Dihydroxy compounds and methods for producing the same

Abstract

To provide a dihydroxy compound having a high refractive index and high purity and a method for producing the same.SOLUTION: A dihydroxy compound has a HPLC purity equal to or higher than 90 area% and is represented by the formula (1) (where Z1 and Z2 independently represent a C1 to 20 aromatic ring, L1 and L2 independently represent a C1 to 15 alkylene group, m1 and m2 independently represent an integer of 0-5, n1 is an integer of 1-4, and n2 is an integer of 0-4).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a dihydroxy compound and a method for producing the same.

Background Art

[0002] Plastic optical materials are lightweight compared to inorganic materials such as glass, have characteristics such as being crack-resistant and easy to process, and are expected to be applied to spectacle lenses, camera lenses, industrial lenses, retardation compensation plates for liquid crystal displays, optical fibers, etc. However, there are many problems to be solved in current plastic optical materials. For example, in the case of lens applications, characteristics such as a 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 improvement is demanded. Under such circumstances, it has been shown that fluorene derivatives and binaphthyl derivatives have a high refractive index as organic compounds (Patent Documents 1 and 2). However, to synthesize the compound, it is necessary to go through a plurality of reaction steps, and it is desired to synthesize a high refractive index compound by a more convenient method.

[0003] Further, as a flame retardant for epoxy resins, a phenol derivative having a carbon triple bond is good, and as Compound 9, 4,4'-(propan-2,2-diyl)bis(2,6-bis(phenylethynyl)phenol) is exemplified, but a detailed synthesis method of the compound is not described, and the yield, purity, and refractive index are also not described (Patent Document 3).

Prior Art Documents

Patent Documents

[0005] The present invention aims to provide a dihydroxy compound with a high refractive index and high purity, and a method for producing the same. [Means for solving the problem]

[0006] 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 higher.

[0007] [ka]

[0008] (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.) 《Aspect 2》 The dihydroxy compound according to embodiment 1, represented by the following formula (2).

[0009] [ka]

[0010] (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).

[0011] [ka]

[0012] (wherein, L1, L2, m1, and m2 are the same as those in the above formula (1).) <<Aspect 4>> The dihydroxy compound according to any one of Aspects 1 to 3, which is represented by the following formula (4).

[0013] [Chemical formula]

[0014] <<Aspect 5>> The dihydroxy compound according to any one of Aspects 1 to 4, having a refractive index of 1.64 or more. <<Aspect 6>> A method for producing the dihydroxy compound according to Aspect 1, wherein the diols represented by the following formula (5) and the aromatic acetylenes represented by the following formula (6) are reacted in a reaction solvent in the presence of a palladium-based catalyst, a copper-based catalyst, and a base.

[0015] [Chemical formula]

[0016] (wherein, 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 of 0 to 5.)

[0017] [Chemical formula]

[0018] (wherein, Y1 is an aromatic group having 1 to 20 carbon atoms.) <<Aspect 7>> A method for producing the dihydroxy compound according to Aspect 6, wherein the diols represented by the above formula (5) are the following formula (7).

[0019] [Chemical formula]

[0020] 《Aspect 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. [Effects of the Invention]

[0021] According to the present invention, a dihydroxy compound having 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. [Brief explanation of the drawing]

[0022] [Figure 1] This figure shows the NMR chart of the dihydroxy compound obtained in Example 1. [Modes for carrying out the invention]

[0023] <Dihydroxy compounds> The novel dihydroxy compound in the present invention is represented by the following formula (1).

[0024] [ka]

[0025] (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.)

[0026] 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.

[0027] [ka]

[0028] (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.)

[0029] 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.

[0030] [ka]

[0031] (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.

[0032] In formulas (1) to (3), m1 and m2 are each an integer 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.

[0033] [ka]

[0034] 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.

[0035] 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, measuring the D-line refractive index at 25°C using an ATAGO DR-M2 Abbe refractometer, and extrapolating the measurement results for each concentration to a concentration of 100% to obtain the refractive index (nD) of the compound.

[0036] <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.

[0037] [ka]

[0038] (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.)

[0039] [ka]

[0040] (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.

[0041] 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 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane represented by the following formula (7) being particularly preferred. These diols may be used individually or mixed in groups of two or more, and can be arbitrarily selected depending on the purpose.

[0042] [ka]

[0043] 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, ethynylbenzene, 1-ethynylnaphthalene, and 2-ethynylnaphthalene are more preferred, and ethynylbenzene 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.

[0044] The ratio of aromatic acetylenes represented by formula (6) to be used 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).

[0045] The aromatic acetylenes represented by formula (6) are preferably reacted dropwise or in divided portions in the presence of the diols represented by formula (5), a reaction solvent, a palladium-based catalyst, a copper-based catalyst, and a base.

[0046] 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.

[0047] The palladium-based catalysts used in the production 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.

[0048] 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).

[0049] 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.

[0050] 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).

[0051] In the production 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. Such solvents may be used alone or in combination of two or more.

[0052] 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.

[0053] In the manufacturing method of the present invention, the reaction temperature varies depending on the 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.

[0054] In the manufacturing method of the present invention, the reaction mixture after the reaction is completed usually contains unreacted raw materials, reaction intermediates, bases, catalysts, by-reaction products, etc., 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 a similar metal removal treatment, column chromatography, or separation methods that combine these. [Examples]

[0055] 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 gist of the invention.

[0056] 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 absence of solvent in HPLC.

[0057] [Table 1]

[0058] (2)NMR measurement The compounds obtained in the examples were dissolved in deuterated chloroform and measured using a JEOL JNM-AL400 (400MHz) instrument.

[0059] (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 values ​​obtained by extrapolating the measurement results for each concentration to 100% concentration were defined as the refractive index (nD) of the compounds obtained in the examples.

[0060] [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%. The reaction mixture was diluted with 300 ml of ethyl acetate, then 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.

[0061] [ka]

[0062] [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 mixture 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 mixture was diluted with 300 ml of ethyl acetate. The diluted reaction mixture 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.

[0063] The TEBA obtained in Example 1 was a high-purity crystal with a high refractive index. Furthermore, it could be manufactured in a single reaction step, making it industrially useful. [Industrial applicability]

[0064] 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

1. 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 excluding the solvent in HPLC measured using a Waters High Performance Liquid Chromatograph Alliance e2695 under the measurement conditions shown in Table 1 below. 【Chemistry 1】 (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.) Table 1

2. The spectacle lens, camera lens, or industrial lens according to claim 1, wherein the dihydroxy compound is represented by the following formula (2). 【Chemistry 2】 (wherein, Z ３ to Z ６ are each independently an aromatic ring having 1 to 20 carbon atoms, L １ , L ２ , m １ , m ２ are the same as in the above formula (1).)

3. 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). 【Transformation 3】 (In the formula, L １ , L ２ , m １ , m ２ This is the same as in equation (1) above.

4. 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). 【Chemistry 4】

5. 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.

6. 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. 【Transformation 5】 (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. 【Transformation 6】 (In the formula, Y １ (It is an aromatic group with 1 to 20 carbon atoms.)

7. The manufacturing method according to claim 6, wherein the diols represented by formula (5) are the following formula (7). 【Transformation 7】

8. The method for producing a dihydroxy compound according to claim 6 or 7, 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.

9. A phase difference compensation plate for a liquid crystal display, 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. 【Transformation 8】 (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.) Table 2

10. The phase difference compensation plate for liquid crystal display according to claim 9, wherein the dihydroxy compound is represented by the following formula (2). 【Chemistry 9】 (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.)

11. 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). 【Chemistry 10】 (In the formula, L1, L2, m1, and m2 are the same as in formula (1) above.)

12. 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). 【Chemistry 11】

13. 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.

14. A method for producing a phase difference compensation plate for a liquid crystal display, 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, forming a resin using the dihydroxy compound according to claim 9 as a raw material, and molding the resulting resin. 【Chemistry 12】 (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.) 【Chemistry 13】 (In the formula, Y1 is an aromatic group having 1 to 20 carbon atoms.)

15. The manufacturing method according to claim 14, wherein the diols represented by formula (5) are the following formula (7). 【Chemistry 14】

16. The method for producing the 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 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.

17. An optical fiber composed of a resin formed using a dihydroxy compound represented by the following formula (1) as a monomer, wherein the HPLC purity is 90 area percent or more. 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. 【Chemistry 15】 (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.) Table 3

18. The optical fiber according to claim 17, wherein the dihydroxy compound is represented by the following formula (2). 【Chemistry 16】 (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.)

19. The optical fiber according to claim 17 or 18, wherein the dihydroxy compound is represented by the following formula (3). 【Chemistry 17】 (In the formula, L1, L2, m1, and m2 are the same as in formula (1) above.)

20. The optical fiber according to any one of claims 17 to 19, wherein the dihydroxy compound is represented by the following formula (4). [Chemistry 18]

21. 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.

22. 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. 【Chemistry 19】 (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.) 【Chemistry 20】 (In the formula, Y1 is an aromatic group having 1 to 20 carbon atoms.)

23. The manufacturing method according to claim 22, wherein the diols represented by formula (5) are the following formula (7). 【Chemistry 21】

24. 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 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.

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