JP2002047221A - Method for producing cyclododecanone and cyclododecanol - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing cyclododecanone and cyclododecanol by reducing 1,2-epoxy-5,9-cyclododecadiene with hydrogen, by which cyclododecanone and cyclododecanol are produced in high yields. SOLUTION: The method for producing cyclododecanone and cyclododecanol, comprises bringing the epoxycyclododecane compound into contact with hydrogen in the presence of a solid catalyst comprising a platinum group metal carried on a carrier, and is characterized by adding the first transition metal salt soluble in a reaction solvent to react the compounds.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing cyclododecanone and cyclododecanol by bringing hydrogen into contact with epoxycyclododecane in the presence of a solid catalyst having a platinum group metal supported on a carrier. The present invention relates to a method for producing a mixture of cyclododecanone and cyclododecanol, which comprises adding a salt. Cyclododecanone and cyclododecanol are important intermediate materials that can be easily derived into laurolactam, laurolactone or dodecane diacid, 1,12-dodecanediol and the like.

[0002]

2. Description of the Related Art Conventionally, as a method for producing cyclododecanone and cyclododecanol by bringing epoxycyclododecanes into contact with hydrogen, 1,2-epoxy-5,9-
The reaction of hydrogenating cyclododecadienes with hydrogen is disclosed in J. Mol. Catal., Vol 69, pp. 95-103 (1991). The reaction conditions in this document are a method in which 1,2-epoxy-5,9-cyclododecadiene is brought into contact with 1,2-epoxy-5,9-cyclododecadiene at a reaction hydrogen pressure of 13 kg / cm ² · G and a reaction temperature of 90 ° C. , Epoxycyclododecane was obtained as the main product, the yield of cyclododecanol was 4%, and no cyclododecanone was formed. Also, the 24th
`` Symposium on Progress in Reactions and Synthesis '' (November 5, 1998
In the presence of a palladium catalyst,
A method is disclosed in which hydrogen is brought into contact with 1,2-epoxy-5,9-cyclododecadiene at a reaction hydrogen pressure of normal pressure and a reaction temperature of normal temperature, but epoxycyclododecane is obtained as a main product, The yield of cyclododecanol was 5%, and no cyclododecanone was formed. Further, Neftekhimiya, 16 (1), 114-119 (1976) was contacted with 1,2-epoxy-5,9-cyclododecadiene at a reaction hydrogen pressure of 80 atm and a reaction temperature of 140 ° C. in the presence of a palladium-supported catalyst. It was described that the yield was 49.5% for epoxycyclododecane, 33.3% for cyclododecanol, and 3.4% for cyclododecanone. As described above, conventionally, there has been no known method for obtaining cyclododecanone and cyclododecanol in a satisfactory yield from epoxycyclododecanes.

[0003]

An object of the present invention is to produce cyclododecanone and cyclododecanol by bringing epoxycyclododecanes into contact with hydrogen in the presence of a solid catalyst having a platinum group metal supported on a carrier. In this case, the present invention provides a method for producing cyclododecanone and cyclododecanol in high yield.

[0004]

The object of the present invention is to produce cyclododecanone and cyclododecanol by bringing hydrogen into contact with epoxycyclododecane in the presence of a solid catalyst having a platinum group metal supported on a carrier. A method for producing cyclododecanone and cyclododecanol, characterized by adding a soluble first transition metal salt to a reaction solvent and reacting.

[0005]

DETAILED DESCRIPTION OF THE INVENTION The epoxycyclododecane used in the reaction of the present invention is a saturated or unsaturated 12-membered cyclic hydrocarbon having an epoxy group, for example, epoxycyclododecadiene, epoxycyclododecene ,
Epoxy cyclododecane and the like. In addition, the structure of the epoxy and the double bond of the epoxycyclododecane may be any structure such as a cis-form or a trans-form. The epoxycyclododecane to be used has no problem even if a commercially available product is used as it is or after being purified by distillation or the like.

The platinum group metal used as a catalyst component in the present invention is at least one element selected from the group consisting of ruthenium, rhodium, palladium, osmium, iridium and platinum, preferably palladium and platinum. And more preferably palladium. These platinum group metals are used in the reaction as a solid catalyst supported on an inert support. As the inert support, activated carbon, α-alumina, γ-alumina, silica, silica alumina, titania, zeolite, spinel and the like are suitably used.

The supported amount of the platinum group element on the inert support is as follows:
Preferably 0.01 to 20% by weight based on the inert support
And more preferably 0.1 to 10% by weight. The platinum group element in the catalyst may be supported on the surface or inside of the inert support, or both.

[0008] The amount of the solid catalyst supporting the platinum group metal of the present invention is based on the amount of the starting material epoxycyclododecane.
It is preferably 0.00001 to 0.1 times mol, more preferably 0.00005 to 0.01 times mol, as a platinum group element. If the amount is too small, the reaction takes a long time.

The soluble metal salt used in the present invention is a metal salt soluble in a reaction solvent, preferably a first transition metal salt, and more preferably at least one selected from the group consisting of iron, nickel and cobalt. It is one metal salt, most preferably a metal salt of iron. Specific examples include iron acetate, iron octylate, cobalt acetate, cobalt naphthenate, organic acid salts such as nickel acetate, iron acetylacetonate, cobalt acetylacetonate, and metal acetylacetonate such as nickel acetylacetonate. The most preferred metal salt is iron acetylacetonate. These may be used alone or in combination of two or more.

The method of adding the soluble metal salt is not particularly limited, but it is convenient and preferable to dissolve it in the epoxycyclododecane at the start of the reaction.

The amount of the soluble metal salt to be used is preferably 1 to 1000 ppm, more preferably 10 to 2 parts by weight, based on the weight of the metal element relative to the raw material epoxycyclododecanes.
00 ppm. If the amount is less than this range, there is no effect.

In the present invention, the hydrogenation of epoxycyclododecane is carried out by mixing epoxycyclododecane, a soluble metal salt and a solid catalyst in a hydrogen gas atmosphere.
The reaction hydrogen pressure is 1 to 150 kg / cm ² · G, preferably ² to 100 kg / cm ² · G, and the reaction temperature is 40 to 250
C., preferably at 50 to 230C.
If the reaction temperature is too high, the generation of high-boiling substances increases, which is not preferable. If the hydrogen pressure and the reaction temperature are too low, the production rate is undesirably reduced.

In the reaction of the present invention, the raw material epoxycyclododecane is usually used as a reaction solvent, but an organic solvent can also be used. For example, n-hexane, n-heptane, n-tetradecane, hydrocarbons such as cyclohexane, tetrahydrofuran, ethers such as dioxane,
Examples include alcohols such as methanol, ethanol, t-butanol, and t-amyl alcohol, and esters such as ethyl acetate and butyl acetate. These solvents alone,
A mixture of two or more may be used. The amount used is preferably 0 to 20 times by weight, more preferably 0 to 10 times by weight, based on the epoxycyclododecane as a raw material.

The cyclododecanone and cyclododecanol obtained in the present invention can be easily separated by distillation.

[0015]

The present invention will be specifically described below with reference to examples and comparative examples.

Example 1 0.32 g of iron acetylacetonate (50 ppm as iron metal) was placed in a glass autoclave having an internal volume of 100 ml.
1 g) of epoxycyclododecane (5.
49 mmol), 1 g of n-tetradecane as an organic solvent and 0.04 g of 5 wt% Pd / γ-alumina (2.0 wt%
And a hydrogen pressure of 5 kg / cm ² · G, 160 ° C.
The reaction was performed for 1 hour under the following conditions. After completion of the reaction, the resultant was cooled to room temperature, and the obtained reaction solution was analyzed. The analysis of the reaction solution
It was performed by gas chromatography. As a result, the conversion of epoxycyclododecane (hereinafter referred to as ECD) was 9
9.7%, cyclododecanone (hereinafter referred to as CDON)
Yield 35.8 mol%, cyclododecanol (hereinafter referred to as CD)
OL) was obtained in a yield of 57.0 mol%.

Examples 2 to 4, Comparative Example 1 The reaction was carried out in the same manner as in Example 1 except that the type and amount of the soluble first transition metal salt and the type and concentration of the catalyst were changed as shown in Table 1. ,Analysis was carried out. The results are shown in Table 1.

[0018]

[Table 1]

[0019]

According to the present invention, cyclododecanone and cyclododecanol can be obtained in high yield from epoxycyclododecanes.

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Claims (3)

[Claims] 1. A method for producing cyclododecanone and cyclododeanol by contacting hydrogen with an epoxycyclododecane in the presence of a solid catalyst having a platinum group metal supported on a carrier, wherein a first transition metal soluble in a reaction solvent is used. A process for producing cyclododecanone and cyclododecanol, characterized by reacting by adding a salt. 2. The process for producing cyclododecanone and cyclododecanol according to claim 1, wherein the platinum group metal is palladium or platinum. 3. The process for producing cyclododecanone and cyclododecanol according to claim 1, wherein the soluble first transition metal salt is at least one metal salt selected from the group consisting of iron, nickel and cobalt.