxyallyl compound is mostly carried out in the presence of a solid catalyst, but the current situation is that the control cannot be completely controlled. The position to which the oxime is attached. In particular, in the production reaction of 1,4-diethoxycarbonyl-2-butene which is a raw material of 1,4-butanediol, 3, 4 which cannot be converted into 1,4-butanediol - Diethyloxy-1-butene. Therefore, in the 1,4-butanediol manufacturing process, the cost of the butadiene of the raw material will be increased.

Therefore, it has been developed to isomerize 3,4-diethyloxy-1-butene which is produced by it to form 1,4-diethyloxy-2-butene and the like. A method of an ethoxylated allyl compound. For example, it has been reported that there is a use of Asia Isomerization reaction of palladium complex catalyst of phosphoric acid ligand from 3,4-diethoxymethoxy-1-butene to 1,4-diethoxycarbonyl-2-butene (patent Literature 2). In addition, an isomerization catalyst having a higher activity is obtained by further adding a ruthenium compound in addition to a palladium complex catalyst and a phosphite ligand (Patent Document 3). However, in the isomerization method of the diethyl ethoxyallyl compound, the deterioration of the catalyst is remarkable, and a large amount of catalyst must be used.

The cause of deterioration of the catalyst is considered to be caused by a catalyst-degraded component contained in the diethyl ethoxyallyl compound, and a method of removing the catalyst-degraded component using a solid base has been reported (Patent Document 4). . However, in this method, since the solid base adsorbs several acidic components in addition to the catalyst-degraded component, it is necessary to have a large amount of solid alkali, and therefore it is required to be industrially advantageous, and the catalyst-degraded component can be efficiently removed. Or a method that can be rendered harmless.

Patent Document 1: Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Bulletin

An object of the present invention is to provide a method for isomerization of an allyl compound, which is a method for isomerization of an allyl compound using a catalyst, which can suppress deterioration of a catalyst and can be used in a high yield with a small amount of catalyst used. The isomer is obtained, which is industrially advantageous.

The inventors of the present invention have intensively studied to solve the above problems, and as a result, have found that the phosphorus compound can remove a component which is contained in a diethyl ethoxyallyl compound liquid and which significantly promotes deterioration of an aerotropic catalyst, and has completed the present invention. That is, the present invention is intended to be as follows [1]~[13] [1] An isomerization method in which a liquid containing an allyl compound of a raw material is contacted with a phosphorus compound, and then the above allyl compound is isomerized in the presence of a catalyst.

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

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

[4] The isomerization method according to [3] above, wherein the organophosphine has two or more aryl groups.

[5] The isomerization method according to [3] or [4] above, wherein the organophosphine is triphenylphosphine.

[6] The isomerization method according to any one of the above [1] to [5] wherein the amount of the phosphorus compound in contact with the liquid containing the allyl compound is 0.0001 based on the allyl compound. Within the range of ~10% by weight.

[7] The isomerization method according to any one of the above [1] to [6] wherein the contact of the allylic compound-containing solution with the phosphorus compound is carried out at 60 ° C or higher.

[8] The isomerization method according to any one of the above [1] to [7], which further comprises the above-mentioned diethyl oximation reaction of a conjugated diene A step of containing a solution of an allyl compound.

[9] The isomerization method according to any one of [1] to [8] wherein the catalyst is a liquid phase homogeneous palladium catalyst and is a phosphorus ligand having at least one PO bond. Catalyst.

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

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

[12] The isomerization method according to any one of [1] to [11] wherein the allyl compound is a 3,4-diethyloxyallyl compound, which is produced by isomerization. A 1,4-diethyloxyallyl compound of the compound corresponding to the above allyl compound.

[13] A method for producing an allyl compound, which comprises using the isomerization method according to any one of the above [1] to [12] to produce a corresponding isomerized allyl compound from an allyl compound. .

According to the present invention, in the isomerization of a diethyl ethoxyallyl compound using a catalyst, an isomer can be obtained in a high yield with a small amount of a catalyst.

Hereinafter, the present invention will be described in detail. The description of the constituent elements described below is an example of an embodiment of the present invention, and is not limited thereto.

Further, the allyl compound in the present invention means a compound having an allyl group, and isomerization of a compound having an allyl group by using a catalyst. The compound to be produced is not particularly limited as long as it has an acetoxy group, a halogen group, a carboxylic acid or the like on the allylic site. For example, a compound obtained by isomerizing a 3,4-diethyloxyallyl compound is 1,4-diethyloxyallyl compound in the present invention.

Further, the isomerization method in the present invention also includes a method of converting a compound having an allyl group by isomerization into a compound having an allyl group.

In the following embodiment, the 3,4-diethyloxyallyl compound which is an allyl compound is obtained by isomerization to form a corresponding allyl compound of 1,4-diethyl hydrazine. The case of the oxyallyl compound is described as an example.

The method for isomerizing a 3,4-diethoxy allylic compound to a 1,4-diethoxy allylic compound according to the present invention is a raw material of 3,4-diethyl hydrazine. A method for isomerizing a oxyallyl compound to a 1,4-diethoxymethoxyallyl compound by a catalyst, characterized in that a 3,4-diethoxypropenyl group containing a starting material is used. After the solution of the compound (hereinafter referred to as 3,4-diethyloxyallyl compound-containing solution) is contacted with the phosphorus compound, the 3,4-diethyloxyallyl compound is treated in the presence of a catalyst. Structure.

By contacting the phosphorus compound with the 3,4-diethyloxyallyl compound-containing solution, the phosphorus compound can be used to remove a component which significantly promotes the deterioration of the isomerization catalyst. Compared with the solid base, the phosphorus compound is easily changed in the process operation, so that the amount of the 1,4-diethoxy allylic compound formed by the isomerization can be monitored while being required. Minimum addition The addition inhibits catalyst degradation. Further, since it is not necessary to fill a predetermined amount of solid alkali before the start of the process operation as in the case of a solid base, it can be completed in a small amount.

The "method of isomerizing a 3,4-diethyloxyallyl compound by a catalyst to a 1,4-diethyloxyallyl compound", for example, "3,4-2 a method in which an ethoxylated allyl compound is contacted with a catalyst to beomerized to a 1,4-diethoxymethoxyallyl compound to obtain a 1,4-diethoxymethoxyallyl compound, "3,4-diethyloxyl in the mixture by contacting a mixture of a 3,4-diethyloxyallyl compound and a 1,4-diethoxymethoxyallyl compound with a catalyst. Isomerization of a propyl compound to a 1,4-diethyloxyallyl compound to increase the concentration of a 1,4-diethyloxyallyl compound or "3,4-diethyl hydrazine" The mixture of the oxyallyl compound and the 1,4-diethoxymethoxyallyl compound is contacted with a catalyst to isomerize the 1,4-diethoxymethoxyallyl compound in the mixture to 3, 4-Diethoxymethoxyallyl compound to increase the concentration of 3,4-diethyloxyallyl compound.

In the present invention, a 3,4-diethyloxyallyl compound (including a mixture of "3,4-diethyloxyallyl compound and 1,4-diethyloxyallyl compound" It is not particularly limited, and it can be produced by a diethyl hydroxylation reaction of a conjugated diene or the like in the presence of a catalyst.

The diethylhydroxylation reaction for producing a conjugated diene of a diethyl ethoxyallyl compound can be carried out by various methods. Most commonly in the presence of a palladium-based catalyst, butadiene, acetic acid and oxygen are reacted to obtain 1,4-diethoxyoxy-2-butene which is a diethyl ethoxyallyl compound and 3,4-diethyl hydrazine Oxy-1-butene. Further, 1-hydroxy-4-ethenyloxy-2-butene, 3-hydroxy-4-ethenyloxy-1- which is a hydrolyzate of these diethyl ethoxyallyl compounds is also combined. Butene, 4-hydroxy-3-ethenyloxy-1-butene, and the like.

Examples of the conjugated diene which can be used in the present invention include butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and 1,3-cyclohexadiene. , 3-cyclopentadiene, 1,3-cycloheptadiene, 1,3-cyclooctadiene, 1,3-pentadiene, 1,3-hexadiene, 2,4-hexadiene, etc. Preferably, butadiene, isoprene, 1,3-cyclohexadiene, 1,3-cyclopentadiene, particularly preferably butadiene, isoprene. A conjugated diene having a small carbon number such as butadiene or isoprene is preferred because it exhibits the highest reactivity.

The catalyst used for the diethyl oximation reaction of the conjugated diene may be any catalyst having the ability to convert a conjugated diene to a diethyl ethoxyallyl compound. Preferably, it is a solid catalyst containing a transition metal of Groups 8 to 10, and particularly preferably a palladium solid catalyst. The palladium solid catalyst is composed of palladium metal or a salt thereof, and as the auxiliary catalyst, a metal such as ruthenium, selenium, tellurium, ruthenium or copper or a salt thereof is preferably used, and particularly preferably ruthenium. The reason why the combination of palladium and rhodium is preferred is that the activity of the catalyst is high, and the selectivity of the obtained diethyl ethoxyallyl compound is high. Therefore, it is preferred to carry palladium and rhodium as a solid catalyst as an active ingredient. The palladium solid catalyst is not particularly limited, and is preferably used by being supported on a carrier such as cerium oxide, aluminum oxide, titanium oxide, zirconium oxide, activated carbon or graphite, and particularly preferably cerium oxide having excellent strength. The physical properties of the carrier are preferably porous, more preferably from 5 to 80 nm. In the case of a catalyst with a carrier, the ratio of the catalytic metal to the entire catalyst is usually 0.1 to 20% by weight, preferably 1 to 10% by weight, and The ratio of the other auxiliary catalyst metal to the entire catalyst is selected from the range of 0.01 to 30% by weight, more preferably 0.1 to 10% by weight. If the value is too small, the cost competitiveness will be degraded due to the decrease in the activity of the catalyst, and if the value is too large, the competitiveness will decrease due to the excessive cost of the catalyst.

The above-mentioned diethyl ethoxylation reaction is preferably carried out in air or oxidized air, air or oxygen diluted with an inert gas such as nitrogen, or an oxygen atmosphere, and the oxygen concentration may be in the range of 1 to 100 vol%. Good is 2~50vol%, especially good is 3~40vol%. The higher the oxygen concentration, the higher the reaction rate, and the product can be efficiently obtained. On the other hand, the lower the oxygen concentration, the less the risk of a process such as an explosion or a fire.

The diethyl ethoxylation reaction can be carried out in any one of a gas phase and a liquid phase. The reaction temperature is in the range of 0 to 300 ° C, preferably 10 to 250 ° C, more preferably 30 to 200 ° C. The higher the reaction temperature, the higher the reaction rate, and the product can be obtained efficiently. On the other hand, the lower the reaction temperature, the less the risk of a process such as an explosion or a fire. The reaction pressure is preferably in the range of atmospheric pressure to 50 MPa, preferably from atmospheric pressure to 30 MPa, and particularly preferably from 1 to 20 MPa.

In the case where the solvent is used in the liquid phase, the solvent used in the reaction is not particularly limited as long as it dissolves the reaction raw material, and it is preferably water or a carboxylic acid such as acetic acid or butadiene. The conjugated diene of the reaction raw material itself, or the diethyl ethoxyallyl compound itself belonging to the product. Further, as the solvent, hydrocarbons such as hexane, heptane, and octane; ethers such as tetrahydrofuran, diethyl ether, and triglyme; ethyl acetate and butyl butyrate may be used. Esters such as esters; ketones such as acetone and methyl isobutyl ketone; alcohols such as 1,4-butanediol; and the like.

The weight of the conjugated diene and the catalyst to be used as the raw material 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 in the range of 100 to 20,000,000. The smaller the weight ratio, the higher the reaction rate, and it is easy to carry out the reaction in a short time. Moreover, the greater the weight ratio, the less the catalyst cost can be achieved.

In addition, the "3,4-diethyloxyallyl compound-containing liquid" in the present invention means a 3,4-diethyloxyallyl compound or 3,4-diethyl. The liquid of the mixture of the methoxy allyl compound and the 1,4-diethoxy allyl compound is not particularly limited. Preferably, any one of the following is referred to as a "3,4-diethyloxyallyl compound-containing liquid": (1) a 3,4-diethyloxyallyl compound-containing liquid and phosphorus Before the contacting of the compound, a step of diacetylating the conjugated diene by the above catalyst is provided, and the reaction obtained by the reaction forms a stream itself; (2) a stream is formed from the reaction, and is removed by distillation or the like. a part or all of a compound having a lower boiling point than a diethyl ethoxyallyl compound formed by a by-product (hereinafter, a compound having a lower boiling point than a diethyl ethoxyallyl compound is simply referred to as a light-boiling compound) (3) a stream is formed from the reaction, and a compound having a higher boiling point than the 3,4-diethyloxyallyl compound formed by by-products is removed by distillation or the like (hereinafter, the boiling point is 3, 4) a part or all of a compound having a high ethylenedioxyallyl compound; or a part of the high-boiling compound; (4) a stream derived from the reaction, and a light-boiling compound and a by-product of the by-product removed by distillation or the like Some or all of the high boiling compounds. Among them, it is particularly preferable to generate a logistic product by reacting (1) a diethyl oxiranation reaction of a conjugated diene by a catalyst. The body is referred to as "3,4-diethyloxyallyl compound-containing solution". The "3,4-diethoxy allyl compound-containing liquid" is a case where a stream is generated from a reaction obtained by a diethyl oximation reaction of a conjugated diene by the above-mentioned catalyst, The corresponding 1,4-diethoxymethoxyallyl compound is present in the containing liquid. Further, the "3,4-diethyloxyallyl compound-containing solution" may contain 3,4-hydroxyethyloxy allylate which is a hydrolyzate of a 3,4-diethyloxyallyl compound. a base compound and/or a 3,4-dihydroxyallyl compound, and further, may contain a 1,4-hydroxyethyloxy allylate which is a hydrolyzate of a 1,4-diethyloxyallyl compound. a base compound and/or a 1,4-dihydroxyallyl compound.

The "3,4-diethyloxyallyl compound-containing liquid" used in the present invention will contain a 3,4-diethyloxyallyl compound, 1,4-diethoxydecene. A liquid of a propyl compound, a low-boiling compound, and a high-boiling compound is introduced into a distillation column, and a liquid containing a high-boiling compound and a 1,4-diethoxymethoxyallyl compound is withdrawn from the bottom of the column, from the upper portion of the column. It was obtained by distilling off a 3,4-diethoxy allylic compound containing liquid. In this case, the 3,4-diethyloxyallyl compound-containing liquid may be extracted together with the light-boiling compound from the top of the column, or may be contained in the 3,4-diethyloxyallyl compound. The liquid is withdrawn from the side stream and the light boiling compounds are distilled off from the top. At this time, almost the total amount of the high-boiling compound is extracted from the bottom of the column, but a small amount of the high-boiling compound is mixed with the 3,4-diethyloxyallyl compound-containing liquid from the upper portion or the side stream. Take out.

Further, the pressure of the distillation column may be set to any, but from the viewpoint of the energy cost of the reboiler of the distillation column, in order to lower the temperature at the bottom of the column, Preferably, the top pressure is set to 1 to 760 mmHg. Further, it is more preferable that the top pressure of the tower is in the range of 5 to 200 mmHg and particularly preferably 10 to 100 mmHg. If the top pressure is too low, it will require too much cost in order to maintain the pressure. Further, the distillation column itself becomes larger, and the process construction cost is increased. Further, when the pressure at the top of the column is too high, the temperature at the bottom of the distillation column becomes high, and the vapor cost increases. The temperature at the top of the column is generally in the range of 0 to 200 ° C, preferably 20 to 160 ° C, more preferably 40 to 140 ° C. If the temperature at the top of the tower is too low, a special device such as a cooler is required to deteriorate the cost. Further, if the temperature is too high, the temperature at the bottom of the column also becomes a higher temperature, so that the steam cost is increased. The reflux ratio can be from 1 to 100, preferably from 1 to 10. If the reflux ratio is too small, the separation ability is deteriorated. If the reflux ratio is too high, the amount of heat required increases, which causes a deterioration in cost. The amount of distillation at the top of the column is preferably a 3,4-diethoxy allylic compound, a 1,4-diethoxy allylic compound, a low boiling point compound, and the like introduced into the distillation column. In the liquid of the high boiling point compound, the total amount of the 3,4-diethyloxyallyl compound and the light boiling point compound are distilled off. Further, in the case where the 3,4-diethyloxyallyl compound-containing liquid is distilled off from the side stream and the light-boiling compound is distilled off from the top, it is preferred to introduce 3,4-diethyl in the introduction liquid. The content of the decyl allyl compound is distilled off from the side stream, and the content of the light-boiling compound in the introduction liquid is distilled off from the top of the column. Extracting a liquid containing a high boiling point compound and a 1,4-diethoxymethoxyallyl compound from the bottom of the distillation column, and distilling 3,4-diethyloxane containing a low boiling point compound from the top of the distillation column In the case of the allylic compound, the distillation column material balance is 1 to 50, preferably 5 to 30, per unit time when the weight of the introduction flow rate per unit time is 100. At this time, every single order from the bottom of the tower The amount of the liquid containing the high-boiling compound and the 1,4-diethoxymethoxyallyl compound in the bit time is preferably from 50 to 99, more preferably from 70 to 95. Further, a liquid containing a high boiling point compound and a 1,4-diethoxymethoxyallyl compound is taken out from the bottom of the distillation column, and a light boiling point compound is distilled off from the top, and 3 is distilled off from the side stream. In the case of a 4-diethoxy allyl compound-containing liquid, when the weight of the introduction flow rate per unit time is set to 100, the overhead flow rate per unit time is 0.1 to 30, preferably 1 to 20 . Further, the amount of the 3,4-diethyloxyallyl compound-containing liquid to be refluxed from the side stream is preferably from 0.9 to 50, more preferably from 2 to 30. Further, the amount of extraction per unit time of the liquid containing the high boiling point compound and the 1,4-diethoxymethoxyallyl compound from the bottom of the column is preferably from 20 to 99, more preferably from 50 to 97.

The above-mentioned 3,4-diethyloxyallyl compound-containing liquid containing a light-boiling compound obtained from the top of the column can be supplied to the isomerization reaction after removing the light-boiling compound by distillation. At this time, the light-boiling compound can be distilled off from the top by a separation distillation column of a light-boiling compound, and the 3,4-diethyloxyallyl compound-containing liquid is withdrawn from the bottom of the column including the side stream.

Further, the pressure of the distillation column may be set to any value. However, from the viewpoint of the energy cost of the reboiler of the distillation column, in order to lower the temperature at the bottom of the column, it is preferred to set the column top pressure to 1 to 760 mmHg. Further, it is more preferable that the top pressure of the tower is in the range of 5 to 400 mmHg and particularly preferably 10 to 200 mmHg. If the top pressure is too low, it will require too much cost in order to maintain the pressure. Further, the distillation column itself becomes larger, and the process construction cost is increased. Further, when the pressure at the top of the column is too high, the temperature at the bottom of the distillation column becomes high, and the vapor cost increases.

The temperature at the top of the tower is generally 0~200°C, preferably 20~160°C, and better 40~140. The range of °C. If the temperature at the top of the tower is too low, a special device such as a cooler is required to deteriorate the cost. Further, if the temperature is too high, the temperature at the bottom of the column also becomes a higher temperature, so that the steam cost is increased. The reflux ratio can be from 1 to 100, preferably from 1 to 10. If the reflux ratio is too small, the separation ability is deteriorated. If the reflux ratio is too high, the amount of heat required increases, which causes a deterioration in cost. The amount of distillation at the top of the column is preferably such that it is introduced into a liquid containing a 3,4-diethyloxyallyl compound and a low-boiling compound in a distillation column, and the total amount of the light-boiling compounds is distilled off. Further, in the case where the 3,4-diethyloxyallyl compound-containing liquid is withdrawn from the bottom of the column including the side stream of the distillation column, and the light-boiling compound is distilled off from the top, the distillation column material balance is When the weight of the introduced flow rate per unit time is set to 100, the overhead flow rate per unit time is 1 to 50, preferably 5 to 45. At this time, the amount of the liquid containing the 3,4-diethyloxyallyl compound per unit time including the bottom of the side stream is preferably from 50 to 99, more preferably from 55 to 95.

In the present invention, the 3,4-diethyloxyallyl compound-containing solution is contacted with a phosphorus compound, but in the step of diacetylation of a conjugated diene by a catalyst. In the case where the obtained reaction product is a "3,4-diethyloxyallyl compound-containing liquid", the reaction product stream may be supplied to the phosphine before being subjected to distillation separation; After the distillative separation reaction of the conjugated diene by the diethylation reaction, the 3,4-diethyloxyallyl compound-containing liquid distilled from the top of the column is contacted with the phosphine; The 3,4-diethyloxyallyl compound distilled from the side stream is contacted with a phosphine. Since the amount of liquid contacted is small and the effect is small with a small amount of phosphorus compound, it is preferred to make it The phosphorus compound is contacted with the liquid distilled from the top of the column or the liquid distilled from the side stream.

The type of the distillation column that can be used may, for example, be a packed column or a plate column, and is preferably a plate column. When the 3,4-diethoxypropenyl compound-containing solution is separated from the 1,4-diethoxy allyl compound-containing solution, the theoretical section of the distillation column is set to 3 or more, and particularly preferably 10 ~50 paragraphs. More than 50 stages of distillation towers are less expensive in terms of economics, operational difficulty and safety management of distillation tower construction. Moreover, if the number of segments is too small, separation is difficult.

The 3,4-diethyloxyallyl compound used in the isomerization reaction of the present invention is specifically preferably 3,4-diethyloxy-1-butene or 3,4-di. Ethyloxy-2-methyl-1-butene, 3,4-diethoxycarbonyl-3-methyl-1-butene, 3,4-diethyloxy-2,3-di Methyl-1-butene, 3,4-diethyloxy-1-cyclohexene, 3,4-diethyloxy-1-cyclopentene, 3,4-diethoxycarbonyl- 1-cycloheptene, 3,4-diethyloxy-1-cyclooctene, more preferably 3,4-diethyloxy-1-butene, 3,4-diethyloxy- 2-methyl-1-butene, 3,4-diethyloxy-3-methyl-1-butene, 3,4-diethyloxy-1-cyclohexene, 3,4- Diethyloxy-1-cyclopentene, particularly preferably 3,4-di of 1,4-diethoxyoxy-2-butene which can be converted into an intermediate of 1,4-butanediol Ethoxylated 1-butene.

Further, 3-hydroxy-4-ethenyloxy-1-butene, 4-hydroxy-3-ethenyloxy-1, which is a hydrolyzate of 3,4-diethyloxy-1-butene The isomerization method of the present invention can also be applied to the isomerization reaction of butene or the like.

In addition, the difference of the 3,4-diethyloxyallyl compound in the present invention The obtained 1,4-diethoxymethoxyallyl compound is an isomer corresponding to the 3,4-diethyloxyallyl compound before isomerization. As the 1,4-diethoxymethoxyallyl compound which is an isomer, specifically, 1,4-diethoxycarbonyl-2-butene and 1,4-diethoxycarbonyl are preferable. -2-methyl-2-butene, 1,4-diethoxycarbonyl-2,3-dimethyl-2-butene, 1,4-diethoxycarbonyl-2-cyclohexene, More preferably 1,4-diethoxyoxy-2-cyclopentene, 1,4-diethoxycarbonyl-2-cycloheptene, 1,4-diethoxycarbonyl-2-cyclooctene Is 1,4-diethoxycarbonyl-1-butene, 1,4-diethoxycarbonyl-2-methyl-1-butene, 1,4-diethoxycarbonyl-3-methyl 1-butene, 1,4-diethoxyoxy-1-cyclohexene, 1,4-diethoxycarbonyl-1-cyclopentene, particularly preferably 1,4-butanediol The intermediate is 1,4-diethoxymethoxy-1-butene.

In the present invention, various solvents can be used in the isomerization reaction of the 3,4-diethyloxyallyl compound. The solvent is not particularly limited, and specific examples thereof include carboxylic acids such as formic acid, acetic acid, propionic acid, and butyric acid; and alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, and octanol. Class; diethyl ether, tetrahydrofuran, two An ether such as an alkane or a triethylene glycol dimethyl ether; an aromatic hydrocarbon such as benzene, toluene or xylene; hexane, heptane, octane, decane, decane, dodecane, and a ring; An organic solvent such as a hydrocarbon such as hexane, cycloheptane or cyclooctane. A carboxylic acid such as formic acid, acetic acid, propionic acid or butyric acid is preferred, and particularly preferred is acetic acid which increases the isomerization rate of the ethoxylated oxy group. A preferred reason for using acetic acid as a solvent is to increase the isomerization rate and to increase the concentration of acetamidine in the reaction liquid, that is, the concentration of acetic acid.

The amount of the solvent added is 0 to 10,000% by weight, preferably 0.05 to 500% by weight, based on the weight of the diethyl ethoxyallyl compound. 1~200wt%. The smaller the amount of the solvent added, the smaller the reactor capacity can be, and the more the amount of addition, the higher the catalyst deterioration rate tends to be.

The catalyst used in the isomerization of the 3,4-diethyloxyallyl compound in the present invention has the isomerization of the 3,4-diethyloxyallyl compound to 1,4 The ability of the -diethoxy allylic compound is not particularly limited, and may be a liquid phase homogeneous conjugate catalyst, preferably a homogeneous tyrosine catalyst of a transition metal of Group 8 to 10, It is a liquid phase homogeneous palladium complex catalyst which exhibits an extremely high activity for the isomerization rate of ethoxylation.

The liquid phase homogeneous chelating catalyst can be prepared from various transition metals, and specific examples thereof include acetate, acetaminoacetic acid compound, chloride, bromide, iodide, sulfate, nitrate, organic salt, and inorganic. A salt, an olefin complex, a carbon monoxide complex, a phosphine complex, a phosphorous acid complex, and the like.

As the liquid phase homogeneous chelating catalyst, it is preferably palladium metal, palladium acetate, palladium chloride, dichlorocyclooctadiene palladium, ruthenium (triphenylphosphine) palladium or bis(dibenzylideneacetone) palladium. , palladium trifluoroacetate, palladium acetylacetonate, nickel acetate, nickel dicyclooctadiene, platinum acetate, dicyclooctadiene platinum, etc., particularly preferably palladium acetate, palladium chloride, trifluoroacetic acid palladium. In the present invention, the form of the metal compound is not particularly limited, and the active complex catalyst may be a monomer, a dimer, and/or a polymer.

Further, in the present invention, a phosphorus compound can be used as a ligand system of the liquid phase homogeneous conjugate catalyst. For example, if it is a phosphorus ligand such as a phosphine, a phosphorous acid, a phosphoric acid, a hypophosphorous acid or a phosphoniumamine, it can be used without particular limitation. These ligands may be mono- or poly-ligands. As a ligand, Preferably, it is a phosphorus compound having a P-O bond, and particularly preferably a phosphorous acid or a phosphorous amine, particularly preferably a phosphorous acid or a phosphonium amine of a double ligand. The reason is that in the isomerization reaction via the π-allyl intermediate, since the ligand having a lower electron density promotes an increase in the reaction rate, it is preferably a P-O bond having a lower electron density. Phosphorus compound. Further, in the present invention, generally, one type of ligand is used, but two or more kinds of phosphorus ligands may be used in combination. Further, other ligands may be used in combination as long as they do not significantly impair the effects of the present invention.

In the present invention, in the case of using a phosphorus compound having a P-O bond as a ligand, for example, the following general formulas (1) to (5) and formulas (6-1) to (6-7) are used. The compound shown. Further, in the present invention, generally, one type of ligand is used, but two or more kinds of phosphorus ligands may be used in combination. Further, other ligands may be used in combination as long as they do not significantly impair the effects of the present invention.

In the above formulas (1) to (5), X~X''' is selected from any one of (X1) to (X5), and Y~Y''' may be any of (Y1) to (Y5). Any choice.

In the above (X1) to (X5), (Y1) to (Y5) and (6-1) to (6-7), R, R' and R ¹ to R ⁵⁴ each independently represent an alkoxy group and an alkoxy group. A cycloalkyl group, an aryloxy group, an alkylaryloxy group, an amine group or an aryl group may further have a substituent. When R, R' and R ¹ to R ⁵⁴ are an alkyl group, or a substituent having an alkyl skeleton (alkyl group in an alkyl aryloxy group, etc.), the carbon number is usually from 1 to 20, preferably. 1~14. Specific examples thereof include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a second butyl group, a tert-butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, and the like. . Further, the alkyl group or the alkyl skeleton moiety 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 amine group, a cyano group, and a carbon number of 2. ~10 ester group, hydroxyl group and halogen atom.

Further, when R, R' and R ¹ to R ⁵⁴ are an aryl group or a substituent having an aryl skeleton, the carbon number is usually 6 to 20, preferably 6 to 14. The aryl or aryl skeleton moiety 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, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and carbon. 6 to 20 aryloxy groups, 6 to 20 carbon aryl groups, 6 to 20 alkyl aryloxy groups, 6 to 20 aryl aryl groups, carbon number 6 to 20 aryl Alkoxy group, cyano group, ester group, ester group, hydroxyl group and halogen atom.

Specific examples of the case where R, R' and R ¹ to R ⁵⁴ are an aryl group include a phenyl group, a 1-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, and 2,3. - dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 2-ethylphenyl, 2-isopropylbenzene , 1-tert-butylphenyl, 2,4-di-t-butylpropyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2,3-dichlorophenyl , 2,4-dichlorophenyl, 2,5-dichlorophenyl, 3,4-dichlorophenyl, 3,5-dichlorophenyl, 4-trifluoromethylphenyl, 2-methoxy Phenylphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 3,5-dimethoxyphenyl, 4-cyanophenyl, 4-nitrophenyl, trifluoromethyl, Pentafluoroethyl, pentafluorophenyl and the following groups (C-1) to (C-8).

Formula (1) to (5) and (Y1) ~ (Y5) in, A ~ A "and A ¹ ~ A ⁵ each independently represent: a substituted group may have a carbon number of the alkyl group having 1 to 20 extension, also a aryl group having 6 to 30 carbon atoms having a substituent, or a diaryl group having a divalent bond group in the middle of Ar ¹ -(Q ¹ ) _n -Ar ² (wherein Ar ¹ and Ar ² independently represents an extended aryl group having 6 to 18 carbon atoms which may have a substituent.

In the formulae (6-1) to (6-7), T ¹ to T ⁷ each independently represent a carbon atom, an alkane tetrayl group, a phenyltetrayl group, or may have a T ⁸ -(Q ² ) _n -T ⁹ The tetravalent group of the substituent, T ⁸ and T ⁹ each independently represent an alkane triyl group having 1 to 10 carbon atoms, and a trivalent group which may be substituted with a benzene triyl group having 6 to 15 carbon atoms. Q ¹ and Q ² respectively represent -CR ⁵⁵ R ⁵⁶ -, -O-, -S-, -CO-, n is 0 or 1, and R ⁵⁵ and R ⁵⁶ independently represent a hydrogen atom and a carbon number of 1 to 10. The alkyl group or the aryl group having 6 to 20 carbon atoms may have a substituent.

Further, A ~ A "and when A ¹ ~ A ⁵ is alkylene includes, for example tetramethyl extending ethyl, propyl dimethyl stretching etc. Also, the A ~ A" and A ¹ ~ A ⁵ In the case of an alkylene group which may have a substituent, examples of the substituent include an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an amine group, a cyano group, a decylamino group, and a trifluoromethyl group. Base. Further, when A to A" and A ¹ to A ⁵ are an extended aryl group which may have a substituent, for example, a phenyl group or a naphthyl group may be mentioned, and as the substituent, for example, an alkyl group having 1 to 10 carbon atoms may be mentioned. An oxy group, a aryl group having 6 to 20 carbon atoms, an amine group, a cyano group, a decylamino group, a trifluoromethyl group or the like.

Further, the A ~ A "and A ¹ ~ A ⁵ to be on _{^{Ar 1 - (Q 1) n}} -Ar ² bis middle arylene group having a divalent bonding group when, Ar ¹ and Ar ² each It is independently an extended aryl group having a carbon number of 6 to 18 which may have a substituent, and the carbon number of the aryl group is 6 to 24, more preferably 6 to 16. As a specific example of a preferable substituent, for example, a carbon number An alkyl group of 1 to 10, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an amine group, a cyano group, a decylamino group, a trifluoromethyl group or the like.

Further, specific examples of A to A" and A ¹ to A ⁵ include -(CH ₂ ) ₂ -, -(CH ₂ ) ₃ -, -(CH ₂ ) ₄ -, -(CH ₂ ). ₅ -(-(CH ₂ ) ₆ -, -CH(CH ₃ )-CH(CH ₃ )-, -CH(CH ₃ )CH ₂ CH(CH ₃ )-, -(CH ₃ ) ₂ -C(CH ₃ ) ₂ -, -C(CH ₃ ) ₂ -CH ₂ -C(CH ₃ ) ₂ -, and the following groups (A-1) to (A-48).

Preferred specific examples of the compounds of the formulae (1) to (5) and (6-1) to (6-7) representing the ligand of the present invention are exemplified by the following monodentate group (L-1). ~(L-16) and multi-ligand (L-17)~(L-44), and a specific example can be exemplified as (L-17) to (L-36).

In the specific examples of the phosphorous acid and the phosphite, it is preferably L20 to L44 and particularly preferably L21 to L30. These preferred reasons are believed to be due to the higher thermal stability of the ligand and the less loss due to the inactivation of the coal-active species.

In the present invention, the amount of the homogeneous conjugate catalyst used for the isomerization of the diethyl ethoxyallyl compound is a metal in the liquid of the 3,4-diethoxy allylic compound. The amount of the 3,4-diethyloxyallyl compound-containing solution is preferably 0.001 to 1000 wtppm, more preferably 0.01 to 100 wtppm, particularly preferably 0.1 to 10 wtppm. If the amount of the catalyst is larger, the reaction rate is higher, the size of the reactor can be reduced, and the equipment cost can be reduced. In addition, if the amount of the catalyst is smaller, the cost of the ligand can be reduced.

Further, the molar ratio of the phosphorus atom in the ligand of the ligand is preferably from 0.1 to 1,000, more preferably from 1 to 100, particularly preferably from 1 to 10, with respect to the transition metal in the complex catalyst. The more the amount of the ligand, the higher the reaction rate. On the other hand, the smaller the amount of the ligand, the lower the catalyst cost.

The reaction temperature in carrying out the isomerization reaction is preferably 40 to 200 ° C, more preferably 80 to 180 ° C, and particularly preferably 100 to 160 ° C. Since the reaction temperature is higher as the reaction temperature is higher, the reactor can be reduced, so that the equipment cost can be reduced. On the other hand, the lower the reaction temperature, the slower the deterioration of the catalyst, so that the catalyst cost can be reduced.

Further, in addition to the above catalyst ligand, other phosphorus compounds may be used in combination as an auxiliary catalyst, whereby the stability of the catalyst or the reaction rate can be improved. The phosphorus compound used herein is not particularly limited as long as it has three substituents bonded to the phosphorus atom. Preferred are: triphenylphosphine, tris(2-methylphenyl)phosphine, tris(4-methylphenyl)phosphine, tris(2-methoxyphenyl)phosphine, tris(4-methoxy) a triarylphosphine such as phenyl)phosphine; a diarylalkylphosphine such as diphenylmethylphosphine, diphenylethylphosphine or diphenylpropylphosphine; dimethylphenylphosphine, diethyl a trialkylphosphine such as a dialkylarylphosphine such as a phenylphosphine, a trioctylphosphine or a tributylphosphine; more preferably a triphenylphosphine, a tris(2-methylphenyl)phosphine or a trisole a triarylphosphine such as (4-methylphenyl)phosphine, tris(2-methoxyphenyl)phosphine or tris(4-methoxyphenyl)phosphine; particularly preferably triphenylphosphine.

The amount of other phosphorus compound other than the auxiliary catalyst other than the ligand is such that the molar ratio of the phosphorus atom in the phosphorus compound is from 1 to 10,000, preferably from 10 to 30, based on the amount of the transition metal in the complex catalyst. 2000, especially good 50~500. If the amount of the phosphorus compound is too small, the reaction rate is lowered, and if it is too large, the cost is increased. If it is such a range, the phosphorus compound used together may be used alone, or a plurality of phosphorus compounds may be used in combination.

The reactor used in the isomerization reaction in the present invention may be in the form used in general liquid phase reaction. Preferred are tubular reactors, tank reactors, which can be used in single or multiple stages. It is a particularly good tank type reactor and a multi-stage tank type reactor, and is preferably a multi-stage tank type reactor in which an open disk is provided.

In the present invention, before the isomerization of the 3,4-diethyloxyallyl compound to the 1,4-diethoxyallyl allyl compound by means of a catalyst, it is necessary to make 3,4-diethyl The decyl allyl compound is contacted with a phosphorus compound. Among the phosphorus compounds, an organic phosphorus compound is preferred, and among the organic phosphorus compounds, organic phosphorous acid, organic phosphorous amines, and organic phosphines are more preferred, and organic phosphines are particularly preferred. As the organic phosphine, an organic phosphine having a monodentate group, a biligand group or a tridentate group or more, preferably an organophosphine having a monodentate group of two or more aryl groups can be used. These are not particularly limited, and commercially available products can be used. Specifically, preferred are trimethylphosphine, triethylphosphine, tripropylphosphine, tributylphosphine, tripentylphosphine, trihexylphosphine, triheptylphosphine, trioctylphosphine, tricyclopentyl An alkylphosphine such as phosphine, tricyclohexylphosphine or tricycloheptylphosphine; or triphenylphosphine, diphenylmethylphosphine, diphenylethylphosphine, diphenylbutylphosphine, dimethylphenyl a phenylphosphine such as phosphine, diethylphenylphosphine, dibutylphenylphosphine, stilbene (tolyl)phosphine, 1,2-bis(diphenylphosphino)ethane or the like; more preferably phenylphosphine, Among them, triphenylphosphine, diphenylmethylphosphine, diphenylethylphosphine, diphenylbutylphosphine, and stilbene (p-tolyl)phosphine are preferred, and triphenylphosphine is most preferred. Further, in the present invention, one type of phosphorus compound is usually used, but two or more kinds of phosphorus compounds may be used in combination. also, Other compounds may be used in combination as long as they do not significantly impair the effects of the present invention.

The temperature at which the 3,4-diethoxy allylic compound is contacted with the phosphorus compound before isomerization to the 1,4-diethoxy allylic compound by a catalyst, usually 60 ° C or higher, preferably 80 ° C or higher, and particularly preferably 100 ° C or higher. On the other hand, the temperature at which the phosphorus compound is usually contacted 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 degradation component of the phosphorus compound. Moreover, the lower the temperature, the lower the energy cost for heating the phosphorus compound.

Further, the contact time is preferably from 1 minute to 100 hours, more preferably from 10 minutes to 10 hours, and particularly preferably from 30 minutes to 5 hours. The longer the contact time, the more sufficient the removal of the catalyst degradation component can be performed. Moreover, the shorter the contact time, the higher the operating efficiency of the process.

Further, the phosphorus compound is used in an amount of 0.00001 to 10% by weight, more preferably 0.0001 to 1% by weight, particularly preferably 0.001, based on the 3,4-diethyloxyallyl compound-containing solution. ~0.1% by weight. The more the amount of the phosphorus compound used, the effect of sufficiently removing the catalyst-degraded component. On the other hand, if the amount of the phosphorus compound used is small, the cost of the phosphorus compound can be reduced.

In the present invention, 3,4-diethyl is used as the 3,4-diethyloxyallyl compound is isomerized to a 1,4-diethoxyoxyallyl compound by a catalyst. The method of contacting the methoxyallyl compound with the phosphorus compound is not particularly limited, but generally, for example, (1) the 3,4-diethyloxyallyl compound and the phosphorus compound are placed in a container. Mixing and mixing (2) additionally preparing a solution of a 3,4-diethyloxyallyl compound containing a phosphorus compound, and a 3,4-diethyloxyallyl compound and a 3,4-di containing a phosphorus compound The ethoxylated allyl compound solution is placed in a container and stirred or mixed; or (3) the 3,4-diethoxy allylic compound and the 3,4-diB containing the phosphorus compound Each of the decyl allyl compound solutions is prepared as a flowing liquid, and each of the pipes is integrated into one pipe to be brought into contact with the mixture. Further, it is also possible to perform heating after the contact, and mixing by the above-mentioned required temperature and time. From the viewpoint of productivity, it is preferably a continuous process, so as a method of contacting, the above (3) may be a 3,4-diethyloxyallyl compound and a 3,4-di containing a phosphorus compound. The ethoxylated allyl compound solution was separately prepared as a flowing liquid, and each line (pipe) was integrated into one line (pipe) to be brought into contact with the mixture.

The method of contacting the phosphorus compound with the 3,4-diethyloxyallyl compound may be either a fractional or a continuous one, but it is particularly preferably a continuous flow type in terms of ease of operation. The phosphorus compound may be separated and recovered by distillation before the isomerization reaction, but from the viewpoint of energy efficiency, it is preferable to generate the same one as the catalyst component after the completion of the isomerization reaction. The 4-diethoxymethoxyallyl compound is isolated by distillation or the like. Here, the separated phosphorus compound can also be recovered, but it is generally discharged as a waste liquid to the outside of the process system.

In the present invention, in the reaction liquid obtained by the isomerization reaction, in addition to the 1,4-diethoxy allylic compound of the reaction product, there is still unreacted 3,4-diethyl oxime. a allylic compound which can be separated from the reaction liquid by distillation or the like to contain a 3,4-diethoxy allylic compound liquid. At this time, the pressure of the distillation column can be arbitrarily set, but in order to lower the temperature at the bottom of the column, it is preferred to set the pressure at the top of the column to 1 to 760 mmHg. Further, it is more preferable that the top pressure of the tower is in the range of 5 to 200 mmHg and particularly preferably 10 to 100 mmHg. If the top pressure is too low, a large cost is required in order to maintain the pressure, and the distillation column itself becomes large, which increases the construction cost of the process. Further, when the pressure at the top of the column is too high, the temperature at the bottom of the distillation column becomes high, and the cost of steam is increased. The temperature at the top of the column is usually in the range of 0 to 200 ° C, preferably 20 to 160 ° C, more preferably 40 to 140 ° C. If the temperature at the top of the tower is too low, a special device such as a cooler is required to deteriorate the cost. Further, if the temperature is too high, the temperature at the bottom of the column also becomes a higher temperature, so that the steam cost is increased. The reflux ratio can be from 1 to 100, preferably from 1 to 10. If the reflux ratio is too small, the separation ability is deteriorated. If the reflux ratio is too high, the amount of heat required increases, which causes a deterioration in cost. The amount of distillation at the top of the column is preferably selected from the group consisting of a 3,4-diethoxy allylic compound, a 1,4-diethoxy allylic compound, and a low boiling point compound introduced into the distillation column. In the liquid of the high boiling point compound, the total amount of the 3,4-diethyloxyallyl compound and the light boiling point compound are distilled off. Further, in the case where the 3,4-diethoxy allylic compound-containing liquid is distilled off from the side stream and the light-boiling compound is distilled off from the top of the column, it is preferred to introduce the 3,4- into the liquid. The content of the diethyl ethoxyallyl compound is distilled off from the side stream, and the content of the light-boiling compound in the introduction liquid is distilled off from the top.

The unreacted 3,4-diethyloxyallyl compound can be introduced into the isomerization reactor by distillation to separate the 3,4-diethyloxyallyl compound-containing liquid. Isomerization to a 1,4-diethyloxyallyl compound. 3,4-diethyloxyallyl propylation recycled to this reactor The compound-containing liquid preferably maintains the temperature at the time of separation by distillation or the temperature in the isomerization reactor, but does not depend on the temperature, pressure, etc. at the time of recirculation, and can be isomerized according to the isomerization reaction conditions. 1,4-Diethoxyoxyallyl compound. Further, the isomerization reaction conditions at this time may be the same conditions as described above.

The 1,4-diethoxymethoxyallyl compound obtained by the isomerization reaction is directly or further purified by distillation or the like, and then hydrogenated in the presence of a transition metal catalyst to be converted into a substituent. A 1,4-diethoxyoxybutane compound. The transition metal catalyst used herein may be a commercially available hydrogenation catalyst, preferably a catalyst containing a precious metal such as palladium or rhodium, or a nickel catalyst. In the presence of such a hydrogenation catalyst, the hydrogen is contacted with the 1,4-diethoxymethoxyallyl compound-containing solution at a temperature ranging from 40 to 180 ° C, and is carried out under a pressure range of from atmospheric pressure to 15 MPa. hydrogenation. When the reaction temperature is too high, the catalyst deterioration proceeds rapidly, and if the reaction temperature is too low, the reaction rate is lowered. If the pressure is too low, the reaction rate is lowered, and if the pressure is too high, an expensive reactor is required.

The 1,4-diethoxyoxybutane compound obtained by the hydrogenation reaction is hydrolyzed by an acid catalyst or a basic substance in the presence of water to be converted into a diol such as 1,4-butanediol. . As the catalyst, a solid acid catalyst, particularly a cation exchange resin, is preferred because it has a faster hydrolysis rate and less by-products such as tetrahydrofuran. Specifically, a copolymer of styrene and divinylbenzene is used as a precursor sulfonic acid type strongly acidic cation exchange resin, and may be either a gel type or a porous type. 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 hydrolysis rate is then reduced, requiring an expensive and bulky reactor. If 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 from 2 to 100 moles, preferably from 4 to 50 moles, per mole of 1,4-diethoxymethoxybutane. If the amount of water is too small, the reaction rate is lowered, and an expensive and bulky reactor is required. Further, when the amount of water is too large, a large amount of energy is required when water is removed from 1,4-butanediol after hydrolysis, so that the energy cost is increased.

(Example)

Hereinafter, the present invention will be described in more detail by way of examples, but without departing from the scope of the invention, the invention is not limited thereto.

Further, in the following examples, the analysis of 3,4-diethyloxy-1-butene and 1,4-diethoxycarbonyl-2-butene was carried out by gas chromatography by an internal standard method. The law is proceeding. Dodecane was used as an internal standard.

Reference Example 1: Step of ethoxylation of butadiene

In the presence of 1 kg of Pd-Te catalyst, 0.24 kg/hr of butadiene, 2.94 kg/hr of acetic acid, and 0.34 kg/hr of nitrogen mixed gas of 6 vol%/94 vol% were circulated in the reactor at 80 ° C. The ethoxylation reaction was carried out under the conditions of 6 MPa to obtain 81% by weight of 1,4-diethoxycarbonyl-2-butene and 9% by weight of 3,4-diethyloxy-1-butene, 3 a mixed liquid of 2% by weight of hydroxy-4-ethenyloxy-1-butene, 3% by weight of acetic acid, 3% by weight of other light-boiling compounds, and 2% by weight of high-boiling compounds.

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

From the mixed liquid 11L obtained in Reference Example 1, a 3,4-diethyloxy-1-butene-containing liquid was separated by continuous distillation. Also, use 20 segments for distillation. Oldershaw distillation tower. Maintaining a temperature range of 20 mmHg at the top of the column, a reflux ratio of 3, a temperature of 95 ° C at the top of the column, and a temperature of 151 ° C at the bottom of the column, continuously introduced at the position of the 10th stage from the bottom of the tower according to the flow rate of 150 cc / hr, from the top of the tower Continuous distillation was carried out at 27 cc/hr, and continuous extraction was carried out at 123 cc/hr from the bottom of the column. By this continuous distillation, a liquid containing 1,4-diethoxycarbonyl-2-butene is obtained as a bottom liquid from the bottom of the column, and 3,4-diethyloxy-1-butene is obtained from the top of the column. The liquid is contained as a distillate. The obtained 3,4-diethyloxy-1-butene-containing liquid contains 45% by weight of 3,4-diethyloxy-1-butene, and 3-hydroxy-4-ethenyloxy-1 - 11% by weight of butene, 22% by weight of acetic acid, 20% by weight of other components having a lower boiling point than 3,4-diethyloxy-1-butene, and a boiling point higher than 3,4-diethyloxy-1- A mixture of 2% by weight of a component of high butene. Further, the content of the 1,4-diethoxycarbonyl-2-butene of the 3,4-diethyloxy-1-butene-containing liquid is 1% by weight or less.

Reference Example 3: Purification distillation of 3,4-diethyloxy-1-butene-containing liquid

The 3,4-diethyloxy-1-butene-containing liquid 1L obtained in Reference Example 2 was subjected to continuous distillation to separate most of the light-boiling compounds. Further, a 40-stage Oldershaw distillation column was used for the distillation. Maintaining a temperature of 100 mmHg at the top of the column, a reflux ratio of 1, a temperature of 95 ° C at the top of the column, and a temperature of 148 ° C at the bottom of the column are continuously introduced at the position of the 20th stage from the bottom of the column according to the flow rate of 100 cc / hr, from the top of the tower to 41cc. The /hr was continuously distilled off and continuously withdrawn from the bottom of the column at 59 cc/hr. By this continuous distillation, light boiling compounds are obtained from the top of the column as a distillate. The distillate contained 59% by weight of acetic acid and 1.6% by weight of 3,4-diethyloxy-1-butene (corresponding to 3,4-diethyloxyallyl compound introduced into the distillation column). 1.5% by weight) The other components having a lower boiling point than 3,4-diethyloxy-1-butene were 39.4% by weight. Further, the liquid extracted from the bottom of the column contained 72% by weight of 3,4-diethoxymethoxy-1-butene and 18% by weight of 3-hydroxy-4-ethenyloxy-1-butene, and the like. A light-boiling compound of 6% by weight and a high-boiling compound of 4% by weight of a 3,4-diethyloxy-1-butene-containing liquid.

Reference Example 4: Catalytic modulation

10.5 mg of palladium acetate, 96.3 mg of a phosphite ligand represented by the above L21, and 49.8 mg of triphenylphosphine were added to the reference example 3 in a glass-made Schlenk flask under a nitrogen atmosphere. The 3,4-diethyloxy-1-butene was contained in 41.3 g of a solution. The mixture was heated at 80 ° C for 1 hour to obtain a completely dissolved catalyst liquid.

Reference Example 5: Catalytic modulation

Under a nitrogen atmosphere, 5.9 mg of palladium acetate, 56.9 mg of a ligand represented by the above L29, and 30.3 mg of triphenylphosphine were added to 13.99 g of toluene in a glass Schlenk apparatus. The mixture was heated at 120 ° C for 20 minutes to give a completely dissolved catalyst solution.

Reference Example 6: Catalytic modulation

In a glass-based Schlenk apparatus, 5.5 mg of palladium acetate, 43.0 mg of a ligand represented by the above L30, and 25.8 mg of triphenylphosphine were added to 12.19 g of toluene in a nitrogen atmosphere. The mixture was heated at 120 ° C for 20 minutes to give a completely dissolved catalyst solution.

(Example 1)

3,4-diethyloxy-1-butene-containing liquid (3,4-di) obtained in the above-mentioned Reference Example 3 "Purified distillation of 3,4-diethyloxy-1-butene-containing liquid" 72% by weight of ethoxylated-1-butene, 18% by weight of 3-hydroxy-4-ethenyloxy-1-butene, and other lower boiling points than 3,4-diethyloxy-1-butene 6 parts by weight of a component having a boiling point higher than that of 3,4-diethyloxy-1-butene and 4% by weight of purified 3,4-diethyloxy-1-butene) 1.5 cc 0.166 mg of triphenylphosphine (0.0073 wt% relative to 3,4-diethyloxy-1-butene) was made into 18 μL of an acetic acid solution having a triphenylphosphine concentration of 0.86% and added thereto at a temperature of 150 ° C. Stirring was carried out for 3 hours.

Next, 1.5 cc of acetic acid was added and mixed into a Schlenk apparatus, and the temperature was raised to 130 ° C by an oil bath. Here, 26 μL of the catalyst liquid prepared in Reference Example 4 was added under a nitrogen atmosphere, and the mixture was heated and stirred at 130 ° C for 3 hours (palladium concentration in the reaction liquid: 1.0 wtppm). The liquid after the isomerization reaction was analyzed by gas chromatography, and as a result, 1,4-diethoxycarbonyl-2-butene (the total of the cis, trans, and 3,4-diethoxy) The weight ratio of keto-1-butene was 45:55. Also, dodecane was used as an internal standard substance. The results are shown in Table 1.

(Example 2)

In the same manner as in Example 1, except that the amount of triphenylphosphine added was changed to 0.332 mg (0.0147% by weight based on 3,4-diethyloxy-1-butene). Implementation. The liquid after the isomerization reaction was analyzed by gas chromatography, and as a result, 1,4-diethoxycarbonyl-2-butene (the total of the cis, trans, and 3,4-diethoxy) The weight ratio of keto-1-butene was 44:56. Also, dodecane was used as an internal standard substance. The results are shown in Table 1.

(Example 3)

In Example 1, except that the addition of triphenylphosphine was followed by stirring at 150. The same procedure as in Example 1 was carried out except that the temperature was allowed to proceed for 1 hour at a temperature of °C. The liquid after the isomerization reaction was analyzed by gas chromatography, and as a result, 1,4-diethoxycarbonyl-2-butene (the total of the cis, trans, and 3,4-diethoxy) The weight ratio of keto-1-butene was 44:56. Also, dodecane was used as an internal standard substance. The results are shown in Table 1.

(Example 4)

In Example 1, except that 0.166 mg of triphenylphosphine (0.0073% by weight based on 3,4-diethoxymethoxy-1-butene) was added, stirring was carried out at a temperature of 30 ° C for 5 hours. The rest was carried out in the same manner as in Example 1. The liquid after the reaction was analyzed by gas chromatography, and as a result, 1,4-diethoxycarbonyl-2-butene (the total of the cis, trans, and 3,4-diethyloxy-1) The weight ratio of butene is 40:60. Also, dodecane was used as an internal standard substance. The results are shown in Table 1.

(Example 5)

In Example 1, except that triphenylphosphine was changed to triphenylphosphoric acid, the amount of triphenylphosphoric acid added was changed to 0.166 mg (relative to 3,4-diethyloxy-1-butene). The same procedure as in Example 1 was carried out except that it was 0.0073% by weight. The liquid after the isomerization reaction was analyzed by gas chromatography, and as a result, 1,4-diethoxycarbonyl-2-butene (the total of the cis, trans, and 3,4-diethoxy) The weight ratio of keto-1-butene was 36:64. Also, dodecane was used as an internal standard substance. The results are shown in Table 1.

(Example 6)

3,4-diethyloxy-1-butene-containing liquid (3,4-di) obtained in the above-mentioned Reference Example 3 "Purified distillation of 3,4-diethyloxy-1-butene-containing liquid" 72% by weight of ethoxylated-1-butene, 18% by weight of 3-hydroxy-4-ethenyloxy-1-butene, and other lower boiling points than 3,4-diethyloxy-1-butene In the 2.94 cc of purified 3,4-diethyloxy-1-butene having a composition of 6 wt% and a higher boiling point than 3,4-diethyloxy-1-butene, 2.94 cc 0.15 mg of triphenylphosphine (0.0050% by weight based on 3,4-diethyloxy-1-butene) was made into 8 μL of an acetic acid solution having a triphenylphosphine concentration of 0.86% and added thereto at a temperature of 150 ° C. Stirring was carried out for 3 hours.

Next, 0.06 cc of acetic acid was added and mixed into a Schlenk apparatus, and the temperature was raised to 130 ° C by an oil bath. Here, 18 μL of the catalyst liquid prepared in Reference Example 5 was added under a nitrogen atmosphere, and the mixture was heated and stirred at 130 ° C for 3 hours (palladium concentration in the reaction liquid was 1.0 wtppm). The liquid after the isomerization reaction was analyzed by gas chromatography, and as a result, 1,4-diethoxycarbonyl-2-butene (the total of the cis, trans, and 3,4-diethoxy) The weight ratio of keto-1-butene was 49:53. Also, dodecane was used as an internal standard substance. The results are shown in Table 2.

(Example 7)

3,4-diethyloxy-1-butene-containing liquid (3,4-di) obtained in the above-mentioned Reference Example 3 "Purified distillation of 3,4-diethyloxy-1-butene-containing liquid" 72% by weight of ethoxylated-1-butene, 18% by weight of 3-hydroxy-4-ethenyloxy-1-butene, and other lower boiling points than 3,4-diethyloxy-1-butene In the 2.94 cc of purified 3,4-diethyloxy-1-butene having a composition of 6 wt% and a higher boiling point than 3,4-diethyloxy-1-butene, 2.94 cc 0.15 mg of triphenylphosphine (0.0050% by weight based on 3,4-diethyloxy-1-butene) was made into 8 μL of an acetic acid solution having a triphenylphosphine concentration of 0.86% and added thereto at a temperature of 150 ° C. Stirring was carried out for 3 hours.

Next, 0.06 cc of acetic acid was added and mixed into a Schlenk apparatus, and the temperature was raised to 130 ° C by an oil bath. Here, 18 μL of the catalyst liquid prepared in Reference Example 6 was added under a nitrogen atmosphere, and the mixture was heated and stirred at 130 ° C for 4 hours (palladium concentration in the reaction liquid was 1.0 wt ppm). The liquid after the isomerization reaction was analyzed by gas chromatography, and as a result, 1,4-diethoxycarbonyl-2-butene (the total of the cis, trans, and 3,4-diethoxy) The weight ratio of keto-1-butene was 52:48. Also, dodecane was used as an internal standard substance. The results are shown in Table 2.

(Comparative Example 1)

In Example 1, 7.8 mg of anion exchange resin (Diaion, WA20) was added in place of triphenylphosphine (0.50% by weight relative to 3,4-diethyloxy-1-butene, equivalent to triphenyl) After the phosphine 0.02% by weight of the amine exchange capacity was added, the mixture was stirred at a temperature of 30 ° C for 1 hour, and the same procedure as in Example 1 was carried out. The liquid after the reaction was analyzed by gas chromatography, and as a result, 1,4-diethoxycarbonyl-2-butene (the total of the cis, trans, and 3,4-diethyloxy-1) The weight ratio of butene is 30:70. Also, dodecane was used as an internal standard substance. The results are shown in Table 1.

(Comparative Example 2)

In Example 1, 38.9 mg of anion exchange resin (Diaion, WA20) was added instead of triphenylphosphine (2.5% by weight relative to 3,4-diethyloxy-1-butene, equivalent to triphenyl) After the amine exchange capacity of 0.1% by weight of the phosphine was carried out, the mixture was stirred at a temperature of 30 ° C for 1 hour, and the same procedure as in Example 1 was carried out. The liquid after the reaction was analyzed by gas chromatography, and as a result, 1,4-diethoxycarbonyl-2-butene (the total of the cis, trans, and 3,4-diethyloxy-1) The weight ratio of butene was 33:67. Again, use Dodecane is used as an internal standard substance. The results are shown in Table 1.

(Comparative Example 3)

3,4-diethyloxy-1-butene-containing liquid (3,4-di) obtained in the above-mentioned Reference Example 3 "Purified distillation of 3,4-diethyloxy-1-butene-containing liquid" 72% by weight of ethoxylated-1-butene, 18% by weight of 3-hydroxy-4-ethenyloxy-1-butene, and other lower boiling points than 3,4-diethyloxy-1-butene The content of 6% by weight of the component, the higher the concentration of 3,4-diethyloxy-1-butene, 4% by weight of purified 3,4-diethyloxy-1-butene), 3.0 cc, 0.06 cc of acetic acid was added and mixed into a Schlenk apparatus, and the temperature was raised to 130 ° C by an oil bath. Here, 18 μL of the catalyst liquid prepared in Reference Example 5 was added under a nitrogen atmosphere, and the mixture was heated and stirred at 130 ° C for 3 hours (palladium concentration in the reaction liquid was 1.0 wtppm). The liquid after the isomerization reaction was analyzed by gas chromatography, and as a result, 1,4-diethoxycarbonyl-2-butene (the total of the cis, trans, and 3,4-diethoxy) The weight ratio of keto-1-butene was 44:56. Also, dodecane was used as an internal standard substance. The results are shown in Table 2.

(Comparative Example 4)

3,4-diethyloxy-1-butene-containing liquid (3,4-di) obtained in the above-mentioned Reference Example 3 "Purified distillation of 3,4-diethyloxy-1-butene-containing liquid" 72% by weight of ethoxylated-1-butene, 18% by weight of 3-hydroxy-4-ethenyloxy-1-butene, and other lower boiling points than 3,4-diethyloxy-1-butene The content of 6% by weight of the component, the higher the concentration of 3,4-diethyloxy-1-butene, 4% by weight of purified 3,4-diethyloxy-1-butene), 3.0 cc, 0.06 cc of acetic acid was added and mixed into a Schlenk apparatus, and the temperature was raised to 130 ° C by an oil bath. Here, 18 μL of the catalyst liquid prepared in Reference Example 6 was added under a nitrogen atmosphere. The mixture was stirred under heating at 130 ° C for 3 hours (palladium concentration in the reaction liquid was 1.0 wtppm). The liquid after the isomerization reaction was analyzed by gas chromatography, and as a result, 1,4-diethoxycarbonyl-2-butene (the total of the cis, trans, and 3,4-diethoxy) The weight ratio of keto-1-butene was 40:60. Also, dodecane was used as an internal standard substance. The results are shown in Table 2.

From the above results, it was found that, in the comparative examples and the comparative examples, the isomerization reaction performance was improved in all of the examples regardless of the actual addition weight of the additive or the exchange capacity of phosphorus and nitrogen atoms.

(industrial availability)

The present invention is an isomerization method of an allyl compound which can suppress catalyst deterioration and obtain an isomer according to a small amount of catalyst usage, which can be used industrially.

The entire contents of the specification, the scope of the patent application, and the abstract of the Japanese Patent Application No. 2007-132184, filed on May 17, 2007, are hereby incorporated herein by reference.

Claims (13)

In an isomerization method, the allylic compound is isomerized in the presence of a catalyst by contacting the allylic compound-containing solution of the raw material with a phosphorus compound for a contact time of 30 minutes to 5 hours. The isomerization method of claim 1, wherein the phosphorus compound is an organic phosphorus compound. The isomerization method of claim 2, wherein the organophosphorus compound is an organic phosphine. The isomerization method of claim 3, wherein the organophosphine has two or more aryl groups. The isomerization method of claim 3, wherein the organophosphine is triphenylphosphine. The isomerization method of the first aspect of the invention, wherein the amount of the phosphorus compound in contact with the allylic compound-containing solution is in the range of 0.0001 to 10% by weight based on the allyl compound. The isomerization method of the first aspect of the invention, wherein the contact of the allylic compound-containing liquid with the phosphorus compound is carried out at 60 ° C or higher. The isomerization method of the first aspect of the invention, further comprising the step of obtaining a liquid containing the allyl compound by a diethyl oximation reaction of a conjugated diene. The isomerization method of claim 1, wherein the catalyst is a liquid phase homogeneous palladium catalyst and is a catalyst containing a phosphorus ligand having at least one P-O bond. The isomerization method according to claim 9, wherein the phosphorus ligand having a P-O bond is a phosphoric acid of a bidentate. The method for isomerization according to claim 9, wherein the phosphorus ligand having a P-O bond is a bis-coordinated Phosphoramidite. The isomerization method of claim 1, wherein the allyl compound is a 3,4-diethyloxyallyl compound, which is formed by isomerization and belongs to the above allyl compound. A 1,4-diethoxy allylic compound of the compound. A method for producing an allyl compound by using the isomerization method of any one of claims 1 to 12 to produce a corresponding isomerized allyl compound from an allyl compound.