JPH08295646A - Production of bis(hydroxyethoxyphenyl) compound - Google Patents

Abstract

PURPOSE: To inexpensively obtain a bis(hydroxyethoxyphenyl) compound useful as a raw material of a heat resistant polymer such as a polyester by a ready reaction and an after treatment in high purity without using ethylene oxide as a raw material. CONSTITUTION: The objective compound e.g. 3,3-bis[4-(hydroxyethoxy) phenyl]phthalide} is obtained by heat reacting (A) a bisphenol compound having a cardo-type quaternary carbon expressed by formula I [R<1> and R<2> are each independently H, a halogen, etc.; Z is substantially at least one kind of a divalent substituting group selected from the group of formula II, formula III, formula IV, formula V or formula VI (R<3> -R<7> and R<10> are each independently H or a halogen; R<8> , R<9> and R<11> are each independently H, a halogen, etc.)] with (B) an ethylene carbonate in a molar ratio of (A) to (B) of (1/2)-(1/5) in the presence of a catalyst (e.g. tetrabutoxytitanium) substantially without solvent, distilling off excess ethylene carbonate from the reaction system and recrystallizing.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a bis (hydroxyethoxyphenyl) compound, and more particularly to a method for producing a hydroxyethoxy compound of a bisphenol having a cardo type quaternary carbon.

[0002]

2. Description of the Related Art Generally, a method using ethylene oxide is widely known as a method for producing a bis (hydroxyethoxyphenyl) compound. However, since ethylene oxide is a gas at room temperature, a pressure reactor such as an autoclave is required during synthesis.

On the other hand, Izv. Akad. Nauk. Gruz. SSR. Khi
m. (1985), 11 (1), p78-79, a production method of reacting ethylene oxide at atmospheric pressure is reported.

However, the production methods using these ethylene oxides have a problem that they are difficult to handle because of the toxicity, flammability, and explosiveness of the ethylene oxides. Further, since by-products such as polyethylene oxide and unreacted substances are generated and the coloring is severe, purification by recrystallization is difficult when the crystallinity of the target product is low.

[0005]

The object of the present invention is to provide a bis (hydroxyethoxyphenyl) which can be easily reacted and treated after the reaction, and which can produce a high-purity target product in a high yield.
It is to provide a novel method for producing a compound.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors achieved the above-mentioned object by subjecting a bisphenol compound to ethylene carbonate under a specific condition for melting reaction and post-treatment. The present invention has been achieved by finding out that

That is, the present invention provides the following formula (1)

[0008]

Embedded image

[In the formula (1), R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 6 carbon atoms or a hydrocarbon oxy group having 1 to 6 carbon atoms.
Z is substantially the following formulas

[0010]

[Chemical 4]

[In the above formula, R³~ R⁷And R^TenIs it
Each independently, a hydrogen atom, a halogen atom, a C1-6
A hydrocarbon group or a hydrocarbon oxy group having 1 to 6 carbon atoms
R ⁸, R⁹And R¹¹Are independent hydrogen
A child, a halogen atom or a hydrocarbon group having 1 to 6 carbon atoms.
It ] At least one divalent selected from the group represented by
Is a substituent of. ] It has a cardo type quaternary carbon represented by
Bisphenol compound (A) and ethylene carbonate
(B), the molar ratio of A and B is 1/2 to 1/5.
Heating in the presence of a catalyst, in proportion, under substantially solvent-free conditions
After reacting, excess ethylene carbonate is added to the reaction system.
The bismuth is characterized in that it is distilled off and then recrystallized.
For the production of bis (hydroxyethoxyphenyl) compounds
Is achieved.

The bisphenol compound (A) used in the present invention has a cardo type quaternary carbon and is substantially represented by the following formula (1).

[0013]

Embedded image

In the above formula (1), R ¹ and R ² are each independently a hydrogen atom, a halogen atom, or a carbon number of 1 to 6.
And a hydrocarbon oxy group having 1 to 6 carbon atoms. Examples of the halogen atom include a chlorine atom,
Examples thereof include bromine atom and iodine atom. Examples of the hydrocarbon group having 1 to 6 carbon atoms include alkyl groups such as methyl group, ethyl group and propyl group, cycloalkyl groups such as cyclohexyl group, phenyl group and the like. Examples of the hydrocarbon oxy group having 1 to 6 carbon atoms include alkoxy groups such as methoxy group and ethoxy group, cycloalkoxy groups such as cyclohexyloxy group and phenoxy group. Of these, a hydrogen atom is preferable.

Z is substantially a divalent substituent selected from the group represented by the following formulas.

[0016]

[Chemical 6]

In the above formula, R ^{3 to} R ⁷ and R ¹⁰ are each independently selected from a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 6 carbon atoms and a hydrocarbon oxy group having 1 to 6 carbon atoms. Examples of the halogen atom include chlorine atom, bromine atom, iodine atom and the like. Examples of the hydrocarbon group having 1 to 6 carbon atoms include alkyl groups such as methyl group, ethyl group and propyl group, cycloalkyl groups such as cyclohexyl group, phenyl group and the like. Examples of the hydrocarbon oxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group alkoxy group, a cycloalkoxy group such as a cyclohexyloxy group, and a phenoxy group. Of these, a hydrogen atom is preferable.

R ⁸ , R ⁹ and R ¹¹ are each independently
It is selected from a hydrogen atom, a halogen atom and a hydrocarbon group having 1 to 6 carbon atoms. Examples of the halogen atom include chlorine atom, bromine atom, iodine atom and the like. Carbon number 1
Examples of the hydrocarbon group 6 include an alkyl group such as a methyl group, an ethyl group and a propyl group, a cycloalkyl group such as a cyclohexyl group, a phenyl group and the like. Of these, a hydrogen atom is preferable.

In the present invention, the bisphenol compound (A) and the ethylene carbonate (B) are heated and reacted at a molar ratio A / B of 1/2 to 1/5. When A / B is larger than 1/2, unreacted substances are generated, and A / B is 1 /
If it is less than 5, by-products are likely to occur. The preferred range is 1/2 to 1/3.

In the present invention, a suitable transesterification catalyst is used. As the transesterification catalyst, generally known ones can be used, but titanium compounds such as tetrabutoxytitanium, dibutyltin diacetate, tin compounds such as dibutyltin oxide, germanium compounds such as germanium oxide, antimony trioxide and the like. Examples thereof include alkali catalysts such as antimony compounds, potassium carbonate, calcium carbonate, magnesium carbonate, magnesium hydroxide, calcium hydroxide, potassium hydroxide, sodium hydroxide, sodium hydrogen carbonate, sodium alkoxy, and phenoxy sodium. The amount of such a catalyst used is 0.001 to 10% by weight, preferably 0.01 to 1% by weight, of the bisphenol compound used.

According to the present invention, the above (A), (B) and the catalyst are heated and reacted under substantially solvent-free conditions. The reaction temperature at this time is preferably 40 ° C to 300 ° C. This is because when the temperature is lower than 40 ° C, ethylene carbonate does not melt, and when it exceeds 300 ° C, by-products increase. The reaction temperature is more preferably 100 ° C to 250 ° C.

The reaction time can be appropriately selected depending on the reactivity of the bisphenol compound, the reaction temperature and the like.
However, in the present invention, since the bisphenol compound is converted to hydroxyethyl carbonate by reacting with ethylene carbonate and then hydroxyethoxylated by decarboxylation reaction, the time point when the generation of carbon dioxide gas is stopped is used as a guide for the end of the reaction. be able to.

In the present invention, it has been found that by distilling off excess ethylene carbonate remaining in the reaction system after completion of the reaction from the reaction system, a high-purity target product can be easily obtained in high yield. It was

According to Japanese Patent Laid-Open No. 3-255044,
A method of hydroxyethoxylating dihydroxybenzene using ethylene carbonate is described, and a method of adding water to the reaction product to form a slurry and then filtering is disclosed as a post-treatment method. However, when such a method is applied to the case of the target compound of the present invention and water is added to the reaction product as a post-treatment, it becomes a viscous substance, which makes subsequent purification difficult.

After the completion of the reaction, the method of distilling off ethylene carbonate from the system is not particularly limited, but a method of reducing the pressure of the reaction system is preferable. The ethylene carbonate thus recovered can be reused as it is, which is desirable.

By purifying the crude reaction product obtained by distilling off ethylene carbonate by the recrystallization method, the desired hydroxyethoxylated bisphenol compound can be obtained. The recrystallization solvent is not particularly limited, but examples thereof include alcohols such as methanol, ethanol and isopropanol, ether solvents such as ether and THF, and aromatic solvents such as benzene, toluene and xylene.

When recrystallizing, activated carbon or the like is preferably used if necessary. When the crystallinity of the target compound is low, it is also preferable to add a small amount of the target compound synthesized in advance as a so-called seed compound to the supercooled solution.

[0028]

EFFECTS OF THE INVENTION According to the present invention, a bis (hydroxyethoxy) compound of a bisphenol having a desired complex structure can be produced, which is easy to react and treat after the reaction and is extremely safe and inexpensive. .

Further, even if the product has a low symmetry and is difficult to crystallize, such as a desired bisphenol compound having a cardo type quaternary carbon, there are few by-products due to the reaction, and ethylene carbonate is removed from the system. By removing it, purification by a recrystallization method becomes easy, and a highly pure target compound can be produced in a high yield, which is of great industrial significance. The bis (hydroxyethoxy) compound of bisphenols produced by the present invention is a heat-resistant polymer such as polyester, or a diol monomer raw material for an optical polymer,
It is useful as other synthetic raw materials and intermediates.

[0030]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto. In the examples
"Parts" means "parts by weight".

Elemental analysis is made by Yanagimoto CHN Coder MT
It was carried out using a -5 type. Nuclear magnetic resonance spectrum ( ¹ H-
As the MMR, JNM-EX270 manufactured by JEOL Ltd. was used, and the measurement was performed by TMS standard and CDCl ₃ solvent. The infrared absorption spectrum was measured by Shimadzu Corporation's Shimadzu infrared spectrophotometer IR-470 by the KBr method.

Example 1 To 64 parts by weight of phenolphthalein and 44 parts by weight of ethylene carbonate, 0.02 part by weight of potassium carbonate was added as a catalyst, and the mixture was stirred at 200 ° C. for 6 hours. 0.1To after the generation of carbon dioxide is stopped
Excessive ethylene carbonate was distilled off under reduced pressure of rr or less.

An appropriate amount of ethanol was added to the obtained crude composition, which was heated under reflux to dissolve it, and then slowly cooled to room temperature to become a supersaturated liquid. When it is left at room temperature, it gradually crystallizes and the desired 3,3-bis (4-
White crystals of (hydroxyethoxy) phenyl) phthalide were obtained. The yield was 80%, the melting point was 91 to 92 ° C, and the elemental analysis values were C: 70.89% and H: 5.49%.

Further, the measurement results of ¹ H-NMR are shown below. The infrared absorption spectrum is shown in FIG. -2.04 ppm (t, 2H) -3.96 ppm (d, t, 4H) -4.07 ppm (t, 4H) -6.86 ppm (m, 4H) -7.24 ppm (m, 4H) -7. 51ppm (d, t, 1H) 7.54ppm (d, t, 1H) 7.69ppm (d, t, 1H) 7.93ppm (d, t, 1H)

Example 2 To 70 parts by weight of 9,9-bis (4-hydroxyphenyl) fluorene and 44 parts by weight of ethylene carbonate, 0.02 part by weight of potassium carbonate was added as a catalyst and stirred at 200 ° C. for 6 hours. . After the generation of carbon dioxide gas was stopped, the pressure was reduced to 0.1 Torr or less to distill off excess ethylene carbonate.

The obtained crude product was recrystallized from ethanol to obtain the desired white crystal of 9,9-bis (4-hydroxyethoxy) phenyl) fluorene. Yield 86%, melting point 138 ° C., elemental analysis value C: 79.41%, H: 5.
It was 99%.

Further, the measurement results of ¹ H-NMR are as follows. The infrared absorption spectrum is shown in FIG. * 2.17 ppm (br.s, 2H) * 3.91 ppm (m, 4H) * 4.02 ppm (m, 4H) * 6.76 ppm (m, 4H) * 7.15 ppm (m, 4H) * 7. 23-7.38 (m, 6H) -7.75ppm (d, t, 2H)

[Comparative Example 1] After the reaction was allowed to proceed under the same conditions as in Example 1 and the production of carbon dioxide gas was stopped, the method of JP-A-3-
When water was added to the reaction product according to the post-treatment method of No. 255044, the viscous material adhered to the wall of the reaction container and the stirring bath, and it became difficult to perform filtration and other treatments.

[Brief description of drawings]

FIG. 1 shows infrared absorption spectra of bis (hydroxyethoxyphenyl) compounds produced in Examples 1 and 2.

Continuation of front page (51) Int.Cl. ⁶ Identification number Office reference number FI Technical display location C07D 209/46 C07D 209/46 307/88 307/88 327/04 327/04 // C07B 61/00 300 C07B 61/00 300

Claims (1)

[Claims] [Claim 1] The following formula (1)[In the formula (1), R¹And R²Are independently hydrogen
Atoms, halogen atoms, hydrocarbon groups having 1 to 6 carbon atoms or
It is a hydrocarbon oxy group having 1 to 6 carbon atoms. Z is substantially
Each of the following formulas[In the above formula, R³~ R⁷And R^TenEach independently,
Hydrogen atom, halogen atom, hydrocarbon group having 1 to 6 carbon atoms
Or a hydrocarbonoxy group having 1 to 6 carbon atoms, R ⁸, R
⁹And R¹¹Are independently hydrogen atom and halogen atom.
A child or a hydrocarbon group having 1 to 6 carbon atoms. ]]
At least one divalent substituent selected from the group
It ] A bisfe having a cardo type quaternary carbon represented by
With a nol compound (A) and ethylene carbonate (B)
At a ratio such that the molar ratio of A and B is 1/2 to 1/5.
Heat reaction in the presence of a medium under substantially solvent-free conditions.
And then remove excess ethylene carbonate from the reaction system.
Bis (hydro) characterized by squeezing and then recrystallization
A method for producing a xyethoxyphenyl compound.