JP2001199927A - Method of manufacturing bis[(arylcarbonyl) aryl]ethers - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide bis[(arylcarbonyl)aryl]ethers which are important compounds as a monomer of a heat resistant and a chemical resistant resin and a terminal modifier, using phenols and/or phenolates as a raw material. SOLUTION: Bis [(arylcarbonyl)aryl]ethers are manufactured by reacting phenols and/or phenolates expressed by general formula (1) (M is one or more kinds of atom selected from H or alkali metal, may be same or different) and 2,2-difluoro-1,3-dimethyl-imidazolidine.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing bis [(arylcarbonyl) aryl] ethers.

[0002]

2. Description of the Related Art Diaryl ethers are used as various industrial raw materials. Bis [(arylcarbonyl) aryl]
Ethers are important compounds as monomers and terminal modifiers for heat and chemical resistant resins.

Hitherto, as a method for producing bis [(arylcarbonyl) aryl] ethers, there has been a production of 4,4'-bis (4-fluorobenzoyl) diphenylether by a Friedel-Crafts reaction between diphenylether and p-fluorobenzoyl chloride. The method is known (US Pat. No. 4,820,790 and JP-A-61-91).
No. 151). Thus, the 4,4′-bis (4-
In the case of producing fluorine-containing bis [(arylcarbonyl) aryl] ethers such as fluorobenzoyl) diphenyl ether, at present, it is necessary to select an expensive fluorine-containing aromatic compound as a raw material. there were.

As a method for producing 4,4'-bis (4-hydroxybenzoyl) diphenyl ether, Japanese Patent Application Laid-Open No. 58-62132 discloses a method for producing 4,4 '-(dicarboxy) diphenyl ether by adding trifluoromethanesulfonic acid. In a method of reacting with phenol in the presence, Japanese Patent Application Laid-Open No. Sho 62-2324042, 4,4 '-(diphenoxycarbonyl) diphenyl ether is synthesized and Fries rearranged using liquid hydrogen fluoride. JP-A-64-42451 discloses a method of synthesizing 4,4'-bis (alkoxybenzoyl) diphenyl ether by cleaving it in the presence of a catalyst. Even in these methods, a special catalyst is used, a special reaction device is required, and the cost in the stage of raw material synthesis is large, so that it cannot be said that the method is industrially satisfactory.

Further, JP-A-49-49934 discloses a method for producing 4- (4-fluorobenzoyl) -4 '-(4-hydroxybenzoyl) diphenyl ether. In this method, 4- (4-fluorobenzoyl) diphenyl ether is synthesized by a Friedel-Crafts reaction between diphenyl ether and p-fluorobenzoyl chloride, and this is reacted with bis (4-chlorocarbonylphenyl) carbonate for acylation. The desired product is obtained by hydrolyzing the acylated product. When producing bis [(arylcarbonyl) aryl] ethers containing fluorine and hydroxyl groups as in this method, many complicated steps were required.

As described above, when producing bis [(arylcarbonyl) aryl] ethers containing a hydroxyl group and / or a fluorine atom, there are various problems in the conventional method and an efficient production method. The development of was desired.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve this problem, and as a result, the general formula (2)

[0008]

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(Wherein R ¹ , R ² , R ³ and R ⁴ are C ₁ -C ₆
And may be the same or different. R ¹ and R ³ in the formula may be combined to form a 5-membered or 6-membered ring;
¹ , R ² or R ³ and R ⁴ may be bonded. X ¹ represents a fluorine atom, and X ² represents a fluorine atom or a chlorine atom. X ¹ and X ² may be covalently bonded to a carbon atom, or only X ¹ may be covalently bonded and X ² may be present in the form of a counter ion. That the bis [(arylcarbonyl) aryl] ethers can be produced from phenols having a substituent and / or phenolates having a substituent, The present invention has been completed.

That is, the present invention provides a compound represented by the general formula (1)

[0011]

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(Wherein M represents a hydrogen atom or an alkali metal atom and may be the same or different), and a phenol and / or phenolate represented by the following general formula (2)

[0013]

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(Wherein R ¹ , R ² , R ³ and R ⁴ are C ₁ -C ₆
And may be the same or different. R ¹ and R ³ in the formula may be combined to form a 5-membered or 6-membered ring;
¹ , R ² or R ³ and R ⁴ may be bonded. X ¹ represents a fluorine atom, and X ² represents a fluorine atom or a chlorine atom. X ¹ and X ² may be covalently bonded to a carbon atom, or only X ¹ may be covalently bonded and X ² may be present in the form of a counter ion. (3) a compound represented by the formula (3):

[0015]

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(Wherein R ⁵ and R ⁶ represent a fluorine atom or a hydroxyl group and may be the same or different from each other). Preparation of bis [(arylcarbonyl) aryl] ethers represented by the formula: And particularly, when the compound of general formula (2) is a compound of formula (4)

[0017]

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2,2-difluoro-1,3-
A process for producing bis [(arylcarbonyl) aryl] ethers, which is dimethyl-imidazolidine.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
In the general formula (2), R ^{2 to} R ⁵ are an alkyl group or an aryl group having 1 to 6 carbon atoms. For example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group,
Examples include an n-pentyl group, an n-hexyl group, and a phenyl group. R ¹ and R ³ in the formula may combine to form a compound that forms a 5- or 6-membered ring. Examples of such a ring include an imidazolidine ring, an imidazolidinone ring, a pyrimidine ring, and a pyrimidinone ring. Further, R ¹ and R ² , or R ³ and R ⁴ may be bonded to each N atom to form a heterocyclic ring having 3 to 5 carbon atoms. Examples of such a ring include a pyrrolidine ring and a piperidine ring.

Among the compounds represented by the general formula (2), specific examples include bis-dimethylamino-difluoromethane,
Bis-diethylamino-difluoromethane, bis-dipropylamino-difluoromethane, bis-di-i-propylamino-difluoromethane, bis-di-n-butylamino-difluoromethane, bis-di-i-butylamino-difluoro Methane, bis-di-t-butylamino-
Difluoromethane, bis-di-n-pentyl-difluoromethane, bis-di-n-hexyl-difluoromethane, 2,2-difluoro-1,3-dimethyl-imidazolidine, 2,2-difluoro-1-ethyl- 3-methyl-imidazolidine, 2,2-difluoro-1,3-diethyl-imidazolidine, 2,2-difluoro-1,3-
Di-n-propyl-imidazolidine, 2,2-difluoro-1,3-di-i-propyl-imidazolidine, 2,
2-difluoro-1,3-di-n-butyl-imidazolidine, N, N-dimethyl-N'-methyl-N'-phenyl-difluoromethane, bis-piperidyl-difluoromethane and the like and one of the compounds mentioned above Compounds in which one fluorine is replaced with chlorine to become a counter ion can be mentioned, but the present invention is not limited to the examples shown here. Preferably, 2,2-difluoro-1,3-
Dimethyl-imidazolidine.

The preparation of these compounds is carried out by the general formula (5)

[0022]

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(Wherein, R ¹ , R ² , R ³ and R ⁴ have the same meanings as described above).
By performing a halogen exchange reaction between chloride and an alkali metal salt of fluorine in a solvent, the compound can be obtained safely and easily. Specific examples of the alkali metal salt of fluorine include cesium fluoride, rubidium fluoride, potassium fluoride, and sodium fluoride.
It is preferable to use spray-dried potassium fluoride for the fluorination reaction, which is economically and reactionally advantageous.

The chloroformamidinium chloride represented by the general formula (5) used as a raw material for producing the compound represented by the general formula (2) is a tetraalkyl urea,
It can be produced by chlorinating 1,3-dialkylimidazolidinone or the like with a chlorinating agent such as phosgene or thionyl chloride. For example, the production of 2-chloro-1,3-dimethylimidazolinium chloride is described in
It can be easily produced by the method described in JP-A-25375.

In the preparation of the compound represented by the general formula (2) of the present invention, when a difluoro compound is prepared, the amount of the alkali metal salt of fluorine used in the halogen exchange reaction is represented by the general formula (5). It is usually at least 2 moles, preferably 2 to 5 moles, per mole of the compound. If the molar ratio is less than 2 times, unexchanged chloride remains and is insufficient. Even if the molar ratio exceeds 5 times, the reaction result is not significantly improved.

In the case of producing a compound in which the counter ion is chlorine, the amount of the alkali metal salt of fluorine used in the halogen exchange reaction is usually at least 1 mol per mol of the compound represented by the general formula (5). Preferably it is 1 to 1.5 times mol. If it is less than 1 mole, unexchanged chloride may remain and be insufficient. If it exceeds 1.5 times, the amount of the generated difluoro compound tends to increase. However, even if the difluoro compound is mixed, bis [(arylcarbonyl) aryl]
There is no problem in the production of ethers.

The reaction solvent is not particularly limited as long as it does not react with the compound represented by the general formula (5) and the compound represented by the general formula (2). Preferred are acetonitrile, dimethylformamide, 1,3-dimethyl-2-imidazolidinone, dichloromethane, ethylene dichloride and the like. The amount of the solvent is not particularly limited, but is preferably 1 to the reaction substrate from the viewpoint of reaction efficiency and operability.
To 10 times by weight. The reaction temperature is not particularly limited,
From the viewpoint of reaction rate and product stability, usually -20 ° C
150 ° C, preferably in the range of 0 ° C to 100 ° C.

In the production of the compound represented by the general formula (2), the halogen exchange reaction can be carried out in the presence of a phase transfer catalyst such as a quaternary alkyl ammonium salt or a quaternary alkyl phosphonium salt.

The obtained compound represented by the general formula (2) can be used in the next synthesis reaction of bis [(arylcarbonyl) aryl] ethers as a halogen exchange reaction solution. Further, the inorganic salt can be filtered from the reaction solution and used, or the inorganic salt can be filtered and then isolated and used by distillation or crystallization.

In the present invention, the phenols and / or phenolates represented by the general formula (1) are used as starting materials
Used for the production of bis [(arylcarbonyl) aryl] ethers. Specific examples of the raw materials include 2,2′-dihydroxybenzophenone, 2,3′-dihydroxybenzophenone, 2,4′-dihydroxybenzophenone,
3,4′-dihydroxybenzophenone, 3,3′-dihydroxybenzophenone, 4,4′-dihydroxybenzophenone and alkali metal salts thereof. Examples of the alkali metal atom include a sodium atom,
Examples include a potassium atom and a lithium atom. Preferably, a sodium atom and a potassium atom are used.

In the method of the present invention, the starting compound is
All phenols or all phenolates may be used, but they may be used in combination, and in such a case, there is no problem.

For the production of phenolates, phenols and an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide are mixed with water, and then mixed with water by a known evaporation method such as simple evaporation or an azeotropic medium. Is removed and dried.

When an etherification reaction of the phenols and / or phenolates represented by the general formula (1) is carried out using the compound represented by the general formula (2), the compound represented by the general formula (2)
The amount of the compound represented by the formula (1)
M] or more, and preferably 0.5 to 2 equivalents. Particularly preferably, it is 0.5 equivalent or more and less than 1 equivalent. If the amount is less than 0.5 equivalent, the progress of the reaction becomes insufficient, which is not preferable. In addition, the use of more than 2 equivalents does not tend to significantly improve the reaction results.

When a compound represented by the general formula (2) is used to carry out an etherification reaction of the phenol and / or phenolate represented by the general formula (1), the reaction solvent is as follows:
A compound represented by the general formula (2), and a phenol and / or phenolate represented by the general formula (1);
The reaction product bis [(arylcarbonyl)
The solvent is not particularly limited as long as it does not react with the aryl] ether, but is preferably an alkane such as hexane, heptane, or cyclohexane, an aromatic solvent such as benzene, toluene, xylene, or nitrobenzene, dichloromethane, chloroform, or ethylene dichloride. And aprotic polar solvents such as acetonitrile, N-methylpyrrolidinone, dimethylformamide, dimethylacetamide, dimethylsulfoxide, and 1,3-dimethyl-2-imidazolidinone.

When the etherification reaction of the phenols and / or phenolates represented by the general formula (1) is carried out using the compound represented by the general formula (2), the reaction temperature is as follows:
Usually, it is in the range of 60 ° C to 200 ° C, preferably 80 ° C to 150 ° C. If the temperature is lower than 60 ° C., the reaction rate becomes extremely slow, which is not preferable. If the temperature exceeds 200 ° C., the stability of the compound represented by the general formula (2) is lowered, so that it is not preferable.

The bis [(arylcarbonyl) aryl] ethers represented by the general formula (3) obtained by the method of the present invention include, for example, 2,2'-bis (2-hydroxybenzoyl) diphenyl ether and 2,3 ' -Bis (2-hydroxybenzoyl) diphenyl ether, 2,4′-bis (2-hydroxybenzoyl) diphenyl ether,
3,3'-bis (2-hydroxybenzoyl) diphenyl ether, 3,4'-bis (2-hydroxybenzoyl) diphenyl ether, 4,4'-bis (2-hydroxybenzoyl) diphenyl ether, 2,2'-bis (3 -Hydroxybenzoyl) diphenyl ether,
2,3′-bis (3-hydroxybenzoyl) diphenyl ether, 2,4′-bis (3-hydroxybenzoyl) diphenyl ether, 3,3′-bis (3-hydroxybenzoyl) diphenyl ether, 3,4′-bis (3 -Hydroxybenzoyl) diphenyl ether,
4,4'-bis (3-hydroxybenzoyl) diphenyl ether, 2,2'-bis (4-hydroxybenzoyl) diphenyl ether, 2,3'-bis (4-hydroxybenzoyl) diphenyl ether, 2,4'-bis (4 -Hydroxybenzoyl) diphenyl ether,
3,3'-bis (4-hydroxybenzoyl) diphenyl ether, 3,4'-bis (4-hydroxybenzoyl) diphenyl ether, 4,4'-bis (4-hydroxybenzoyl) diphenyl ether, 2,2'-bis (2 -Fluorobenzoyl) diphenyl ether, 2,
3'-bis (2-fluorobenzoyl) diphenyl ether, 2,4'-bis (2-fluorobenzoyl) diphenyl ether, 3,3'-bis (2-fluorobenzoyl) diphenyl ether, 3,4'-bis (2-fluoro Benzoyl) diphenyl ether, 4,4′-bis (2-fluorobenzoyl) diphenyl ether, 2,
2'-bis (3-fluorobenzoyl) diphenyl ether, 2,3'-bis (3-fluorobenzoyl) diphenyl ether, 2,4'-bis (3-fluorobenzoyl) diphenyl ether, 3,3'-bis (3-fluoro Benzoyl) diphenyl ether, 3,4′-bis (3-fluorobenzoyl) diphenyl ether, 4,
4'-bis (3-fluorobenzoyl) diphenyl ether, 2,2'-bis (4-fluorobenzoyl) diphenyl ether, 2,3'-bis (4-fluorobenzoyl) diphenyl ether, 2,4'-bis (4-fluoro Benzoyl) diphenyl ether, 3,3′-bis (4-fluorobenzoyl) diphenyl ether,
4'-bis (4-fluorobenzoyl) diphenyl ether, 4,4'-bis (4-fluorobenzoyl) diphenyl ether, 2- (2-hydroxybenzoyl)-
2 '-(2-fluorobenzoyl) diphenyl ether, 2- (2-hydroxybenzoyl) -3'-(2-
Fluorobenzoyl) diphenyl ether, 2- (2-
(Hydroxybenzoyl) -4 '-(2-fluorobenzoyl) diphenyl ether, 3- (2-hydroxybenzoyl) -3'-(2-fluorobenzoyl) diphenyl ether, 3- (2-hydroxybenzoyl) -4 '
-(2-fluorobenzoyl) diphenyl ether, 4
-(2-hydroxybenzoyl) -4 '-(2-fluorobenzoyl) diphenyl ether, 2- (3-hydroxybenzoyl) -2'-(3-fluorobenzoyl)
Diphenyl ether, 2- (3-hydroxybenzoyl) -3 ′-(3-fluorobenzoyl) diphenyl ether, 2- (3-hydroxybenzoyl) -4′-
(3-fluorobenzoyl) diphenyl ether, 3-
(3-hydroxybenzoyl) -3 ′-(3-fluorobenzoyl) diphenyl ether, 3- (3-hydroxybenzoyl) -4 ′-(3-fluorobenzoyl) diphenyl ether, 4- (3-hydroxybenzoyl)
-4 '-(3-fluorobenzoyl) diphenyl ether, 2- (4-hydroxybenzoyl) -2'-(4-
Fluorobenzoyl) diphenyl ether, 2- (4-
(Hydroxybenzoyl) -3 ′-(4-fluorobenzoyl) diphenyl ether, 2- (4-hydroxybenzoyl) -4 ′-(4-fluorobenzoyl) diphenyl ether, 3- (4-hydroxybenzoyl) -3 ′
-(4-fluorobenzoyl) diphenyl ether, 3
-(4-hydroxybenzoyl) -4 '-(4-fluorobenzoyl) diphenyl ether, 4- (4-hydroxybenzoyl) -4'-(4-fluorobenzoyl)
Examples thereof include diphenyl ether, but are not limited to these exemplified compounds.

The bis [(arylcarbonyl) aryl] ethers formed by the reaction can be easily removed from the reaction mixture by concentration, extraction or the like. or,
After completion of the reaction, the compound represented by the general formula (2) can be recovered as a tetraalkylurea, 1,3-dialkylimidazolidinone, or the like. The recovered compound is chlorinated by the above method to form chloroformamidinium chloride represented by the general formula (5), and further, a compound represented by the general formula (5) and an alkali metal salt of fluorine. The compound can be used again as a compound represented by the general formula (2) by performing a halogen exchange reaction with

[0038]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.
In addition, 2,2-difluoro-1,3-dimethylimidazolidin (hereinafter referred to as DFI) in an acetonitrile solution in Synthesis Example 1
The concentration was abbreviated by reacting DFI with aniline, followed by high performance liquid chromatography (hereinafter referred to as HPL).
C). The concentration of fluorine ions (hereinafter abbreviated as F ⁻ ) was measured by an absorption spectrophotometry using a lanthanum-alizarin complexone reagent. Each reaction result of the etherification was evaluated by HPLC or gas chromatography (hereinafter abbreviated as GC).

(Synthesis Example 1) 2,2-difluoro-1,3-dimethylimidazolidine
Synthesis of (DFI) 80.0 g (0.452 mol) of 2-chloro-1,3-dimethylimidazolinium chloride and 105.1 g (1.810 mol) of potassium fluoride as a spray-dried product
l) and 320 ml of acetonitrile were charged into a 500 ml four-necked reaction flask and reacted at 80 ° C. for 17 hours under a nitrogen atmosphere. After cooling the reaction solution to 25 ° C., inorganic salts were separated from the reaction solution to obtain 414.2 g of a solution of DFI (MW 136.14) in acetonitrile. The DFI concentration in the solution was 11.4 wt%, and the yield was 77%. The reaction solution was distilled under reduced pressure to obtain 32 g of DFI (purity: 97.8%). The physical properties are as follows.

Boiling point 47.0 ° C./37 mmHg, EIMS: 136 (M ⁺ ), 117 (M ⁺ -F ⁺ ), IR (neat) cm ^-1 : 1486, 1385, 129
5,1242, 1085,966, F analysis: calculated value 27.9%, measured value 27.7%, ¹ H-NMR (δ, ppm, CDCl ₃ , TMS standard): 2.52 (s, 6H, − CH ₃ × 2), 3. O5
(S, 4H, —CH ₂ CH ₂ —), ¹³ C-NMR (δ, ppm, CDCl ₃ , −45 ° C., C
DCL ₃ standard): 31.4 (s, -CH ₃ × 2), 4
_{7.6 (s, -CH 2 CH 2} -), 128.5 (t, J
= 230 Hz, = CF ₂ ), ¹⁹ F-NMR (δ, ppm, CDCl ₃ , -45 ° C,
CFCl ₃ standard): -70.9 (s, = CF ₂ ).

Synthesis Example 2 Dipotassium salt of 4,4′-dihydroxybenzophenone
In a 1000 ml four-necked flask equipped with a synthetic Dean-Stack tube, 42.8 g of dihydroxybenzophenone (0.
2 mol) and 13.6 wt% potassium hydroxide aqueous solution 16
5 g (0.4 mol) was charged and 30 ° C. under a nitrogen atmosphere.
For 30 minutes. Thereafter, 500 g of toluene was charged and heated under a nitrogen atmosphere, and the distilled water-toluene was separated in a Dean-Stack tube to reflux only toluene. Then, the temperature was maintained for 2 hours from the time when the internal temperature reached 110 ° C., and the processing was continued. The resulting toluene slurry of the dipotassium salt of 4,4′-dihydroxybenzophenone was filtered, and then filtered at 160 ° C. and 5.33 kPa (40 mmH
g) and dried for 4 hours to obtain 56.9 g of dipotassium salt of 4,4′-dihydroxybenzophenone. Yield 98
%.

Example 1 Dried 4,4'- was placed in a 100 ml flask equipped with a stirring blade and a condenser.
Dihydroxybenzophenone dipotassium salt 0.88
g (3.03 mmol) and 80 g of acetonitrile, and then 0.62 g (4.55 mmol) of DFI. After stirring at 25 ° C. for 3 hours under a nitrogen atmosphere, the mixture was heated to reflux (84 ° C.) and the treatment was continued for 15 hours. After the treatment, LC analysis of the reaction mass was performed, and 4,4′-bis (4-hydroxybenzoyl) diphenyl ether,
4- (4-fluorobenzoyl) -4 ′-(4-hydroxybenzoyl) diphenyl ether, and 4,4 ′
It was confirmed that -bis (4-fluorobenzoyl) diphenyl ether was produced at yields of 6.6%, 9.9%, and 5.7%, respectively.

Example 2 Dried 4,4'- was placed in a 100 ml flask equipped with a stirring blade and a condenser.
Dihydroxybenzophenone dipotassium salt 0.88
g (3.03 mmol) and 80 g of acetonitrile, and then 0.83 g (6.06 mmol) of DFI. After stirring at 25 ° C. for 3 hours under a nitrogen atmosphere, the mixture was heated to reflux (84 ° C.) and the treatment was continued for 15 hours. After the treatment, LC analysis of the reaction mass was performed, and 4,4′-bis (4-hydroxybenzoyl) diphenyl ether,
4- (4-fluorobenzoyl) -4 ′-(4-hydroxybenzoyl) diphenyl ether, and 4,4 ′
It was confirmed that -bis (4-fluorobenzoyl) diphenyl ether was produced at a yield of 4.4%, 6.2%, and 4.6%, respectively.

Example 3 0.65 g (3.03 mmol) of 4,4'-dihydroxybenzophenone was placed in a 100 ml flask equipped with a stirring blade and a condenser.
And 80 g of acetonitrile, then DFI 0.
62 g (4.55 mmol) were charged. After stirring at 25 ° C. for 3 hours under a nitrogen atmosphere, the mixture was heated to reflux (84 ° C.) and the treatment was continued for 15 hours. After the treatment, LC analysis of the reaction mass was performed, and 4,4′-bis (4-hydroxybenzoyl) diphenyl ether, 4- (4-fluorobenzoyl) -4 ′-(4-hydroxybenzoyl) diphenyl ether, and 4,4 ′ -Bis (4-fluorobenzoyl) diphenyl ether was obtained in a yield of 3.1, respectively.
%, 4.0%, and 2.9%.

Example 4 0.65 g (3.03 mmol) of 4,4'-dihydroxybenzophenone was placed in a 100 ml flask equipped with a stirring blade and a condenser.
And 80 g of acetonitrile, then DFI 0.
83 g (6.06 mmol) were charged. After stirring at 25 ° C. for 3 hours under a nitrogen atmosphere, the mixture was heated to reflux (84 ° C.) and the treatment was continued for 15 hours. After the treatment, LC analysis of the reaction mass was performed, and 4,4′-bis (4-hydroxybenzoyl) diphenyl ether, 4- (4-fluorobenzoyl) -4 ′-(4-hydroxybenzoyl) diphenyl ether, and 4,4 ′ -Bis (4-fluorobenzoyl) diphenyl ether has a yield of 1.5
%, 3.2%, and 2.6%.

[0046]

Industrial Applicability The present invention provides bis [(arylcarbonyl) aryl] ethers which are phenols and / or phenolates as raw materials and are important compounds as monomers and terminal modifiers for heat-resistant and chemical-resistant resins. Can be manufactured.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Junko Naruse, 30 Asamuta-cho, Omuta-shi, Fukuoka Mitsui Chemicals, Inc. (72) Inventor Hidetoshi Hayashi 30-30 Asamuta-cho, Omuta, Fukuoka, Japan 72) Inventor Hideaki Oikawa 30 Asamuta-cho, Omuta-shi, Fukuoka Mitsui Chemicals, Inc. F-term (reference) 4H006 AA02 AC30 AC42 AC43

Claims (2)

[Claims] 1. A compound of the general formula (1) (Wherein, M represents a hydrogen atom or an alkali metal atom,
They may be the same or different. ) Is converted to a phenol and / or phenolate represented by the following general formula (2): ^{(Wherein, R 1, R 2, R} 3, R 4 represents an alkyl group or an aryl group of C ₁ -C _6, or different from each other were respectively the same. Further, R ¹ in the formula And R ³ combine to form a 5-membered ring,
Alternatively, a 6-membered ring may be formed, and R ¹ and R ² or R ³ and R ⁴ may be bonded. X ¹ is a fluorine atom, X ²
Represents a fluorine atom or a chlorine atom. Even if X ¹ and X ² are covalently bonded to a carbon atom, only X ¹ is covalently bonded and X ²
May be present in the form of a counter ion. Wherein the compound is reacted with a compound represented by the general formula (3): (Wherein, R ⁵ and R ⁶ represent a fluorine atom or a hydroxyl group, and may be the same or different from each other.) A method for producing bis [(arylcarbonyl) aryl] ethers represented by the formula: 2. The compound of the general formula (2) is a compound of the formula (4) The production method according to claim 1, wherein the compound is 2,2-difluoro-1,3-dimethyl-imidazolidine represented by the following formula: