JP7849161B2 - Dihydroxy compounds and methods for producing the same - Google Patents

Description

This invention relates to dihydroxy compounds and methods for producing the same.

Plastic optical materials possess advantages such as being lighter, less prone to breakage, and easier to process compared to inorganic materials like glass, and are expected to have applications in eyeglass lenses, camera lenses, industrial lenses, phase difference compensation plates for liquid crystal displays, and optical fibers. However, current plastic optical materials have many problems that need to be solved. For example, in lens applications, properties such as high refractive index are required, but the refractive index of currently commercialized plastic lenses does not reach that of high refractive index glass materials, and further performance improvements are needed. Against this backdrop, fluorene derivatives and binaphthyl derivatives have been shown to have high refractive indexes as organic compounds (Patent Documents 1 and 2). However, synthesizing these compounds requires multiple reaction steps, and there is a desire for a simpler method to synthesize high refractive index compounds.

Furthermore, phenol derivatives having a carbon triple bond are suitable as flame retardants for epoxy resins, and compound 9, 4,4'-(propane-2,2-diyl)bis(2,6-bis(phenylethynyl)phenol), is given as an example. However, the detailed synthesis method of this compound is not described, nor are the yield, purity, and refractive index (Patent Document 3).

International Publication No. 2020/226126 International Publication No. 2020/175353 Japanese Patent Publication No. 2002-363261

The present invention aims to provide a dihydroxy compound with a high refractive index and high purity, and a method for producing the same.

The inventors have found that the above problems can be solved by the present invention having the following aspects.
《Aspect 1》
A dihydroxy compound represented by the following formula (1), having an HPLC purity of 90 area percent or more.

(In the formula, _Z1 and _Z2 are each independently aromatic rings having 1 to 20 carbon atoms, _L1 and _L2 are each independently alkylene groups having 1 to 15 carbon atoms, _m1 and _m2 are each independently integers from 0 to 5, _n1 is an integer from 1 to 4, and _n2 is an integer from 0 to 4.)
Appearance 2
The dihydroxy compound according to embodiment 1, represented by the following formula (2).

(In the formula, _Z3 to _Z6 are each independently aromatic rings having 1 to 20 carbon atoms, and _L1 , _L2 , _m1 , and _m2 are the same as in formula (1) above.)
《Aspect 3》
The dihydroxy compound according to embodiment 1 or 2, represented by the following formula (3).

(In the formula, _L1 , _L2 , _m1 , and _m2 are the same as in formula (1) above.)
《Aspect 4》
A dihydroxy compound according to any one of embodiments 1 to 3, represented by the following formula (4).

《Aspect 5》
A dihydroxy compound according to any one of embodiments 1 to 4, wherein the refractive index is 1.64 or higher.
《Aspect 6》
A method for producing a dihydroxy compound according to Embodiment 1, comprising reacting a diol represented by the following formula (5) with an aromatic acetylene represented by the following formula (6) in a reaction solvent in the presence of a palladium-based catalyst, a copper-based catalyst, and a base.

(In the formula, _X1 to _X4 are each independently a halogen atom or a hydrogen atom, _L1 and _L2 are each independently an alkylene group having 1 to 15 carbon atoms, and _m1 and _m2 are each independently an integer from 0 to 5.)

(In the formula, _Y1 is an aromatic group having 1 to 20 carbon atoms.)
《Aspect 7》
A method for producing a dihydroxy compound according to embodiment 6, wherein the diols represented by formula (5) are the following formula (7).

《Appearance 8》
A method for producing a dihydroxy compound according to embodiment 6 or 7, wherein the reaction is carried out in the presence of a diol represented by formula (5), a reaction solvent, a palladium-based catalyst, a copper-based catalyst, and a base, while adding aromatic acetylenes represented by formula (6) dropwise or in divided portions.

According to the present invention, a dihydroxy compound with a high refractive index and high purity can be provided. Furthermore, a method for producing the dihydroxy compound in a single reaction step can be provided.

This figure shows the NMR chart of the dihydroxy compound obtained in Example 1.

<Dihydroxy compounds>
The novel dihydroxy compound in the present invention is represented by the following formula (1).

(In the formula, _Z1 and _Z2 are each independently aromatic rings having 1 to 20 carbon atoms, _L1 and _L2 are each independently alkylene groups having 1 to 15 carbon atoms, _m1 and _m2 are each independently integers from 0 to 5, _n1 is an integer from 1 to 4, and _n2 is an integer from 0 to 4.)

In formula (1), _n1 is an integer from 1 to 4, preferably from 1 to 2, and particularly preferably 2. Also, _n2 is an integer from 0 to 4, preferably from 1 to 2, and particularly preferably 2. That is, among the dihydroxy compounds represented by formula (1), the dihydroxy compound represented by the following formula (2) is particularly preferred.

(In the formula, _Z3 to _Z6 are each independently aromatic rings having 1 to 20 carbon atoms, and _L1 , _L2 , _m1 , and _m2 are the same as in formula (1) above.)

In formulas (1) and (2), _Z1 to _Z6 are each independently aromatic rings having 1 to 20 carbon atoms, and examples include benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, pyrene rings, chrysene rings, fluorene rings, biphenylene rings, etc., with benzene rings and naphthalene rings being preferred, and benzene rings being particularly preferred. That is, among the dihydroxy compounds represented by formula (2), the dihydroxy compounds represented by the following formula (3) are particularly preferred.

(In the formula, _L1 , _L2 , _m1 , and _m2 are the same as in formula (1) above.)
In formulas (1) to (3), _L1 and _L2 are each independently an alkylene group having 1 to 15 carbon atoms, with an alkylene group having 1 to 4 carbon atoms being preferred, and an ethylene group being particularly preferred.

In formulas (1) to (3), _m1 and _m2 are each independently integers from 0 to 5, preferably 0 or 1, and particularly preferably 0. That is, among the dihydroxy compounds represented by formula (3), the dihydroxy compound represented by the following formula (4) is particularly preferred.

The dihydroxy compound of the present invention has an HPLC purity of 90 area% or higher, preferably 95 area% or higher, more preferably 98 area% or higher, and even more preferably 99 area% or higher.

The dihydroxy compound of the present invention preferably has a refractive index of 1.64 or higher, more preferably 1.66 or higher, even more preferably 1.68 or higher, and particularly preferably 1.70 or higher. The refractive index was determined by dissolving the dihydroxy compound in dimethyl sulfoxide to prepare solutions of predetermined concentrations. The refractive index of each solution was measured at 25°C using an ATAGO DR-M2 Abbe refractometer, and the refractive index (nD) of the compound obtained by extrapolating the measurement results for each concentration to 100% concentration was defined as the nD of the compound.

<Method for producing dihydroxy compounds>
The dihydroxy compound represented by formula (1) of the present invention can be produced by reacting a diol represented by formula (5) below with an aromatic acetylene represented by formula (6) below in a reaction solvent in the presence of a palladium-based catalyst, a copper-based catalyst, and a base.

(In the formula, _X1 to _X4 are each independently a halogen atom or a hydrogen atom, _L1 and _L2 are each independently an alkylene group having 1 to 15 carbon atoms, and _m1 and _m2 are each independently an integer from 0 to 5.)

(In the formula, _Y1 is an aromatic group having 1 to 20 carbon atoms.)
In formula (5), _X1 to _X4 are each independently a halogen atom or a hydrogen atom, with bromine and iodine atoms being preferred, and bromine atoms being more preferred.

Specific examples of diols represented by formula (5) include 2,2-bis(3-chloro-4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, 2,2-bis(3-bromo-4-hydroxyphenyl)propane, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, 2,2-bis(3-iodo-4-hydroxyphenyl)propane, and 2,2-bis(3,5-diiodo-4-hydroxyphenyl)propane, with 2,2-bis(3,5-bromo-4-hydroxyphenyl)propane and 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane being more preferred, and particularly preferred is 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane represented by formula (7) below. These diols may be used individually or mixed in groups of two or more, and can be arbitrarily selected depending on the purpose.

Specific examples of aromatic acetylenes represented by formula (6) include: ethynylbenzene, 1-ethynylnaphthalene, 2-ethynylnaphthalene, 1-ethynylanthracene, 2-ethynylanthracene, 9-ethynylanthracene, 1-ethynylphenanthrene, 2-ethynylphenanthrene, 3-ethynylphenanthrene, 4-ethynylphenanthrene, 9-ethynylphenanthrene, 1-ethynylpyrene, and 2-ethynylpyrene. 4-ethynylpyrene, 2-ethynylchrysene, 5-ethynylchrysene, 6-ethynylchrysene, 1-ethynylfluorene, 2-ethynylfluorene, 3-ethynylfluorene, 9-ethynylfluorene, 2-ethynylbiphenyl, 3-ethynylbiphenyl, and 4-ethynylbiphenyl are preferred, ethinylbenzene, 1-ethynylnaphthalene, and 2-ethynylnaphthalene are more preferred, and ethinylbenzene is particularly preferred. These aromatic acetylenes may be used individually or as a mixture of two or more, and can be arbitrarily selected depending on the purpose.

The usage ratio of aromatic acetylenes represented by formula (6) is preferably 2.0 to 6.0 moles, more preferably 3.0 to 5.0 moles, and even more preferably 4.0 to 4.5 moles per mole of diols represented by formula (5).

The aromatic acetylenes represented by formula (6) are preferably reacted dropwise or in divided doses in the presence of the diols represented by formula (5), a reaction solvent, a palladium-based catalyst, a copper-based catalyst, and a base.

In the manufacturing method of the present invention, amines are preferred as bases, with triethylamine, piperidine, pyridine, and N,N-diisopropylethylamine being more preferred. Such bases may be used individually or in combination of two or more types.

The palladium-based catalysts used in the manufacturing method of the present invention are preferably tetrakis(triphenylphosphine)palladium, bis(triphenylphosphine)palladium dichloride, palladium acetate, tris(dibenzylideneacetone)dipalladium, bis(dibenzylideneacetone)palladium, bis[4-(N,N-dimethylamino)phenyl]di-tert-butylphosphine palladium dichloride, bis(di-tert-butylprenylphosphine)palladium dichloride, and bis(di-tert-clotylphosphine)palladium dichloride. These palladium-based catalysts may be used individually or in combination of two or more.

The amount of palladium-based catalyst used is preferably 0.001 to 1 mole, and more preferably 0.005 to 0.05 moles, per mole of the diol represented by formula (5).

The copper-based catalyst used in the manufacturing method of the present invention is preferably copper(I) iodide or copper(I) bromide. These copper-based catalysts may be used individually or in combination of two or more.

The amount of copper-based catalyst used is preferably 0.001 to 1 mole, and more preferably 0.005 to 0.05 moles, per mole of the diol represented by formula (5).

In the manufacturing method of the present invention, it is preferable to use the above-mentioned base as the reaction solvent. Alternatively, aromatic hydrocarbon solvents such as toluene and xylene, alcoholic solvents such as methanol, ethanol, isopropyl alcohol, and n-butanol, and aprotic solvents such as tetrahydrofuran, acetonitrile, N,N-dimethylformamide, or N,N-dimethylacetamide may be used. These solvents may be used individually or in combination of two or more.

The amount of the reaction solvent used is preferably 1 to 100 times the weight of the diol represented by formula (5), and more preferably 5 to 50 times the weight.

In the manufacturing method of the present invention, the reaction temperature varies depending on the type of raw materials and solvent used, but is preferably 50 to 150°C, more preferably 60 to 130°C, and even more preferably 70 to 120°C. The reaction can be tracked by analytical means such as liquid chromatography.

In the manufacturing method of the present invention, the reaction mixture after the reaction typically contains unreacted raw materials, reaction intermediates, bases, catalysts, and by-reaction products, in addition to the dihydroxy compound represented by formula (1) that is produced. Therefore, it can be separated and purified by conventional separation methods, such as filtration, concentration, distillation, extraction, crystallization, recrystallization, reprecipitation, activated carbon treatment or similar metal removal treatments, column chromatography, or combinations thereof.

The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following examples unless it exceeds the essence of the invention.

In the examples, various measurements were performed as follows.
(1) HPLC measurement (purity (area %))
Measurements were performed using a Waters Alliance e2695 high-performance liquid chromatograph under the conditions shown in Table 1. In the examples, unless otherwise specified, purity (area %) is the area percentage value corrected for the solvent in HPLC.

(2) NMR measurement The compounds obtained in the examples were dissolved in deuterated chloroform and measured using a JEOL JNM-AL400 (400 MHz) NMR analyzer.

(3) Refractive index (nD)
The dihydroxy compounds obtained in the examples were dissolved in dimethyl sulfoxide to prepare solutions of predetermined concentrations. The refractive index of each solution concentration was measured at 25°C using an ATAGO DR-M2 Abbe refractometer, specifically the D-line refractive index. The refractive index (nD) of the compounds obtained in the examples was defined as the value obtained by extrapolating the measurement results for each concentration to 100% concentration.

[Example 1]
Under a nitrogen atmosphere, 5.00 g (9 mmol) of tetrabromobisphenol A (hereinafter sometimes abbreviated as TBA), 0.53 g (0.5 mmol) of tetrakis(triphenylphosphine)palladium, 0.05 g (0.3 mmol) of copper(I) iodide, and 50 ml of triethylamine were added to a flask equipped with a stirrer, condenser, and thermometer, and the temperature was raised to 90°C. After confirming that the TBA had dissolved and the reaction mixture was homogeneous, 4.13 g (40 mmol) of ethynnylbenzene was added dropwise over 30 minutes. The reaction was carried out under reflux for 6 hours, and the HPLC purity of 2,2-bis(3,5-di(phenylethynyl)-4-hydroxyphenyl)propane (hereinafter sometimes abbreviated as TEBA), represented by the following formula (4), was 86.25 area%. After diluting the reaction mixture with 300 ml of ethyl acetate, it was transferred to a separatory funnel and washed five times with distilled water. The water-washed organic layer was treated with activated carbon, then concentrated and recrystallized in toluene/hexane. The resulting crystals were collected and dried to obtain 2.04 g of TEBA with an HPLC purity of 99.88 area%. The refractive index of TEBA was 1.70.

[Comparative Example 1]
Under a nitrogen atmosphere, 5.00 g (9 mmol) of TBA, 4.13 g (40 mmol) of ethynylbenzene, 0.53 g (0.5 mmol) of tetrakis(triphenylphosphine)palladium, 0.05 g (0.3 mmol) of copper(I) iodide, and 50 ml of triethylamine were added to a flask equipped with a stirrer, condenser, and thermometer, and the temperature was raised to 90°C. The reaction was carried out under reflux for 7 hours, and the HPLC purity of the TEBA after the reaction was 29.62 area%. The reaction solution was diluted with 300 ml of ethyl acetate, then transferred to a separatory funnel and washed five times with distilled water. The washed organic layer was treated with activated carbon, then concentrated and recrystallized with toluene/hexane. The reaction solution was diluted with 300 ml of ethyl acetate. The diluted reaction solution was transferred to a separatory funnel and washed five times with distilled water. After washing the organic layer and treating it with activated carbon, the layer was concentrated and recrystallized with toluene/hexane. However, it was in an oily state and no crystals were obtained.

The TEBA obtained in Example 1 was a high-purity crystal with a high refractive index. Furthermore, it can be manufactured in a single reaction step, making it industrially useful.

The dihydroxy compounds obtained in this invention are suitable as monomers for forming resins that constitute optical components such as optical lenses and optical films.

Claims (24)

Eyeglass lenses, camera lenses , or industrial lenses are made of a resin formed using a dihydroxy compound represented by the following formula (1) as a monomer, with an HPLC purity of 90 area percent or more.
However, HPLC purity is the area percentage value corrected for the solvent in HPLC measured using a Waters High Performance Liquid Chromatograph Alliance e2695 under the measurement conditions shown in Table 1 below.
(In the formula, _Z1 and _Z2 are each independently aromatic rings having 1 to 20 carbon atoms, _L1 and _L2 are each independently alkylene groups having 1 to 15 carbon atoms, _m1 and _m2 are each independently integers from 0 to 5, _n1 is an integer from 1 to 4, and _n2 is an integer from 0 to 4.)
The spectacle lens, camera lens , or industrial lens according to claim 1, wherein the dihydroxy compound is represented by the following formula (2).
(In the formula, _Z3 to _Z6 are each independently aromatic rings having 1 to 20 carbon atoms, and _L1 , _L2 , _m1 , and _m2 are the same as in formula (1) above.) The spectacle lens, camera lens , or industrial lens according to claim 1 or 2, wherein the dihydroxy compound is represented by the following formula (3).
(In the formula, _L1 , _L2 , _m1 , and _m2 are the same as in formula (1) above.) The spectacle lens, camera lens , or industrial lens according to any one of claims 1 to 3, wherein the dihydroxy compound is represented by the following formula (4).
The spectacle lens, camera lens , or industrial lens according to any one of claims 1 to 4, wherein the refractive index of the dihydroxy compound is 1.64 or higher. A method for producing eyeglass lenses, camera lenses, or industrial lenses, comprising reacting diols represented by the following formula (5) with aromatic acetylenes represented by the following formula (6) in a reaction solvent in the presence of a palladium-based catalyst, a copper-based catalyst, and a base, forming a resin using the dihydroxy compound according to claim 1 as a raw material, and molding the resulting resin .
(In the formula, _X1 to _X4 are each independently a halogen atom or a hydrogen atom, _L1 and _L2 are each independently an alkylene group having 1 to 15 carbon atoms, and _m1 and _m2 are each independently an integer from 0 to 5.)
(In the formula, _Y1 is an aromatic group having 1 to 20 carbon atoms.) The manufacturing method according to claim 6, wherein the diols represented by formula (5) are the following formula (7).
The production method according to claim 6 or 7, wherein the dihydroxy compound is obtained by reacting aromatic acetylenes represented by formula (6) dropwise or in divided additions in the presence of diols represented by formula (5), a reaction solvent, a palladium-based catalyst, a copper-based catalyst, and a base. A phase difference compensation plate for liquid crystal displays, comprising a resin formed using a dihydroxy compound represented by the following formula (1), having an HPLC purity of 90 area percent or more, as a monomer.
However, HPLC purity is the area percentage value corrected for excluding the solvent in HPLC measured using a Waters High Performance Liquid Chromatograph Alliance e2695 under the measurement conditions shown in Table 1 below.
(In the formula, Z ₁ and Z ₂ Each is an aromatic ring with 1 to 20 carbon atoms, L ₁ and L ₂ Each of these is an alkylene group with 1 to 15 carbon atoms, m ₁ and m ₂ Each of these is an integer from 0 to 5, n ₁ n is an integer between 1 and 4. ₂ (This is an integer between 0 and 4.)
A phase difference compensation plate for a liquid crystal display according to claim 9, wherein the dihydroxy compound is represented by the following formula (2).
(In the formula, Z ₃ ~Z ₆ Each is an aromatic ring with 1 to 20 carbon atoms, L ₁ , L ₂ , m ₁ , m ₂ This is the same as in equation (1) above. A phase difference compensation plate for a liquid crystal display according to claim 9 or 10, wherein the dihydroxy compound is represented by the following formula (3).
(In the formula, L ₁ , L ₂ , m ₁ , m ₂ This is the same as in equation (1) above. A phase difference compensation plate for a liquid crystal display according to any one of claims 9 to 11, wherein the dihydroxy compound is represented by the following formula (4).
A phase difference compensation plate for a liquid crystal display according to any one of claims 9 to 12, wherein the refractive index of the dihydroxy compound is 1.64 or higher. A method for producing a phase difference compensation plate for a liquid crystal display, comprising reacting diols represented by the following formula (5) with aromatic acetylenes represented by the following formula (6) in a reaction solvent in the presence of a palladium-based catalyst, a copper-based catalyst, and a base, forming a resin using the dihydroxy compound according to claim 9 as a raw material, and molding the resulting resin.
(In the formula, X ₁ ~X ₄ Each is independently a halogen atom or a hydrogen atom, L ₁ and L ₂ Each of these is an alkylene group with 1 to 15 carbon atoms, m ₁ and m ₂ Each of these is an independent integer between 0 and 5.
(In the formula, Y ₁ (It is an aromatic group with 1 to 20 carbon atoms.) The manufacturing method according to claim 14, wherein the diols represented by formula (5) are the following formula (7).
The method for producing a dihydroxy compound according to claim 14 or 15, wherein the dihydroxy compound is obtained by reacting aromatic acetylenes represented by formula (6) dropwise or in divided additions in the presence of diols represented by formula (5), a reaction solvent, a palladium-based catalyst, a copper-based catalyst, and a base. An optical fiber composed of a resin formed using a dihydroxy compound represented by the following formula (1) as a monomer, having an HPLC purity of 90 area percent or more.
However, HPLC purity is the area percentage value corrected for the solvent in HPLC measured using a Waters High Performance Liquid Chromatograph Alliance e2695 under the measurement conditions shown in Table 1 below.
(In the formula, Z ₁ and Z ₂ Each is an aromatic ring with 1 to 20 carbon atoms, L ₁ and L ₂ Each of these is an alkylene group with 1 to 15 carbon atoms, m ₁ and m ₂ Each of these is an integer from 0 to 5, n ₁ n is an integer between 1 and 4. ₂ (This is an integer between 0 and 4.)
The optical fiber according to claim 17, wherein the dihydroxy compound is represented by the following formula (2).
(In the formula, Z ₃ ~Z ₆ Each is an aromatic ring with 1 to 20 carbon atoms, L ₁ , L ₂ , m ₁ , m ₂ This is the same as in equation (1) above. The optical fiber according to claim 17 or 18, wherein the dihydroxy compound is represented by the following formula (3).
(In the formula, L ₁ , L ₂ , m ₁ , m ₂ This is the same as in equation (1) above. The optical fiber according to any one of claims 17 to 19, wherein the dihydroxy compound is represented by the following formula (4).
The optical fiber according to any one of claims 17 to 20, wherein the refractive index of the dihydroxy compound is 1.64 or higher. A method for producing optical fibers, comprising reacting diols represented by the following formula (5) with aromatic acetylenes represented by the following formula (6) in a reaction solvent in the presence of a palladium-based catalyst, a copper-based catalyst, and a base, forming a resin using the dihydroxy compound according to claim 17 as a raw material, and molding the resulting resin.
(In the formula, X ₁ ~X ₄ Each is independently a halogen atom or a hydrogen atom, L ₁ and L ₂ Each of these is an alkylene group with 1 to 15 carbon atoms, m ₁ and m ₂ Each of these is an independent integer between 0 and 5.
(In the formula, Y ₁ (It is an aromatic group with 1 to 20 carbon atoms.) The manufacturing method according to claim 22, wherein the diols represented by formula (5) are the following formula (7).
The method for producing the dihydroxy compound according to claim 22 or 23, wherein the dihydroxy compound is obtained by reacting aromatic acetylenes represented by formula (6) dropwise or in partial addition in the presence of diols represented by formula (5), a reaction solvent, a palladium-based catalyst, a copper-based catalyst, and a base.