JP2014070036A - Method of producing 1,8-tetralin dicarboxylic anhydride - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a one-step and high yield method of producing 1,8-tetralin dicarboxylic anhydride from 1,8-naphthalenedicarboxylic acid with catalyst of only one kind of noble metal.SOLUTION: There is provided a method of producing of 1,8-tetralin dicarboxylic anhydride by reacting 1,8-tetralin dicarboxylic anhydride with hydrogen using a palladium catalyst under a condition of water concentration in a reaction system of less than 0.2 wt.%.

Description

  The present invention relates to a method for producing 1,8-tetralin dicarboxylic acid anhydride.

  1,8-tetralin dicarboxylic acid anhydride (hereinafter, 1,8-TDCan) represented by the following formula (1) is 1,8-naphthalenedicarboxylic acid anhydride (hereinafter, 1,1) represented by the following formula (2). Compared with 8-NDCann), it is rich in reactivity due to the difference in steric stability, and it can be used as a liquid crystal composition, polymer modifier, pharmaceutical intermediate, etc. as polyester, polycarbonate, polyimide, polyamide. Therefore, its industrial significance is great.

＜１，８−テトラリンジカルボン酸無水物（１，８−ＴＤＣＡｎ）＞

<1,8-tetralin dicarboxylic acid anhydride (1,8-TDCan)>

＜１，８-ナフタレンジカルボン酸無水物（１，８−ＮＤＣＡｎ）＞

<1,8-Naphthalenedicarboxylic anhydride (1,8-NDCan)>

As a method for producing 1,8-TDCan, Patent Document 1 discloses a method of synthesizing a tetralin derivative by hydrogenating a naphthalene derivative in the presence of a palladium / silver catalyst. 1,8-NDCan is used as a naphthalene derivative. 1,8-TDCAn is exemplified as the tetralin derivative.

In Non-Patent Document 1, 1,8-NDCan is hydrogenated with a Raney catalyst in an aqueous caustic soda solution, and 1,8-tetralindicarboxylic acid (hereinafter, 1,8-TDCA) represented by the following formula (3) is obtained. A method of synthesis is disclosed. Non-Patent Document 2 describes a method in which 1,8-TDCA is dehydrated and closed by heating to obtain 1,8-TDCan.

＜１，８−テトラリンジカルボン酸（１，８−ＴＤＣＡ）＞

<1,8-tetralindicarboxylic acid (1,8-TDCA)>

JP 2001-278836 A

Journal of Organic Chemistry, 1949, 14, p. 366-374. Chemische Berichte, 1894, 27, p. 2694-2695.

However, in Patent Document 1, expensive silver is essential as a catalyst, and since two kinds of metals of palladium and silver are used, the recycling cost as a catalyst is high. Furthermore, there is no specific description of a method for producing 1,8-TDCan by preventing the ring opening of 1,8-NDCann from opening and hydrogenating.
In addition, 1,8-TDCan can be produced by combining the methods of Non-Patent Documents 1 and 2, but once the anhydrous ring of 1,8-NDCan as a raw material is opened once during the hydrogenation reaction. The reaction is a multistage process in which ring closure is performed again by dehydration.

An object of the present invention is to synthesize 1,8-TDCAn from 1,8-NDCan in one step with a catalyst using only one kind of metal as a noble metal in a high yield.

  The present inventor made 1,8-TDCan be reacted with hydrogen using a palladium catalyst under the condition that the water concentration in the reaction system was controlled to be less than 0.2% by weight. The inventors have found that it can be synthesized in a high yield, and have reached the present invention.

  That is, the present invention relates to a method for producing 1,8-TDCan by reacting 1,8-NDCan with a hydrogenation reaction using a palladium catalyst under conditions where the water concentration in the reaction system is less than 0.2% by weight. is there.

According to the present invention, 1,8-TDCan can be industrially produced in one step of hydrogenation reaction using only palladium as a noble metal as a catalyst from 1,8-NDCan.
Compared with 1,8-NDCann, 1,8-TDConn is rich in reactivity due to the difference in steric stability. As polyester, polycarbonate, polyimide, polyamide, liquid crystal composition, polymer modifier, pharmaceutical intermediate Since it can be used as a body, its industrial significance is great.

[1. Palladium catalyst used for reaction]
The catalyst used in this reaction is a palladium catalyst, and it is preferable to use a catalyst in which palladium is supported on a carrier.

Examples of the carrier include activated carbon, alumina, silica, zeolite and the like, and activated carbon is particularly preferable from the viewpoint of availability and price.

  The palladium content in the supported catalyst is preferably 0.1 to 50% by weight, particularly preferably 1.0 to 10% by weight. The amount of the catalyst used is preferably 0.1 to 10%, more preferably 0.3 to 5% by weight ratio of palladium to 1,8-NDCan of the raw material.

  A commercially available catalyst may be used, or a catalyst prepared according to a known method such as an impregnation support method may be used.

  In the present invention, in order to prevent the carboxylic anhydride from being hydrated, the lower the water content in the catalyst, the better. The water content in the catalyst is preferably 0.5% by weight or less, more preferably 0.1% by weight or less. When a hydrous catalyst is used, it may be used after drying by a conventional method such as drying under reduced pressure before the reaction.

[2. Solvent used for reaction]
The solvent used for the reaction is not particularly limited as long as it does not cause a reaction that opens the anhydrous ring of the carboxylic acid anhydride, and does not inhibit the hydrogenation reaction. For example, heptane, decane, etc. Examples thereof include aliphatic hydrocarbon solvents, ester solvents such as ethyl acetate and n-butyl acetate, and ether solvents such as diethyl ether and tetrahydrofuran.

In the reaction of the present invention, in order to prevent the carboxylic anhydride from being hydrated, the lower the water concentration in the solvent, the better. The water concentration in the solvent is preferably 0.2% by weight or less, more preferably 0.1% by weight or less, and particularly preferably 0.05% by weight or less.
When the water concentration of the solvent is higher than the above range, the water content in the solvent may be used for the reaction after performing an operation of removing the water by an operation such as distillation or adsorption.

As for the usage-amount of a solvent, the weight ratio (SR) of the solvent with respect to 1,8-NDCanan becomes like this. Preferably it is 0.5-20, More preferably, SR = 1-10. If SR is in the above range, the reaction can be carried out in an appropriate reactor volume, and the solvent can be easily separated and recovered, which is preferable.

[3. Reaction conditions]
This reaction is usually carried out in a pressure vessel such as an autoclave, and the hydrogen pressure is not particularly limited, but is preferably 1 to 10 MPa, more preferably 3 to 8 MPa. By performing the reaction in the above hydrogen pressure range, the selectivity of the reaction is increased and 1,8-TDCAn can be produced efficiently.

The reaction temperature is usually 0 to 200 ° C., preferably 50 to 100 ° C. By performing hydrogenation at a hydrogen pressure and a reaction temperature within the above ranges, 1,8-TDCan can be produced with a high selectivity and a good reaction rate.

In the present invention, the hydrogenation reaction is carried out under the condition that the water concentration in the reaction system is less than 0.2% by weight. A more preferred water concentration is less than 0.1% by weight, and even more preferably less than 0.05% by weight. In the normal case, water generation in the hydrogenation reaction is negligible, so the water concentration in the reaction system is defined by the sum of the weights of water contained in all the substances supplied relative to the total substance weight supplied to the reaction system. The In the case of batch reaction, it is determined from the total amount of water contained in 1,8-NDCan, hydrogen, catalyst, solvent, etc. charged in the reactor. In the case of continuous reaction, it is determined from the total amount of water contained in each component continuously supplied to the reactor. In addition, when performing a continuous reaction using a fixed bed catalyst, you may exclude the moisture content in a catalyst from concentration calculation.

  In order to keep the water concentration in the reaction system within the above range, the water concentration in the catalyst and the solvent is preferably set to the above concentration or less. Although the influence of moisture contained in the raw materials 1,8-NDCan and hydrogen is relatively small, the moisture concentration may be reduced by supplying it to the reactor after drying if necessary.

[4. Purification]
After completion of the reaction, for example, the catalyst is filtered off from the reaction mixture, and if necessary, the liquid obtained by washing the catalyst with the solvent exemplified above is combined with the mother liquor. -TDCAn can be removed. Further, purification may be performed by means such as recrystallization, distillation or column chromatography.

The method of the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. In the following examples and comparative examples, the composition indicates an area percentage value obtained by gas chromatography analysis.

<Example 1>
In a 500 mL autoclave (manufactured by SUS316L), 7.5 g of 1,8-NDCan 50 g, 5 wt% palladium supported on activated carbon (dry product, moisture content less than 0.1%), 200 g of ethyl acetate (water concentration 430 ppm) Prepared. It was 480 ppm when the preparation liquid was sampled and the water concentration was measured. At room temperature, the inside of the autoclave was replaced twice with 1 MPa of nitrogen, and then replaced twice with 1 MPa of hydrogen. Thereafter, the pressure was reduced to normal pressure, the temperature was raised to 80 ° C., the pressure was increased to 5 MPa with hydrogen, and the mixture was stirred at the same temperature and the same pressure for 2 hours (500 rpm).
After the reaction, the reaction mixture was cooled to room temperature, released hydrogen, and replaced with 1 MPa of nitrogen twice. Then, the catalyst was filtered off, and the catalyst was washed with 20 g of acetone three times. The solvent was removed from the obtained mother liquor to obtain 49.8 g of crude 1,8-TDCan. As a result of gas chromatography analysis, the compositions were 1,8-NDCan: 0.1% and 1,8-TDCan: 92.8%.

<Example 2>
A 500 mL autoclave (manufactured by SUS316L) is charged with 10 g of 1,8-NDCan, 5 g of a catalyst in which 5 wt% palladium is supported on activated carbon (dry product, moisture content of less than 0.1%), and 200 g of tetrahydrofuran (moisture concentration of 710 ppm). It is. The charged liquid was sampled and the water concentration was measured and found to be 730 ppm. At room temperature, the inside of the autoclave was replaced twice with 1 MPa of nitrogen, and then replaced twice with 1 MPa of hydrogen. Thereafter, the pressure was reduced to normal pressure, the temperature was raised to 80 ° C., the pressure was increased to 5 MPa with hydrogen, and the mixture was stirred at the same temperature and the same pressure for 10 minutes (500 rpm).
After the reaction, the reaction mixture was cooled to room temperature, released hydrogen, and replaced with 1 MPa of nitrogen twice. Then, the catalyst was filtered off, and the catalyst was washed with 20 g of acetone three times. The solvent was removed from the resulting mother liquor to obtain 9.8 g of crude crystals. As a result of gas chromatography analysis, the compositions were 1,8-NDCan: 0.0% and 1,8-TDCan: 78.9%.

<Comparative Example 1>
A 500 mL autoclave (manufactured by SUS316L) was charged with 20 g of 1,8-NDCan, 5 g of a catalyst in which 5 wt% palladium was supported on activated carbon (water content 52 wt%), and 100 g of ethyl acetate (water concentration 450 ppm). The charged liquid was sampled and the water concentration was measured and found to be 2.5% by weight. At room temperature, the inside of the autoclave was replaced twice with 1 MPa of nitrogen, and then replaced twice with 1 MPa of hydrogen. Thereafter, the pressure was reduced to normal pressure, the temperature was raised to 80 ° C., the pressure was increased to 5 MPa with hydrogen, and the mixture was stirred at the same temperature and the same pressure for 30 minutes (500 rpm).
After the reaction, the reaction mixture was cooled to room temperature, released hydrogen, and replaced with 1 MPa of nitrogen twice. Then, the catalyst was filtered off, and the catalyst was washed with 20 g of acetone three times. The solvent was removed from the obtained mother liquor to obtain 20.2 g of crude crystals. As a result of gas chromatography analysis, the composition was 1,8-NDCan: 0.0%, 1,8-TDCA: 90.6%, and 1,8-TDCan: 0.0%.

According to the present invention, 1,8-TDCan can be industrially produced from 1,8-NDCan by using 1,8-TDCan as a noble metal and only palladium as a catalyst. In general, since a naphthalene ring having an anhydrous ring is less reactive to a hydrogenation reaction, the hydrogenation reaction is performed after the anhydrous ring is opened, and then the ring is closed. Can simplify the reaction route.
1,8-TDCan is rich in reactivity due to the difference in steric stability compared to 1,8-NDCan, and as polyester, polycarbonate, polyimide, polyamide, liquid crystal composition, polymer modifier, pharmaceutical intermediate Since it can be used as a body, its industrial significance is great.

Claims (2)

1,8-tetralindicarboxylic acid anhydride is obtained by subjecting 1,8-naphthalenedicarboxylic acid anhydride to a hydrogenation reaction using a palladium catalyst under the condition that the water concentration in the reaction system is less than 0.2% by weight. Manufacturing method. The 1,8-tetralin dicarboxylic acid according to claim 1, wherein a hydrogenation reaction is performed in a solvent having a water concentration of 0.2 wt% or less using a palladium catalyst having a water content of 0.5 wt% or less. Method for producing acid anhydride.