JP2004035463A - Method for producing 2-hydroxycyclododecanone and dibasic acid derived from the compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new simple method by which 2-hydroxycyclododecanone to become a useful precursor for a dibasic acid such as dodecanedioic acid is produced from 1, 2-dihydroxy-5, 9-cyclododecadiene. <P>SOLUTION: The method comprises reducing 1, 2-dihydroxy-5, 9-cyclododecadiene with hydrogen in the presence of (a) a platinum group catalyst under (b) 0.01-4 Mpa hydrogen pressure at (c) 40-230°C. <P>COPYRIGHT: (C)2004,JPO

Description

[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for reducing 1,2-dihydroxy-5,9-cyclododecadiene with hydrogen in the presence of a platinum group catalyst to give 2-hydroxycyclododecanone.
2-Hydroxycyclododecanone is easily oxidized to a useful oxide. Specifically, dodecanedioic acid can be derived, and the obtained dodecaneedioic acid can be used not only as a resin component such as a paint and an adhesive, but also as an important compound as a raw material of a synthetic fiber such as polyamide 12, polyester, and a synthetic resin. It is.
[0002]
[Prior art]
Conventionally, there has been known a method for producing a dibasic acid by oxidizing cycloalkanediols with hydrogen peroxide in the presence of a tungsten catalyst. (J. Org. Chem. 1986, 51, 1602-1604).
However, in this method, although a corresponding dibasic acid is obtained in a high yield in cycloalkanediols having a small number of carbon atoms, when a cycloalkanediol having a large number of carbon atoms, for example, cyclododecanediol is used, , Dodecanedioic acid can be obtained only in a low yield of ten-odd percent.
Furthermore, this method uses a large amount of a catalyst, which is not preferable for the environment, and is not economical because the amount of hydrogen peroxide used is theoretically three times or more.
On the other hand, 2-hydroxycyclododecanone used as an intermediate material of dodecanediacid is produced by oxidizing cyclododecanone with an organic hydroperoxide such as t-butyl hydroperoxide in the presence of formic acid (US Pat. No. 3,755,453). )It has been known. However, this method requires the use of an expensive organic peroxide and is not economical.
As described above, no report describing a method for producing 2-hydroxycyclododecanone by hydrogen reduction of 1,2-dihydroxy-5,9-cyclododecadiene has been known at all.
[0003]
[Problems to be solved by the invention]
An object of the present invention is to provide a simple and novel method for producing 2-hydroxycyclododecanone, which is a precursor from which useful oxides such as dodecanedioic acid can be obtained from 1,2-dihydroxy-5,9-cyclododecadiene. Is provided.
[0004]
[Means for Solving the Problems]
The object of the present invention is to
1,2-dihydroxy-5,9-cyclododecadiene is reacted with (a) a platinum group catalyst in the presence of
(B) a hydrogen pressure of 0.01 to 4 Mpa;
(C) at a reaction temperature of 40 to 230 ° C.
The problem is solved by a method for producing 2-hydroxycyclododecanone, which is characterized by hydrogen reduction.
[0005]
BEST MODE FOR CARRYING OUT THE INVENTION
The 1,2-dihydroxy-5,9-cyclododecadiene used in the reaction of the present invention can be obtained, for example, by hydrating 1,2-epoxy-5,9-cyclododecadiene in the presence of an acid catalyst. Can be easily obtained.
In addition, 1,2-epoxy-5,9-cyclododecadienes can be obtained by, for example, epoxidizing cyclododecatriene using a peracid.
1,2-Dihydroxy-5,9-cyclododecadiene has cis- and trans-isomers, but there is no limitation on the use of these isomers. Good.
[0006]
The platinum group catalyst used in the hydrogen reduction reaction of the present invention is a solid catalyst in which a compound containing at least one element selected from ruthenium, rhodium, palladium, iridium and platinum is supported on an inert support, preferably powder. A catalyst, more preferably a powder catalyst having an average particle size of several μm to several hundred μm. As the inert support, activated carbon, alumina, silica, silica-alumina, zeolite, spinel and the like are preferably used. The amount of the platinum group element supported on the inert support is preferably from 0.1 to 10% by weight, more preferably from 0.2 to 8% by weight, based on the inert support. The platinum group element in the catalyst may be supported on the surface or inside of the inert support, or on both. The preferred platinum group metal is palladium or platinum, and the more preferred platinum group metal is palladium.
[0007]
The amount of the platinum group catalyst used in the hydrogen reduction reaction of the present invention is preferably 0.00001 to 0.1 times mol as a platinum group element with respect to 1,2-dihydroxy-5,9-cyclododecadiene as a raw material. , More preferably 0.00005 to 0.05 times mol. If the amount is too small, the reaction takes a long time. If the amount is too large, the yield of the target product tends to decrease, which is not preferable.
[0008]
In the hydrogen reduction reaction of the present invention, an organic solvent is generally used. Examples of the organic solvent used include hydrocarbons such as n-hexane, n-heptane, n-tetradecane and cyclohexane, and ethers such as tetrahydrofuran and dioxane. And alcohols such as methanol, ethanol, t-butanol, and t-amyl alcohol, and esters such as ethyl acetate and butyl acetate. Particularly, alcohols are preferably used.
These solvents may be used alone or as a mixture of two or more. The amount used is preferably 0.1 to 100 times by weight, more preferably 0.2 to 50 times by weight, based on the raw material 1,2-dihydroxy-5,9-cyclododecadiene.
[0009]
In the present invention, the hydrogen reduction reaction is carried out under the conditions of a reaction hydrogen pressure of 0.01 to 4 MPa, a reaction temperature of 40 to 230 ° C, preferably 0.1 to 3 MPa, 50 to 200 ° C, more preferably 70 to 200 ° C. Below, the initial yield is about 50 mol% of 2-hydroxycyclododecanone at 1 MPa or less, followed by hydrogenation at 1-3 Mpa.
If the reaction hydrogen pressure is too low, or if the reaction temperature is too low, the reaction takes a long time, which is not preferable. On the other hand, if the reaction hydrogen pressure is 5 MPa or more and the reaction temperature is too high, reduction proceeds and the yield of the target product decreases, and a large amount of cyclododecanediol is generated, which is not preferable.
The 2-hydroxycyclododecanone obtained in the present invention is usually obtained by distilling off the solvent and then distilling the 2-hydroxycyclododecanone as it is or obtaining high-purity 2-hydroxycyclododecanone by crystallization or the like. After that, it is supplied to an oxidation reaction step and is derived into a dibasic acid.
[0010]
As an example of the oxidation method of 2-hydroxycyclododecanone, oxidation with an organic peracid or hydrogen peroxide is performed.
As the dibasic acid when an organic peracid or hydrogen peroxide is used, dodecanedioic acid and undecandioic acid are exemplified.
Examples of the organic peracid used include peracetic acid, perpropionic acid, perphthalic acid, and m-chloroperbenzoic acid.
The hydrogen peroxide used is not particularly limited, but is an aqueous solution of 10 to 70% by weight, preferably 30 to 70% by weight.
In the case of obtaining dodecanedioic acid using an organic peracid or hydrogen peroxide, the oxidizing agent used is theoretically 2 mole times the 2-hydroxycyclododecanone as a raw material, but preferably 1 mole. The molar ratio is from 0.5 to 3.0 times, more preferably from 2.0 to 2.8 times, even more preferably from 2.1 to 2.5 times. If the amount used is less than this range, unreacted raw materials increase, and if it is large, it is not economical.
In the oxidation reaction to dodecanedioic acid, a catalyst may not be particularly used, but when using hydrogen peroxide, it is desirable to use an acid catalyst such as sulfuric acid, toluenesulfonic acid, phosphoric acid or a tungsten compound. Preferred are acid catalysts such as sulfuric acid, toluenesulfonic acid and phosphoric acid.
The amount of the acid catalyst used is preferably 5.0% by weight or less, more preferably 3.0% by weight or less, based on the raw material 2-hydroxycyclododecanone.
[0011]
Examples of the organic solvent usually used in the oxidation reaction of the present invention include lower fatty acids such as formic acid, acetic acid and propionic acid, ethers such as tetrahydrofuran and dioxane, alcohols such as t-butanol and t-amyl alcohol, and ethyl acetate. And esters such as butyl acetate, and it is particularly preferable to use lower fatty acids. Although not an organic solvent, water can also be used.
These solvents may be used alone or as a mixture of two or more. The amount used is preferably 0.2 to 50 times by weight, more preferably 0.3 to 10 times by weight, relative to the raw material 2-hydroxycyclododecanone.
The reaction temperature varies depending on the oxidizing agent and the solvent used, but is preferably 50 to 150 ° C, more preferably 60 to 120 ° C.
[0012]
Dodecanedioic acid derived from 2-hydroxycyclododecanone is usually separated and purified from an oxidation reaction solution by recrystallization.
[0013]
【Example】
Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples.
[0014]
Example 1 (Synthesis of 2-hydroxycyclododecanone)
In a 100 ml SUS autoclave equipped with a stirrer, 2.5 g (12.8 mmol) of 1,2-dihydroxy-5,9-cyclododecadiene, 50 ml of isopropyl alcohol, and 0.03 g of 5 wt% Pd / C catalyst. (Manufactured by NE Chemcat; 0.014 mmol as Pd atom) was added, and the mixture was heated to 170 ° C. in a nitrogen gas atmosphere, and then hydrogen gas was passed at normal pressure. After reacting for 2 hours, 0.06 g of a 5 wt% Pd / C catalyst was newly added at room temperature, and reacted at 100 ° C. for 1 hour at a hydrogen pressure of 3 MPa.
After completion of the reaction, the catalyst was filtered at room temperature and analyzed by gas chromatography GC. As a result, the yield of 2-hydroxycyclododecanone was 91.9 mol%, and 1,2-cyclododecanedione was a by-product. Was 4.6 mol%, and 1,2-cyclododecanediol was 1.9 mol%.
[0015]
Comparative Example 1
In a 100 ml SUS autoclave equipped with a stirrer, 2.5 g (12.8 mmol) of 1,2-dihydroxy-5,9-cyclododecadiene, 50 ml of isopropyl alcohol, and 0.03 g of 5 wt% Pd / C catalyst. Was added, and reacted at a hydrogen pressure of 5 MPa and 80 ° C. for 3 hours. After completion of the reaction, the catalyst was filtered at room temperature and analyzed by GC. As a result, 96 mol% of 1,2-cyclododecanediol was formed and 2-hydroxycyclododecanone was not formed.
[0016]
Example 2 (Synthesis of dodecanedioic acid and undecandioic acid)
1.0 g (5.0 mmol) of 2-hydroxycyclododecanone (purity 98%), 1.4 ml of acetic acid, 0.70 g (12.4 mmol) of 60% by weight hydrogen peroxide in a glass flask having an inner volume of 50 ml. And 0.012 g (0.12 mmol) of concentrated sulfuric acid, and reacted at 90 ° C. for 3 hours with stirring. After the reaction, the mixture was cooled to room temperature, the generated crystals were separated by filtration, and the crystals and the filtrate were analyzed by LC. As a result, 100% of the raw material 2-hydroxycyclododecanone was converted, the yield of dodecanedioic acid was 82.0 mol%, and 1.7 mol% of undecanedioic acid was produced as a by-product. .
[0017]
【The invention's effect】
According to the present invention, it is possible to provide a simple and novel method for producing 2-hydroxycyclododecanone, which is an intermediate raw material for dodecanedioic acid, from 1,2-dihydroxy-5,9-cyclododecadien. Furthermore, dibasic acid can be obtained by oxidizing the obtained 2-hydroxycyclododecanone.

Claims (3)

1,2-dihydroxy-5,9-cyclododecadiene is reacted with (a) a platinum group catalyst in the presence of
(B) a hydrogen pressure of 0.01 to 4 Mpa;
(C) at a reaction temperature of 40 to 230 ° C.
A method for producing 2-hydroxycyclododecanone, comprising reducing with hydrogen. (A) the platinum group catalyst is palladium,
A method for producing 2-hydroxycyclododecanone according to claim 1. A dibasic acid obtained by oxidizing the 2-hydroxycyclododecanone obtained in claim 1 with an oxidizing agent.