JPH09255609A - Production of 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene - Google Patents

Abstract

PROBLEM TO BE SOLVED: To safely, economically and industrially obtain a compound of high quality in high yiled, useful as a raw material for epoxy resin, polyester and the like. SOLUTION: The objective 9,9-bis(4-(2-hydroxyethoxy)phenyl)fluorene is obtained by reaction of 9,9-bis(4-hydroxyphenyl)fluorene with ethylene carbonate in the presence of a decarboxylation catalyst (for example, a triorganophosphine) in an organic solvent boiling at >=100 deg.C at 100-250 deg.C where the amount of ethylene carbonate is preferably 2.0-4.0 moles per mole of the fluorene compound.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an improvement in a method for producing a fluorene derivative.

[0002]

2. Description of the Related Art 9,9-Bis (4- (2-hydroxyethoxy) phenyl) fluorene is a substance useful as a raw material for producing epoxy resins, polyesters and the like. A method of reacting 9-bis (4-hydroxyphenyl) fluorene with 2 mol or more of ethylene oxide, or a method of reacting fluorenone with phenoxyethanol by using sulfuric acid and thiol as a catalyst (JP-A-7-165657). Etc. are known.

However, in these conventional methods, the former using ethylene oxide is complicated because it is an explosive compound, and it is not industrial, and the latter using a sulfuric acid catalyst converts sulfuric acid from a target product. It is difficult to completely remove the residual sulfuric acid, and residual sulfuric acid becomes a problem in the production of the intended resin, and therefore improvement thereof has been demanded.

[0004]

The object of the present invention is to provide a method for producing a fluorene derivative which is suitable for industrial implementation, is excellent in safety, and is economically advantageous, that is, high quality and high yield. The purpose of the present invention is to provide a method for industrially advantageously producing 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene at a rate.

[0005]

That is, the present invention provides:
9,9-Bis- (4-hydroxyphenyl) fluorene and ethylene carbonate are reacted in the presence of a decarboxylation catalyst, 9,9-bis (4- (2-hydroxyethoxy) phenyl). This is a method for producing fluorene.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION A feature of the present invention is that 9,9-bis (4-hydroxyphenyl) fluorene is reacted with ethylene carbonate in the presence of a specific decarboxylation catalyst, and optionally in the presence of a solvent. Especially. Here, as the decarboxylation catalyst used in the present invention, a triorganophosphine compound, an alkali metal carbonate, an alkali metal hydroxide,
One or more compounds selected from alkaline earth metal carbonates, alkaline earth metal hydroxides, alkali metal halides, alkaline earth metal halides and quaternary alkyl ammonium halides are used.

Specific examples of the triorganophosphine compound include triphenylphosphine compounds, tributylphosphine compounds, diphenylbutylphosphine compounds and dibutylphenylphosphine compounds.

Here, the alkali metal carbonate, the alkali metal hydroxide, the alkaline earth metal carbonate, and the alkaline earth metal hydroxide are, for example, alkali metal carbonates and hydroxides of lithium, sodium, potassium, calcium, and magnesium. Examples include alkalis, alkaline earth carbonates, and alkaline earth hydroxides.

Examples of the alkali metal halides and alkaline earth metal halides include alkali chlorides such as salt, alkali iodides such as potassium iodide, alkali bromides such as sodium bromide, and alkali fluorides. As the alkali, the above-mentioned alkali or alkaline earth metal is used.

Examples of the quaternary ammonium halide include tetraethylammonium chloride, tetramethylammonium chloride, tetrabutylammonium chloride and tetraethylammonium bromide.

In the method of the present invention, the decarboxylation catalyst is used in an amount of 0.01 to 10% by weight, preferably 0.1 to 5% by weight based on the raw material 9,9-bis (4-hydroxyphenyl) fluorene. % By weight.

In the method of the present invention, the reaction temperature is 100.
C. to 250.degree. C., preferably 130.degree. C. to 200.degree.

In the method of the present invention, a reaction solvent is preferably used. The reaction solvent used in the method of the present invention is preferably an organic solvent having a boiling point of 100 ° C. or higher which dissolves 9,9-bis (4-hydroxyphenyl) fluorene and is difficult to react with ethylene carbonate. Specifically, ethylene glycol, diethylene glycol,
Glycols such as propylene glycol, aromatic hydrocarbons such as toluene and xylene, methyl isobutyl ketone,
And ketone solvents such as cyclohexanone.

The amounts of these reaction solvents used are the raw materials 9,9-
50 ml to 400 ml per 1 mol of bis (4-hydroxyphenyl) fluorene, preferably 100 m
1 to 250 ml. If the amount of the reaction solvent is too small, the reaction liquid becomes non-uniform in the initial stage of the reaction, and the viscosity increases in the latter stage of the reaction, making stirring difficult. Further, when the amount of the reaction solvent is too large, the reaction efficiency becomes poor and the reaction tends to take a long time.

In the method of the present invention, the amount of ethylene carbonate used is 1.5 to 4.0 mol, preferably 2.0 to 4 mol, based on 1 mol of 9,9-bis (4-hydroxyphenyl) fluorene. It is 0.0 mol.

As a method for taking out and recovering 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene obtained by the method of the present invention, a conventionally known method is applied. For example, the reaction solution obtained by the method of the present invention is further homogenized by adding a solvent and then cooled to crystallize the target 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene. Can be collected.

The inventors of the present invention further added an organic solvent and water which are hardly compatible with water to the reaction solution obtained by the reaction after the reaction, dissolved and washed with water to separate into an aqueous layer and an oil layer, By crystallizing and recovering the target 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene from the oil layer, industrially advantageous target 9,9-bis (4-) is obtained.
It has been found that (2-hydroxyethoxy) phenyl) fluorene can be produced with high purity and high yield.

As the solvent for crystallizing and recovering the desired product from the reaction system, alcohols such as methanol, ethanol and propanol, aromatic compounds such as toluene and xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone And the like, and ester compounds such as methyl acetate, ethyl acetate, and butyl acetate.
It is also possible to use mixtures of more than one species. The amount of the solvent used is 1000 with respect to 1 mol of the fluorenone skeleton.
~ 8000 ml, preferably 2000-6000 ml.

Regarding the purification method in this crystallization method,
Although not particularly limited, a solvent is added to the obtained crude product,
After being uniformly dissolved under heating and stirring, hot filtration is performed. At this time, treatment with activated carbon, activated clay, acid clay, activated alumina, zeolite, ion exchange resin or the like used in a usual purification method can be performed together.

For taking out the desired product, it is preferable to precipitate crystals by stirring the obtained filtrate at room temperature or by gradually cooling with cold water, and then filter and dry the obtained crystals. Thus, as compared with the conventionally known methods, no special reaction operation and equipment are required, and there is almost no side reaction production, that is, the industrially extremely advantageous object is achieved.
9-bis (4- (2-hydroxyethoxy) phenyl)
Fluorene can be produced with high purity and high yield.

[0021]

INDUSTRIAL APPLICABILITY According to the present invention, a method for producing a fluorene derivative which is suitable for industrial use, excellent in safety, and economically advantageous, that is, high quality and high yield 9
-Bis (4- (2-hydroxyethoxy) phenyl) fluorene can be prepared.

[0022]

EXAMPLES The method of the present invention will now be described in more detail by way of examples, which should not be construed as limiting the invention. The raw material 9,9-bis (4-hydroxyphenyl) fluorene used in the following Examples was produced by the method described in Example 3 of JP-A-6-145087 with a purity of 99%. used.

Example 1 30.3 g (0.0857 mol) of 9,9-bis (4-hydroxyphenyl) fluorene (purity 99.0%) was placed in a 4-necked flask having an inner volume of 500 ml equipped with a stirrer and a cooling tube. ), 15.1 g (0.172 mol) of ethylene carbonate and 0.3 g of triphenylphosphine were charged, and the reaction was completed by heating at 145 ° C. for 10 hours under a nitrogen atmosphere. The reaction was heterogeneous in the initial stage, but became a uniform viscous liquid in the latter stage of the reaction.

Next, 450 ml of toluene was gradually added to the solution, which was dissolved with stirring under heating, filtered by heat, and then cooled to room temperature to precipitate crystals. The precipitated crystals were filtered and dried under reduced pressure at 70 ° C. for 1 day. The LC purity of the obtained 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene was 9
The yield was 9.5% and the yield was 33.6 g (yield 89%).

Example 2 30.3 g (0.0857 mol) of 9,9-bis (4-hydroxyphenyl) fluorene (purity 99.0%) was placed in a 4-necked flask having an inner volume of 500 ml equipped with a stirrer and a cooling tube. ), Ethylene carbonate 15.1 g (0.172 mol), xylene 12 ml and tributylphosphine 0.
3 g was charged, and the reaction was completed by heating at 140 ° C. for 10 hours under a nitrogen atmosphere. The reaction system was homogeneous throughout and had a low viscosity.

Then, in the same manner as in Example 1, toluene 4 was added.
50 ml was added and crystallized to obtain the desired product. The purity of 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene obtained was LC 99.5%, and the yield was 34.
It was 1 g (yield 90%).

Example 3 30.3 g (0.0857) of 9,9-bis (4-hydroxyphenyl) fluorene (purity 99.0%) was placed in a 4-necked flask having an internal volume of 1000 ml equipped with a stirrer and a cooling tube.
Mol), 18 g (0.205 mol) of ethylene carbonate, 12 ml of ethylene glycol and 0.4 g of tetraethylammonium bromide were charged, and the reaction was completed by heating at 145 ° C. for 18 hours under a nitrogen atmosphere.

Then, 800 ml of methanol was added and crystallized in the same manner as in Example 1 to obtain the desired product. The obtained 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene had a purity of LC 98.1% and a yield of 29.
It was 9 g (yield 78%).

Example 4 30.3 g (0.0857 mol) of 9,9-bis (4-hydroxyphenyl) fluorene (purity 99.0%) was placed in a four-necked flask having an inner volume of 500 ml equipped with a stirrer and a cooling tube. ), Ethylene carbonate 15.1 g (0.172 mol), cyclohexanone 12 ml and potassium carbonate 0.
3 g was charged and the reaction was completed by heating at 145 ° C. for 6 hours under a nitrogen atmosphere.

Then, 300 ml of toluene was gradually added to dissolve the mixture uniformly, and then the contents 10 equipped with a stirrer and a cooling pipe were added.
The mixture was transferred to a 00 ml separating funnel, 100 ml of water was added under heating, and washing with water was repeated 3 times. Next, the oil layer was hot filtered and then cooled to room temperature to precipitate crystals. The precipitated crystals were filtered and dried under reduced pressure at 70 ° C. for 1 day. The LC purity of the obtained 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene was 99.4%, and the yield was 31.4 g (83% yield). The K content in the target product is 100.
It was below ppm.

Example 5 30.3 g (0.0857 mol) of 9,9-bis (4-hydroxyphenyl) fluorene (purity 99.0%) was placed in a 500-neck four-necked flask equipped with a stirrer and a condenser. ), 15.1 g (0.172 mol) of ethylene carbonate, 12 ml of xylene and 0.3 g of potassium iodide were charged and heated at 140 ° C. for 8 hours under a nitrogen atmosphere to complete the reaction.

Then, in the same manner as in Example 4, toluene 4 was added.
50 ml was added and washed with water to obtain the desired product. The obtained 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene had an LC purity of 98.7% and a yield of 33.
It was 1 g (yield 87%). The K content in the target product was 100 ppm or less.

Example 6 30.3 g (0.0857 mol) of 9,9-bis (4-hydroxyphenyl) fluorene (purity 99.0%) was placed in a 500-neck four-necked flask equipped with a stirrer and a condenser. ), 15.1 g (0.172 mol) of ethylene carbonate, 12 ml of xylene and 0.3 g of lithium hydroxide were charged and the reaction was completed by heating at 140 ° C. for 8 hours under a nitrogen atmosphere.

Then, in the same manner as in Example 4, toluene 4 was added.
50 ml was added and washed with water to obtain the desired product. The obtained 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene had an LC purity of 98.8% and a yield of 37.
It was 6 g (yield 83%). In addition, Li in the target product
The content was 100 ppm or less.

Example 7 In place of 0.3 g of potassium carbonate used in Example 4,
Using sodium chloride, sodium hydroxide, magnesium chloride, and calcium chloride, the same procedure was performed, and almost the same results were obtained.

Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI Technical display location B01J 31/24 B01J 31/24 Z C07C 41/16 7419-4H C07C 41/16 // C07B 61/00 300 C07B 61/00 300

Claims (11)

[Claims] 1. 9,9-Bis- (4-hydroxyphenyl) fluorene and ethylene carbonate are reacted in the presence of a decarboxylation catalyst. Process for producing hydroxyethoxy) phenyl) fluorene. 2. A decarboxylation catalyst comprising a triorganophosphine compound, an alkali metal carbonate, an alkali metal hydroxide, an alkaline earth metal carbonate, an alkaline earth metal hydroxide, an alkali metal halide, an alkaline earth metal halide, and The 9,9-bis (4- (2-hydroxyethoxy)) according to claim 1, which is selected from quaternary alkyl ammonium halides.
Method for producing phenyl) fluorene. 3. The 9,9-bis (4- (2-) as claimed in claim 2, wherein the decarboxylation catalyst is a triorganophosphine compound.
Process for producing hydroxyethoxy) phenyl) fluorene. 4. The decarboxylation catalyst is an alkali metal carbonate, an alkali metal hydroxide, an alkaline earth metal carbonate, an alkaline earth metal hydroxide, an alkali metal halide or an alkaline earth metal halide. 9,9-bis (4
A method for producing-(2-hydroxyethoxy) phenyl) fluorene. 5. The method for producing 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene according to claim 2, wherein the decarboxylation catalyst is an alkali metal halide or an alkaline earth metal halide. 6. The 9,9-bis (4-) compound according to claim 2, wherein the decarboxylation catalyst is a quaternary alkyl ammonium halide.
A method for producing (2-hydroxyethoxy) phenyl) fluorene. 7. The decarboxylation catalyst is used in an amount of 0.01 to 10% by weight based on 9,9-bis (4-hydroxyphenyl) fluorene.
-A method for producing bis (4- (2-hydroxyethoxy) phenyl) fluorene. 8. The method for producing 9,9-bis (4- (2-hydroxyethoxy) phenyl) fluorene according to claim 1, wherein the reaction is performed in a solvent. 9. The organic solvent having a boiling point of 100 ° C. or higher which is difficult to react with ethylene carbonate and which is 9,9-bis (4-hydroxyphenyl) fluorene is used as the reaction solvent. -A method for producing bis (4- (2-hydroxyethoxy) phenyl) fluorene. 10. The 9,9-bis (4) according to claim 1, wherein the reaction temperature is 100 ° C. to 250 ° C.
A method for producing-(2-hydroxyethoxy) phenyl) fluorene. 11. An ethylene carbonate in an amount of 2.0 to 4.0 mol per mol of 9,9-bis (4-hydroxyphenyl) fluorene is used.
The 9,9-bis (4- (2
A method for producing -hydroxyethoxy) phenyl) fluorene.