JP2001288135A - 4-(4'-fluorobenzoyl)-2,6-diisopropylphenol, and aromatic polyetherketone obtained therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide 4-(4'-fluorobenzoyl)-2,6-diisopropylphenol as a new substance, from which conventionally unavailable pharmaceuticals, agrochemicals, antioxidants, heat-resistant polymers, photosensitive polymers, etc., in particular a new aromatic polyetherketone composed of recurring unit of formula (IV) having good physical properties in heat resistance and photosensitivity are obtained. SOLUTION: This new substance, 4-(4'-fluorobenzoyl)-2,6-diisopropylphenol having chemical structural formula shown by formula (I) is provided. The new aromatic polyetherketone composed of recurring unit of formula (IV) is also obtained by polycondensation reaction of 4-(4'-fluorobenzoyl)-2,6-diisopropylphenol (I).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel compound useful as a raw material monomer of a heat-resistant polymer or a photosensitive polymer, or as an intermediate of pharmaceuticals and agricultural chemicals.
(4′-Fluorobenzoyl) -2,6-diisopropylphenol, a method for producing the same, and 4-
The present invention relates to a novel aromatic polyether ketone which can be produced from (4'-fluorobenzoyl) -2,6-diisopropylphenol and a method for producing the same.

[0002]

2. Description of the Related Art Hitherto, 4- (4'-fluorobenzoyl) -2,6-dimethylphenol has been disclosed in
No. 10140 reports this as a new compound. In addition, a new method for producing a series of 4- (4′-fluorobenzoyl) phenols has been reported (for example, Japanese Patent Publication No. 6-81738).
Furthermore, the 4- (4′-fluorobenzoyl) -2,
6-dimethylphenol is converted to an alkali metal carbonate and / or
Alternatively, a polyether ketone having a repeating unit represented by the formula (A) obtained by heating in the presence of an alkali metal bicarbonate is disclosed in Japanese Patent Publication No. 1-49376 as a novel polymer together with its production method Had been reported.

[0003]

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[0004]

SUMMARY OF THE INVENTION 4- (4'-) is a compound useful as a raw material monomer of a heat-resistant polymer or a photosensitive polymer, or as an intermediate of pharmaceuticals and agricultural chemicals.
(Fluorobenzoyl) -2,6-diisopropylphenol has not been reported at all. Further, no aromatic polyether ketone having a repeating unit represented by the formula (IV) has been reported at all.

[0005]

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[0006]

DISCLOSURE OF THE INVENTION The present invention provides a novel compound, 4- (4'-fluorobenzoyl) -2,6-diisopropylphenol, a process for producing the same, and 4- (4 '
Disclosed is a novel aromatic polyether ketone which can be produced from -fluorobenzoyl) -2,6-diisopropylphenol, and a method for producing the same. That is, the present invention relates to: [1] A compound having a chemical structure represented by the formula (I):
(4'-Fluorobenzoyl) -2,6-diisopropylphenol.

[0007]

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[2] 4-fluorobenzoic acid halide having a chemical structure represented by the formula (II):
Characterized by reacting with 2,6-diisopropylphenol having the chemical structure represented by the following formula (I):
A method for producing 4- (4′-fluorobenzoyl) -2,6-diisopropylphenol having a chemical structure represented by the formula [(In the formula (II), X is F, Cl, B
represents at least one selected from the halogen group consisting of r and I. ].

[0009]

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[3] 4-fluorobenzoic halide having a chemical structure represented by the formula (II):
Characterized by reacting 2,6-diisopropylphenol having a chemical structure represented by the following formula in the presence of an acid catalyst:
A method for producing (4′-fluorobenzoyl) -2,6-diisopropylphenol [(in the formula (II), X
Represents at least one selected from the halogen group consisting of F, Cl, Br, and I. ].

[0011]

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[3] An aromatic polyether ketone having a repeating unit represented by the formula (IV):

[0013]

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[4] Polycondensation of 4- (4'-fluorobenzoyl) -2,6-diisopropylphenol having a chemical structure represented by the formula (I),
A method for producing an aromatic polyether ketone having a repeating unit represented by the formula (IV).

[0015]

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[0016]

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[0017]

DETAILED DESCRIPTION OF THE INVENTION The 4- (4'-fluorobenzoyl) -2,6-diisopropylphenol of the present invention is a novel compound. It may be manufactured by any method. The reaction used in the method of the present invention for producing 4- (4'-fluorobenzoyl) -2,6-diisopropylphenol is an application of the Friedel-Crafts reaction. Examples of the acid catalyst used in this reaction include mineral acids such as sulfuric acid, phosphoric acid, hydrochloric acid, and hydrogen fluoride; boron halide, aluminum halide, silicon halide, titanium halide,
Tin halide, iron halide, nickel halide,
Lewis acids such as copper halide and lead halide; and organic sulfonic acids such as methanesulfonic acid and trifluoromethanesulfonic acid. Particularly preferred are Lewis acids such as anhydrous aluminum chloride.

This reaction can be carried out without using a solvent, but a solvent which does not adversely influence the reaction may be used. Such solvents include chloroform, dichloromethane, carbon tetrachloride, dichloroethane, trichloroethane,
Halogenated aliphatic compounds such as tetrachloroethane; halogenated aromatic compounds such as chlorobenzene, dichlorobenzene, and bromobenzene; nitro compounds such as nitrobenzene and nitrotoluene; and carbon disulfide are used. The reaction temperature and reaction time vary depending on the catalyst and solvent used, but are usually 0 ° C. to 300 ° C., and 1 minute to 200 hours. Preferably 0 ° C to 200 ° C, 10 minutes to 1
00 hours, more preferably 0 ° C to 150 ° C,
1 hour to 20 hours.

The 4- (4'-fluorobenzoyl) -2,6-diisopropylphenol of the present invention can be used as an intermediate for pharmaceuticals and agricultural chemicals, an antioxidant, and a monomer for a heat-resistant or photosensitive polymer. it can. The aromatic polyether ketone having a repeating unit represented by the formula (IV) of the present invention is a novel polymer. It may be manufactured by any method.

One of preferred methods for producing an aromatic polyether ketone having a repeating unit represented by the formula (IV) is 4- (4'-fluorobenzoyl) -2,6 represented by the formula (I). -A method of polycondensing diisopropylphenol in the presence of an alkali metal carbonate and / or an alkali metal bicarbonate.

[0021] Polycondensation is a polymerization-forming reaction caused by repetition of a condensation reaction. This polymerization reaction can be carried out without using a solvent, but a solvent that does not adversely affect the reaction may be used. Such solvents include, for example, N, N-
Dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-
Amide solvents such as 2-imidazolidinone; nitrile solvents such as benzonitrile; dialkyls such as dimethyl sulfone and diethyl sulfone; sulfolane such as sulfolane and methyl sulfolane; diaryl sulfones such as diphenyl sulfone and ditolyl sulfone; Diaryl ethers such as diphenyl ether and ditolyl ether; ketones such as benzophenone and acetophenone are used. The polymerization reaction temperature and the polymerization reaction time vary depending on the type and solvent of the alkali metal carbonate and / or alkali metal bicarbonate used, but usually from 100 ° C to 300 ° C,
1 minute to 200 hours, preferably 150 ° C to 250 ° C, 1 hour
0 minutes to 100 hours. Examples of the alkali metal carbonate and the alkali metal hydrogencarbonate include lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, and lithium hydrogencarbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, rubidium hydrogencarbonate, cesium hydrogencarbonate, and the like. Used.

The aromatic polyether ketone having a repeating unit represented by the formula (IV) of the present invention has excellent heat resistance, solvent solubility and mechanical strength, has photosensitivity, and has good moldability. Expected to be relatively good.

[0023]

EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto.

[Example] Nitrogen introduction pipe, cooling pipe, thermometer,
In a 5-neck reactor equipped with a stir bar and a dropping funnel, 4-
1 of fluorobenzoic acid chloride (33 mmol)
A solution of 2-dichloroethane (50 ml) was prepared. The mixture was cooled in an ice water bath, and anhydrous aluminum chloride (69 mmol) was added while stirring under a nitrogen atmosphere. To this, 2,6-
1,2 of diisopropylphenol (33 mmol)
A solution of -dichloroethane (10 ml) was slowly dropped from the dropping funnel over 2 minutes.

After the completion of the dropwise addition, the temperature was raised, and the reaction mixture was reacted under reflux for 10 hours. Then, ethyl acetate was added to carry out liquid separation. The organic layer was washed with 0.36% by weight hydrochloric acid, dried over magnesium sulfate, and filtered under reduced pressure.

The solvent of the obtained filtrate was distilled off under reduced pressure to obtain yellow crystals. The crystals were washed with hexane, dissolved in chloroform, washed with a 5% by weight aqueous sodium hydrogen carbonate solution, dried over magnesium sulfate, and filtered under reduced pressure to give a melting point of 127.0 to 17.0.
3.6 g (yield 36%) of yellow crystals at 30.9 ° C. was obtained.
According to liquid chromatography, the crystal purity was 99.4%
Was confirmed. The crystals were identified as 4- (4′-fluorobenzoyl) -2,6-diisopropylphenol by the following analysis method.

¹ H-NMR (CDCl ₃ ): δ7.8 (2H, dd, J = 8.5,
5.5 Hz), 7.6 (2H, s), 7.2 (2H, t, J = 8.5 Hz), 5.7 (1
H, s), 3.2 (1H, m, J = 6.7 Hz), 1.3 (12H, d, J = 6.7 Hz)
Hz) ¹³ C-NMR (CDCl ₃ ): δ 195.1, 167.0, 163.2, 154.6, 134.8
(2 signals), 133.7, 132.5, 132.3, 129.8, 126.7, 11
5.5, 115.1, 27.2, 22.7 Infrared absorption spectrum: 3348 cm ^-1 (OH stretching), 1636 cm
^-1 (conjugated C = O stretch), 1597 cm ^-1 and 1570 cm ^-1 (aromatic ring C-
C stretch), elemental analysis (C ₁₉ H ₂₁ FO ₂ ): measured C, 75.9; H, 7.2; F, 6.1 calculated C, 75.97; H, 7.05; F, 6.33

[0028]

According to the present invention, production has become possible for the first time,
By using-(4'-fluorobenzoyl) -2,6-diisopropylphenol as a raw material, it is possible to produce pharmaceuticals and agricultural chemicals, antioxidants, and heat-resistant or photosensitive polymers that could not be obtained until now. became.
Further, the aromatic polyether ketone of the present invention has heat resistance,
Shows good physical properties in photosensitivity.

[Brief description of the drawings]

1 shows the ¹ H-NM of 4- (4′-fluorobenzoyl) -2,6-diisopropylphenol according to the present invention.
It is an R spectrum.

[Explanation of symbols]

 The horizontal axis indicates chemical shift, and the vertical axis indicates intensity.

FIG. 2 is an infrared absorption spectrum of 4- (4′-fluorobenzoyl) -2,6-diisopropylphenol according to the present invention.

[Explanation of symbols]

The horizontal axis indicates the wave number (the number of waves per unit length), and the vertical axis indicates the transmittance%.

Continuation of the front page F term (reference) 4H006 AA01 AA02 AB46 AC44 BA67 4H039 CA62 CD10 CD20 4J005 AA23 BB02

Claims (5)

[Claims] 1. A compound having a chemical structure represented by the formula (I):
-(4'-fluorobenzoyl) -2,6-diisopropylphenol. Embedded image 2. A method comprising reacting a 4-fluorobenzoic acid halide having a chemical structure represented by the formula (II) with 2,6-diisopropylphenol having a chemical structure represented by the formula (III). A method for producing 4- (4′-fluorobenzoyl) -2,6-diisopropylphenol having a chemical structure represented by the formula (I) [(In the formula (II), X is F, Cl, Br,
And at least one selected from the halogen group consisting of ]. Embedded image 3. A 4-fluorobenzoic halide having a chemical structure represented by the formula (II) and 2,6-diisopropylphenol having a chemical structure represented by the formula (III) are reacted with an acid catalyst. 4- (4′-) having a chemical structure represented by the formula (I),
Method for producing fluorobenzoyl) -2,6-diisopropylphenol [(In the formula (II), X is F,
Represents at least one selected from the halogen group consisting of Cl, Br and I. ]. Embedded image 4. An aromatic polyether ketone having a repeating unit represented by the formula (IV). Embedded image 5. A compound having a chemical structure represented by the formula (I):
-(4'-fluorobenzoyl) -2,6-diisopropylphenol, wherein polycondensation is carried out.
A method for producing an aromatic polyether ketone having a repeating unit represented by V). Embedded image Embedded image