JP7166107B2 - Method for producing binaphthol compound - Google Patents

Description

The present invention relates to a method for producing a binaphthol compound.

In recent years, resin materials having a binaphthalene skeleton have attracted attention as optical system materials such as optical lenses and optical sheets because of their excellent optical properties. For example, Patent Document 1 below discloses a polyacrylate resin in which a binaphthalene skeleton is introduced using a binaphthol compound such as 2,2'-bis(2-hydroxyalkoxy)-1,1'-binaphthalenes. .

In addition to polyacrylate resins, resin materials such as polyester resins, polyurethane resins and epoxy resins have been studied, and the above binaphthol compounds are required as raw material monomers for these resin materials.

As a method for producing the above binaphthol-based compound, a method of reacting 1,1′-bi-2-naphthols with alkylene oxide or alkylene carbonate is known (see, for example, Patent Document 2 below). .

JP 2011-157437 A JP 2010-18753 A

However, in the alkylene oxide addition reaction to binaphthols, in addition to the target binaphthol compounds in which 2 mol of oxyalkylene groups are added to 1 mol of binaphthols, a compound in which 1 mol of oxyalkylene groups is added to binaphthols, binaphthol A compound in which 3 moles of an oxyalkylene group is added to a compound and a compound in which 4 moles or more of an oxyalkylene group is added to a binaphthol are by-produced. These by-products cause deterioration of the heat resistance and optical properties of the resin material, so if the amount produced is large, the purification load will be large.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for producing a binaphthol-based compound that can obtain a desired binaphthol-based compound with high selectivity.

［式（１）中、Ｒ^１１及びＲ^１２はそれぞれ独立に、ハロゲン原子、又は炭素数１～２２の１価の炭化水素基を示し、Ｒ^１３及びＲ^１４はそれぞれ独立に、水素原子、又はメチル基を示し、Ｙ^１１及びＹ^１２はそれぞれ独立に、単結合、又は酸素原子を示し、ｎ１及びｍ１はそれぞれ０～４の整数を示す。ｎ１が２以上の整数である場合、複数存在するＲ^１１はそれぞれ同一であっても異なっていてもよく、複数存在するＹ^１１はそれぞれ同一であっても異なっていてもよい。ｍ１が２以上の整数である場合、複数存在するＲ^１２はそれぞれ同一であっても異なっていてもよく、複数存在するＹ^１２はそれぞれ同一であっても異なっていてもよい。］

［式（２）中、Ｒ^２１及びＲ^２２はそれぞれ独立に、メチル基、エチル基、ｎ－プロピル基、又はイソプロピル基を示し、Ｒ^２３は、水素原子、メチル基、又はエチル基を示す。］

［式（３）中、Ｒ^３１及びＲ^３２はそれぞれ独立に、ハロゲン原子、又は炭素数１～２２の１価の炭化水素基を示し、Ｙ^３１及びＹ^３２はそれぞれ独立に、単結合、又は酸素原子を示し、ｎ３及びｍ３はそれぞれ０～４の整数を示す。ｎ３が２以上の整数である場合、複数存在するＲ^３１はそれぞれ同一であっても異なっていてもよく、複数存在するＹ^３１はそれぞれ同一であっても異なっていてもよい。ｍ３が２以上の整数である場合、複数存在するＲ^３２はそれぞれ同一であっても異なっていてもよく、複数存在するＹ^３２はそれぞれ同一であっても異なっていてもよい。］ In order to solve the above problems, the present invention provides a method for producing a binaphthol compound represented by the following general formula (1), wherein in the presence of a compound represented by the following general formula (2), the following Provided is a method for producing a binaphthol-based compound comprising a step of adding ethylene oxide and/or propylene oxide to a compound represented by general formula (3).

[In formula (1), R ¹¹ and R ¹² each independently represent a halogen atom or a monovalent hydrocarbon group having 1 to 22 carbon atoms, and R ¹³ and R ¹⁴ each independently represent a hydrogen atom, or represents a methyl group, Y ¹¹ and Y ¹² each independently represent a single bond or an oxygen atom, n1 and m1 each represent an integer of 0 to 4; When n1 is an integer of 2 or more, multiple R ¹¹ may be the same or different, and multiple Y ¹¹ may be the same or different. When m1 is an integer of 2 or more, multiple R ¹² may be the same or different, and multiple Y ¹² may be the same or different. ]

[In formula (2), R ²¹ and R ²² each independently represent a methyl group, an ethyl group, an n-propyl group or an isopropyl group, and R ²³ represents a hydrogen atom, a methyl group or an ethyl group. ]

[In formula (3), R ³¹ and R ³² each independently represent a halogen atom or a monovalent hydrocarbon group having 1 to 22 carbon atoms, and Y ³¹ and Y ³² each independently represent a single bond, or represents an oxygen atom, n3 and m3 each represents an integer of 0 to 4; When n3 is an integer of 2 or more, multiple R ³¹ may be the same or different, and multiple Y ³¹ may be the same or different. When m3 is an integer of 2 or more, multiple R ³² may be the same or different, and multiple Y ³² may be the same or different. ]

According to the method for producing a binaphthol compound of the present invention, the binaphthol compound represented by the general formula (1) can be obtained with high selectivity.

In the above step, 100 parts by mass of the compound represented by the general formula (3) and 10 to 1000 parts by mass of the compound represented by the general formula (2) are mixed to obtain the compound represented by the general formula (3). Ethylene oxide and/or propylene oxide may be added to the compound.

The reaction temperature in the above step may be 90-150°C.

ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the binaphthol compound which can obtain a desired binaphthol compound with high selectivity can be provided.

The binaphthol-based compound obtained by the method of the present invention has a high purity of the compound represented by the general formula ( 1 ), and can be purified with a small load. In addition, the binaphthol-based compound obtained by the method of the present invention can improve the optical properties and heat resistance properties of the resin by being used as a raw material monomer for polyacrylate resins and the like.

Preferred embodiments of the present invention are described in detail below. However, the present invention is not limited to the following embodiments.

A method for producing a binaphthol-based compound represented by the following general formula (1) (hereinafter sometimes referred to as "binaphthol-based compound 1") of the present embodiment includes a compound represented by the following general formula (2) (hereinafter referred to as A step of adding ethylene oxide and/or propylene oxide to a compound represented by the following general formula (3) (hereinafter sometimes referred to as “compound 3”) in the presence of “compound 2”) Prepare.

［式（１）中、Ｒ^１１及びＲ^１２はそれぞれ独立に、ハロゲン原子、又は炭素数１～２２の１価の炭化水素基を示し、Ｒ^１３及びＲ^１４はそれぞれ独立に、水素原子、又はメチル基を示し、Ｙ^１１及びＹ^１２はそれぞれ独立に、単結合、又は酸素原子を示し、ｎ１及びｍ１はそれぞれ０～４の整数を示す。ｎ１が２以上の整数である場合、複数存在するＲ^１１はそれぞれ同一であっても異なっていてもよく、複数存在するＹ^１１はそれぞれ同一であっても異なっていてもよい。ｍ１が２以上の整数である場合、複数存在するＲ^１２はそれぞれ同一であっても異なっていてもよく、複数存在するＹ^１２はそれぞれ同一であっても異なっていてもよい。］

[In formula (1), R ¹¹ and R ¹² each independently represent a halogen atom or a monovalent hydrocarbon group having 1 to 22 carbon atoms, and R ¹³ and R ¹⁴ each independently represent a hydrogen atom, or represents a methyl group, Y ¹¹ and Y ¹² each independently represent a single bond or an oxygen atom, n1 and m1 each represent an integer of 0 to 4; When n1 is an integer of 2 or more, multiple R ¹¹ may be the same or different, and multiple Y ¹¹ may be the same or different. When m1 is an integer of 2 or more, multiple R ¹² may be the same or different, and multiple Y ¹² may be the same or different. ]

［式（２）中、Ｒ^２１及びＲ^２２はそれぞれ独立に、メチル基、エチル基、ｎ－プロピル基、又はイソプロピル基を示し、Ｒ^２３は、水素原子、メチル基、又はエチル基を示す。］

[In formula (2), R ²¹ and R ²² each independently represent a methyl group, an ethyl group, an n-propyl group or an isopropyl group, and R ²³ represents a hydrogen atom, a methyl group or an ethyl group. ]

［式（３）中、Ｒ^３１及びＲ^３２はそれぞれ独立に、ハロゲン原子、又は炭素数１～２２の１価の炭化水素基を示し、Ｙ^３１及びＹ^３２はそれぞれ独立に、単結合、又は酸素原子を示し、ｎ３及びｍ３はそれぞれ０～４の整数を示す。ｎ３が２以上の整数である場合、複数存在するＲ^３１はそれぞれ同一であっても異なっていてもよく、複数存在するＹ^３１はそれぞれ同一であっても異なっていてもよい。ｍ３が２以上の整数である場合、複数存在するＲ^３２はそれぞれ同一であっても異なっていてもよく、複数存在するＹ^３２はそれぞれ同一であっても異なっていてもよい。］

[In formula (3), R ³¹ and R ³² each independently represent a halogen atom or a monovalent hydrocarbon group having 1 to 22 carbon atoms, and Y ³¹ and Y ³² each independently represent a single bond, or represents an oxygen atom, n3 and m3 each represents an integer of 0 to 4; When n3 is an integer of 2 or more, multiple R ³¹ may be the same or different, and multiple Y ³¹ may be the same or different. When m3 is an integer of 2 or more, multiple R ³² may be the same or different, and multiple Y ³² may be the same or different. ]

First, the compound represented by the general formula (3), which is the reaction substrate for the alkylene oxide addition reaction, will be described.

When at least one of R ³¹ and R ³² is a halogen atom, the halogen atom may be fluorine, chlorine, bromine, or iodine. The halogen atom is preferably chlorine, bromine or iodine, more preferably bromine or iodine, from the viewpoint of obtaining the desired binaphthol compound 1 with high selectivity.

When at least one of R ³¹ and R ³² is a monovalent hydrocarbon group having 1 to 22 carbon atoms, the hydrocarbon group is an aliphatic hydrocarbon group (a chain aliphatic hydrocarbon group) or an alicyclic hydrocarbon group. It may be a hydrogen group (cycloaliphatic hydrocarbon group) or an aromatic hydrocarbon group.

Aliphatic hydrocarbon groups may be either saturated or unsaturated, and may be linear or branched. Examples of aliphatic hydrocarbon groups include methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, isobutyl, amyl, isoamyl, hexyl, heptyl, 2- Ethylhexyl group, octyl group, isooctyl group, nonyl group, isononyl group, decyl group, isodecyl group, undecyl group, lauryl group, tridecyl group, tetradecyl group, stearyl group, octadecyl group, behenyl group and dodecyl group.

The number of carbon atoms in the aliphatic hydrocarbon group is preferably 1 to 12, more preferably 1 to 6, even more preferably 1 to 3, from the viewpoint of solubility in compound 2.

Alicyclic hydrocarbon groups may be either saturated or unsaturated. Examples of alicyclic hydrocarbon groups include cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl groups. When the alicyclic hydrocarbon group has two or more ring structures, such alicyclic hydrocarbon groups include, for example, decahydronaphthyl group, adamantyl group and norbornyl group.

Examples of aromatic hydrocarbon groups include aryl groups such as phenyl group, tolyl group, xylyl group and naphthyl group; and aralkyl groups such as benzyl group, phenethyl group and naphthylmethyl group.

The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 12, more preferably 6 to 10, even more preferably 6 to 8, from the viewpoint of solubility in compound 2.

In the compound represented by the general formula (3), from the viewpoint of solubility in compound 2, R ³¹ and R ³² are bromine, iodine, methyl group, ethyl group, propyl group, isopropyl group, phenyl group, tolyl group , xylyl, benzyl and phenethyl groups.
In the compound represented by the general formula (3), Y ³¹ and Y ³² are preferably single bonds from the viewpoint of solubility in compound 2.

From the viewpoint of solubility in compound 2, each of n3 and m3 is preferably 0 to 3, more preferably 0 to 2, and even more preferably 0, that is, unsubstituted.

Examples of the compound represented by the general formula (3) include 1,1'-bi-2-naphthol.

The compounds represented by the general formula (3) can be used singly or in combination of two or more.

Next, the compound represented by the general formula (2) will be described. The compound can function as a solvent for the compound represented by the general formula (3).

R ²¹ and R ²² are preferably a methyl group or an ethyl group from the viewpoint of obtaining the desired binaphthol compound 1 with high selectivity.

From the viewpoint of dissolving compound 3, R ²³ is preferably a hydrogen atom or a methyl group.

Examples of the compound represented by the general formula (2) include dimethylformamide, dimethylacetamide, ethylmethylformamide, ethylmethylacetamide, diethylformamide, and diethylacetamide. From the viewpoint of dissolving compound 3, dimethylformamide and dimethylacetamide are preferred.

The compounds represented by the general formula (2) can be used singly or in combination of two or more.

The compound represented by the general formula (1) is a target product produced by the method of the present embodiment, and R ¹¹ and R ¹² respectively correspond to R ³¹ and R ³² in the general formula (3). . Y ¹¹ and Y ¹² respectively correspond to Y ³¹ and Y ³² in the general formula (3). Moreover, n1 and m1 respectively correspond to n3 and m3 in the general formula (3).

Examples of the binaphthol compound 1 produced by the method of the present embodiment include 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene and 2,2'-bis(2-hydroxypropoxy). -1,1'-binaphthalene and 2-(2-hydroxyethoxy)-2'-(2-hydroxypropoxy)-1,1-binaphthalene. Binaphthol-based compound 1 is preferably 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene from the viewpoint of obtaining a raw material monomer that improves the optical properties and heat resistance properties of the resin material.

Next, embodiments of the addition reaction step will be described.

In this embodiment, the compound 2 and the compound 3 can be mixed in a predetermined reaction vessel, and the reaction of adding ethylene oxide and/or propylene oxide can be performed.

Examples of reaction vessels include autoclaves.

The mixing ratio is preferably 100 parts by mass of compound 3 and 10 to 1000 parts by mass of compound 2, more preferably 50 to 1000 parts by mass, and more preferably 100 to 1000 parts by mass. It is particularly preferable to mix 200 to 800 parts by mass. When the mixing ratio is within the above range, it is easy to dissolve part or all of compound 3 in compound 2, and the amount of compound 2 used can be reduced, which is economical.

The reaction of adding ethylene oxide and/or propylene oxide can be carried out by adding one or more alkylene oxide raw materials selected from the group consisting of ethylene oxide and propylene oxide to the above mixture.

From the viewpoint of increasing the yield of the binaphthol compound 1, it is preferable that the compound 3 is completely dissolved in the compound 2 before starting the alkylene oxide addition reaction (before adding the alkylene oxide starting material) or during the reaction. More preferably, compound 3 is completely dissolved in compound 2 before starting the alkylene oxide addition reaction.

Whether or not compound 3 is completely dissolved in compound 2 can be visually confirmed. In addition, cloudiness is seen when it is in an insoluble state.

In the present embodiment, a solubility curve of compound 3 with respect to compound 2 as a solvent is prepared in advance, and compound 3 is completely The mixing ratio of compound 2 and compound 3 may be set so as to dissolve.

From the viewpoint of obtaining high-purity binaphthol-based compound 1, the amount of the alkylene oxide raw material added (charged amount) is preferably 2.00 to 3.00 mol per 1.00 mol of charged amount of compound 3. , 2.30 to 2.70 mol.

Although the reaction temperature is not particularly limited, it is preferably 90 to 150°C, more preferably 100 to 140°C, from the viewpoint of reactivity.

The reaction time in the addition reaction step is not particularly limited, but from the viewpoint of productivity, it is preferably 2 to 12 hours, more preferably 4 to 10 hours.

The pressure conditions in the addition reaction step are not particularly limited, and may be, for example, atmospheric pressure or under pressure. When under pressure, from the viewpoint of safety, it is preferably 1.00 MPa or less, more preferably 0.50 MPa or less.

The addition reaction step can be performed under an inert gas atmosphere such as nitrogen or argon.

In the addition reaction step, a catalyst and a solvent other than compound 2 (another solvent) may coexist.

Examples of catalysts include, but are not limited to, sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide, trimethylamine, triethylamine, triphenylphosphine, pyridine and N,N-dimethyl-4-amino. Examples thereof include dimethylaminopyridine such as pyridine. These can be used alone or in combination of two or more.

The amount of the catalyst added can be 0.01 to 1.0 parts by mass with respect to 100 parts by mass of compound 3 charged.

According to the method of the present embodiment, the binaphthol-based compound 1 can be obtained with high purity without using a catalyst. In this case, the step of removing the catalyst after completion of the reaction becomes unnecessary, and the process for producing the binaphthol compound 1 can be simplified.

Other solvents include, but are not limited to, dialkyls having 1 to 4 carbon atoms such as dimethylglycol, dimethyldiglycol, dimethyltriglycol, methylethyldiglycol, diethyldiglycol, dibutyldiglycol and dimethylpropylenediglycol. glycol ethers. Alcohols such as methanol, ethanol, n-propanol, isopropanol, 1-butanol, 2-methyl-1-propanol, 2-butanol, 2-methyl-2-propanol; benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene aromatic hydrocarbons such as; aliphatic hydrocarbons such as pentane, hexane and heptane; You may use these in combination of 2 or more types.

Other solvents are preferably dialkyl glycol ethers, alcohols and aromatic hydrocarbons, more preferably dialkyl glycol ethers and aromatic hydrocarbons, from the viewpoint of dissolving compound 3.

The mixing ratio of compound 2 and other solvent can be compound 2:other solvent=1:0.01 to 1:10 in mass ratio.

The reaction product obtained in the addition reaction step contains the binaphthol compound 1 with high purity. The purity of the binaphthol compound 1 in the reaction product can be 60% or more, 85% or more, or 90% or more in GC area % by gas chromatography analysis.

The obtained binaphthol-based compound 1 can improve the optical properties and heat resistance properties of the resin by being used as a raw material monomer for a polyacrylate resin or the like.

This embodiment may further include a purification step for purifying the reaction product obtained in the above steps. As a method for purification, a known method can be used, and examples thereof include crystallization such as recrystallization, chromatography and filtration.

When purification is performed by recrystallization, examples of the solvent used for recrystallization include alcohols having 1 to 4 carbon atoms and aqueous solutions thereof. Examples of alcohols having 1 to 4 carbon atoms include methanol, ethanol, propanol and isopropanol. The alcohol concentration in the solvent used for recrystallization is preferably 20 to 80% by mass, more preferably 40 to 60% by mass, from the viewpoint of dissolving Compound 3.

When purification is performed by recrystallization, the amount of the solvent used for recrystallization is preferably 2 to 5 parts by mass with respect to 1 part by mass of crystals. By performing such recrystallization, the purity of the binaphthol compound 1 after purification can be 99% or more in GC area % by gas chromatography analysis.

EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these Examples.

(Example 1)
50.0 g (0.17 mol) of 1,1′-bi-2-naphthol and 200.0 g of N,N-dimethylformamide were placed in a 1 L autoclave and sealed. Then, the inside of the autoclave was maintained at 20 to 30°C, and the inside of the autoclave was replaced with nitrogen. The inside of the autoclave was heated to 120° C. to completely dissolve 1,1′-bi-2-naphthol in N,N-dimethylformamide. Then, 19.2 g (0.44 mol) of ethylene oxide was introduced into the autoclave so that the pressure inside the autoclave did not exceed 0.5 MPa. Thereafter, the alkylene oxide addition reaction was allowed to proceed under the reaction conditions of a reaction temperature of 120° C. and a reaction time of 4 hours. After completion of the reaction, the content of the autoclave was cooled to 50° C. or less to obtain 266.6 g of reactant.

(Example 2)
A reaction was carried out in the same manner as in Example 1 except that N,N-dimethylacetamide was used instead of N,N-dimethylformamide to obtain 265.9 g of a reactant.

(Example 3)
The charged amount of N,N-dimethylformamide was changed from 200.0 g to 25.0 g, and the charged amount of ethylene oxide was changed from 19.2 g (0.44 mol) to 18.4 g (0.42 mol). Except for this, the reaction was carried out in the same manner as in Example 1 to obtain 92.5 g of a reactant.

(Example 4)
The charged amount of N,N-dimethylformamide was changed from 200.0 g to 50.0 g, and the charged amount of ethylene oxide was changed from 19.2 g (0.44 mol) to 18.4 g (0.42 mol). Except for this, the reaction was carried out in the same manner as in Example 1 to obtain 115.6 g of a reactant.

(Example 5)
The reaction was carried out in the same manner as in Example 1, except that the amount of N,N-dimethylformamide charged was changed from 200.0 g to 75.0 g to obtain 141.7 g of reactant.

(Example 6)
The reaction was carried out in the same manner as in Example 1, except that the amount of N,N-dimethylformamide charged was changed from 200.0 g to 100.0 g to obtain 166.7 g of reactant.

(Example 7)
Except that in addition to 50.0 g (0.17 mol) of 1,1'-bi-2-naphthol and 200.0 g of N,N-dimethylformamide, 0.10 g of potassium hydroxide as a catalyst were charged in a 1 L autoclave. was reacted in the same manner as in Example 1 to obtain 267.9 g of reactant.

(Example 8)
In addition to 50.0 g (0.17 mol) of 1,1'-bi-2-naphthol and 200.0 g of N,N-dimethylformamide, 0.18 g of triethylamine as a catalyst was charged in a 1 L autoclave. A reaction was carried out in the same manner as in Example 1 to obtain 267.1 g of reactant.

(Example 9)
Except that in addition to 50.0 g (0.17 mol) of 1,1'-bi-2-naphthol and 200.0 g of N,N-dimethylformamide, 0.46 g of triphenylphosphine as a catalyst were charged in a 1 L autoclave. was reacted in the same manner as in Example 1 to obtain 266.8 g of reactant.

(Example 10)
In addition to 50.0 g (0.17 mol) of 1,1′-bi-2-naphthol and 200.0 g of N,N-dimethylformamide, 1 L of 0.21 g of N,N-dimethyl-4-aminopyridine as a catalyst was added. The reaction was carried out in the same manner as in Example 1, except that the autoclave was charged, and 268.0 g of reaction product was obtained.

(Example 11)
50.0 g (0.17 mol) of 1,1′-bi-2-naphthol and 25.0 g of N,N-dimethylformamide were placed in a 1 L autoclave and sealed. Then, the inside of the autoclave was maintained at 20 to 30°C, and the inside of the autoclave was replaced with nitrogen. The inside of the autoclave was heated to 105° C. to partially dissolve 1,1′-bi-2-naphthol in N,N-dimethylformamide. Then, 18.4 g (0.42 mol) of ethylene oxide was introduced into the autoclave so that the pressure inside the autoclave did not exceed 0.5 MPa. After that, it was confirmed that 1,1'-bi-2-naphthol was completely dissolved in N,N-dimethylformamide. Then, the alkylene oxide addition reaction was allowed to proceed under the reaction conditions of a reaction temperature of 105° C. and a reaction time of 4 hours. After completion of the reaction, the contents of the autoclave were cooled to 50° C. or less to obtain 91.5 g of reactant.

( Reference example 12)
50.0 g (0.17 mol) of 1,1′-bi-2-naphthol and 5.0 g of N,N-dimethylformamide were placed in a 1 L autoclave and sealed. Then, the inside of the autoclave was maintained at 20 to 30°C, and the inside of the autoclave was replaced with nitrogen. The inside of the autoclave was heated to 120° C. to partially dissolve 1,1′-bi-2-naphthol in N,N-dimethylformamide. Then, 19.2 g (0.44 mol) of ethylene oxide was introduced into the autoclave so that the pressure inside the autoclave did not exceed 0.5 MPa. After that, it was confirmed that 1,1'-bi-2-naphthol was completely dissolved in N,N-dimethylformamide. Then, the alkylene oxide addition reaction was allowed to proceed under the reaction conditions of a reaction temperature of 120° C. and a reaction time of 4 hours. After completion of the reaction, the content of the autoclave was cooled to 50° C. or less to obtain 65.8 g of reactant.

(Comparative example 1)
A 1 L autoclave was charged with 50.0 g (0.17 mol) of 1,1′-bi-2-naphthol, 200.0 g of a 30% by mass isopropanol aqueous solution, and 0.10 g of potassium hydroxide as a catalyst and sealed. Then, the inside of the autoclave was maintained at 20 to 30°C, and the inside of the autoclave was replaced with nitrogen. The inside of the autoclave was heated to 90 ° C. (1,1'-bi-2-naphthol was confirmed to be in an undissolved state at this time), and ethylene oxide was added so that the pressure inside the autoclave did not exceed 0.5 MPa. 19.2 g (0.44 mol) of was introduced into the autoclave. Thereafter, the alkylene oxide addition reaction was allowed to proceed under the reaction conditions of a reaction temperature of 90° C. and a reaction time of 3 hours. After completion of the reaction, the content of the autoclave was cooled to 50° C. or less to obtain 258.9 g of reactant.

(Comparative example 2)
50.0 g (0.17 mol) of 1,1'-bi-2-naphthol, 200.0 g of deionized water, and 0.10 g of potassium hydroxide as a catalyst were placed in a 1 L autoclave and sealed. Then, the inside of the autoclave was maintained at 20 to 30°C, and the inside of the autoclave was replaced with nitrogen. The inside of the autoclave was heated to 100 ° C. (1,1'-bi-2-naphthol was confirmed to be in an undissolved state at this time), and ethylene oxide was added so that the pressure inside the autoclave did not exceed 0.5 MPa. 16.9 g (0.38 mol) of was introduced into the autoclave. Thereafter, the alkylene oxide addition reaction was allowed to proceed under the reaction conditions of a reaction temperature of 100° C. and a reaction time of 10 hours. After completion of the reaction, the content of the autoclave was cooled to 50° C. or less to obtain 257.3 g of reactant.

(Comparative Example 3)
50.0 g (0.17 mol) of 1,1′-bi-2-naphthol, 200.0 g of toluene, and 0.10 g of potassium hydroxide as a catalyst were placed in a 1 L autoclave and sealed. Then, the inside of the autoclave was maintained at 20 to 30°C, and the inside of the autoclave was replaced with nitrogen. The inside of the autoclave was heated to 150° C. to completely dissolve 1,1′-bi-2-naphthol in toluene. 16.9 g (0.38 mol) of ethylene oxide was introduced into the autoclave so that the pressure inside the autoclave did not exceed 0.5 MPa. Thereafter, the alkylene oxide addition reaction was allowed to proceed under the reaction conditions of a reaction temperature of 150° C. and a reaction time of 8 hours. After completion of the reaction, the content of the autoclave was cooled to 50° C. or less to obtain 257.9 g of reactant.

(Comparative Example 4)
25.0 g (0.09 mol) of 1,1'-bi-2-naphthol, 100.0 g of 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene, and 0 potassium hydroxide as a catalyst 0.06 g was charged into a 1 L autoclave and sealed. Then, the inside of the autoclave was maintained at 20 to 30°C, and the inside of the autoclave was replaced with nitrogen. The inside of the autoclave was heated to 120° C. (1,1′-bi-2-naphthol was confirmed to be in an undissolved state at this time), and ethylene was added so that the pressure inside the autoclave did not exceed 0.5 MPa. 8.5 g (0.19 mol) of oxide were introduced into the autoclave. Thereafter, the alkylene oxide addition reaction was allowed to proceed under the reaction conditions of a reaction temperature of 120° C. and a reaction time of 12 hours. After completion of the reaction, the content of the autoclave was cooled to 50° C. or less to obtain 130.5 g of reactant.

<Composition analysis>
The composition of the reaction product obtained above was analyzed according to the following method. The results are shown in Tables 1-3.

[Sample pretreatment]
Silylating agent (mixture of trimethylchlorosilane, 1,1,1,3,3,3-hexamethyldisilazane, pyridine, manufactured by Tokyo Chemical Industry Co., Ltd., product name: TMS-HT) was added to obtain a solution. Then, the obtained solution was heated in a water bath heated to 70-80° C. for 2-3 minutes to obtain a sample solution.

[Gas chromatography measurement conditions]
Measurement conditions for gas chromatography are shown below.

Gas chromatography: Shimadzu GC-16A [manufactured by Shimadzu Corporation]
Carrier gas: Helium Make-up gas: Helium make-up gas Flow rate: 50 mL/min Detector: Hydrogen flame ionization detector Helium pressure: 1.5 kg/cm ²
Hydrogen pressure: 0.6 kg/cm2
Air pressure: 0.5kg/cm2
Column: GL Science TC-1 (15 m × 0.25 mm ID 0.25 μm)
Column temperature: 180 to 300°C (heating rate: 15°C/min)
Injection temperature: 320°C
Detector temperature: 320°C
Split ratio: 1:25
Sample injection volume: 1 μL

The sample solution was analyzed by gas chromatography under the above conditions, and the unreacted product of 1,1'-bi-2-naphthol, the EO 1 mol adduct of 1,1'-bi-2-naphthol, and the EO 2 mol adduct , EO 3 mol adducts and EO 4 mol or more adducts were calculated. The component composition is the unreacted product of 1,1′-bi-2-naphthol, 1,1′-bi-2- Ratios of peak area values derived from naphthol EO 1 mol adduct (1EO), EO 2 mol adduct (2EO), EO 3 mol adduct (3EO) and EO 4 mol or more adduct (4EO or more) expressed as percentages is. The results are shown in Tables 1-3.

Abbreviations used in Tables 1 to 3 are as follows.
BINOL: 1,1'-bi-2-naphthol DMF: N,N-dimethylformamide DMAc: N,N-dimethylacetamide DMAP: N,N-dimethyl-4-aminopyridine AO: alkylene oxide DMF: N,N- Dimethylformamide 30% IPA: 30 wt% isopropanol aqueous solution IEW: ion-exchanged water BINOL-1EO: EO 1 mole adduct of 1,1'-bi-2-naphthol BINOL-2EO: 2,2'-bis(2-hydroxyethoxy )-1,1′-Binaphthalene BINOL-3EO: EO 3 mol adduct of 1,1′-bi-2-naphthol BINOL-4 EO or more: 1,1′-bi-2-naphthol EO 4 mol or more adduct Compound 2 : compound represented by the above general formula (2) Compound 3: compound represented by the above general formula (3)

As shown in Tables 1 and 2, in the presence of DMF or DMAc, Examples 1 to 11 and Reference Example 12 in which EO was added to BINOL were treated in the presence of 30% IPA, IEW, toluene, or BINOL-2EO. , and BINOL with EO added, it was confirmed that the ratio of 2EO was higher than in Comparative Examples 1 to 4.

Claims (2)

A method for producing a binaphthol compound represented by the following general formula (1),
A step of adding ethylene oxide and/or propylene oxide to a compound represented by the following general formula (3) in the presence of a compound represented by the following general formula (2) ;
In the step, 100 parts by mass of the compound represented by the general formula (3) and 50 to 1000 parts by mass of the compound represented by the general formula (2) are mixed to obtain the compound represented by the general formula (3). A method for producing a binaphthol compound, comprising adding ethylene oxide and/or propylene oxide to a compound.

[In formula (1), R ¹¹ and R ¹² each independently represent a halogen atom or a monovalent hydrocarbon group having 1 to 22 carbon atoms, and R ¹³ and R ¹⁴ each independently represent a hydrogen atom, or represents a methyl group, Y ¹¹ and Y ¹² each independently represent a single bond or an oxygen atom, n1 and m1 each represent an integer of 0 to 4; When n1 is an integer of 2 or more, multiple R ¹¹ may be the same or different, and multiple Y ¹¹ may be the same or different. When m1 is an integer of 2 or more, multiple R ¹² may be the same or different, and multiple Y ¹² may be the same or different. ]

[In formula (2), R ²¹ and R ²² each independently represent a methyl group, an ethyl group, an n-propyl group or an isopropyl group, and R ²³ represents a hydrogen atom, a methyl group or an ethyl group. ]

[In formula (3), R ³¹ and R ³² each independently represent a halogen atom or a monovalent hydrocarbon group having 1 to 22 carbon atoms, and Y ³¹ and Y ³² each independently represent a single bond, or represents an oxygen atom, n3 and m3 each represents an integer of 0 to 4; When n3 is an integer of 2 or more, multiple R ³¹ may be the same or different, and multiple Y ³¹ may be the same or different. When m3 is an integer of 2 or more, multiple R ³² may be the same or different, and multiple Y ³² may be the same or different. ] The method for producing a binaphthol compound according to claim 1 , wherein the reaction temperature in said step is 90 to 150°C.