JP5657465B2 - Method for producing allyl alcohol compound - Google Patents

Description

  The present invention relates to a method for producing an allyl alcohol compound. The allyl alcohol compound obtained by the present invention is useful as a raw material for intermediates such as agricultural chemicals, medicines and fragrances, resin monomers and resin additives.

As a method for producing an allyl alcohol compound, a method of hydrolyzing an allyl halide compound is known (see Patent Documents 1 to 3).
In order to improve the reaction rate, a method is disclosed in which hydrolysis is performed by reacting with an aqueous alkali solution at a high temperature equal to or higher than the boiling point of the raw material and / or reaction product (see Patent Document 1). Also disclosed is a method for producing an allyl unsaturated alcohol by hydrolyzing an allyl chloride in the presence of a cuprous compound. To increase the selectivity of the allyl unsaturated alcohol, the reaction mixture is neutralized. It is known that it is important to keep a weak alkalinity and to add a required amount of alkali sequentially as the reaction proceeds when a strong alkali is used (see Patent Document 2). Furthermore, as a method of hydrolyzing methallyl chloride to obtain methallyl alcohol, a method of performing hydrolysis using a monovalent copper catalyst in the presence of a hydrogen chloride absorber is known (see Patent Document 3).

U.S. Patent No. 2072015 Japanese Patent Publication No. 45-10126 JP-A-61-33

  Patent Document 1 describes that it is desirable to carry out under a pressure equal to or higher than the vapor pressure of the content liquid in order to trap the raw materials and / or reaction products in the liquid phase. There is no detailed description of the pressurized atmosphere. In Patent Document 2, it is desirable to keep the reaction mixture neutral to weakly alkaline. In Patent Document 3, alkali metal hydroxides, carbonates, and bicarbonates are used as hydrogen chloride absorbers. In this case, when the pH in the system is 6 or less, isomerization proceeds and lowers the yield. On the other hand, when the pH is 8 or more, the reaction rate decreases and dimethallyl ether increases to decrease the yield. Although it is described that the dropping rate of the hydrogen chloride absorber is adjusted to be in the range of 6 to 8, it is difficult to adjust the dropping rate industrially while measuring the pH during the reaction. . In addition, since the reaction is carried out at normal pressure, there is a problem that the reaction temperature cannot be raised above the boiling point of the contents. On the other hand, if alkali metal bicarbonate, which is a weak base, is used as the hydrogen chloride absorber, pH adjustment is not necessary, but inexpensive sodium bicarbonate (sodium bicarbonate) has low solubility in water, and potassium bicarbonate (carbonate Potassium hydrogen) has good solubility in water, but is expensive and difficult to use industrially in terms of cost.

  As a result of intensive studies, the present inventors have carried out hydrolysis of an allyl halide compound in a carbon dioxide atmosphere in the presence of a basic compound and a monovalent copper compound, thereby performing complicated operations such as pH adjustment in the reaction system. It has been found that an allyl alcohol compound can be obtained with high selectivity without performing the above step.

That is, the present invention provides the following [1] to [3].
[1] A method for producing an allyl alcohol compound, comprising hydrolyzing an allyl halide compound in a carbon dioxide atmosphere in the presence of a basic compound and a monovalent copper compound.
[2] The method for producing an allyl alcohol compound according to [1], wherein the partial pressure of carbon dioxide is 0.01 to 2 MPa (gauge pressure).
[3] The method for producing an allyl alcohol compound according to [1] or [2], wherein the basic compound is at least one selected from sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate.

  According to the present invention, an allyl alcohol compound useful as a raw material for synthesizing functional compounds such as pharmaceuticals, agricultural chemicals and fragrances can be obtained with high selectivity without performing complicated operations such as pH adjustment in the reaction system.

  In the method of the present invention, an allyl alcohol compound is produced by hydrolyzing an allyl halide compound in a carbon dioxide atmosphere in the presence of a basic compound and a monovalent copper compound.

  The allyl halide compound used in the method of the present invention is a compound in which one of the hydrogen atoms at the allylic position of an unsaturated hydrocarbon compound is substituted with a halogen atom. For example, 3-chloropropene (allyl chloride), 3-bromo Propene (allyl bromide), 3-chloro-2-methyl-1-propene (methallyl chloride), 3-bromo-2-methyl-1-propene (methallyl bromide), 1-chloro-2-butene (crotyl chloride) ), 3-chloro-1-butene, 1-chloro-3-methyl-2-butene (prenyl chloride), 3-chloro-1-pentene, 3-chlorocyclohexene, 1-chloro-2-octene, 3-chloro -1-octene, 1-chloro-2,7-octadiene, 3-chloro-1,7-octadiene, 1-phenyl-3-chloro-1-propene (cinnamyl chloride), 3 Such as chloro-3-phenyl-1-propene, and the like. Among these, 3-chloropropene (allyl chloride) and 3-chloro-2-methyl-1-propene (methallyl chloride) are preferable from the viewpoint of industrial availability.

In the method of the present invention, a basic compound is used as a halogen scavenger for capturing a halogen atom liberated from an allyl halide by hydrolysis. The basic compound is not particularly limited as long as it has an ability to capture a halogen atom, but it is inorganic from the viewpoint of hydrolysis reaction rate, selectivity of the desired allyl alcohol compound, solubility in the reaction system, and the like. A base is preferred. Examples of such inorganic bases include alkali metal or alkaline earth metal hydroxides, carbonates and acetates, and sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate are preferred from the viewpoint of availability. . These basic compounds may be used individually by 1 type, and may be used in combination of 2 or more type.
As for the usage-amount of a basic compound, 1-2 equivalent is preferable with respect to the halogen atom which a halogenated allyl compound has. When the amount of the basic compound used is less than 1 equivalent, the reaction does not proceed sufficiently or the selectivity of the allyl alcohol compound tends to decrease, whereas when it exceeds 2 equivalents, the economy tends to be inferior. . The basic compound may be in the form of a powder or an aqueous solution, and is preferably used as an aqueous solution from the viewpoint of workability.

  Examples of the monovalent copper compound used in the method of the present invention include cuprous oxide, cuprous chloride, cuprous bromide, cuprous acetate and the like. Among these, cuprous oxide and cuprous chloride are preferable from the viewpoint of availability. Although there is no restriction | limiting in particular in the usage-amount of a monovalent copper compound, 0.1-5 mol% is preferable with respect to an allyl halide. When the amount of the monovalent copper compound used is less than 0.1 mol%, the reaction rate tends to be slow, and when it is more than 5 mol%, the economy tends to be inferior.

  Although there is no restriction | limiting in particular in the quantity of the water to be used by the method of this invention, 1.5-5 mass times is preferable with respect to an allyl halide. When the amount is less than 1.5 times by mass, the reaction tends not to proceed sufficiently. When the amount is more than 5 times by mass, the volumetric efficiency is lowered and the economy tends to be inferior.

  The process of the present invention can be carried out in the presence or absence of a solvent. The solvent to be used is not particularly limited as long as it does not affect the reaction, ethers such as tetrahydrofuran, 1,3-dioxane and diethyl ether; esters such as ethyl acetate and butyl acetate; hexane, heptane, toluene and xylene And aliphatic or aromatic hydrocarbons such as mesitylene. These solvents may be used alone or in combination of two or more. In the method of this invention, it is preferable to implement in absence of a solvent from a viewpoint which abbreviate | omits separation operation with a product.

  The method of the present invention performs the reaction under a carbon dioxide atmosphere. Carbon dioxide gas or dry ice can be used as carbon dioxide. Carbon dioxide gas is preferably used from the viewpoint of condition control and the like. The partial pressure of carbon dioxide is preferably in the range of 0.01 to 2 MPa (gauge pressure), and more preferably in the range of 0.01 to 1 MPa (gauge pressure). If the partial pressure of carbon dioxide is lower than 0.01 MPa, the selectivity of the allyl alcohol compound tends to decrease, and if it is higher than 2 MPa, the economy tends to be inferior. The reaction temperature is preferably in the range of 40 to 140 ° C, and more preferably in the range of 60 to 120 ° C. If the reaction temperature is lower than 40 ° C, the reaction tends to be extremely slow, and if it is higher than 140 ° C, the selectivity tends to decrease. Although there is no restriction | limiting in particular in reaction time, Usually, it is preferable that it is the range of 1 to 20 hours. Moreover, although inert gas, such as nitrogen and argon, may coexist in the reaction system, it is preferable that only carbon dioxide exists from the viewpoint of reactivity.

  The method of the present invention can be carried out using a stirring reaction tank, a circulation reaction tank or the like, and may be carried out by either a batch system or a continuous system. If necessary, unreacted raw materials can be separated and recovered by distillation, extraction, etc., and recycled before use. The continuous mode can be carried out using a single reactor or a plurality of reactors in series or in parallel.

  The allyl alcohol compound thus obtained can be separated by means such as filtration, layer separation, distillation, extraction and the like, and the purity can be increased by further performing purification distillation as necessary.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited to these. Gas chromatography measurement was performed under the following conditions.

(Gas chromatography measurement)
Analytical instrument: GC-17A (manufactured by Shimadzu Corporation)
Detection equipment: FID (hydrogen flame ionization detector)
Column used: CBP-10 (column length 50 m, inner diameter 0.22 mm, film thickness 0.25 μm) (manufactured by Shimadzu Corporation)
Analysis conditions: Injection Temp. 250 ° C., Detection Temp. 250 ° C
Temperature rising condition: 60 ° C. (2 minutes hold) → Temperature rising at 10 ° C./min→250° C.

<Example 1>
Into a 1 L pressure-resistant reaction vessel equipped with an electromagnetic stirrer, thermometer, and heating device, 172 g of water, 113.3 g of 40% sodium hydroxide aqueous solution (1.13 mol of sodium hydroxide) and 0.28 g of cuprous chloride were added. The inside of the reactor was replaced with carbon dioxide gas. Further, after carbon dioxide gas was absorbed, the partial pressure of carbon dioxide in the reactor was adjusted to 0.02 MPa. Thereafter, 100 g (1.11 mol) of methallyl chloride was supplied over 2 hours while gradually heating to 70 ° C. and maintaining the reaction temperature at 70 ° C., and the reaction was further continued at 70 ° C. for 2 hours after completion of the supply. After completion of the reaction, the reaction mixture was cooled to room temperature, the solid content was filtered, and the filtrate was analyzed by gas chromatography. The conversion of methallyl chloride was 99%, the selectivity of methallyl alcohol was 98%, and the selectivity of dimethallyl ether was 1%.

<Example 2>
In Example 1, the carbon dioxide partial pressure was changed from 0.02 MPa to 0.8 MPa, the reaction temperature was changed from 70 ° C. to 120 ° C., and the reaction time after completion of the supply of methallyl chloride was changed from 2 hours to 1 hour. The operation was performed. The conversion of methallyl chloride was 99%, the selectivity of methallyl alcohol was 97%, and the selectivity of dimethallyl ether was 2%.

<Example 3>
In Example 1, the same operation was performed except that 84 g (1.11 mol) of allyl chloride was used instead of 100 g (1.11 mol) of methallyl chloride. The conversion rate of allyl chloride was 99%, the selectivity of allyl alcohol was 98%, and the formation of diallyl ether was 1% or less.

<Example 4>
In Example 2, the same operation was performed except that the amount of water was changed from 172 g to 240 g, and 60 g (1.13 mol) of sodium carbonate was used instead of 113.3 g (sodium hydroxide 1.13 mol) of 40% aqueous sodium hydroxide. went. The conversion of methallyl chloride was 99%, the selectivity of methallyl alcohol was 98%, and the production of dimethallyl ether was 1% or less.

<Example 5>
In Example 1, the same operation was performed except that the supply time of methallyl chloride was changed from 2 hours to 0.5 hours. The conversion of methallyl chloride was 94%, the selectivity of methallyl alcohol was 97%, and the production of dimethallyl ether was 2%.

<Comparative Example 1>
In Example 1, the same operation was performed except that the inside of the reactor was replaced and pressurized with nitrogen gas instead of carbon dioxide gas. The conversion of methallyl chloride was 99%, the selectivity of methallyl alcohol was 89%, and the selectivity of dimethallyl ether was 9%, indicating a significant increase in by-products.

  As mentioned above, the method (Examples 1-5) of this invention which manufactures an allyl alcohol compound by hydrolyzing a halogenated allyl compound in presence of a basic compound and a monovalent copper compound in a carbon dioxide atmosphere is nitrogen. Allyl alcohol could be obtained with higher efficiency than in a gas atmosphere (Comparative Example 1).

  According to the present invention, an allyl alcohol compound useful as a raw material for synthesizing functional compounds such as pharmaceuticals, agricultural chemicals and fragrances can be obtained with high selectivity without performing complicated operations such as pH adjustment in the reaction system.

Claims (3)

  A method for producing an allyl alcohol compound, comprising hydrolyzing an allyl halide compound in a carbon dioxide atmosphere in the presence of a basic compound and a monovalent copper compound.    The method for producing an allyl alcohol compound according to claim 1, wherein the partial pressure of carbon dioxide is 0.01 to 2 MPa (gauge pressure). 3. The method for producing an allyl alcohol compound according to claim 1, wherein the basic compound is at least one selected from sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate.