JP2012017302A - 1, 5-diketones and method of producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of efficiently producing 1, 5-diketones useful as a raw material for various chemical products.SOLUTION: An aromatic compound and a glutaric acid derivative or 4-aroyl butyrates are reacted in the presence of a solid acid catalyst and 1, 5-diketones having the same aromatic substituent or aromatic substituents different from each other is produced. A solid acid catalyst, such as zeolite can be used as a catalyst. Beta type, Y-type, etc. can be used as zeolite, and it is preferable to use one having a silica/alumina ratio of 2-1,000.

Description

  The present invention relates to 1,5-diketones having the same or different aromatic substituents and an efficient production method thereof.

  Diketones having an aromatic substituent are important functional chemicals used as medical / agricultural chemicals, optical / electronic materials, or synthetic intermediates thereof. Further, 1,5-diketones among diketones having an aromatic substituent are pyridine derivatives (for example, non-patent documents 1 to 3) and cyclopentadiene derivatives (for example, non-patent documents 1 to 3) that are highly useful as various functional substances and materials. And non-patent documents 4, 5, and 7).

As the main production method of such 1,5-diketones, 2 equivalents of acetophenone derivative and aromatic aldehyde, or 1 equivalent of acetophenone and vinyl ketone derivative, a base catalyst such as sodium hydroxide or barium hydroxide A method of reacting in the presence has been known (for example, Non-Patent Documents 1, 3, 5, and 6). However, these methods have problems such as (1) it is difficult to recover the base catalyst and it is difficult to reuse the catalyst, and (2) the catalyst is expensive when a base such as barium hydroxide is used. It was.
Moreover, although the method of making the Mannich base obtained from a ketone, formaldehyde, and an amine react with a ketone was known (for example, nonpatent literature 7), (1) Mannich base manufacture is required and a process is complicated. 2) There were problems such as the generation of a large amount of amine waste, and it was not an industrially advantageous production method.
On the other hand, in the presence of a Lewis acid catalyst of a dicarboxylic acid dihalide of glutaric acid (pentane-1,5-dicarboxylic acid), which is also known as a C5 compound in the biorefinery industry, as a process for producing 1,5-diketones. Friedel-Crafts type reaction was known (eg, Non-Patent Documents 4 and 8). Although this production method has the advantage that it is easy to obtain raw material glutaric acid and aromatic compounds, (1) a conversion step from glutaric acid to its carboxylic acid halide is necessary. (2) Lewis such as aluminum chloride There are problems such as the use of a large amount of acid, and (3) the production of a large amount of highly corrosive hydrogen halide as waste, and there has been a demand for an industrially more advantageous production method.

J. et al. Chem. Soc. , 2242 (1961) Synthesis, 1 (1970) J. et al. Chem. Soc. , Dalton Trans, 2497 (1992) J. et al. Am. Chem. Soc. , 84, 2726 (1962) J. et al. Org. Chem. , 43, 4090 (1978) Tetrahedron, 63, 8581 (2007) J. et al. Am. Chem. Soc. , 74, 4923 (1952) Chem. Lett. , 970 (2001)

  The present invention has been made in view of the above circumstances, and aims to more efficiently produce 1,5-diketones having the same or different aromatic substituents. .

（式中、メチレン基の水素原子の一部が反応に関与しない基で置換されていてもよい。
で表されるグルタル酸誘導体を、固体酸触媒の存在下で反応させることを特徴とする下記一般式（IIIＡ）
Ｒ¹ＣＯ−ＣＨ_２ＣＨ_２ＣＨ_２−ＣＯＲ¹ （IIIＡ）
（式中、Ｒ¹は前記と同じ意味であり、メチレン基の水素原子の一部が、式（IIＡ）又は式（IIＢ）に由来する反応に関与しない基で置換されていてもよい。）
で表される１，５−ジケトン類の製造方法。
〈２〉上記一般式（IIＡ）又は一般式（IIＢ）の代わりに、下記一般式（IIＣ）
Ｒ²ＣＯ−ＣＨ_２ＣＨ_２ＣＨ_２−ＣＯ_２Ｈ （IIＣ）
（式中、Ｒ²は１価の炭化水素環系又は複素環系の芳香族有機基であり、前記炭化水素環又は複素環の水素原子及び／又はメチレン基の水素原子の一部が反応に関与しない基で置換されていてもよい。）
で表される４−アロイル酪酸誘導体を用いることを特徴とする下記一般式（IIIＢ）
Ｒ²ＣＯ−ＣＨ_２ＣＨ_２ＣＨ_２−ＣＯＲ¹ （IIIＢ）
（式中、Ｒ¹及びＲ²は前記と同じ意味であり、メチレン基の水素原子の一部が、式（IIＣ）に由来する反応に関与しない基で置換されていてもよい。）
の製造方法。
〈３〉前記の固体酸触媒として、ゼオライト、モンモリロナイト又はヘテロポリ酸を用いることを特徴とする〈１〉又は〈２〉に記載の製造方法。
〈４〉前記のゼオライトとして、ベータ型、Ｙ型、モルデナイト型又はＺＳＭ−５型のゼオライトを使用することを特徴とする〈３〉に記載の製造方法。
〈５〉前記のゼオライトとして、シリカ／アルミナ比が２〜１０００のゼオライトを使用することを特徴とする〈３〉又は〈４〉に記載の製造方法。
〈６〉反応をマイクロ波照射下で行うことを特徴とする〈１〉、〈２〉、〈３〉、〈４〉又は〈５〉に記載の製造方法。
〈７〉下記一般式（IV）で表される１，５−ジケトン類。
Ｒ³ＣＯ−ＣＨ_２ＣＨ_２ＣＨ_２−ＣＯＲ⁴ （IV）
（式中、Ｒ³及びＲ⁴は、両者とも２，３−ジヒドロベンゾフラン−５−イル基、両者とも１，４−ベンゾジオキサン−６−イル基、又は、片方がフェニル基で他方が２，３−ジヒドロベンゾフラン−５−イル基である。） As a result of intensive studies to solve the above problems, the present inventors have (1) an aromatic compound and a glutaric acid derivative (glutaric acid or an acid anhydride thereof) in the presence of a specific solid acid catalyst. When the reaction proceeds efficiently and 1,5-diketones having two identical aromatic substituents can be obtained in good yield. (2) When a 4-aroylbutyric acid derivative is used instead of a glutaric acid derivative The reaction proceeds efficiently, and 1,5-diketones having two identical or different aromatic substituents are obtained, and (3) those reactions are accelerated by microwave irradiation, and more efficiently 1 , 5-diketones were found, and the present invention was completed.
That is, this application provides the following inventions.
<1> The following general formula (I)
R ¹ H (I)
(In the formula, R ¹ represents a monovalent hydrocarbon ring system or heterocyclic aromatic organic group, and a part of hydrogen atoms of the hydrocarbon ring or heterocyclic ring is substituted with a group not participating in the reaction. May be.)
An aromatic compound represented by the following general formula (IIA)
_{HO 2 C-CH 2 CH 2} CH 2 -CO 2 H (IIA)
(In the formula, a part of hydrogen atoms of the methylene group may be substituted with a group not participating in the reaction.)
Or the following general formula (IIB)

(In the formula, a part of hydrogen atoms of the methylene group may be substituted with a group which does not participate in the reaction.
The following general formula (IIIA) is characterized by reacting a glutaric acid derivative represented by the following formula in the presence of a solid acid catalyst:
^{_{R 1 CO-CH 2 CH 2}} CH 2 -COR 1 (IIIA)
(In the formula, R ¹ has the same meaning as described above, and a part of the hydrogen atom of the methylene group may be substituted with a group not involved in the reaction derived from the formula (IIA) or the formula (IIB).)
The manufacturing method of 1,5- diketones represented by these.
<2> Instead of the above general formula (IIA) or general formula (IIB), the following general formula (IIC)
^{_{R 2 CO-CH 2 CH 2}} CH 2 -CO 2 H (IIC)
(In the formula, R ² is a monovalent hydrocarbon ring or heterocyclic aromatic organic group, and a part of hydrogen atoms of the hydrocarbon ring or heterocyclic ring and / or a hydrogen atom of the methylene group is reacted. It may be substituted with a non-participating group.)
4-aroylbutyric acid derivative represented by the following general formula (IIIB)
^{_{R 2 CO-CH 2 CH 2}} CH 2 -COR 1 (IIIB)
(In the formula, R ¹ and R ² have the same meaning as described above, and a part of the hydrogen atoms of the methylene group may be substituted with a group not involved in the reaction derived from the formula (IIC).)
Manufacturing method.
<3> The production method according to <1> or <2>, wherein zeolite, montmorillonite, or heteropolyacid is used as the solid acid catalyst.
<4> The production method according to <3>, wherein a zeolite of a beta type, a Y type, a mordenite type, or a ZSM-5 type is used as the zeolite.
<5> The production method according to <3> or <4>, wherein zeolite having a silica / alumina ratio of 2 to 1000 is used as the zeolite.
<6> The production method according to <1>, <2>, <3>, <4> or <5>, wherein the reaction is performed under microwave irradiation.
<7> 1,5-diketones represented by the following general formula (IV).
^{_{R 3 CO-CH 2 CH 2}} CH 2 -COR 4 (IV)
(In the formula, R ³ and R ⁴ are both 2,3-dihydrobenzofuran-5-yl groups, both are 1,4-benzodioxan-6-yl groups, or one is a phenyl group and the other is 2, 3-dihydrobenzofuran-5-yl group.)

  According to the present invention, the reaction proceeds without converting glutaric acid derivatives and the like to their carboxylic acid halides, and the separation and recovery of the solid acid catalyst is easy, so that it is the same as the 2,5-position. Alternatively, 1,5-diketones having different aromatic substituents can be produced more efficiently than conventional methods without discharging a large amount of hazardous waste.

Hereinafter, the present invention will be described in detail.
The production method of the present invention is characterized in that an aromatic compound and a glutaric acid derivative or a 4-aroylbutyric acid derivative are reacted in the presence of a solid acid catalyst.
In the present invention, the aromatic compound used as a raw material is represented by the following general formula (I)
R ¹ H (I)
(In the formula, R ¹ represents a monovalent hydrocarbon ring system or heterocyclic aromatic organic group, and a part of hydrogen atoms of the hydrocarbon ring or heterocyclic ring is substituted with a group not participating in the reaction. May be.)
It is a hydrocarbon ring system compound or heterocyclic compound represented by these.

In the general formula (I), R ¹ is a monovalent hydrocarbon ring system or heterocyclic aromatic organic group.
When R ¹ is a hydrocarbon ring-type aromatic organic group, the number of carbon atoms in the ring is preferably 6-22, more preferably 6-14. Specific examples of these carbocyclic aromatic organic groups Include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a pentacenyl group, and the like. Specific examples of the hydrocarbon ring aromatic compound having these groups include benzene, naphthalene, anthracene. Phenanthrene, pyrene, perylene, pentacene and the like.
Moreover, when R < ¹ > is a heterocyclic aromatic organic group, a hetero atom is sulfur, an oxygen atom, etc., Preferably carbon number in a ring is 4-12, More preferably, it is 4-8. Specific examples of these heterocyclic aromatic organic groups include thienyl group, benzothienyl group, dibenzothienyl group, furyl group, benzofuryl group, dibenzofuryl group, etc., and heterocyclic aromatics having these groups Specific examples of the compound include thiophene, benzothiophene, dibenzothiophene, furan, benzofuran, dibenzofuran and the like.

In the general formula (I), R ¹ may be substituted with a group in which some of the hydrogen atoms on the ring do not participate in the reaction. Specific examples of these groups include a methyl group, an isopropyl group, a hexyl group, Alkyl groups having 1 to 10 carbon atoms such as decyl group, etc., alkoxy groups having 1 to 10 carbon atoms such as methoxy group, ethoxy group, isopropoxy group, hexyloxy group, octyloxy group, fluorine atom, chlorine In addition to halogen atoms such as atoms and bromine atoms, there can be mentioned oxyethylene groups and oxyethyleneoxy groups which are divalent groups for bonding two carbon atoms on the ring.
Therefore, specific examples of aromatic compounds having these groups include toluene, anisole, ethoxybenzene, butoxybenzene, methylanisole, fluoroanisole, chloroanisole, bromoanisole, dihydrobenzofuran, 1,4-benzodioxane and the like. It is done.

（式中、メチレン基の水素原子の一部が反応に関与しない基で置換されていてもよい。）
で表されるグルタル酸誘導体である。 The glutaric acid derivative to be reacted with the aromatic compound is represented by the following general formula (IIA)
_{HO 2 C-CH 2 CH 2} CH 2 -CO 2 H (IIA)
(In the formula, a part of hydrogen atoms of the methylene group may be substituted with a group not participating in the reaction.)
Or the following general formula (IIB)

(In the formula, a part of hydrogen atoms of the methylene group may be substituted with a group not participating in the reaction.)
It is a glutaric acid derivative represented by these.

In the glutaric acid derivative represented by the general formula (IIA) or the general formula (IIB), a part of the hydrogen atoms of the methylene group may be substituted with a group that does not participate in the reaction. Specific examples of these groups include An alkyl group having 1 to 10 carbon atoms such as methyl group, isopropyl group, hexyl group, octyl group, etc., alkoxy having 1 to 10 carbon atoms such as methoxy group, ethoxy group, isopropoxy group, and hexyloxy group. In addition to a group and a halogen atom such as a fluorine atom, an oxyethylene group and an oxyethyleneoxy group, which are divalent groups for bonding two carbon atoms on a ring, can be exemplified.
Therefore, specific examples of these glutaric acid derivatives include glutaric acid, 2- or 3-methylglutaric acid, 2,2- or 3,3-dimethylglutaric acid, glutaric anhydride, 2,2- or 3,3. -Dimethyl glutaric anhydride etc. are mentioned.

On the other hand, instead of the above general formula (IIA) or general formula (IIB), the following general formula (IIC)
^{_{R 2 CO-CH 2 CH 2}} CH 2 -CO 2 H (IIC)
(In the formula, R ² is a monovalent hydrocarbon ring or heterocyclic aromatic organic group, and a part of hydrogen atoms of the hydrocarbon ring or heterocyclic ring and / or a hydrogen atom of the methylene group is reacted. It may be substituted with a non-participating group.)
The reaction can also be carried out using a 4-aroylbutyric acid derivative represented by:

In the general formula (IIC), R ² is a monovalent hydrocarbon ring system or heterocyclic aromatic organic group.
When R ² is a hydrocarbon ring system, the number of carbon atoms in the ring is preferably 6-22, more preferably 6-14, and when R ² is a heterocyclic system, the heteroatom is sulfur, oxygen An atom or the like, and the number of carbon atoms in the ring is preferably 4 to 12, and more preferably 4 to 8. Specific examples of these aromatic organic groups include those exemplified above as specific examples of R ¹ in formula (I).
Accordingly, specific examples of these 4-aroylbutyric acid derivatives include 4-benzoylbutyric acid, 4- (4-chlorobenzoyl) butyric acid, 4- (4-bromobenzoyl) butyric acid, 4- (3-fluorobenzoyl) butyric acid, 4 -(4-methylbenzoyl) butyric acid, 4- (4-methoxybenzoyl) butyric acid, 4- (2-naphthylcarbonyl) butyric acid, 4- (2-thienylcarbonyl) butyric acid, 4- (2-furylcarbonyl) butyric acid and the like Can be mentioned.

The molar ratio of the aromatic compound to the glutaric acid derivative of the general formula (IIA) or the general formula (IIB) can be arbitrarily selected, but 1 for the glutaric acid derivative of the general formula (IIA) or the general formula (IIB). In consideration of the yield of 1,5-diketones, it is usually 0.4 or more and 300 or less, more preferably 0.5 or more and 200 or less, and further preferably 0.5 or more and 150 or less.
Similarly, the molar ratio of the aromatic compound to the 4-aroylbutyric acid derivative of the general formula (IIC) can be arbitrarily selected, but 1,5-diketones to the 4-aroylbutyric acid derivative of the general formula (IIC) In consideration of the yield of the above, it is usually 0.4 or more and 300 or less, more preferably 0.5 or more and 200 or less, and further preferably 0.5 or more and 150 or less.

According to the present invention, the following general formula (IIIA) is obtained by reacting the aromatic compound of the general formula (I) with the glutaric acid derivative represented by the general formula (IIA) or the general formula (IIB).
^{_{R 1 CO-CH 2 CH 2}} CH 2 -COR 1 (IIIA)
(In the formula, R ¹ has the same meaning as described above, and a part of the hydrogen atom of the methylene group may be substituted with a group not involved in the reaction derived from the formula (IIA) or the formula (IIB).)
1,5-diketones having an aromatic substituent represented by the formula:
In the reaction of the aromatic compound of the general formula (I) and the aroylbutyric acid derivative represented by the general formula (IIC), the following general formula (IIIB)
^{_{R 2 CO-CH 2 CH 2}} CH 2 -COR 1 (IIIB)
(In the formula, R ¹ and R ² have the same meaning as described above, and a part of the hydrogen atoms of the methylene group may be substituted with a group not involved in the reaction derived from the formula (IIC).)
1,5-diketones having an aromatic substituent represented by the formula:
Specific examples of R ¹ and R ² in general formula (IIIA) and general formula (IIIB) include those exemplified in general formula (I) and general formula (IIC).
Furthermore, in the present invention, novel 1,5-diketones represented by the following general formula (IV) can be provided.
^{_{R 3 CO-CH 2 CH 2}} CH 2 -COR 4 (IV)
(In the formula, R ³ and R ⁴ are both 2,3-dihydrobenzofuran-5-yl groups, both are 1,4-benzodioxan-6-yl groups, or one is a phenyl group and the other is 2, 3-dihydrobenzofuran-5-yl group.)
The 1,5-diketones of the above general formula (IV) are a reaction of 2,3-dihydrobenzofuran or 1,4-benzodioxane and a glutaric acid derivative, a reaction of 2,3-dihydrobenzofuran and 4-benzoylbutyric acid. Can be manufactured. These novel 1,5-diketones can be used as synthetic intermediates for pyridine derivatives and cyclopentadiene derivatives that are highly useful as various functional substances and materials.

In the production method of the present invention, when the aromatic ring of the aromatic compound of the general formula (I) has a plurality of reactive points having different reactivity, the glutaric acid derivative or 4-aroylbutyric acid derivative has the highest electron density and is three-dimensional. Reacts preferentially with less ring carbon atoms.
For example, in a benzene ring having an alkoxy substituent, the glutaric acid derivative or 4-aroylbutyric acid derivative reacts preferentially with the carbon in the para position relative to the alkoxy group to give the p-acylated product as the main product. Furthermore, an aromatic compound such as 2,3-dihydrobenzofuran has a para-position carbon atom with respect to the alkoxy group and a para-position carbon atom with respect to the alkyl group, but is considered to have higher electron donating properties. The carbon atom in the para position reacts preferentially with the alkoxy group.
As described above, the reaction of the present invention exhibits regioselectivity generally found in electrophilic substitution reaction, but the structure of the catalyst greatly affects the regioselectivity. For example, a catalyst having regular pores such as a zeolite catalyst is particularly advantageous for the regioselective reaction of an aromatic ring because it exhibits shape selectivity based on the pore shape, pore diameter and the like. For example, when anisole, which is monosubstituted benzene, is used as a raw material, a p-acylated product having the smallest steric hindrance is usually produced with a selectivity of 98% or more with respect to other positional isomers. Can do.

In the present invention, various conventionally known solid acid catalysts used in Friedel-Crafts type electrophilic substitution reaction and the like can be used.
Specific examples thereof include solid inorganic substances such as metal salts and metal oxides, and solid organic substances having an acidic functional group.
More specifically, the solid inorganic substances in them include zeolites, montmorillonites, silicas, heteropoly acids and carbon-based materials having protic hydrogen atoms or metal cations (aluminum, titanium, gallium, iron, cerium, scandium, etc.). Examples thereof include inorganic solid acids used as a carrier. The solid inorganic substance having a metal cation can be prepared by a usual method, for example, treating a commercially available sodium-type solid inorganic substance with an aqueous solution of a metal cation.
In more detail, solid organic substances are represented by Nafion having a sulfo group (Nafion, registered trademark, available from DuPont), Dowex (registered trademark, available from Dow Chemical), Amberlite ( Acidic polymers such as Amberlite, registered trademark, available from Rohm & Hass) and other organic solid acids. Further, a catalyst in which an organic acidic compound such as Nafion is supported on silica or the like (for example, Nafion SAC-13 etc.) can be used, and a plurality of inorganic solid acids and organic solid acids can be used in combination.

When zeolite is used as a catalyst, various types of zeolites having a basic skeleton such as beta type, Y type, mordenite type, ZSM-5 type, SAPO type can be used. Y type and mordenite type are preferable, and beta type and Y type are more preferable.
In these zeolites, various types of zeolites such as Bronsted acid type having a protonic hydrogen atom and Lewis acid type having a metal cation can be used. Among these, the proton type having a protonic hydrogen atom is represented by H-beta type, HY type, H-SDUSY type, H-SUSY type, H-mordenite type, H-ZSM-5 type, etc. Is done. Furthermore, those of ammonium type, NH ₄ - beta, _NH 4 -Y _type, NH 4 -VUSY type, NH ₄ - _mordenite, by firing the NH 4 -ZSM-5 type or the like of the zeolite, the proton type You can also use the one converted to. The proton-type and ammonium-type zeolites represented by the H-SDUSY type, H-SUSY type, and NH ₄ -VUSY type all have a Y-type basic skeleton.
Furthermore, about the silica / alumina ratio of a zeolite, although various ratios can be selected according to reaction conditions, Preferably it is 2-1000, More preferably, it is 5-900, More preferably, it is 10-800. A known method may be used as a method for measuring the silica / alumina ratio.

  As these zeolites, various types including commercial products can be used. Specific examples of commercially available products include, as beta-type zeolite, CP811C, CP814N, CP7119, CP814E, CP7105, CP814C, CP811TL, CP814T, CP814Q, CP811Q, CP811E-75, CP811E, CP811C, which are commercially available from Zeolist. -300 and USZ-1, etc., such as HSZ-930HOA and HSZ-940HOA commercially available from Tosoh Corporation, and UOP-Beta available from UOP Corporation. Examples of the Y-type zeolite include CBV760, CBV780, CBV720, CBV712, and CBV600 that are commercially available from Zeolis Corporation, and HSZ-360HOA and HSZ-320HOA that are commercially available from Tosoh Corporation. Further, examples of the mordenite type zeolite include CBV21A and CBV90A commercially available from Zeolist, HSZ-660HOA, HSZ-620HOA, HSZ-690HOA and the like commercially available from Tosoh Corporation. CBV5524G, CBV8020, and CBV8014, which are commercially available from Zeolist.

  The amount of catalyst relative to the raw material can be arbitrarily determined, but in terms of weight ratio, it is usually about 0.0001 to 100, preferably about 0.001 to 70, and more preferably about 0.001 to 50.

  The reaction of the present invention can be carried out in a liquid phase or a gas phase depending on the reaction temperature and reaction pressure. Moreover, as a form of a reaction apparatus, it can carry out with various forms conventionally known, such as a batch type and a flow type. The reaction temperature is 20 ° C. or higher, preferably 20 to 400 ° C., more preferably 20 to 350 ° C. Furthermore, the reaction pressure is usually 0.1 to 100 atm, preferably 0.1 to 80 atm, and more preferably 0.1 to 60 atm. The reaction time depends on the reaction temperature, the amount of catalyst, the form of the reaction apparatus, etc., but is 1 to 400 minutes, preferably 1 to 320 minutes, more preferably about 1 to 240 minutes.

  Further, when the reaction is carried out in a liquid phase system, it can be carried out with or without a solvent, but when a solvent is used, hydrocarbons such as decalin (decahydronaphthalene) and decane, chlorobenzene, 1,2- or 1, Various solvents other than those that react with the raw material, such as halogenated hydrocarbons such as 3-dichlorobenzene, 1,2,3- or 1,2,4-trichlorobenzene, ethers such as dibutyl ether can be used, A mixture of two or more types can also be used. Moreover, when performing reaction in a gaseous phase, it can also react by mixing inert gas, such as nitrogen.

The reaction of the present invention can also be performed under microwave irradiation. In this reaction system, water and solid acid catalysts, which are co-products, have large dielectric loss coefficients, and they absorb microwaves efficiently. Therefore, under microwave irradiation, water desorption from the catalyst surface and solid acid catalysts Activation is promoted and the reaction can proceed more efficiently.
When the reaction is performed under microwave irradiation, in order to heat the reaction system more efficiently, a heating material (susceptor) that absorbs microwaves and generates heat can be added to the reaction system. As the kind of the heating material, various conventionally known materials such as activated carbon, graphite, silicon carbide, titanium carbide and the like can be used. Further, a molded catalyst obtained by mixing the catalyst described above and the heating material powder and calcining using an appropriate binder such as sepiolite or holmite can also be used.

  In the microwave irradiation reaction, various commercially available devices equipped with contact-type or non-contact-type temperature sensors can be used. The output of microwave irradiation, the type of cavity (multimode, single mode), the form of irradiation (continuous, intermittent), etc. can be arbitrarily determined according to the scale and type of reaction. The frequency of the microwave is usually 0.3 to 30 GHz. As a specific frequency band, a 2.4 GHz band, a 5.8 GHz band, or the like known as an ISM frequency band (frequency band in the radio wave method that can be used in the fields of industry, science, and medicine) can be used.

  In the reaction of the present invention, since a solid acid is used as a catalyst, the separation and recovery of the catalyst after the reaction can be easily performed by a method such as filtration or centrifugation. Further, purification of the produced 1,5-diketone can be easily achieved by means usually used in organic chemistry such as recrystallization, distillation, column chromatography and the like.

EXAMPLES Next, although an Example demonstrates this invention further more concretely, this invention is not limited to these Examples.
In addition, the apparatus used by the analysis of the product in each Example, etc. is GC-2014 made by Shimadzu Corporation for gas chromatographic analysis (GC), and GCMS-QP2000plus made by Shimadzu Corporation for gas chromatograph mass spectrometry (GC-MS), melting point measurement. In the case of Aswan ATM-02, for elemental analysis CE INSTRUMENTS EA1110, for nuclear magnetic resonance analysis (NMR) JEOL JNM-LA600, for infrared spectroscopic analysis (IR) FT / IR-660plus It is.
Example 1
Anisole (Ia) 20 mmol, glutaric anhydride (IIa) 0.20 mol, 1,2-dichlorobenzene 1 mL, H-beta type zeolite CP811C (manufactured by Zeolis) 100 mg of mixture was put into a reaction tube, and a radiation thermometer was provided. Using a microwave irradiation device (CEM, Discover LabMate, single mode type, 2.45 GHz, microwave maximum output 300 W), the reaction was carried out at 210 ° C. for 30 minutes with stirring. As a result of analyzing the product with a gas chromatograph and a gas chromatograph mass spectrometer, it was found that 1,5-bis (4-methoxyphenyl) -1,5-pentanedione (IIIAa) was produced in a yield of 56.8%. Okay (see Table 1).

(Examples 2 to 20)
Table 1 shows the results obtained by carrying out the reaction and analysis in the same manner as in Example 1 while changing the reaction conditions (raw materials, catalyst, temperature, time, etc.) and measuring the yield of the product.

1) Ia: anisole, Ib: 2,3-dihydrobenzofuran, Ic: 1,4-benzodioxane, Id: thiophene.
2) IIAa: glutaric acid, IIBa: glutaric anhydride, IICa: 4-benzoylbutyric acid.
All zeolites are calcined at 500 ° C.
3) CP811C: H-beta zeolite CP811C (Zeolist), UOP-Beta: H-beta zeolite (UOP), CP814N: NH ₄ -beta zeolite CP814N (Zeolist), CP814Q: NH ₄ -Beta zeolite CP814Q (Zeolist), CP811E75: H-beta zeolite CP811E-75 (Zeolist), CP811C300: H-beta zeolite CP811E-75 (Zeolist), 980HOA: H-beta zeolite HSZ-980HOA (manufactured by Tosoh Corporation), USZ-1: H-beta type zeolite USZ-1 (manufactured by Zeolis Corporation), CBV720: H-SDUSY type zeolite CBV720 (manufactured by Zeolis Corporation), CBV780: H-SDUSY type zeolite CBV780 ( Zeolist), CBV90A: H-mordenite zeolite CBV90A (Zeolist), CBV5524G: NH ₄ -ZSM-5 zeolite CBV5524G (Zeolist), Al-mont: Al ³⁺ containing montmorillonite, SAC-13: Nafion SAC13 (DuPont), CB V760: H-SDUSY type zeolite CBV760 (Zeolist).
4) Prepared by treating Na ⁺ type montmorillonite (Kunimine Kogyo, Kunipia F) with Al ³⁺ aqueous solution.
5) 1,2-DCB: 1,2-dichlorobenzene.
6) MW1: Microwave reactor (manufactured by CEM, Discover LabMate), MW2: Microwave reactor (manufactured by Biotage, Initiaor), OB: Oil bath reactor (manufactured by Riko Kagaku Sangyo Co., Ltd., MH-5E).
7) IIIAa: 1,5-bis (4-methoxyphenyl) -1,5-pentanedione, IIIAb: 1,5-bis (2,3-dihydrobenzofuran-5-yl) -1,5-pentanedione, IIIAc: 1,5-bis (1,4-benzodioxan-6-yl) -1,5-pentanedione, IIIBa: 1- (4-methoxyphenyl) -5-phenyl-1,5-pentanedione, IIIBb : 1- (2,3-dihydrobenzofuran-5-yl) -5-phenyl-1,5-pentanedione, IIIBc: 1- (1,4-benzodioxan-6-yl) -5-phenyl-1, 5-pentanedione, IIIBd: 1-phenyl-5- (2-thienyl) -1,5-pentanedione.
8) Yield of raw material with respect to II by gas chromatographic analysis.

(Examples 21 to 40)
Table 2 shows the results obtained by carrying out the reaction and analysis in the same manner as in Example 1 while changing the reaction conditions (raw materials, catalyst, temperature, time, etc.) and measuring the yield of the product.

1)〜8)は表１と同じ。

1) to 8) are the same as in Table 1.

(Example 41)
2,3-dihydrobenzofuran (Ib) 40 mmol, glutaric anhydride (IIBa) 1.0 mmol, 1,2-dichlorobenzene 6 mL, H-beta type zeolite CP811C (manufactured by Zeolis) 500 mg of a mixture was put into a reaction tube, The reaction was carried out at 250 ° C. for 1 hour with stirring using a microwave reactor equipped with a radiation thermometer (Biotage, Initiator, single mode type, 2.45 GHz, maximum microwave output 400 W). The solid was separated from the supernatant with a centrifuge, and the solid was washed with acetone (8 mL) and toluene (10 mL). The supernatant and the washings were combined, concentrated under reduced pressure, and the product was separated by column chromatography (silica gel, ethyl acetate / hexane = 2/3). As a result, 1,5-bis (2,3-dihydrobenzofuran- 0.52 mmol (yield 52%, pale yellow solid) of 5-yl) -1,5-pentanedione (IIIAb) was obtained.

IIIAb is a compound not yet described in the literature, and its spectrum data and the like were as follows.
Melting point: 131-132 ° C.
Elemental analysis: C 75.02, H 6.01 (measured); C 74.98, H 5.99 (calculated).
¹ H-NMR (CDCl ₃ ): δ 2.16 (quint, J = 7.0 Hz, 2H, C H ₂ CH ₂ CO),
3.02 (t, J = 7.0 Hz, 4H, C H ₂ CO), 3.23 (t, J = 8.8 Hz, 4H, C H ₂ CH ₂ O),
4.65 (t, J = 8.8 Hz, 4H, CH ₂ O), 6.79 (d, J = 8.4 Hz, 2H, aromatic ring H), 7.82 (dd, J = 8.4, 1.8 Hz, 2H, aromatic ring H), 7.86 (d,
J = 1.8 Hz, 2H, aromatic ring H).
¹³ C-NMR (CDCl ₃ ): δ 19.4, 29.0, 37.4, 72.1, 109.0, 125.4, 127.6, 130.0, 130.3, 164.3, 198.5.
IR (KBr): ν 1677, 1604, 1491, 1435, 1415,1370,
1279, 1236, 1193, 1108, 976, 940, 818, 750, 639 cm ^-1 .
GC-MS (EI, 70eV): m / z (relative intensity) 336 (M ⁺ , 5),
162 (49), 147 (100), 119 (15), 91 (34), 65 (20).

(Example 42)
As a result of carrying out the reaction, post-treatment and purification in the same manner as in Example 41 except that 1,4-benzodioxane (Ic) was used instead of 2,3-dihydrobenzofuran (Ib), 1,5-bis (1, 4-benzodioxan-6-yl) -1,5-pentanedione (IIIAc) was obtained in an amount of 0.50 mmol (yield 50%, pale yellow solid).

IIIAc is a compound not yet described in the literature, and its spectrum data and the like were as follows.
Melting point: 141-142 ° C.
Elemental analysis: C 68.53, H 5.44 (measured); C 68.47, H 5.47 (calculated).
¹ H-NMR (CDCl ₃ ): δ 2.14 (quint, J = 7.0 Hz, 2H, C H ₂ CH ₂ CO), 3.00
(t, J = 7.0 Hz, 4H, C H ₂ CO), 4.25-4.33 (m, 8H, CH ₂ O), 6.87-6.92
(m, 2H, aromatic ring H), 7.49-7.53 (m, 4H, aromatic ring H).
¹³ C-NMR (CDCl ₃ ): δ 19.2, 37.3, 64.1, 64.7, 117.2, 117.6, 122.2, 130.8, 143.3, 147.9, 198.4.
IR (KBr): ν 1678, 1608, 1578, 1506, 1349,
1319, 1286, 1258, 1166, 1117, 1065, 988, 901, 874, 819, 808 cm ^-1 .
GC-MS (EI, 70eV): m / z (relative intensity) 368 (M ⁺ , 7),
178 (52), 163 (100), 135 (25), 107 (35), 79 (22), 77 (11), 55 (11), 51 (15).

(Example 43)
Anisole (Ia) 4 mmol, glutaric anhydride (IIBa) 0.50 mmol, 1,2-dichlorobenzene 2 mL, H-beta type zeolite CP811C (manufactured by Zeolis) 150 mg of mixture was put into a reaction tube, and a radiation thermometer was provided. The reaction was carried out at 210 ° C. for 30 minutes with stirring using a microwave reactor (CEM, Discover LabMate, single mode type, 2.45 GHz, microwave maximum output 300 W). The solid was separated from the supernatant with a centrifuge, and the solid was washed with acetone (2 mL) and toluene (2 mL twice). The same reaction and post-treatment are repeated 4 times. The supernatant and washing solution for 5 times in total are combined, concentrated under reduced pressure, and the product is separated by column chromatography (silica gel, ethyl acetate / hexane = 1/2). As a result, 0.75 mmol (yield 30%, pale yellow solid) of (IIIAa) was obtained.

(Example 44)
2,3-dihydrobenzofuran (Ib) 9.1 mmol, 4-benzoylbutyric acid (IICa) 1.0 mmol, 1,2-dichlorobenzene 10 mL, H-beta type zeolite CP811C (Zeolist) 500 mg The reaction was carried out at 200 ° C. for 3 hours with stirring using a microwave reactor equipped with a radiation thermometer (Biotage, Initiator, single mode type, 2.45 GHz, maximum microwave output 400 W). The solid was separated from the supernatant with a centrifuge, and the solid was washed with toluene (6 mL) and acetone (3 × 8 mL). The same reaction and post-treatment are repeated, and the supernatant and washing solution for two times in total are combined, the supernatant and washing solution are combined, concentrated under reduced pressure, and column chromatography (silica gel, ethyl acetate / hexane = 1/4). As a result of separating the product by 1), 0.80 mmol (yield 40%, pale yellow solid) of 1- (2,3-dihydrobenzofuran-5-yl) -5-phenyl-1,5-pentanedione (IIIBb) was obtained. ) Obtained.

IIIBb is a compound not yet described in the literature, and its spectrum data and the like were as follows.
Melting point: 97-98 ℃.
Elemental analysis: C 77.65, H 6.16 (measured); C 77.53, H 5.16 (calculated).
¹ H-NMR (CDCl ₃ ): δ 2.18 (quint, J = 7.0 Hz, 2H, C H ₂ CH ₂ CO),
3.04 (t, J = 7.0 Hz, 4H, C H ₂ CO), 3.10 (t, J = 7.0 Hz, 4H, C H ₂ CO),
3.23 (t, J = 8.8Hz, 2H, C H ₂ CH ₂ O), 4.64 (t, J = 8.8
Hz, 2H, CH ₂ O), 6.79 (d, J = 8.4 Hz, 1H, aromatic ring H), 7.43-7.48
(m, 2H, aromatic ring H), 7.53-7.57 (m, 1H, aromatic ring H), 7.81-7.84 (m, 1H, aromatic ring H), 7.85-7.88 (m, 1H,
Aromatic ring H), 7.96-8.00 (m, 2H, aromatic ring H).
¹³ C-NMR (CDCl ₃ ): δ 19.1,29.0, 37.3, 37.7, 72.1, 109.0, 125.4, 127.6, 128.0, 128.5,130.0,
130.3, 133.0, 136.8, 164.3, 198.3, 200.0.
IR (KBr): ν 1681, 1669, 1602, 1492, 1438, 1411, 1376, 1279, 1239, 1192, 1113,
1071, 977, 936, 815, 740, 695 cm ^-1 .
GC-MS (EI, 70eV): m / z (relative intensity) 294 (M ⁺ , 5), 162 (29),
147 (100), 119 (12), 105 (23), 91 (26), 77 (28), 65 (16).

In Example 1 and Example 6, reaction and analysis were performed using an oil bath heating device (manufactured by Riko Kagaku Sangyo Co., Ltd., MH-5E) instead of the microwave irradiation device. In Example 5 and Example 7, IIIAa The yields were 47.8% and 37.9%, respectively, which values were lower than 56.8% and 50.7% obtained in the microwave irradiation apparatus reaction.
This indicates that the reaction using microwave irradiation tends to give IIIAa in a higher yield than the reaction of normal heating with an oil bath at the same reaction temperature and time.

  Since the 1,5-diketone useful as an intermediate of various functional chemicals can be produced more efficiently and safely by the method of the present invention, the utility value of the present invention is high, and its industrial significance is great. It is.

Claims (7)

The following general formula (I)
R ¹ H (I)
(In the formula, R ¹ represents a monovalent hydrocarbon ring system or heterocyclic aromatic organic group, and a part of hydrogen atoms of the hydrocarbon ring or heterocyclic ring is substituted with a group not participating in the reaction. May be.)
An aromatic compound represented by the following general formula (IIA)
_{HO 2 C-CH 2 CH 2} CH 2 -CO 2 H (IIA)
(In the formula, a part of hydrogen atoms of the methylene group may be substituted with a group not participating in the reaction.)
Or the following general formula (IIB)

(In the formula, a part of hydrogen atoms of the methylene group may be substituted with a group not participating in the reaction.)
The following general formula (IIIA) is characterized by reacting a glutaric acid derivative represented by the following formula in the presence of a solid acid catalyst:
^{_{R 1 CO-CH 2 CH 2}} CH 2 -COR 1 (IIIA)
(In the formula, R ¹ has the same meaning as described above, and a part of the hydrogen atom of the methylene group may be substituted with a group not involved in the reaction derived from the formula (IIA) or the formula (IIB).)
The manufacturing method of 1,5- diketones represented by these. Instead of the above general formula (IIA) or general formula (IIB), the following general formula (IIC)
^{_{R 2 CO-CH 2 CH 2}} CH 2 -CO 2 H (IIC)
(In the formula, R ² is a monovalent hydrocarbon ring or heterocyclic aromatic organic group, and a part of hydrogen atoms of the hydrocarbon ring or heterocyclic ring and / or a hydrogen atom of the methylene group is reacted. It may be substituted with a non-participating group.)
4-aroylbutyric acid derivative represented by the following general formula (IIIB)
^{_{R 2 CO-CH 2 CH 2}} CH 2 -COR 1 (IIIB)
(In the formula, R ¹ and R ² have the same meaning as described above, and a part of the hydrogen atoms of the methylene group may be substituted with a group not involved in the reaction derived from the formula (IIC).)
The manufacturing method of 1,5- diketones represented by these. The production method according to claim 1 or 2, wherein zeolite, montmorillonite or heteropoly acid is used as the solid acid catalyst. The production method according to claim 3, wherein a zeolite of a beta type, a Y type, a mordenite type or a ZSM-5 type is used as the zeolite. The production method according to claim 3 or 4, wherein a zeolite having a silica / alumina ratio of 2 to 1000 is used as the zeolite. 6. The production method according to claim 1, 2, 3, 4, or 5, wherein the reaction is performed under microwave irradiation. 1,5-diketones represented by the following general formula (IV).
R ³ COCH ₂ CH ₂ CH ₂ COR ⁴ (IV)
(In the formula, R ³ and R ⁴ are both 2,3-dihydrobenzofuran-5-yl groups, both are 1,4-benzodioxan-6-yl groups, or one is a phenyl group and the other is 2, 3-dihydrobenzofuran-5-yl group.)