JP3941608B2 - Process for producing 2-hydroxycyclododecanone and dibasic acid derived from the compound - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method in which 1,2-dihydroxy-5,9-cyclododecadiene is hydrogen-reduced to 2-hydroxycyclododecanone in the presence of a platinum group catalyst. 2-Hydroxycyclododecanone is easily oxidized to a useful oxide. Specifically, it can be derived into dodecanedioic acid, and the resulting dodecanedioic acid can not only be a resin component for paints, adhesives, etc., but also synthetic fibers such as polyamide 12 and polyester, and important compounds that can be used as raw materials for synthetic resins It is.
[0002]
[Prior art]
Conventionally, a method for producing a dibasic acid by oxidizing a cycloalkanediol with hydrogen peroxide in the presence of a tungsten catalyst is known. (J. Org. Chem. 1986, 51, 1602-1604)
However, in this method, the corresponding dibasic acid is obtained in a high yield in the case of cycloalkanediols having a small number of carbon atoms, but when a cycloalkanediol having a large number of carbon atoms, for example, cyclododecanediol is used. , Dodecanedioic acid can only be obtained in low yields of a few tens of percent.
Furthermore, since this method uses a large amount of catalyst, it is not preferable for the environment, and the amount of hydrogen peroxide used is theoretically more than 3 times mol, so it is not economical.
On the other hand, 2-hydroxycyclododecanone used as an intermediate raw material for dodecanedioic acid is produced by oxidizing cyclododecanone with 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 expensive organic peroxides and is not economical.
Thus, there has been no report so far describing a method for producing 1,2-dihydroxy-5,9-cyclododecadiene by hydrogen reduction to produce 2-hydroxycyclododecanone.
[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 a useful oxide such as dodecanedioic acid is obtained from 1,2-dihydroxy-5,9-cyclododecadiene. Is to provide.
[0004]
[Means for Solving the Problems]
The subject of the present invention is
1,2-dihydroxy-5,9-cyclododecadiene (a) in the presence of a platinum group catalyst,
(B) Hydrogen pressure 0.01-4 Mpa,
(C) at a reaction temperature of 40 to 230 ° C.
This is solved by a method for producing 2-hydroxycyclododecanone, which is characterized by hydrogen reduction.
[0005]
DETAILED DESCRIPTION OF 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.
1,2-epoxy-5,9-cyclododecadiene can be obtained, for example, by epoxidizing cyclododecatriene with a peracid.
There are cis and trans isomers of 1,2-dihydroxy-5,9-cyclododecadiene, but there are no restrictions on the use of these isomers, and these isomers may be used alone or in combination. 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 a powder. A catalyst, more preferably a powder catalyst having an average particle diameter of several μm to several hundred μm. As the inert support, activated carbon, alumina, silica, silica alumina, zeolite, supinel and the like are preferably used. The amount of platinum group element supported on the inert support is preferably 0.1 to 10% by weight, more preferably 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 both. Preferable platinum group metal is palladium or platinum, and more preferable 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 the raw material 1,2-dihydroxy-5,9-cyclododecadiene. More preferably, it is 0.00005 to 0.05 times mol. If it 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 usually 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. , Alcohols such as methanol, ethanol, t-butanol and t-amyl alcohol, and esters such as ethyl acetate and butyl acetate, but alcohols are particularly preferably used.
These solvents may be used alone or in combination 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, relative to the raw material 1,2-dihydroxy-5,9-cyclododecadiene.
[0009]
In the present invention, the hydrogen reduction reaction is performed under the conditions of a reaction hydrogen pressure of 0.01 to 4 MPa and 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 approximately 50 mol% of 2-hydroxycyclododecanone at a yield of 1 MPa or less, followed by hydrogenation at 1 to 3 Mpa.
If the reaction hydrogen pressure is too low, or if the reaction temperature is too low, it takes a long time for the reaction. On the other hand, when the reaction hydrogen pressure is 5 MPa or more and the reaction temperature is too high, the reduction proceeds and the yield of the target product decreases, and a large amount of cyclododecanediol is produced, 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 by crystallization to obtain high purity 2-hydroxycyclododecanone. After that, it is donated to the oxidation reaction step and 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.
Examples of the dibasic acid when organic peracid or hydrogen peroxide is used include dodecanedioic acid and undecanedioic acid.
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 organic peracid or hydrogen peroxide, the oxidizing agent used is theoretically 2 mol times with respect to 2-hydroxycyclododecanone as a raw material, but preferably 1 0.5 to 3.0 mol times, more preferably 2.0 to 2.8 mol times, and still more preferably 2.1 to 2.5 mol times. If the amount used is less than this range, the amount of unreacted raw materials increases, and if it is large, it is not economical.
In the oxidation reaction to dodecanedioic acid, a catalyst is not particularly required. However, when hydrogen peroxide is used, 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 to be 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, for example, 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, but it is particularly preferable to use a lower fatty acid. Although not an organic solvent, water can also be used.
These solvents may be used alone or in combination 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.
Although reaction temperature changes also with the oxidizing agent and solvent to be used, Preferably it is 50-150 degreeC, More preferably, it is 60-120 degreeC.
[0012]
Dodecanedioic acid derived from 2-hydroxycyclododecanone is usually separated and purified from the oxidation reaction solution by recrystallization.
[0013]
【Example】
The present invention will be specifically described below 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, heated to 170 ° C. in a nitrogen gas atmosphere, and then hydrogen gas was bubbled 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 as 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 And reacted at 80 ° C. for 3 hours with a hydrogen pressure of 5 MPa. 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 produced and 2-hydroxycyclododecanone was not produced.
[0016]
Example 2 (Synthesis of dodecanedioic acid and undecanedioic acid)
In a glass flask with an internal volume of 50 ml, 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 water Then, 0.012 g (0.12 mmol) of concentrated sulfuric acid was added, and the mixture was reacted at 90 ° C. for 3 hours with stirring. After the reaction, the reaction mixture was cooled to room temperature, the produced crystals were filtered off, and the crystals and the filtrate were analyzed by LC. As a result, the raw material 2-hydroxycyclododecanone was 100% 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】
The present invention can provide a simple and novel method for producing 2-hydroxycyclododecanone, which is an intermediate raw material of dodecanedioic acid, from 1,2-dihydroxy-5,9-cyclododecadiene. Furthermore, a dibasic acid can be obtained by oxidizing the obtained 2-hydroxycyclododecanone.

Claims (2)

1,2-dihydroxy-5,9-cyclododecadiene (a) in the presence of a platinum group catalyst,
(B) Hydrogen pressure 0.01-4 Mpa,
(C) at a reaction temperature of 40 to 230 ° C.
A process for producing 2-hydroxycyclododecanone, characterized by hydrogen reduction. (A) the platinum group catalyst is palladium;
A process for producing 2-hydroxycyclododecanone according to claim 1.