JP2000026441A - Method for producing 1,2-epoxy-5,9-cyclododecadiene - Google Patents

Abstract

PROBLEM TO BE SOLVED: To efficiently obtain epoxycyclododecadiene useful as an intermediate raw material for synthetic fibers in high purity and yield by bringing cyclododecatriene into contact with a specified quantity of hydrogen peroxide in the presence of a mixture containing a tungsten compound, etc. SOLUTION: This method for producing 1,2-epoxy-5,9-cyclododecadiene is to epoxydize 1,5,9-cyclododecatriene by bringing it into contact with 0.04-0.50 times mole of hydrogen perioxide in the presence of a mixture or a complex compound containing a tungsten compound such as tungstic acid or the like and a quaternary pyridinium salt expressed by formula I [R1 to R4 are each a (substituted) 1-18C alkyl, a 7-12C aralkyl or a 6-8C aryl; X is a counterion], (e.g. a quaternary ammonium halide). It is preferable to make a mineral acid such as phosphoric acid, sulfuric acid or the like present in the reaction system.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to monoepoxidation of 1,5,9-cyclododecatriene with hydrogen peroxide to form 1,2-
The present invention relates to a method for producing epoxy-5,9-cyclododecadiene. 1,2-Epoxy-5,9-cyclododecadiene has an active epoxy group and a carbon-carbon unsaturated bond, so it can be used not only as a resin component for paints and adhesives, but also for conversion to cyclododecanone. Is further derived from lactams, lactones or dibasic acids by a known method, so that polyamide, synthetic fibers of polyesters,
It is an important compound that serves as an intermediate material for synthetic resins.

[0002]

2. Description of the Related Art Conventionally, 1,5,9-cyclododecatriene is brought into contact with hydrogen peroxide to monoepoxidize 1,5,9-cyclododecatriene to form 1,2-epoxy-5,9-epoxide. As a method for producing cyclododecadienes, a method of monoepoxidizing 1,5,9-cyclododecatriene with formic acid formed in situ from formic acid and hydrogen peroxide (Japanese Patent Publication No. 56-104877). However, this method requires the use of formic acid, which has a low yield based on the charged peroxide and is highly corrosive to the apparatus. A method of monoepoxidizing 1,5,9-cyclododecatriene using selenium dioxide, selenous acid or an alkyl selenite as a catalyst (Japanese Patent Publication No.
No. -13331), it is necessary to use a highly toxic selenium compound as a catalyst as well as a very long reaction time.
Furthermore, a method of monoepoxy the 1,5,9 cyclododecatriene using 90% hydrogen peroxide tungstate as catalyst (Bull.Chem.Soc.Jpn., 42 .1604 (1969 )) is known However, in this method, it is necessary to carry out the reaction for a long time using a highly dangerous high concentration of hydrogen peroxide, and the yield based on the charged peroxide is low. That is, any of these methods has a problem as an industrial production method.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of the prior art, and to obtain 1,2-epoxy-enzyme from 1,5,9-cyclododecatriene with high reaction rate and high yield. 5,9-
It is intended to provide a method for producing cyclododecadiene.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a tungsten compound and a compound represented by the general formula (1):

[0005]

Embedded image (Wherein, R ¹ , R ² , R ³ and R ⁴ may be the same or different, and may be an unsubstituted or substituted alkyl group having 1 to 18 carbon atoms, A quaternary ammonium salt represented by the formula (2) or a quaternary ammonium ion or an atomic group capable of forming a counter ion with a quaternary ammonium ion. )

[0006]

Embedded image (Wherein, R ⁵ represents an unsubstituted or optionally substituted alkyl group having 1 to 18 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an aryl group having 6 to 8 carbon atoms;
Represents an atom or an atomic group capable of forming a counter ion with a quaternary pyridinium ion. )

In the presence of a mixture or a complex compound containing a quaternary pyridium salt represented by the following formula, 1,5,9-cyclododecatriene is
1,5,9-cyclododecatriene is brought into contact with 0.04 to 0.50 moles of hydrogen peroxide to perform monoepoxidation of 1,5,9-cyclododecatriene 1,2, -Solved by a method for producing epoxy-5,9-cyclododecadiene.

[0008]

DETAILED DESCRIPTION OF THE INVENTION The tungsten compound used in the reaction of the present invention is preferably an inorganic acid containing a tungsten atom or a salt thereof, for example, tungstic acid, sodium tungstate, potassium tungstate, lithium tungstate. , A tungstic acid such as ammonium tungstate or a salt thereof; a tungstic acid salt such as sodium dodecungstate, potassium dodecungstate, ammonium dodecungstate; phosphotungstic acid, sodium phosphotungstate, silicotungstic acid, Heteropoly acids such as sodium silicate tungstate, phosphovanadotungstic acid, phosphomolybdotungstic acid or salts thereof, and the like,
Preferably, tungstic acid, sodium tungstate, potassium tungstate, and phosphotungstic acid are used. These tungsten compounds may be used alone or in combination of two or more.

The amount of the tungsten compound used in the reaction of the present invention is preferably 0.0007 to 5% by weight, more preferably 0.002 to 5,5,9-cyclododecatriene.
~ 3% by weight.

In the reaction of the present invention, a quaternary ammonium salt represented by the above general formula (1) or a quaternary pyridinium salt represented by the general formula (2) is present in the reaction system in addition to the tungsten compound. A monoepoxidation reaction of 1,5,9-cyclododecatriene is performed. In the general formula (1),
R ¹ , R ² , R ³ and R ⁴ may be the same or different, and may have 1 to 1 carbon atoms which may be unsubstituted or have a substituent.
8 represents an alkyl group, an aralkyl group having 7 to 12 carbon atoms, or an aryl group having 6 to 8 carbon atoms. In the general formula (2), R ⁵ represents an unsubstituted or substituted alkyl group having 1 to 18 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an aryl group having 6 to 8 carbon atoms. Show. In the general formulas (1) and (2), X represents an atom or an atomic group capable of forming a counter ion with a quaternary ammonium ion or a quaternary pyridinium ion. For example, a halogen atom, HSO ₄ , ClO ₄ , H ₂ PO ₄ , NO ₃ , BF ₄ , HSiF ₆ , OCOH or OC
Shows OCH ₃ .

The quaternary ammonium salt used in the reaction of the present invention includes, for example, trioctylmethylammonium chloride, tridecylmethylammonium chloride, trioctylmethylammonium bromide,
Quaternary ammonium halides such as benzyldimethyltetradecylammonium chloride, benzyltriethylammonium chloride, dimethyldidodecylammonium chloride, benzyltributylammonium chloride, benzyltributylammonium iodide, and phenyltrimethylammonium chloride; quaternary ammonium halides such as trioctylmethylammonium hydrogen sulfate Ammonium hydrogensulfate; quaternary ammonium perchlorate such as trioctylmethylammonium perchlorate; quaternary ammonium dihydrogenphosphate such as trioctylmethylammonium dihydrogen phosphate; quaternary ammonium phosphate such as trioctylmethylammonium nitrate Ammonium nitrate; quaternary ammonium hydrofluorosilicate such as trioctylmethylammonium hydrofluorosilicate; trioctyl acetate Including but quaternary ammonium acetate salts such as chill ammonium, preferably quaternary ammonium halide, more preferably trioctylmethylammonium chloride, tridecyl methyl ammonium chloride is used.

The quaternary pyridinium salts used in the reaction of the present invention include, for example, quaternary pyridinium halides such as cetyl pyridinium chloride and cetyl pyridinium bromide, and quaternary ammonium hydrogen sulfate salts such as lauryl pyridinium hydrogen sulfate. Preferably quaternary pyridinium halides, more preferably cetyl pyridinium chloride are used.

The amount of the quaternary ammonium salt or quaternary pyridinium salt used in the reaction of the present invention is 1,5,9-
It is preferably 0.003 to 4% by weight, more preferably 0.003 to 2.5% by weight, based on cyclododecatriene. These quaternary ammonium salts or quaternary pyridinium salts alone,
A mixture of two or more may be used.

The complex compound includes, for example, a tungsten compound and a quaternary ammonium salt represented by the general formula (1) or a quaternary pyridinium salt represented by the general formula (2), hydrogen peroxide and, if necessary, a mineral acid (described later). ), And a complex compound containing a phosphorus atom is particularly preferably used.

The hydrogen peroxide used in the reaction of the present invention may be of any concentration, but in consideration of handling safety and economy, a 3 to 70% by weight aqueous solution is used. It is preferably used. Its usage is 1,5,
0.04-0.50 preferably for 9-cyclododecatriene
The molar amount is more preferably 0.10 to 0.30 times.

In the reaction of the present invention, a mineral acid is used if necessary. Examples of the mineral acid include phosphoric acid, sulfuric acid, hydrochloric acid, perchloric acid, hexafluorosilicic acid, nitric acid and tetrafluorosilicic acid. Among them, phosphoric acid and sulfuric acid are preferably used. These mineral acids may be used alone or in combination of two or more. 1,5,9-
It is preferably 0 to 15% by weight, more preferably 0 to 10% by weight, based on cyclododecatriene.

In the reaction of the present invention, an organic solvent can be used as a reaction solvent. The organic solvent used is not particularly limited as long as it is not uniformly mixed with water and does not inhibit the reaction. For example, chloroform, dichloroethane,
Aliphatic halogenated hydrocarbons such as dichloromethane; aliphatic non-halogenated hydrocarbons such as cyclohexane and n-heptane; aromatic non-halogenated hydrocarbons such as benzene, toluene and xylene; aromatic halogenation such as chlorobenzene And hydrocarbons. These solvents may be used alone or in combination of two or more. The amount used is preferably 0 to 1,5,9-cyclododecatriene.
It is 30 times by weight, more preferably 0 to 20 times by weight.

The reaction of the present invention is preferably carried out in a two-liquid phase in which 1,5,9-cyclododecatriene and hydrogen peroxide have been separated. Cyclododecatriene, hydrogen peroxide, a tungsten compound, and a quaternary ammonium salt or a quaternary pyridium salt are mixed, and the mixture is heated or stirred under normal pressure or pressure. The reaction temperature at that time is preferably 20 to 120 ° C, more preferably 30 to 120 ° C. Further, the obtained product can be isolated and purified by, for example, distillation after separation.

[0019]

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

EXAMPLE 1 0.4 g of sodium tungstate dihydrate was placed in a 100 ml glass two-necked flask equipped with a reflux condenser and a thermometer.
In 9 ml of water, 0.6 g of 40% phosphoric acid aqueous solution, 30%
0.1 g of sulfuric acid aqueous solution, 2.91 g (0.03 mol) of 35% hydrogen peroxide solution, 1,
9.74 g (0.06 mol) of 5,9-cyclododecatriene, Aliquat 33
6 (manufactured by Aldrich; mixture of trioctylmethylammonium chloride and tridecylammonium chloride) (0.2 g) and toluene (8 g) were added, and the mixture was heated to 70 ° C in a nitrogen atmosphere.
For 1 hour. After the reaction, the resultant was cooled to room temperature, and the obtained reaction solution was analyzed. In the analysis of the reaction solution, the remaining hydrogen peroxide was generated by iodometry, and the remaining 1,5,9-cyclododecatriene (hereinafter referred to as CDT) was generated.
1,2-Epoxy-5,9-cyclododecadien (hereinafter referred to as monoepoxide) was performed by gas chromatography. As a result, the conversion of hydrogen peroxide was 98.5%, the conversion of CDT was 40.5%, and the monoepoxide selectivity based on the consumed CDT was
The monoepoxide yield based on 91.2 mol% and the charged hydrogen peroxide was 73.1 mol%.

Comparative Example 1 A reaction was carried out in the same manner as in Example 1 except that Aliquat 336 (manufactured by Aldrich; a mixture of trioctylmethylammonium chloride and tridecylammonium chloride) was not added. As a result, the conversion of hydrogen peroxide was 13.1%, and the yield of monoepoxide based on the charged hydrogen peroxide was 0.6 mol%.

Example 2 In Example 1, sodium tungstate dihydrate was used.
A solution obtained by dissolving 0.4 g in 9 ml of water was changed to 0.01 g of solid phosphotungstic acid, and the amount of Aliquat 336 (manufactured by Aldrich; a mixture of trioctylmethylammonium chloride and tridecylammonium chloride) was changed to 0.005 g. The reaction was carried out in the same manner as in Example 1 except that a 40% aqueous phosphoric acid solution and a 30% aqueous sulfuric acid solution were not added. as a result,
Hydrogen peroxide conversion rate is 99.5%, CDT conversion rate is 41.5%, monoepoxide selectivity based on consumed CDT is 91.8mol%, monoepoxide yield based on charged hydrogen peroxide is 75.4mol%
Met.

Example 3 In Example 1, the amount of sodium tungstate dihydrate was changed to 0.04 g and the amount of Aliquat 336 (manufactured by Aldrich; a mixture of trioctylmethylammonium chloride and tridecylammonium chloride) was changed to 0.02 g. Except for this, the reaction was carried out in the same manner as in Example 1. As a result, the hydrogen peroxide conversion rate was 97.2%, the CDT conversion rate was 39.3%, and the consumption C
The monoepoxide selectivity based on DT was 91.3 mol%, and the monoepoxide yield based on the charged hydrogen peroxide was 71.0 mol%.

Example 4 A two-neck glass flask having a capacity of 200 ml equipped with a reflux condenser and a thermometer was charged with 0.39 g of phosphotungstic acid, 4.86 g (0.05 mol) of 35% aqueous hydrogen peroxide, 1,5,9 -Cyclododecatriene 1
6.23 g (0.1 mol), 0.14 g of cetylpyridinium chloride and 100 g of chloroform were added, and the mixture was added
The mixture was heated and stirred for hours. After the reaction, the mixture was cooled to room temperature,
The reaction solution obtained was analyzed in the same manner as in. As a result, the conversion of hydrogen peroxide was 99.3%, the conversion of CDT was 39.1%, the selectivity of monoepoxide based on the consumed CDT was 96.8 mol%, and the yield of monoepoxide based on the charged hydrogen peroxide was 75.7 mol%.

Comparative Example 2 In Example 4, the amount of 1,5,9-cyclododecatriene was
The reaction was carried out in the same manner as in Example 4 except that the amount was changed to 5.44 g (0.0335 mol). As a result, the conversion of hydrogen peroxide was 99.1.
%, The CDT conversion was 92.1%, the monoepoxide selectivity based on the consumed CDT was 59.8 mol%, and the monoepoxide yield based on the charged hydrogen peroxide was 36.8 mol%.

Example 5 In Example 2, 0.004 g of phosphotungstic acid was added.
In addition, except that the amount of Aliquat 336 (manufactured by Aldrich; a mixture of trioctylmethylammonium chloride and tridecylammonium chloride) was changed to 0.004 g, and the amount of 60% hydrogen peroxide was changed to 1.70 g (0.03 mol). The reaction was carried out in the same manner as in Example 2. As a result, the hydrogen peroxide conversion was 99.8
%, CDT conversion was 42.2%, monoepoxide selectivity based on consumed CDT was 90.0 mol%, and monoepoxide yield based on charged hydrogen peroxide was 74.9 mol%.

Examples 6 to 8 Reactions were carried out in the same manner as in Example 5, except that the amount of cyclododecatriene was changed. Table 1 shows the results.

[Table 1]

[0028]

Industrial Applicability According to the present invention, 1,2-epoxy-5,9-cyclopentadecane can be produced from 1,5,9-cyclododecatriene at high reaction rate and high yield.
A method for producing cyclododecadiene can be provided.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hirofumi Takemoto 5 Ube Kogushi, 1978 Kogushi, Ube City, Yamaguchi Prefecture

Claims (7)

[Claims] 1. A tungsten compound and a compound represented by the general formula (1): (Wherein, R ¹ , R ² , R ³ and R ⁴ may be the same or different, and may be an unsubstituted or substituted alkyl group having 1 to 18 carbon atoms, A quaternary ammonium salt represented by the formula (2) or a quaternary ammonium ion or an atomic group capable of forming a counter ion with a quaternary ammonium ion. ) (Wherein, R ⁵ represents an unsubstituted or optionally substituted alkyl group having 1 to 18 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an aryl group having 6 to 8 carbon atoms;
Represents an atom or an atomic group capable of forming a counter ion with a quaternary pyridium ion. ) In the presence of a mixture or complex containing a quaternary pyridium salt represented by the formula: 0.04 to 0,5 to 1,5,9-cyclododecatriene and 1,5,9-cyclododecatriene.
Monoepoxidation of 1,5,9-cyclododecatriene by contacting it with 50 times mole of hydrogen peroxide
A method for producing 1,2-epoxy-5,9-cyclododecadiene. 2. The method according to claim 1, wherein the tungsten compound is an inorganic acid containing a tungsten atom or a salt thereof.
A method for producing epoxy-5,9-cyclododecadiene. 3. The method according to claim 1, wherein the tungsten compound is tungstic acid,
Sodium tungstate, potassium tungstate,
The 1,2- compound according to claim 2, which is at least one tungsten compound selected from the group consisting of phosphotungstic acid.
A method for producing epoxy-5,9-cyclododecadiene. 4. The method for producing 1,2-epoxy-5,9-cyclododecadiene according to claim 1, wherein the quaternary ammonium salt is a quaternary ammonium halide. 5. The 1,2-epoxy-5,4,5,4,5,5,5,6,7,8,9,10 compound according to claim 4, wherein the quaternary ammonium salt is at least one quaternary ammonium salt selected from the group consisting of trioctylmethyl ammonium chloride and tridecylmethyl ammonium chloride. A method for producing 9-cyclododecadiene. 6. The method for producing 1,2-epoxy-5,9-cyclododecadien according to claim 1, wherein a mineral acid is present in the reaction system. 7. The method for producing 1,2-epoxy-5,9-cyclododecadiene according to claim 6, wherein the mineral acid is phosphoric acid or sulfuric acid.