JP3044878B2 - Production method of epoxy compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an epoxy compound having a hydroxyl group of 4 or more and having a hydroxyl group which is important as an intermediate for pharmaceuticals and agricultural chemicals, a resin modifier and the like.

[0002]

2. Description of the Related Art As a method for synthesizing a corresponding 2,3-epoxybutan-1-ol by epoxidizing 2-buten-1-ol, which is an unsaturated compound having 4 carbon atoms having a hydroxyl group, for example, Y . Ishii et al. (J. Or.
g. Chem. 52, 1868-70 (1987))
Report a method using hydrogen peroxide as an oxidizing agent and using a heteropolyacid as a catalyst. B. M. Chou
dary et al. (J. Chem. Soc. Chem. Com.
mun. , 1186-7 (1990)) uses montmorillonite, a clay-intercalation compound modified with titanium, as a catalyst and hydroperoxide as an oxidizing agent.
2,3-epoxybutane-1 by epoxidizing all
-Reports that all can be synthesized.

[0003] Furthermore, a method is also known in which crystalline titanosilicate is used as a catalyst, and olefin having a functional group having 3 or less carbon atoms is epoxidized using hydrogen peroxide as an oxidizing agent to obtain a corresponding epoxy compound. For example, JP-A-62-150881 discloses that epichlorohydrin can be obtained by epoxidizing allyl chloride with a crystalline titanosilicate catalyst using hydrogen peroxide as an oxidizing agent.

[0004]

However, in the method using a heteropoly acid as a catalyst, the reaction is a liquid phase homogeneous system,
There is a problem that separation of products is difficult. In addition, the method using montmorillonite as a catalyst has low activity, and
Since hydroperoxide is used as an oxidizing agent, there is a problem that an equivalent amount of alcohol is by-produced from the hydroperoxide by the reaction.

[0005] Further, there has been no example in which a compound having a hydroxyl group having 4 or more carbon atoms is epoxidized using a crystalline titanosilicate as a catalyst to determine whether a corresponding epoxy compound can be obtained.

[0006]

Means for Solving the Problems In view of such circumstances, the present inventors have intensively studied an epoxidation reaction using crystalline titanosilicate as a catalyst. As a result, when hydrogen peroxide is used as an oxidizing agent and crystalline titanosilicate is used as a catalyst, epoxidation of an unsaturated alcohol having 4 or more carbon atoms proceeds, and a corresponding epoxy compound having a hydroxyl group having 4 or more carbon atoms. Have been obtained, and the present invention has been completed.

That is, the present invention provides a method for epoxidizing an unsaturated alcohol having 4 or more carbon atoms with hydrogen peroxide, which comprises using crystalline titanosilicate as a catalyst. It is intended to provide a novel method for producing an epoxy compound having a group.

Hereinafter, the method of the present invention will be specifically described.

The hydroxyl group-containing 4 carbon atoms of the present invention
In the above method for producing an epoxy compound, crystalline titanosilicate is used as a catalyst. The crystalline titanosilicate referred to herein is E.C. M. (Nature, 271, 512 (1
978)) A compound obtained by substituting a part of silicon forming a crystal lattice of “silicalite” (crystalline SiO ₂ having a zeolite structure) mainly with titanium. The crystalline titanosilicate may be one synthesized by a known method, and examples of the synthesis include a method disclosed in JP-A-56-97720. That is, an alkoxide of titanium and an alkoxide of silicon are mixed, and a tetrapropylammonium salt is added thereto, followed by hydrolysis.
Ethanol is distilled off from the obtained mixture, distilled water is added, and the mixture is transferred to an autoclave, heated and aged to obtain a precipitate. The precipitate can be washed, dried and calcined to obtain the desired crystalline titanosilicate.

The amount of titanium contained in the crystalline titanosilicate can be expressed as a silica / titania ratio (molar ratio). The silica / titania ratio of the crystalline titanosilicate used in the present invention is preferably from 5 to 200, and more preferably from 5 to 1.
00. In addition, the components contained in the crystalline titanosilicate are not limited to titanium, and are selected from boron, aluminum, phosphorus, vanadium, chromium, manganese, iron, gallium, zirconium, and the like, if necessary, in addition to titanium. One or more elements may be included.

The thus-prepared crystalline titanosilicate, which is the catalyst of the present invention, can be used as it is in the reaction as a catalyst, but may be used by molding if desired. In the case of molding, a binder may be used as necessary. In this case, the kind of the binder is not particularly limited, and for example, silica, alumina, a mixture thereof and the like are used.

The amount of the catalyst used in the reaction can be defined as the concentration of the crystalline titanosilicate catalyst in the reaction solution.
Since the reactivity of the epoxidation is affected by the amount of titanium in the crystalline titanosilicate, it is difficult to define the range entirely. If the concentration is intentionally specified, the concentration of the crystalline titanosilicate in the reaction solution is 0.01% by weight to 30% by weight.
% By weight.

The hydroxyl group-having 4 carbon atoms of the present invention
In the above method for producing an epoxy compound, an unsaturated alcohol having 4 or more carbon atoms is used as a reaction raw material. The position of the hydroxyl group of the unsaturated alcohol is not particularly limited, and may be at any position.
Examples of the unsaturated alcohol that can be used in the present invention include primary unsaturated alcohols such as 3-buten-1-ol, 2-buten-1-ol and 2-penten-1-ol, and 3-buten-1-ol. 2-ol, 4-pentene-
Secondary unsaturated alcohols such as 2-ol and 4-penten-3-ol can be exemplified.

In the method of the present invention, hydrogen peroxide is used as the oxidizing agent, but the concentration is not particularly limited, and a low-concentration or high-concentration aqueous hydrogen peroxide solution can be used as appropriate. However, if the concentration is too low, the efficiency is poor, the amount of the solvent required increases, and if the concentration is too high, handling becomes difficult. For this reason, usually 5 to 90%, more preferably 5 to 80% hydrogen peroxide is used.

There is no particular limitation on the ratio of the unsaturated alcohol and hydrogen peroxide which are the reaction raw materials, and it is sufficient to use an amount of hydrogen peroxide which can obtain a desired epoxidation product. If the by-products are within the allowable range, hydrogen peroxide may be used in excess with respect to the reaction raw materials, or may be used in small amounts depending on the purpose.

In the method of the present invention, the reaction is preferably performed in a liquid phase. In this case, the unsaturated alcohol of the reaction raw material itself may be used as the solvent, or a solvent may be used if necessary. In this case, the solvent is preferably one that does not react with the unsaturated alcohol and hydrogen peroxide as the raw materials, does not adversely affect the epoxidation reaction, and does not react with the epoxy compound having a hydroxyl group that is a reaction product. Solvent is selected. Examples of such a solvent include water, ethanol, alcohols having 6 or less carbon atoms such as tert-butanol, ketones such as acetone, glycols such as ethylene glycol, acetic acid,
Examples thereof include carboxylic acids such as propionic acid.

According to the present invention, the procedure and method of the epoxidation reaction are not particularly limited. For example, crystalline titanosilicate may be added to the unsaturated alcohol and the solvent as the reaction raw materials, heated while stirring, and the reaction may be performed by dropping hydrogen peroxide at an appropriate rate. Alternatively, the reaction may be carried out at a predetermined reaction temperature after all components including the solvent and the catalyst are mixed in advance. Furthermore, the raw materials used in the reaction may be supplied collectively or individually and continuously to cause the reaction to proceed.

The reaction temperature is preferably from 0 to 150 ° C.,
00 ° C is preferred. When the reaction temperature exceeds the boiling point of the reaction raw materials or the solvent, the reaction may be performed under pressure. The reaction pressure is not particularly limited, but may be in the range of normal pressure to 50 atm.

[0019]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples. However, these Examples are merely an outline of the present invention, and the present invention is not limited to these Examples. .

Example 1 A crystalline titanosilicate catalyst was prepared according to the method described in JP-A-56-97720. That is, tetraethyl titanate was added to tetraethyl orthosilicate under a nitrogen atmosphere, and an aqueous solution of tetrapropylammonium hydroxide was gradually added dropwise thereto. Incubate for 1 hour at room temperature, then 8 more
After reacting at 0 to 90 ° C. for 5 hours, the produced ethanol was separated out of the system. After distilled water was added to the obtained mixture, the mixture was transferred to an autoclave and aged at 175 ° C. for 55 hours to obtain white crystals. The obtained white crystals were sufficiently washed with warm water, dried at 120 ° C. overnight, and calcined at 550 ° C. for 6 hours to obtain a crystalline titanosilicate catalyst. The silica / titania ratio in the obtained crystalline titanosilicate is 52.
(Determined by atomic absorption analysis).

A 50 ml reactor was charged with 10 ml of 3-buten-1-ol and 0.05 g of a catalyst, and heated to 50 ° C. A 30% by weight aqueous hydrogen peroxide solution was added thereto and reacted for 3 hours. When the product was analyzed by gas chromatography, 2,3-epoxybutan-1-ol was found to be 14 mol / mol.
It was obtained in a yield of mol-Ti.

Examples 2 to 10 The reaction was carried out in exactly the same manner as in Example 1 except that the reaction raw materials were changed. Table 1 shows the results.

[0023]

According to the present invention, there is no stoichiometric by-product such as alcohol as in the case where hydroperoxide is used as an oxidizing agent as in the reference, and a heterogeneous system is used. Since the catalyst is a catalyst, the catalyst can be easily separated, and the desired epoxy compound having 4 or more carbon atoms can be obtained, which is significant from an industrial viewpoint.

[Table 1]

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C07D 301/12 CA (STN)

Claims (1)

(57) [Claims] 1. A method for producing a hydroxyepoxy compound, comprising using crystalline titanosilicate as a catalyst in epoxidizing an unsaturated alcohol having 4 or more carbon atoms in the presence of hydrogen peroxide.