JP2010059098A - Method for producing 9,9-biscresol fluorene - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for industrially advantageously producing a high quality product, which is very pure and inhibits discoloring, not containing sulfur even not performing a complicated catalyst elimination operation or purification operation in a method for producing 9,9-biscresol fluorene by a reaction of fluorenone and cresol. <P>SOLUTION: Fluorenone and cresol are made to react under reduced pressure of 30×10<SP>3</SP>Pa or less at a temperature range of 30-95°C under existence of a heteropolyacid catalyst, and thereby high quality 9,9-biscresol fluorene which inhibits discoloring can be produced in high yield. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

The present invention relates to a method for producing 9,9-biscresol fluorene useful as a raw material for polyester, polyurethane, polycarbonate, epoxy resin, modified acrylic resin and the like.

As a method for producing 9,9-biscresol fluorene, a method of dehydrating and condensing fluorenone and cresol using sulfuric acid and thiol as a catalyst is disclosed (Patent Document 1). However, in this method, problems such as coloring of the product and a decrease in stability occur due to the sulfur component derived from the catalyst mixed in the product. Further, in order to obtain a high-purity product such as an optical resin raw material, it is necessary to repeat purification in order to remove the sulfur content, which is not an industrially advantageous method.
As a method not using sulfuric acid or hydrogen chloride gas, we previously proposed a method for producing a fluorene derivative from a fluorenone and a phenol under a heteropolyacid catalyst. (Patent Document 2). However, in this method, when cresol is used for phenols, 9,9-biscresol fluorene may be colored or by-products such as isomers and multimers may be produced, resulting in a decrease in purity and yield. there were.

JP 2003-221352 A JP 2007-23016 A

  In the production of 9,9-biscresol fluorene by the reaction of fluorenone and cresol, the present invention does not contain a complicated catalyst removal operation or purification operation, and does not contain sulfur, has a high purity and is prevented from being colored. It is an object of the present invention to provide a method for industrially manufacturing such a product.

  The inventors of the present invention focused on the reaction conditions in order to solve the above-mentioned problems, and as a result of extensive research, fluorenone and cresol were subjected to a reduced pressure of 200 mmHg or less in the temperature range of 30 to 95 ° C. in the presence of a heteropolyacid catalyst. By carrying out the reaction, it was found that high-quality 9,9-biscresol fluorene, which was prevented from being colored in a high yield, could be produced, and the present invention was completed.

That is, the present invention provides the following (1) to (3).
(1) In a method for producing 9,9-biscresol fluorene by reacting fluorenone and cresol in the presence of a heteropolyacid, the reaction is carried out in a temperature range of 30 to 95 ° C. under a reduced pressure of 30 × 10 ³ Pa or less. A method for producing 9,9-biscresol fluorene, which is characterized.
(2) The process according to claim 1, wherein the reaction is carried out using 11 to 20 moles of cresol with respect to fluorenone.
(3) The method for producing 9,9-bis (4-hydroxy-3-methylphenol) fluorene according to claim 1 or 2, wherein the cresol is o-cresol.

According to the present invention, in the production of 9,9-biscresol fluorene by the reaction of fluorenone and cresol, sulfur is not contained and high purity and coloration can be prevented without performing complicated catalyst removal operation and purification operation. In addition, it is possible to provide a method for producing a high-quality product in an industrially advantageous manner.

  Hereinafter, the present invention will be described together with embodiments thereof.

  The heteropolyacid preferably used in the present invention is a general term for compounds formed by condensation of two or more different inorganic oxygen acids, and is a generic name of a central oxygen acid and another oxygen acid condensed around it. Various heteropolyacids are possible depending on the combination. A small number of elements that form a central oxygen acid are called heteroelements, and an element that forms oxygen acid that condenses around them is called a polyelement. A polyelement may be a single type or multiple types May be used.

  The hetero element of the oxygen acid constituting the heteropolyacid is not particularly limited, for example, copper, beryllium, boron, aluminum, carbon, silicon, germanium, tin, titanium, zirconium, cerium, thorium, nitrogen, phosphorus, Examples include arsenic, antimony, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, uranium, selenium, tellurium, manganese, iodine, iron, cobalt, nickel, rhodium, osmium, irdium, and platinum. Preferably it is phosphorus or silicon. Moreover, the poly element of the oxygen acid which comprises heteropoly acid is not specifically limited, For example, vanadium, molybdenum, tungsten, niobium, and tantalum are mentioned. Vanadium, molybdenum and tungsten are preferred.

As the heteropolyacid anion constituting the heteropolyacid skeleton, those having various compositions can be used. For _example, such _{XM 12 O 40, XM 12 O} 42, XM 18 O 62, XM 6 O 24 and the like. A preferred heteropolyacid anion composition is XM ₁₂ O ₄₀ . In each formula, X is a hetero element, and M is a poly element. Specific examples of heteropolyacids having these compositions include phosphomolybdic acid, phosphotungstic acid, silicomolybdic acid, silicotungstic acid, and phosphovanadomolybdic acid.

  The heteropolyacid may be a free heteropolyacid, and may be used as a salt of a heteropolyacid by replacing some or all of the protons with other cations. Accordingly, the heteropolyacid referred to in the present invention includes salts of these heteropolyacids. Examples of cations that can be substituted with protons include ammonium, alkali metals, alkaline earth metals, and the like.

  The heteropolyacid may be an anhydride or a crystal water-containing product, but the anhydride is preferred because the reaction is faster and the formation of by-products is suppressed. In the case of a crystal water-containing material, the same effect as that of the anhydride can be obtained by performing dehydration treatment such as drying under reduced pressure or azeotropic dehydration with a solvent in advance. The heteropolyacid may be used in a form supported on a support such as activated carbon, alumina, silica-alumina, or diatomaceous earth. These heteropolyacids may be used alone or in combination of two or more. Moreover, you may use together other catalysts other than heteropoly acid in the range which does not impair the objective of this invention as needed.

  The amount of the heteropolyacid used is not particularly limited, but in order to obtain a sufficient reaction rate, it is 0.0001 times by weight or more, preferably 0.001 to 30 times by weight, more preferably 0 to fluorenone. 0.01 to 5 times by weight.

  Examples of the cresol in the present invention include o-cresol, m-cresol, and p-cresol, and these may be used alone or as a mixture of two or more thereof, but o-cresol is preferable. Although the usage-amount is not specifically limited, From the point of workability | operativity and economical efficiency, it is 11-25 mol normally with respect to 1 mol of fluorenones, Preferably it is 11-20 mol. When the amount of cresol used is less than 11 mol times, crystals (product) may be precipitated during the reaction, and workability may deteriorate. Further, if the amount of cresol used is more than 25 mol times, it is economically disadvantageous.

  The method of reacting fluorenone and phenols can be carried out, for example, by charging fluorenone, phenols and heteropolyacid into a reaction apparatus and stirring them with heating. At this time, by carrying out the reaction under dehydrating conditions for removing water in the reaction system such as catalyst-containing water and reaction product water, the reaction proceeds faster than when water in the reaction system is not removed, and by-products Generation is suppressed.

  Although the reaction temperature in this invention changes with the kind of solvent, and a pressure reduction degree, it is 30-95 degreeC, Preferably it is 40-80 degreeC, More preferably, it is 55-80 degreeC. When the reaction temperature is higher than 95 ° C., the purity and yield are reduced due to the increase of by-products. Moreover, coloring of a product arises and it is not preferable. A reaction temperature lower than 30 ° C. is not preferable because the reaction does not proceed or it takes a long time to complete the reaction.

Vacuum degree in the present invention is 30 × ¹⁰ 3 Pa or less, preferably 7 × ¹⁰ 3 Pa or less, more preferably ^{0.5 × 10 3 Pa~3 × 10 3} Pa. When the reaction temperature is 30 to 95 ° C. and the degree of vacuum exceeds 30 × 10 ³ Pa, the 9,9-biscresol fluorene obtained is colored and cannot be used industrially.

In the present invention, if necessary, the reaction can be carried out under reduced pressure using an azeotropic dehydration solvent as long as the object of the present invention is not impaired. The azeotropic dehydration solvent used in the reaction is not particularly limited, but is an aromatic hydrocarbon solvent such as toluene or xylene, a halogenated aromatic hydrocarbon solvent such as chlorobenzene or dichlorobenzene, pentane, hexane or heptane. Aliphatic hydrocarbon solvents such as dichloromethane, halogenated aliphatic hydrocarbon solvents such as dichloromethane and 1,2-dichloroethane, aliphatic ethers such as diethyl ether, di-iso-propyl ether, methyl-t-butyl ether, diphenyl ether, tetrahydrofuran and dioxane And cyclic ether solvents, ester solvents such as ethyl acetate and butyl acetate, nitrile solvents such as acetonitrile, propionitrile, butyronitrile, and benzonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl Amide solvents such as 2-pyrrolidinone, and the like. Preferred are aromatic hydrocarbon solvents and halogenated aromatic hydrocarbon solvents, and more preferred are toluene, xylene, chlorobenzene and dichlorobenzene. The amount used is not particularly limited, but is usually 10 parts by weight or less, preferably 5 parts by weight or less, more preferably 2 parts by weight or less based on fluorenone. An appropriate amount of solvent accelerates the reaction, but if the amount used is large, the reaction may be slow.

After the reaction, 9,9-biscresol fluorene can be obtained as a crystal by adding a solvent to the reaction solution and crystallization by cooling, and the precipitated crystal is recovered by filtration or the like. If necessary, purification such as washing, adsorption, steam distillation, recrystallization and the like can be performed.

(Example)
Examples of the present invention are shown below, but the present invention is not limited thereto.
In the examples, unless otherwise specified,% is an area percentage value in HPLC, and parts are based on weight.
HPLC measurement conditions:
Equipment: Shimadzu LC-2010A
Column: L-Column ODS (5 μm, 4.6 mmφ × 150 mm)
Mobile phase: Liquid A: water / methanol = 70/30 (v / v), liquid B: methanol liquid B concentration: 30% → 100% (25 minutes) → 100% (35 minutes)
Flow rate: 1.0 ml / min, column temperature: 40 ° C., detection wavelength: UV 254 nm

Sulfur content measurement method and measurement condition test method: Oxyhydrogen flame combustion-ion chromatography apparatus: Oxyhydrogen flame combustion apparatus: N-LS (Tokyo Kagaku Seiki)

Ion chromatograph: DX-120 (manufactured by DIONEX)
Column; DIONEX IonPac AS14
Detector; DS4 DETECTION STABILIZER
MODEL DS4-1

A glass reactor equipped with a stirrer, a nitrogen blowing tube, a thermometer, and a T-tube was charged with 23 g (0.128 mol) of fluorenone, 184 g (1.70 mol) of o-cresol and phosphotungstic acid [(H ₃ PW ₁₂ O ₄₀ ) · nH ₂ O] was added, and the reaction was carried out for 4 hours while removing the water produced at a temperature of 70 ° C. under reduced pressure of 1.3 × 10 ³ Pa from the system.
To the resulting reaction mixture, 130 g of toluene and an aqueous sodium hydroxide solution were added, neutralized at 70 ° C., and washed with water. The organic layer obtained by separating the organic layer was concentrated under reduced pressure to remove toluene and excess o-cresol. 161 g of toluene was added to the resulting concentrate, and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene was dissolved at 115 ° C., and the resulting solution was then cooled to 10 ° C. as it was. The precipitated crystals were removed by filtration and dried to give 41.0 g of 9,9-bis (4-hydroxy-3-methylphenyl) fluorene white crystals (yield 84.9%, HPLC purity 99.4%). Got. The sulfur content in the obtained crystals was less than the detection limit (10 ppm).

A glass reactor equipped with a stirrer, a nitrogen blowing tube, a thermometer and a T-tube was charged with 23 g (0.128 mol) of fluorenone, 184 g (1.70 mol) of o-cresol, 10 g of toluene and phosphotungstic acid as a catalyst [ (H ₃ PW ₁₂ O ₄₀ ) · nH ₂ O] was added in an amount of 0.58 g, and the mixture was reacted for 3 hours while removing water generated at a temperature of 70 ° C. under a reduced pressure of 1.3 × 10 ³ Pa from the system. To the resulting reaction mixture, 130 g of toluene and an aqueous sodium hydroxide solution were added, neutralized at 70 ° C., and washed with water. The organic layer obtained by separating the organic layer was concentrated under reduced pressure to remove toluene and excess o-cresol. 161 g of toluene was added to the resulting concentrate, and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene was dissolved at 115 ° C., and the resulting solution was then cooled to 10 ° C. as it was. The precipitated crystals were removed by filtration and dried to give 37.7 g of white crystals of 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (yield 78.0%, HPLC purity 99.4%). Got. The sulfur content in the obtained crystals was less than the detection limit (10 ppm).

A glass reactor equipped with a stirrer, a nitrogen blowing tube, a thermometer and a T-tube was charged with 23 g (0.128 mol) of fluorenone, 184 g (1.70 mol) of o-cresol and phosphotungstic acid [(H ₃ 0.58 g of PW ₁₂ O ₄₀ ) · nH ₂ O] was added, and the reaction was carried out for 2 hours while removing the water produced at a temperature of 90 ° C. under reduced pressure of 6.5 × 10 ³ Pa from the system.
To the obtained reaction mixture, 130 g of toluene and an aqueous sodium hydroxide solution were added, neutralized at 70 ° C., and washed with water. The organic layer obtained by separating the organic layer was concentrated under reduced pressure to remove toluene and excess o-cresol. 161 g of toluene was added to the resulting concentrate, and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene was dissolved at 115 ° C., and the resulting solution was then cooled to 10 ° C. as it was. The precipitated crystals were taken out by filtration and dried to give 35.1 g of white crystals of 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (yield 72.7%, HPLC purity 99.0%). Got. The sulfur content in the obtained crystals was less than the detection limit (10 ppm).

(Comparative Example 1)
In a glass reactor equipped with a stirrer, a nitrogen blowing tube, a thermometer and a cooling tube, 10.0 g (0.056 mol) of fluorenone, 36.7 g (0.339 mol) of o-cresol and phosphotungstic acid [( H ₃ PW ₁₂ O ₄₀ ) · nH ₂ O] was added and reacted under a nitrogen atmosphere for about 5 hours while maintaining the temperature at 160 ° C. under normal pressure. To the obtained reaction mixture, 65 g of toluene and an aqueous sodium hydroxide solution were added, neutralized at 70 ° C., and washed with water. The organic layer obtained by separating the organic layer was concentrated under reduced pressure to remove toluene and excess o-cresol. After adding 80 g of toluene to the obtained concentrate and dissolving 9,9-bis (4-hydroxy-3-methylphenyl) fluorene at 115 ° C., the resulting solution was cooled to 10 ° C. as it was. The precipitated crystals were removed by filtration and dried to give 9.15 g of 9,9-bis (4-hydroxy-3-methylphenyl) fluorene brown crystals (yield 43.6%, HPLC purity 95.3%). Got. The sulfur content in the obtained crystals was less than the detection limit (10 ppm).

(Comparative Example 2)
A glass reactor equipped with a stirrer, a nitrogen blowing tube, a thermometer, and a T-tube was charged with 23 g (0.128 mol) of fluorenone, 184 g (1.70 mol) of o-cresol and phosphotungstic acid [(H ₃ 0.58 g of PW ₁₂ O ₄₀ ) · nH ₂ O] was added, and the reaction was performed for 4 hours while removing the water produced at a temperature of 100 ° C. under a reduced pressure of 13 × 10 ³ Pa from the system. To the resulting reaction mixture, 130 g of toluene and an aqueous sodium hydroxide solution were added, neutralized at 70 ° C., and washed with water. The organic layer obtained by separating the organic layer was concentrated under reduced pressure to remove toluene and excess o-cresol. 161 g of toluene was added to the resulting concentrate, and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene was dissolved at 115 ° C., and the resulting solution was then cooled to 10 ° C. as it was. The precipitated crystals were removed by filtration and dried to give 28.5 g of 9,9-bis (4-hydroxy-3-methylphenyl) fluorene pale yellow crystals (yield 59.0%, HPLC purity 96.8%). ) The sulfur content in the obtained crystals was less than the detection limit (10 ppm).

(Comparative Example 3)
A glass reactor equipped with a stirrer, a nitrogen blowing tube, a thermometer, and a T-tube was charged with 23 g (0.128 mol) of fluorenone, 184 g (1.70 mol) of o-cresol and phosphotungstic acid [(H ₃ 0.58 g of PW ₁₂ O ₄₀ ) · nH ₂ O] was added, and the reaction was carried out for 25 hours while removing water generated outside the system at a temperature of 70 ° C. and a reduced pressure of 40 × 10 ³ Pa. To the resulting reaction mixture, 130 g of toluene and an aqueous sodium hydroxide solution were added, neutralized at 70 ° C., and washed with water. The organic layer obtained by separating the organic layer was concentrated under reduced pressure to remove toluene and excess o-cresol. 161 g of toluene was added to the resulting concentrate, and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene was dissolved at 115 ° C., and the resulting solution was then cooled to 10 ° C. as it was. The precipitated crystals were removed by filtration and dried to give 28.5 g of 9,9-bis (4-hydroxy-3-methylphenyl) fluorene pale yellow crystals (yield 59.0%, HPLC purity 96.8%). ) The sulfur content in the obtained crystals was less than the detection limit (10 ppm).

(Comparative Example 4)
In a glass reactor equipped with a stirrer, a nitrogen blowing tube, a thermometer and a cooling tube, 10.0 g (0.056 mol) of fluorenone, 36.7 g (0.339 mol) of o-cresol and phosphotungstic acid [( H ₃ PW ₁₂ O ₄₀ ) · nH ₂ O] was added, and the reaction was conducted for 4 hours while removing the water produced at a temperature of 70 ° C. under reduced pressure of 1.3 × 10 ³ Pa from the system. , 9-bis (4-hydroxy-3-methylphenyl) fluorene crystals were precipitated, making stirring difficult.

Claims (3)

In the method of producing 9,9-biscresol fluorene by reacting fluorenone and cresol in the presence of a heteropoly acid, the reaction is carried out in a temperature range of 30 to 95 ° C. under a reduced pressure of 30 × 10 ³ Pa or less. A process for producing 9,9-biscresol fluorene. The process according to claim 1, wherein the reaction is carried out using 11 to 20 moles of cresol with respect to fluorenone. The method for producing 9,9-bis (4-hydroxy-3-methylphenol) fluorene according to claim 1 or 2, wherein the cresol is o-cresol.