JPH1017505A - Production of 1,7-octane diol - Google Patents

Abstract

PROBLEM TO BE SOLVED: To industrially advantageously produce 1,7-octane diol, useful as a raw material for various high polymers such as a polyester, a polycarbonate and a polyurethane, and also as a raw material for E-9-oxo-2-decenoic acid known as a 'pheromone for a queen bee'. SOLUTION: This method of producing 1,7-octane diol comprises reacting 7-octene-1-ol with a lower aliphatic carboxylic acid for forming a lower aliphatic carboxylic acid ester of 1,7-octane diol and then hydrolyze the ester.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing 1,7-octanediol. The 1,7-octanediol obtained by the present invention is useful as a raw material for various polymers such as polyester, polycarbonate, polyurethane, and the like, and E-9-oxo-2 known as "queen bee pheromone". -Raw material of decenoic acid (Indi
an J. Chem., Sect. B, 22B, 158 (1983)].

[0002]

2. Description of the Related Art Conventionally, the following methods have been known as methods for producing 1,7-octanediol. Starting with 5-hydroxy-2-pentanone, which is dehydrogenated and converted to the corresponding aldehyde,
Reacting with a Grignard reagent derived from chloro-1-propanol, dehydrating the obtained product, hydrogenating it with palladium carbon to form 7-oxooctyl acetate, and then reducing it with lithium aluminum hydride [ Oil Chemistry, Vol. 37, No. 6, p. 453 (1988)], using tetrahydrofurfuryl chloride as a starting material, condensing with propylene oxide in liquid ammonia in the presence of lithium amide to obtain 2,8 Hydrogenation of oct-3-yne-diol using palladium carbon [Tetrahedron, 45 , 6263 (1989)], coupling of rubric acid and glutaric acid monomethyl ester by Kolbe electrolysis to obtain 7-oxo Reduction of methyl octanoate by lithium aluminum hydride That way [Biovigyanam, 16, 66 (1990)
And 9,10,16-trihydroxypalmitic acid as a starting material, which is oxidatively cleaved with sodium periodate, and the resulting 7-hydroxyheptanal is reacted with a Grignard reagent derived from methyl iodide. [Indian J. Chem., Sect. B, 22B, 158 (1983)], and a fermentation method using methyl octyl ketone as a starting material (JP-A-4-237495).

[0003]

However, all of the above-mentioned methods are expensive starting materials and difficult to obtain in large quantities. These methods also have problems in industrially implementing the following points. That is, the method has many steps, a low yield of the target substance, and expensive reagents used for the reaction. Requires a reaction step carried out at a very low temperature of -78 ° C., which is complicated and increases the production cost. Although the number of steps is short, it is difficult to obtain methyl 7-oxooctanoate as a coupling product in a high yield in the electrolytic reaction step, and the reagent used for the reduction is expensive. In this method, it is necessary to use sodium periodate, which is expensive and has a problem in terms of waste liquid treatment and safety, in an equimolar amount or more based on the starting material.

[0004] On the other hand, the method has an advantage of using a raw material which may be available on an industrial scale,
The yield of the desired product, 1,7-octanediol, remains at an extremely low level of 0.2%, despite the reaction time of 4 days. Therefore, the method of
This is not an advantageous method for industrially producing 1,7-octanediol. The present invention has been made in view of such circumstances, and has as its object to provide a method capable of industrially and advantageously producing 1,7-octanediol.

[0005]

According to the present invention, the above object is achieved by reacting 7-octen-1-ol with a lower aliphatic carboxylic acid to form a lower aliphatic carboxylic acid ester of 1,7-octanediol. And then hydrolyzing the resulting ester to provide a method for producing 1,7-octanediol.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, "lower aliphatic carboxylic acid ester of 1,7-octanediol" means:
It refers to the lower aliphatic carboxylic acid monoester of 1,7-octanediol, or a mixture of such a monoester and the lower aliphatic carboxylic acid diester of 1,7-octanediol.

The 7-octen-1-ol used as a starting material in the present invention is 7-octene, an isomerization product of 2,7-octadien-1-ol obtained by the hydration dimerization reaction of butadiene. By hydrogenating -1-R using a copper-based catalyst, it can be industrially manufactured at low cost.

[0008] As the lower aliphatic carboxylic acid in the present invention, an aliphatic carboxylic acid having 1 to 6 carbon atoms is used. Specific examples of the lower aliphatic carboxylic acid include formic acid, acetic acid, propionic acid, butanoic acid, valeric acid, and isovaleric acid. Among them, formic acid is preferred.

The amount of the lower aliphatic carboxylic acid to be used is generally 0.1 to 20 mol, preferably 1 to 10 mol, per 1 mol of 7-octen-1-ol.

The reaction between 7-octen-1-ol and a lower aliphatic carboxylic acid proceeds even in the absence of a catalyst, but is preferably carried out in the presence of an acid catalyst. Here, as the acid catalyst, those conventionally used in the esterification reaction can be used, for example, sulfuric acid, nitric acid,
Mineral acids such as phosphoric acid; organic acids such as p-toluenesulfonic acid and trifluoroacetic acid; and solid acids such as acidic ion exchange resins. Of these, sulfuric acid is preferred.

The amount of the acid catalyst used is usually in the range of 0.01 to 1 mol, preferably 0.05 to 0.5 mol, per 1 mol of 7-octen-1-ol.

The reaction of 7-octen-1-ol with a lower aliphatic carboxylic acid does not necessarily require a solvent, but any solvent that does not adversely affect the reaction can be used. Examples of such a solvent include ethers such as diethyl ether, diisopropyl ether, and dioxane; aliphatic hydrocarbons such as hexane, cyclohexane, and octane;
Aromatic hydrocarbons such as benzene, toluene and xylene;
Halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane; and water. These solvents may be used alone or as a mixture of two or more.

In the present invention, when 7-octen-1-ol is reacted with a lower aliphatic carboxylic acid by using a solvent, the reaction may be carried out in a homogeneous phase or in an aqueous phase-organic phase. It may be carried out in a phase system. When a reaction between 7-octen-1-ol and a lower aliphatic carboxylic acid is carried out in a two-phase system, it is desirable to perform sufficient stirring in order to allow the reaction to proceed smoothly.

The reaction of 7-octen-1-ol with a lower aliphatic carboxylic acid is usually carried out at a temperature in the range of -10 ° C. to the reflux temperature, preferably 20 ° C. to the reflux temperature.

The reaction time varies depending on the reaction conditions such as the reaction temperature and whether or not a solvent is used, but is generally 2 to 20 hours.

The reaction can be carried out in a batch system,
A mixture of octen-1-ol and a lower aliphatic carboxylic acid may be continuously fed together with an acid catalyst to a reaction vessel at a predetermined temperature and continuously withdrawn after a predetermined residence time. it can.

By the above reaction, a lower aliphatic carboxylic acid is added to the terminal double bond of 7-octen-1-ol to selectively form a lower aliphatic carboxylic acid monoester of 1,7-octanediol. I do. At this time, the hydroxyl group at the 1-position of 7-octen-1-ol is also converted to a lower aliphatic carboxylic acid ester, and a lower aliphatic carboxylic acid diester of 1,7-octanediol may be formed. Further, when water is present in the reaction system in the reaction between 7-octen-1-ol and a lower aliphatic carboxylic acid, the carboxylic acid ester of 1,7-octanediol is partially hydrolyzed to form 1,7-octanediol. May be generated,
There is no particular problem in the present invention.

From the reaction solution containing the carboxylic acid ester of 1,7-octanediol thus obtained, an acid catalyst or unreacted lower aliphatic carboxylic acid is neutralized with a basic substance such as sodium hydroxide. After the addition, the carboxylic acid ester of 1,7-octanediol can be separated and obtained by a known method such as a method of purification by distillation.

In the hydrolysis reaction of the carboxylic acid ester of 1,7-octanediol according to the present invention, the starting material is separated and obtained from the reaction mixture of 7-octen-1-ol and the lower aliphatic carboxylic acid as described above. A carboxylic acid ester of 7,7-octanediol may be used, but a reaction mixture of 7-octen-1-ol and a lower aliphatic carboxylic acid may be used as a starting material as it is, or an unreacted reaction mixture may be used. A residue obtained by collecting the reaction raw materials by distillation, or a residue obtained by removing a high-boiling substance or a salt generated during neutralization by simple evaporation from the residue may be used. In order to efficiently carry out the hydrolysis, it is desirable to use a reaction mixture of 7-octen-1-ol and a lower aliphatic carboxylic acid from which at least unreacted raw materials have been removed.

The hydrolysis of the lower aliphatic carboxylic acid ester of 1,7-octanediol can be carried out under the same conditions as those for the usual hydrolysis of a carboxylic acid ester, but is carried out under neutral or alkaline conditions. Is preferred.

When the hydrolysis of the lower aliphatic carboxylic acid ester of 1,7-octanediol is carried out under alkaline conditions, for example, hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide and potassium hydroxide are used. Hydroxides of alkaline earth metals such as calcium hydroxide; and basic compounds such as carbonates or bicarbonates of alkali metals such as lithium carbonate, sodium carbonate and sodium hydrogen carbonate. The amount of these basic compounds used is 7-
It is usually 1 to 10 gram equivalents, preferably 1 to 5 gram equivalents, per mol of octen-1-ol.

The hydrolysis of the lower aliphatic carboxylic acid ester of 1,7-octanediol does not necessarily require a solvent, but any solvent that does not adversely affect the reaction can be used. Such solvents include, for example, methanol,
Examples include alcohol solvents such as ethanol; ether solvents such as tetrahydrofuran and 1,4-dioxane. These solvents may be used alone or 2
More than one kind may be mixed and used.

The hydrolysis of the lower aliphatic carboxylic acid ester of 1,7-octanediol is usually carried out at a temperature ranging from 0 ° C. to reflux conditions. The reaction time varies depending on the reaction temperature, but is usually within 100 hours.

The 1,7-octanediol produced by the hydrolysis can be isolated according to a conventional method. For example, a reaction mixture obtained by hydrolysis of a lower aliphatic carboxylic acid ester of 1,7-octanediol is converted to 1,7-octanediol with an organic solvent such as dichloromethane or chloroform.
1,7-octanediol can be isolated by extracting octanediol and distilling off the solvent from the obtained organic layer.

The purity of the thus obtained 1,7-octanediol can be further increased by means such as distillation and silica gel column chromatography, if desired.

[0026]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited by the examples.

EXAMPLE 1 28 g of 7-octen-1-ol (0.3 g) was placed in a 300 ml three-necked flask equipped with a reflux condenser and a stirrer.
22 mol) and 46 g of a 90% by weight aqueous solution of formic acid (0.9 mol as formic acid).
Mmol) was added dropwise. After completion of the dropwise addition, the mixture was refluxed (10
(3 ° C.) for 5 hours. When the reaction mixture was analyzed by gas chromatography, a peak corresponding to formate of 1,7-octanediol was observed. After cooling the reaction mixture obtained above to 50 ° C.,
After adding 0 ml and stirring for a short time, the mixture was allowed to stand and separated into two layers to obtain an organic layer (upper layer).

The organic layer obtained above, 100 ml of water and 20 g (0.5 mol) of sodium hydroxide were charged into a 300-ml three-necked flask equipped with a reflux condenser and a stirrer. And stirred vigorously for 4 hours. The resulting reaction mixture is diluted with dichloromethane 25
Extracted 4 times with ml. When the dichloromethane layer was made into one and analyzed by gas chromatography, it was found that 15.5 g (yield: 56.1%) of 1,7-octanediol was contained. The conversion of 7-octen-1-ol was 85.1%. The solvent was distilled off from the methylene chloride layer under reduced pressure, and the obtained residue was distilled under reduced pressure to give 1,7-octanediol (bp 155 ° C./10 m
mHg) were obtained.

[0029]

According to the present invention, 1,7-octanediol can be produced inexpensively and easily, and an industrially advantageous method for producing 1,7-octanediol is provided.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Takashi Onishi 36 Towada, Kamisu-cho, Kashima-gun, Ibaraki Pref. Kuraray Co., Ltd.

Claims (2)

[Claims] 1. A method comprising reacting 7-octen-1-ol with a lower aliphatic carboxylic acid to form a lower aliphatic carboxylic acid ester of 1,7-octanediol, and then hydrolyzing the resulting ester. To produce 1,7-octanediol. 2. The method for producing 1,7-octanediol according to claim 1, wherein the reaction between 7-octen-1-ol and a lower aliphatic carboxylic acid is carried out in the presence of sulfuric acid.