WO2023176687A1 - Composé de biphénanthrène ou sel de métal alcalin de celui-ci - Google Patents

Composé de biphénanthrène ou sel de métal alcalin de celui-ci Download PDF

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WO2023176687A1
WO2023176687A1 PCT/JP2023/009059 JP2023009059W WO2023176687A1 WO 2023176687 A1 WO2023176687 A1 WO 2023176687A1 JP 2023009059 W JP2023009059 W JP 2023009059W WO 2023176687 A1 WO2023176687 A1 WO 2023176687A1
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general formula
formula
carbon atoms
crystal
compound
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雅斗 小寺
利恵 藤岡
裕貴 橋本
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本州化学工業株式会社
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Priority to CN202380025954.5A priority Critical patent/CN118786113A/zh
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C59/40—Unsaturated compounds
    • C07C59/58—Unsaturated compounds containing ether groups, groups, groups, or groups
    • C07C59/64—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings
    • C07C59/66—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings the non-carboxylic part of the ether containing six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/67—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of saturated acids
    • C07C69/708—Ethers
    • C07C69/712—Ethers the hydroxy group of the ester being etherified with a hydroxy compound having the hydroxy group bound to a carbon atom of a six-membered aromatic ring

Definitions

  • the present invention relates to a biphenanthrene compound or an alkali metal salt thereof.
  • Dicarboxylic acid compounds are used as raw materials for polyamides, raw materials for allyl ester compounds, and additives such as plasticizers and curing agents, and dicarboxylic acid compounds using bisphenol compounds as raw materials are also known (Patent Document 1) , 2nd prize).
  • Patent Document 1 2nd prize
  • the demands for various performance improvements have become increasingly sophisticated.In particular, further improvements in optical properties such as heat resistance, water resistance, electrical properties, and refractive index are required. There is a need for new compounds that express this.
  • An object of the present invention is to provide a novel dicarboxylic acid compound with a further improved refractive index.
  • biphenanthrene compounds or their alkali metal salts derived from biphenanthrols as raw materials into dicarboxylic acid compounds have a high refractive index. , completed the invention.
  • the present invention is as follows. 1. A biphenanthrene compound or an alkali metal salt thereof represented by general formula (1).
  • R 1 each independently represents an alkylene group having 1 to 4 carbon atoms
  • R 2 each independently represents an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, represents a group or a halogen atom
  • n each independently represents 0 or an integer of 1 to 4
  • R 3 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a halogen atom having 2 to 4 carbon atoms.
  • the biphenanthrene compound or its alkali metal salt as described in . (In the formula, R 1 , R 2 , R 3 , and n have the same definitions as in general formula (1).) 3. 1. Represented by general formula (1a-1). The biphenanthrene compound or its alkali metal salt as described in . (In the formula, R 1 , R 2 , R 3 , and n have the same definitions as in general formula (1).) 4. Crystals of 10,10'-bis(carboxymethoxy)-9,9'-biphenanthrile. 5.
  • the diffraction angles 2 ⁇ are 9.9 ⁇ 0.2°, 13.8 ⁇ 0.2°, 20.0 ⁇ 0.2°, 20.7 ⁇ 0. 4. Having diffraction peaks at 2°, 22.0 ⁇ 0.2° and 22.4 ⁇ 0.2°. Crystals described in. 6. Crystals of 10,10'-bis(ethoxycarbonylmethoxy)-9,9'-biphenanthrile. 7. In the powder X-ray diffraction peak pattern using Cu-K ⁇ rays, the diffraction angles 2 ⁇ are 10.8 ⁇ 0.2°, 17.5 ⁇ 0.2°, 21.7 ⁇ 0.2°, and 23.0 ⁇ 0. 6. Having a diffraction peak at 2°. Crystals described in.
  • the onset temperature of the endothermic peak by differential scanning calorimetry is in the range of 153 to 162°C. Crystals described in. 9. In the powder X-ray diffraction peak pattern using Cu-K ⁇ rays, the diffraction angles 2 ⁇ are 10.1 ⁇ 0.2°, 10.6 ⁇ 0.2°, 19.0 ⁇ 0.2°, and 25.1 ⁇ 0. 6. Having a diffraction peak at 2°. Crystals described in. 10. 6. The onset temperature of the endothermic peak by differential scanning calorimetry is in the range of 160 to 170°C. Crystals described in. 11. 6. The purity as determined by high performance liquid chromatography is 95.0% or more. Crystals described in. 12. 6.
  • Crystals described in. 13 Crystals of potassium salt of 10,10'-bis(carboxymethoxy)-9,9'-biphenanthrile. 14. In the powder X-ray diffraction peak pattern using Cu-K ⁇ rays, the diffraction angles 2 ⁇ are 5.4 ⁇ 0.2°, 10.4 ⁇ 0.2°, 13.4 ⁇ 0.2°, 17.4 ⁇ 0. 13. Having diffraction peaks at 2°, 20.0 ⁇ 0.2° and 22.0 ⁇ 0.2°. Crystals described in. 15.
  • a method for producing a biphenanthrene compound represented by general formula (1) which comprises reacting biphenanthrols represented by general formula (2) with halogenated carboxylic acids represented by general formula (3).
  • R 1 each independently represents an alkylene group having 1 to 4 carbon atoms
  • R 2 each independently represents an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, represents a group or a halogen atom
  • n each independently represents 0 or an integer of 1 to 4
  • R 3 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a halogen atom having 2 to 4 carbon atoms.
  • the biphenanthrols represented by the general formula (2) are biphenanthrols represented by the general formula (2a-1), and the biphenanthrene compound represented by the general formula (1) is a general 15.
  • a biphenanthrene compound represented by formula (1a-1). A method for producing a biphenanthrene compound as described in .
  • R 2 and n have the same definition as in general formula (1).
  • R 1 , R 2 , R 3 , and n have the same definitions as in general formula (1).
  • Heating crystals of 10,10'-bis(ethoxycarbonylmethoxy)-9,9'-biphenanthryl to a temperature of 150°C or more and 165°C or less to melt and cool.9. or 10.
  • the biphenanthrene compound or alkali metal salt thereof of the present invention has a high refractive index due to having a biphenanthrene skeleton. Therefore, a material obtained using this compound as a raw material is expected to have an excellent refractive index.
  • the biphenanthrene compound or its alkali metal salt of the present invention is useful as a raw material for materials such as polyamide materials and curable materials, additives such as plasticizers and curing agents, and raw materials for various other chemical products.
  • the crystal of the present invention can be handled as a solid having crystallinity and has excellent handling properties, so it is very useful.
  • crystals of 10,10'-bis(ethoxycarbonylmethoxy)-9,9'-biphenanthrile can be handled as a solid with crystallinity, and have excellent handling properties and low hygroscopicity and storage stability. Excellent and very useful.
  • the method for producing the biphenanthrene compound of the present invention has a high refractive index and is useful as a raw material for materials such as polyamide materials and curable materials, additives such as plasticizers and curing agents, and raw materials for various other chemical products. It is very useful because it can produce biphenanthrene compounds.
  • the method for producing crystals of 10,10'-bis(ethoxycarbonylmethoxy)-9,9'-biphenanthrile of the present invention comprises converting 10,10'-bis(ethoxycarbonylmethoxy)-9,9'-biphenanthrile into crystalline It is very useful because it can be handled as a solid having a .
  • Example 1 is a diagram showing a chart of powder X-ray diffraction (PXRD) measurement of the potassium salt of 10,10'-bis(carboxymethoxy)-9,9'-biphenanthrile obtained in Example 1.
  • Crystal ⁇ (crystal I) of 10,10′-bis(ethoxycarbonylmethoxy)-9,9′-biphenanthrile (compound represented by formula (1a-1-2)) obtained in Example 2 It is a figure which shows the chart of powder X-ray diffraction (PXRD) measurement. Difference between crystal I and (crystal ⁇ ) of 10,10′-bis(ethoxycarbonylmethoxy)-9,9′-biphenanthrile (compound represented by formula (1a-1-2)) obtained in Example 3 It is a figure which shows the chart of scanning calorimetry.
  • the biphenanthrene compound of the present invention is represented by general formula (1).
  • R 1 each independently represents an alkylene group having 1 to 4 carbon atoms
  • R 2 each independently represents an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, represents a group or a halogen atom
  • n each independently represents 0 or an integer of 1 to 4
  • R 3 each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a halogen atom having 2 to 4 carbon atoms.
  • the alkali metal salt of the biphenanthrene compound of the present invention is represented by general formula (1').
  • M each independently represents an alkali metal atom, and R 1 , R 2 , and n have the same definitions as in general formula (1).
  • R 1 in general formulas (1) and (1') each independently represents an alkylene group having 1 to 4 carbon atoms, and this alkylene group may be either linear or branched. Specific examples include methylene group, 1,1-ethylene group, 1,2-ethylene group, 1,2-propylene group, 1,3-propylene group, and 1,4-butylene group.
  • R 1 in general formulas (1) and (1') is preferably an alkylene group each independently having 1 or 2 carbon atoms, and a methylene group, a 1,1-ethylene group or a 1,2-ethylene group is preferable. More preferred are methylene groups or 1,2-ethylene groups, and particularly preferred are methylene groups.
  • R 2 in the general formulas (1) and (1') each independently represents an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 18 carbon atoms, or a halogen atom. Among these, an aryl group having 6 to 18 carbon atoms or a halogen atom is preferred.
  • R 2 is an alkyl group, in addition to linear or branched alkyl groups, cyclic alkyl groups having 5 to 6 carbon atoms are included, and among these, each group independently has 1 to 4 carbon atoms. Alkyl groups are preferred, alkyl groups each independently having 1 or 2 carbon atoms are more preferred, and methyl groups are particularly preferred.
  • R 2 is an aryl group, it is preferably an aryl group each independently having 6 to 12 carbon atoms, more preferably each independently having 6 to 8 carbon atoms, and particularly preferably a phenyl group.
  • R 2 is a halogen atom
  • examples of the halogen atom include a chlorine atom, a bromine atom, and an iodine atom.
  • n each independently represents 0 or an integer of 1 to 4. Among these, each independently is preferably 0, 1, or 2, each independently more preferably 0 or 1, and particularly preferably 0.
  • R 3 in the general formula (1) each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 4 carbon atoms.
  • R 3 is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. It is preferable from the viewpoint of solvent solubility that R 3 is an alkyl group having 1 to 6 carbon atoms.
  • R 3 is an alkyl group having 1 to 6 carbon atoms, it includes linear or branched alkyl groups as well as cyclic alkyl groups having 5 to 6 carbon atoms.
  • Alkyl groups having 1 to 4 carbon atoms are preferred, alkyl groups each independently having 1 or 2 carbon atoms are more preferred, and ethyl groups are particularly preferred.
  • R 3 is an alkenyl group having 2 to 4 carbon atoms, each independently is preferably an alkenyl group having 2 or 3 carbon atoms, and each independently is more preferably a vinyl group or an allyl group.
  • allyl group is particularly preferable.
  • M in general formula (1') each independently represents an alkali metal atom.
  • M is each independently preferably lithium, sodium, or potassium, each independently more preferably sodium or potassium, and even more preferably potassium.
  • the biphenanthrene compound of the present invention has the formula (1a) as a 9,9'-biphenanthrene compound. expressed. (In the formula, R 1 , R 2 , R 3 , and n have the same definitions as in general formula (1).)
  • biphenanthrene compounds of the present invention represented by general formula ( 1a )
  • the general formula ( A biphenanthrene compound represented by 1a-1) is preferred.
  • R 1 , R 2 , R 3 , and n have the same definitions as in general formula (1).
  • biphenanthrene compounds of the present invention represented by general formula (1a-1), preferred compounds are shown below.
  • Examples of the biphenanthrene compound of the present invention represented by the general formula (1b) include the compound groups (1b-1) to (1b-4). (1b-1) 1,1'-biphenanthrene compound (1b-2) 2,2'-biphenanthrene compound
  • the biphenanthrene compound of the present invention represented by general formula (1) is preferably a biphenanthrene compound represented by formula (1a), and more preferably a biphenanthrene compound represented by formula (1a-1).
  • crystals of 10,10'-bis(carboxymethoxy)-9,9'-biphenanthrile which is a compound represented by formula (1a-1-1) are solids having crystallinity. It is very useful because it can be handled as In powder X-ray diffraction peak patterns using Cu-K ⁇ rays, such crystals have diffraction angles 2 ⁇ of 9.9 ⁇ 0.2°, 13.8 ⁇ 0.2°, 20.0 ⁇ 0.2°, and 20.7. It has characteristic diffraction peaks at ⁇ 0.2°, 22.0 ⁇ 0.2° and 22.4 ⁇ 0.2°.
  • crystals of 10,10'-bis(ethoxycarbonylmethoxy)-9,9'-biphenanthrile which is a compound represented by formula (1a-1-2) have crystallinity. It is very useful because it can be handled as a solid and has excellent handling properties, and has low hygroscopicity and excellent storage stability.
  • ⁇ Crystal ⁇ of 10,10'-bis(ethoxycarbonylmethoxy)-9,9'-biphenanthrile As one embodiment of the crystal of 10,10'-bis(ethoxycarbonylmethoxy)-9,9'-biphenanthrile, which is a compound represented by formula (1a-1-2), powder X-ray diffraction using Cu-K ⁇ rays was performed. In the peak pattern, characteristic diffraction peaks were found at diffraction angles 2 ⁇ of 10.8 ⁇ 0.2°, 17.5 ⁇ 0.2°, 21.7 ⁇ 0.2° and 23.0 ⁇ 0.2°.
  • crystals that have This crystal further has diffraction peaks at diffraction angles 2 ⁇ of 12.3 ⁇ 0.2°, 15.0 ⁇ 0.2°, 20.0 ⁇ 0.2° and 20.8 ⁇ 0.2°. is preferred. It is preferable that these diffraction peaks have a relative integrated intensity of 10 or more based on the peak with the highest integrated intensity. Since the integrated intensity may vary, the crystalline phase can be identified based on the analysis method of normal powder X-ray diffraction analysis. Hereinafter, such a crystal may be referred to as "crystal ⁇ ".
  • the onset temperature of the endothermic peak of this crystal ⁇ by differential scanning calorimetry is preferably in the range of 153 to 162°C, more preferably in the range of 154 to 160°C, and more preferably in the range of 155 to 159°C. It is particularly preferable.
  • the onset temperature of an endothermic peak measured by differential scanning calorimetry (DSC) is sometimes referred to as the melting point.
  • ⁇ Crystal I of 10,10'-bis(ethoxycarbonylmethoxy)-9,9'-biphenanthrile Another aspect of the crystal of 10,10'-bis(ethoxycarbonylmethoxy)-9,9'-biphenanthrile, which is a compound represented by formula (1a-1-2), is that the endothermic peak is determined by differential scanning calorimetry.
  • such a crystal may be referred to as "crystal I”.
  • the onset temperature of an endothermic peak determined by differential scanning calorimetry (DSC) may be referred to as a melting point.
  • crystals that have This crystal preferably has peaks at diffraction angles 2 ⁇ of 6.0 ⁇ 0.2° and 11.9 ⁇ 0.2°, and further has peaks at diffraction angles 2 ⁇ of 9.7 ⁇ 0.2° and 19. It is more preferable to have peaks at 7 ⁇ 0.2° and 22.4 ⁇ 0.2°. It is preferable that these diffraction peaks have a relative integrated intensity of 10 or more based on the peak with the highest integrated intensity. Since the integrated intensity may vary, the crystalline phase can be identified based on the analysis method of normal powder X-ray diffraction analysis. Hereinafter, such a crystal may be referred to as "crystal ⁇ ".
  • the onset temperature of the endothermic peak determined by differential scanning calorimetry is preferably in the range of 160 to 170°C, more preferably in the range of 164 to 170°C, and more preferably in the range of 165 to 170°C. It is particularly preferable.
  • the onset temperature of an endothermic peak measured by differential scanning calorimetry (DSC) is sometimes referred to as the melting point.
  • Crystal of 10,10'-bis(ethoxycarbonylmethoxy)-9,9'-biphenanthrile II Another aspect of the crystal of 10,10'-bis(ethoxycarbonylmethoxy)-9,9'-biphenanthrile, which is a compound represented by formula (1a-1-2), is that the endothermic peak is determined by differential scanning calorimetry.
  • the endothermic peak is determined by differential scanning calorimetry.
  • crystals whose set temperature is in the range of 160 to 170°C. This onset temperature is preferably in the range 164-170°C, particularly preferably in the range 165-170°C.
  • crystal II Such a crystal may be referred to as "crystal II”.
  • the onset temperature of an endothermic peak measured by differential scanning calorimetry (DSC) is sometimes referred to as the melting point.
  • Crystals (crystal ⁇ , crystal I, crystal ⁇ and crystal II) of 10,10'-bis(ethoxycarbonylmethoxy)-9,9'-biphenanthrile, which is a compound represented by formula (1a-1-2), are:
  • the purity by high performance liquid chromatography is preferably 95.0% or more, more preferably 98.0% or more, even more preferably 98.5% or more, and 99.0% or more. It is particularly preferable.
  • Crystals (crystal ⁇ , crystal I, crystal ⁇ and crystal II) of 10,10'-bis(ethoxycarbonylmethoxy)-9,9'-biphenanthrile, which is a compound represented by formula (1a-1-2), are:
  • the hue measured in a tetrahydrofuran solution with a concentration of 10% by weight of the crystal is preferably APHA 250 or less, more preferably APHA 150 or less, even more preferably APHA 100 or less, and APHA 50 or less. Particularly preferred.
  • the potassium salt crystal of 10,10'-bis(carboxymethoxy)-9,9'-biphenanthrile which is a compound represented by formula (1a-1-1)
  • Such crystals have diffraction angles 2 ⁇ of 5.4 ⁇ 0.2°, 10.4 ⁇ 0.2°, 13.4 ⁇ 0.2°, and 17.4 in powder X-ray diffraction peak patterns using Cu-K ⁇ rays. It has characteristic diffraction peaks at ⁇ 0.2°, 20.0 ⁇ 0.2° and 22.0 ⁇ 0.2°.
  • biphenanthrene compound represented by general formula (1) in the present invention there are no particular restrictions on the starting materials and manufacturing method for its production.
  • the biphenanthrene compound represented by the general formula (2) it is preferable to use biphenanthrols represented by the general formula (2) as raw materials, and among them, the biphenanthrene compound represented by the general formula (2a) is preferably used as a raw material. More preferably, they are rolls, and even more preferably biphenanthrols represented by the general formula (2a-1).
  • R 2 and n have the same definition as in general formula (1).
  • R 2 and n have the same definition as in general formula (1).
  • the formula, R 2 and n have the same definition as in general formula (1).
  • the method for producing the biphenanthrene compound represented by the general formula (1) includes, for example, biphenanthrols represented by the general formula (2) and halogenated carboxylic acids represented by the general formula (3).
  • Examples include a method of obtaining a compound represented by general formula (1) by an etherification reaction in which the following compounds are reacted under alkaline conditions.
  • the target compound, a compound represented by general formula (1) is produced by an etherification reaction of one molecule of a halogenated carboxylic acid represented by general formula (3) with a biphenanthrol represented by general formula (2).
  • the monoetherified product is produced as an intermediate, and the monoetherified product undergoes an etherification reaction with another molecule of halogenated carboxylic acid represented by the general formula (3).
  • a method for obtaining a compound represented by general formula (1'), that is, an alkali metal salt, by alkaline hydrolysis or neutralization of the compound represented by general formula (1) with an alkali metal hydroxide is mentioned.
  • the compound represented by the general formula (1') By protonating the compound represented by the general formula (1') using an acid, the compound represented by the general formula (1''), which corresponds to the case where R 3 in the general formula (1) is a hydrogen atom, is obtained. Examples include methods for obtaining dicarboxylic acid compounds.
  • R 1 , R 2 , n, and R 3 have the same definitions as in general formula (1)
  • M has the same definition as in general formula (1')
  • X represents a halogen atom
  • MOH represents an alkali metal hydroxide (means something.)
  • 9,9'-biphenanthrene-10,10'-diol which is a biphenanthrole represented by the general formula (2), and ethyl chloroacetate, which is a halogenated carboxylic acid represented by the general formula (3).
  • the reaction formula of the etherification reaction is shown to obtain the compound represented by the formula (1a-1-2), which is the biphenanthrene compound represented by the general formula (1).
  • a potassium salt among alkali metal salts is obtained by using a compound represented by formula (1a-1-2) as a compound represented by general formula (1) and potassium hydroxide as an alkali metal hydroxide.
  • the reaction formula is shown below.
  • the obtained potassium salt is converted into a dicarboxylic acid compound represented by the general formula (1'') corresponding to the case where R 3 is a hydrogen atom in the general formula (1).
  • the reaction formula for obtaining 1-1) is shown below.
  • Biphenanthrols In the production of the biphenanthrene compound of the present invention represented by general formula (1), biphenanthrols represented by general formula (2) are used. (In the formula, R 2 and n have the same definition as in general formula (1).) Biphenanthrols represented by general formula (2) can be produced, for example, by the production method described in JP-A-2001-039898. The biphenanthrene skeleton-containing dihydroxy compound of the present invention represented by general formula (1a-1) can be produced using biphenanthrols represented by general formula (2a-1) as raw materials. (In the formula, R 2 and n have the same definition as in general formula (1).)
  • Examples of the biphenanthrols represented by the general formula (2a-1) include 10,10'-dihydroxy-9,9'-biphenanthrile (CAS registration number: 110071-78-8). This compound can be produced, for example, by the method described in JP-A-60-181043, Journal of American Chemical Society, 2008, 130, 6840, and the like. In addition, 10,10'-dihydroxy-6,6'-diphenyl-9,9'-biphenanthryl (CAS registration number: 1564249-14-4), 10,10'-dihydroxy-6,6'-dibromo-9, 9′-biphenanthryl (CAS registration number: 1564249-12-2) is mentioned, and these compounds are described in Tetrahedron, 70, 1786-1793 (2014).
  • the biphenanthrene skeleton-containing dihydroxy compound of the present invention represented by the general formula (1b) can be produced using a biphenanthrole represented by the general formula (2b) as a raw material.
  • Examples of the biphenanthrols represented by the general formula (2b) include the following compounds. Mention may be made of 2,2'-dihydroxy-1,1'-biphenanthryl (CAS Registration Number: 196865-17-5), which compound is described in Chinese Patent Application No. 103787837. 1,1'-dihydroxy-3,3'-diphenyl-2,2'-biphenanthryl (CAS registration number: 1624364-17-5), and these compounds are described in Catalysis Science & Technology, 4, 4406-4415 (2014). It is described in.
  • Examples include 1,1'-dihydroxy-2,2'-biphenanthryl, 1,1'-dihydroxy-3,3'-biphenanthryl, and 2,2'-dihydroxy-3,3'-biphenanthryl.
  • 2,2'-dihydroxy-4,4'-diphenyl-3,3'-biphenanthryl (CAS registration number: 1793116-18-3) is mentioned, and this compound is described in Chemical Communications (Cambridge, United Kingdom), 51, 10498-10501 (2015).
  • Mention may be made of 4,4'-dihydroxy-3,3'-biphenanthryl (CAS Registration Number: 2376151-04-9), which compound is described in Chinese Patent Application No. 109336887.
  • halogenated carboxylic acids represented by the general formula (3) to be reacted with biphenanthrols
  • Halogenated alkyl acetate such as isobutyl acetate, tert-butyl chloroacetate, methyl bromoacetate, ethyl bromoacetate, n-propyl bromoacetate, isopropyl bromoacetate, n-butyl bromoacetate, isobutyl bromoacetate, tert-butyl bromoacetate
  • chloro Halogenated alkenyl acetates such as vinyl acetate, allyl chloroacetate, vinyl bromoacetate, allyl bromoacetate
  • halogenated alkenyl acetates such as vinyl acetate, ally
  • halogenated alkyl acetate or halogenated alkenyl acetate is preferred, methyl chloroacetate, ethyl chloroacetate, methyl bromoacetate, ethyl bromoacetate, vinyl chloroacetate, allyl chloroacetate are more preferred, and methyl chloroacetate, ethyl chloroacetate, bromoethyl acetate are more preferred.
  • Methyl acetate and ethyl bromoacetate are more preferred, and methyl chloroacetate and ethyl chloroacetate are particularly preferred.
  • the molar ratio of halogenated carboxylic acids to biphenanthrols is not particularly limited as long as it is at least the theoretical value (2.0), but it is usually in the range of 2 to 20 times the molar amount, preferably 2 to 20 times the molar amount. It is used in a range of 10 times the molar amount, more preferably in a range of 2 to 6 times the molar amount.
  • the reaction is carried out in the presence of a base, and examples of the base used include triethylamine, pyridine, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, and the like.
  • the molar ratio of the base to be charged is usually 0.8 to 4 times the molar amount, preferably 0.85 to 3 times the molar amount, more preferably 0.9 to 2 times the molar amount of the halogenated carboxylic acid. Amount range.
  • catalysts may be used, such as alkali metal bromide salts such as sodium bromide and potassium bromide, alkali metal iodide salts such as sodium iodide and potassium iodide, ammonium bromide and ammonium iodide, etc. can be mentioned.
  • the amount of the catalyst used is usually in the range of 0.1 to 100% by weight, preferably in the range of 0.1 to 20% by weight, and more preferably in the range of 0.1 to 10% by weight, based on the biphenanthrols. be.
  • the reaction temperature is usually in the range of 25 to 120°C, preferably in the range of 40 to 100°C, more preferably in the range of 50 to 90°C, particularly preferably in the range of 60 to 80°C. If the reaction temperature is high, the yield will decrease, and if the reaction temperature is low, the reaction rate will be slow, which is not preferable.
  • reaction pressure there is no restriction on the reaction pressure, and the reaction may be carried out under normal pressure, reduced pressure, or increased pressure. Normal pressure or reduced pressure is preferred.
  • the reaction under pressure the reaction can be carried out in a pressurized state in which, for example, a gas inert to the reaction, such as nitrogen, is passed. By doing so, the carbon dioxide gas generated from the carbonate or hydrogen carbonate used in the reaction can be discharged out of the reaction system, thereby promoting the reaction. From the viewpoint of shortening the reaction time, it is more preferable to perform the reaction under reduced pressure.
  • the reaction under reduced pressure By conducting the reaction under reduced pressure, the carbon dioxide gas generated from the carbonate or hydrogen carbonate used in the reaction can be discharged out of the reaction system, so the reaction is accelerated and is faster than the reaction under normal pressure.
  • the reaction pressure is preferably in a range of 5 kPa or more and 80 kPa or less, more preferably 10 kPa or more and 80 kPa or less, and even more preferably 30 kPa or more and 60 kPa or less.
  • the reaction pressure can be reduced by a pressure reducing device, and if the reaction pressure is maintained within the above range, the pressure reducing device may be operated intermittently or continuously, but it cannot be operated continuously. More preferred.
  • the reaction solvent is not particularly limited as long as it cannot be distilled out from the reaction vessel at the reaction temperature and is inert to the reaction, but examples include acetone, ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, tetrahydrofuran, and 1,4- Ethers such as dioxane, 1,3-dioxane, diethoxyethane, aprotic polar solvents such as acetonitrile, dimethylsulfoxide, dimethylformamide, N-methylpyrrolidone, aromatic hydrocarbon solvents such as toluene, xylene, mesitylene, etc.
  • organic solvents may be used alone or in combination of two or more to adjust polarity.
  • ketone solvents having 3 to 9 carbon atoms such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, and cyclooctanone, or acetonitrile, dimethyl sulfoxide, dimethyl formamide, N-methyl pyrrolidone, etc.
  • Aprotic polar solvents are preferred, ketone solvents having 3 to 8 carbon atoms or acetonitrile are more preferred, ketone solvents having 3 to 6 carbon atoms or acetonitrile are even more preferred, and methyl isobutyl ketone is particularly preferred.
  • methyl isobutyl ketone is used as a reaction solvent, it is also preferable because water washing can be performed to remove water-soluble impurities such as salts.
  • the amount of solvent used is not particularly limited as long as it does not interfere with the reaction, but it is usually preferably used in a range of 1 to 7 times the weight of the biphenanthrols, more preferably 2 to 4 times the weight of the biphenanthrols.
  • the amount of solvent to be used is preferably 1.5 to 10 times the weight of the biphenanthrols; It is more preferable to use the amount in a range of 8 times by weight, and even more preferably in a range of 2 to 6 times by weight.
  • the amount of distillation per hour during the reaction by distilling the solvent out of the reaction system is preferably in the range of 0.05 to 1.5 times the weight of the biphenanthrols;
  • the range of 1 to 1.0 times by weight is more preferable, the range of 0.3 to 1.0 times by weight is even more preferable, and the range of 0.3 to 0.8 times by weight is particularly preferable.
  • the amount of distillation per hour may vary within the above range, or the amount of distillation may temporarily exceed the upper or lower limit of the above range.
  • the end point of the reaction can be confirmed by liquid chromatography or gas chromatography analysis. It is hardly seen at the time when unreacted biphenanthrols disappear and no increase in the target product is observed, or after unreacted biphenanthrols disappear and a monoetherified product, which is a reaction intermediate, is generated. It is preferable that the end point of the reaction is the point at which the amount disappears. Regarding the point at which the monoetherified product, which is a reaction intermediate, is almost no longer seen after being produced, specifically, the point at which it becomes 1.5 area% or less in the above analysis of the monoetherified product, more preferably 1.0 area. % or less, more preferably 0.8 area % or less, particularly preferably 0.5 area % or less.
  • the reaction time varies depending on the reaction conditions such as reaction temperature, but it is usually completed in about 1 to 30 hours.
  • the water content of the reaction solution in the etherification reaction is preferably in the range of 0.01% by weight or more and 2.0% by weight or less based on the biphenanthrols. be.
  • the amount of water in the reaction solution within the above range the biphenanthrene compound of the present invention can be produced with a good reaction yield.
  • the upper limit of this moisture content is more preferably 1.5% by weight or less, even more preferably 1.0% by weight or less, and particularly preferably 0.5% by weight or less.
  • methods for controlling the water content of the reaction solution within this range include a method of using previously dehydrated raw materials and solvents, and a method of removing water by distillation before the etherification reaction.
  • the biphenanthrene compound represented by general formula (1) is an ester compound
  • the etherification reaction neutralization, water washing, crystallization, filtration, distillation, column chromatography, etc.
  • Purification and isolation can be achieved by performing post-processing operations such as separation.
  • purification by distillation, recrystallization, or column chromatography may be performed according to conventional methods.
  • the reaction product mixture is preferably neutralized and washed with water, and then a crystallization operation is performed.
  • crystal I and crystal ⁇ of 10,10'-bis(ethoxycarbonylmethoxy)-9,9'-biphenanthrile which is a compound represented by formula (1a-1-2)
  • the manufacturing method is selected from 10,10'-bis(ethoxycarbonylmethoxy)-9,9'-biphenanthrile, an aromatic hydrocarbon solvent having 6 to 9 carbon atoms, and a ketone solvent having 3 to 9 carbon atoms.
  • aromatic hydrocarbon solvent having 6 to 9 carbon atoms include benzene, toluene, xylene, and mesitylene, and aromatic hydrocarbon solvents having 7 to 9 carbon atoms are preferable. 7 or 8 aromatic hydrocarbon solvents are more preferred, and toluene is particularly preferred.
  • ketone solvents having 3 to 9 carbon atoms include linear ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and methyl isoamyl ketone, and cyclic ketone solvents such as cyclopentanone, cyclohexanone, cycloheptanone, and isophorone. Examples include ketone solvents. Among these, chain ketone solvents having 3 to 9 carbon atoms are preferred, chain ketone solvents having 3 to 6 carbon atoms are more preferred, and acetone or methyl isobutyl ketone is particularly preferred.
  • the amount of the organic solvent used can be adjusted as appropriate in consideration of the solubility depending on the type of organic solvent used, but the amount of the compound represented by formula (1a-1-2) is 0. .5 to 10 times by weight, more preferably 1 to 8 times by weight, even more preferably 1 to 6 times by weight, and even more preferably 1.5 to 4 times by weight. Particularly preferred.
  • the temperature at which the compound represented by formula (1a-1-2) is dissolved in an organic solvent to form a solution can be adjusted as appropriate in consideration of the type of organic solvent used, but is within the range of 40 to 90°C. It is.
  • Examples of the poor solvent used when crystals are precipitated by mixing a poor solvent include water, an alcohol solvent having 1 to 4 carbon atoms, and an aliphatic hydrocarbon solvent having 5 to 8 carbon atoms.
  • the poor solvent to be mixed is at least one selected from these, and it is preferable to select one from among these.
  • Specific examples of alcohol solvents having 1 to 4 carbon atoms include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, etc. Alcohol solvents having 1 to 3 carbon atoms are preferred; Alcohol solvents having 1 or 2 carbon atoms are more preferred, and methanol is particularly preferred.
  • Examples of the aliphatic hydrocarbon solvent having 5 to 8 carbon atoms include, for example, chain aliphatic hydrocarbon solvents having 5 to 8 carbon atoms such as pentane, hexane, heptane, octane, and isooctane, and cyclopentane.
  • Examples include cyclic aliphatic hydrocarbon solvents having 5 to 8 carbon atoms such as cyclohexane, cycloheptane, and the like.
  • chain aliphatic hydrocarbon solvents having 5 to 8 carbon atoms are preferred, chain aliphatic hydrocarbon solvents having 6 to 8 carbon atoms are more preferred, and chain aliphatic hydrocarbon solvents having 7 carbon atoms are preferred.
  • Hydrocarbon solvents are more preferred, with normal heptane being particularly preferred.
  • the amount of the poor solvent used should be adjusted as appropriate, taking into account the amount of solution of the compound represented by formula (1a-1-2), the type of organic solvent, and the solubility depending on the type of poor solvent used.
  • the amount of the compound represented by formula (1a-1-2) is in the range of 0.5 to 10 times by weight, more preferably 1 to 8 times by weight, and 1 It is more preferably in the range of ⁇ 6 times by weight, and particularly preferably from 1.5 to 4 times by weight.
  • the temperature at which crystals of the compound represented by formula (1a-1-2) are precipitated by the operation of mixing a poor solvent is not particularly limited, but is in the range of 20 to 85°C.
  • the poor solvent used when crystals are precipitated by the operation of mixing the poor solvents described above may be mixed.
  • the temperature at which the solution of the compound represented by formula (1a-1-2) is cooled to precipitate crystals is from the temperature at which it is dissolved to form a solution, and is not particularly limited; The temperature range is 80°C.
  • seed crystals do not need to be used when crystals are precipitated, it is preferable to use seed crystals.
  • crystal II and crystal ⁇ of 10,10'-bis(ethoxycarbonylmethoxy)-9,9'-biphenanthrile which is a compound represented by formula (1a-1-2)
  • a method for producing it is to heat crystals of 10,10'-bis(ethoxycarbonylmethoxy)-9,9'-biphenanthrile to a temperature of 150° C. or higher and 165° C. or lower to melt the crystal, and then cool it.
  • the crystals of 10,10'-bis(ethoxycarbonylmethoxy)-9,9'-biphenanthrile used are preferably Crystal I and Crystal ⁇ .
  • the purity by high performance liquid chromatography is preferably 95.0% or more, more preferably 98.0% or more, even more preferably 98.5% or more, and 99.0% or more. It is particularly preferable.
  • the temperature range during heating is preferably 150°C or more and 163°C or less, more preferably 150°C or more and 160°C or less.
  • the cooling temperature is not particularly limited as long as it crystallizes and becomes solid, and may be cooled to room temperature. When melting by heating, it is preferable that the 10,10'-bis(ethoxycarbonylmethoxy)-9,9'-biphenanthrile crystals do not remain unmelted.
  • the alkali metal salt of the biphenanthrene compound represented by the general formula (1') of the present invention can be prepared by performing post-reaction treatments such as neutralization and water washing after the completion of the above etherification reaction, and purifying the obtained ester compound.
  • the alkali metal salt of the biphenanthrene compound represented by the general formula (1') can be obtained by subjecting the crude product to alkaline hydrolysis.
  • the alkaline compound used in alkaline hydrolysis is not particularly limited, but preferably is an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, and is usually prepared as an aqueous solution with a concentration of 12 to 60% by weight. used.
  • such an alkali compound is usually used in an amount of 2 mol or more, preferably in the range of 2.1 to 10 mol, per 1 mol of the ester compound of the biphenanthrene compound represented by the general formula (1).
  • water is used as a reaction solvent in the hydrolysis reaction, but if necessary, organic solvents such as alcohols and ketones that are miscible with water in any proportion, or mixtures of such organic solvents and water may be used. Solvents are also used. It is also possible to continue to use the reaction solvent used in the etherification reaction, such as methyl isobutyl ketone or acetonitrile.
  • the reaction temperature for hydrolysis is usually in the range of 30 to 100°C, preferably in the range of 50 to 90°C, and under such reaction conditions, the reaction is usually completed in about 1 to 5 hours.
  • crystals of potassium salt of 10,10'-bis(carboxymethoxy)-9,9'-biphenanthrile which is a compound represented by formula (1a-1-1)
  • It can be produced by, for example, using potassium hydroxide as the alkaline compound used in the hydrolysis and precipitating crystals of the potassium salt by the method described above.
  • the ester compound obtained by the etherification reaction is subjected to alkaline hydration. It can be obtained by decomposing the reaction solution and making it acidic using a strong acid such as hydrochloric acid. This method is preferable in order to obtain a highly pure carboxylic acid compound. It can be purified and isolated by performing post-treatment operations such as neutralization, water washing, crystallization, filtration, distillation, and separation by column chromatography according to conventional methods.
  • a suitable production method is one in which a carboxylic acid salt is once extracted from a reaction mixture obtained by alkaline hydrolysis of the ester compound obtained by the method, and a carboxylic acid compound is obtained using this carboxylic acid salt and an acid.
  • the crystals of 10,10'-bis(carboxymethoxy)-9,9'-biphenanthrile, which is a compound represented by formula (1a-1-1) are crystallized. It can be manufactured by performing post-processing operations.
  • a solvent selected from 10,10'-bis(carboxymethoxy)-9,9'-biphenanthrile, an aromatic hydrocarbon solvent having 6 to 9 carbon atoms, and a ketone solvent having 3 to 9 carbon atoms.
  • the solvent is preferably a ketone solvent having 3 to 9 carbon atoms, more preferably a chain ketone solvent having 3 to 9 carbon atoms, even more preferably a chain ketone solvent having 3 to 6 carbon atoms, and acetone. or methyl isobutyl ketone is particularly preferred.
  • the operations for precipitating crystals include mixing a poor solvent in which the compound represented by formula (1a-1-1) has low solubility, cooling the solution, and removing the solvent of the solution by distillation. can do.
  • Each process such as reaction, alkaline hydrolysis, neutralization, water washing, crystallization, filtration, distillation, separation by column chromatography, drying, packaging, melting, cooling, etc., is free from oxidation, deterioration, coloring, etc. due to the influence of oxygen.
  • an inert gas such as nitrogen or argon, or under an atmosphere containing less oxygen than air.
  • NMR analysis Measuring device Fourier transform nuclear magnetic resonance AVANCE III HD 400 (manufactured by BRUKER) The measurement sample was dissolved in deuterated dimethyl sulfoxide, and the 1 H-NMR spectrum was measured. 3. Melting point 3 mg of the crystals obtained in Examples was weighed into an aluminum pan, and the melting point was measured using a differential scanning calorimeter (DSC7020, manufactured by Hitachi High-Tech Science Co., Ltd.) under the following operating conditions using aluminum oxide as a control. The onset temperature of the endothermic peak measured by differential scanning calorimetry (DSC) was defined as the melting point.
  • DSC7020 differential scanning calorimeter
  • Temperature increase rate 10°C/min Measurement temperature range: 30-400°C Measurement atmosphere: open, nitrogen 50mL/min 4.
  • Refractive index measuring device Refractometer (manufactured by Kyoto Electronics Industry Co., Ltd.: RA-500) Tetrahydrofuran solutions (concentrations of 20%, 15%, and 10% solutions) of measurement samples were prepared, and the refractive index was measured using a refractometer. From the obtained results, the relationship between concentration and refractive index was derived, and the value at 100% concentration was calculated by extrapolation, and this value was taken as the refractive index of the measurement sample. 5.
  • Powder X-ray diffraction method (PXRD) 0.1 g of the compound obtained in the example was filled into the sample filling part of a glass test plate, and the measurement was performed using the following apparatus and the following conditions.
  • [Measurement condition] X-ray source: CuK ⁇ Tube voltage: 40kV Tube current: 15mA Scan axis: 2 ⁇ / ⁇ Mode: Continuous Measurement range: 2 ⁇ 5° to 90° Step: 0.03° Speed measurement time: 1.0°/min Entrance slit: 0.25° Light receiving slit: 13.00mm 6.
  • Hue A tetrahydrofuran solution having a concentration of 10% by weight of the obtained target product was prepared, and the hue of the solution was measured using the following device to evaluate the hue of the obtained target product.
  • Equipment Color difference meter (manufactured by Nippon Denshoku Kogyo Co., Ltd., ZE6000) Cell used: Glass test tube (diameter 24mm)
  • Example 1 Production of 10,10'-bis(carboxymethoxy)-9,9'-biphenanthrile (compound represented by formula (1a-1-1)) 9,9'-binaphthalene-10,10'-diol 50 g, acetonitrile 152 g of potassium carbonate, 44 g of potassium carbonate, and 5.1 g of potassium iodide were placed in a four-necked flask, heated to 70°C, and stirred at the same temperature for 1 hour. While maintaining the temperature of the reaction solution at 70 to 80°C, 44.8 g of ethyl chloroacetate was added dropwise.
  • the obtained compound was determined by liquid chromatography mass spectrometry and 1 H-NMR analysis to be a compound represented by 10,10'-bis(carboxymethoxy)-9,9'-biphenanthrile (formula (1a-1-1)). ) was revealed.
  • Liquid chromatography mass spectrometry (mass spectrometry/electrospray ionization): mass 501.5 (MH)
  • 1 H-NMR analysis 400 MHz, solvent: heavy DMSO) ⁇ ⁇ ppm>: 4.08 (d, 2H), 4.37 (d, 2H), 7.15 (dd, 2H), 7.41 (ddd , 2H), 7.65 (ddd, 2H), 7,79 (ddd, 2H) 7,86 (ddd, 2H), 8.45 (dd, 2H), 8.99 (dd, 2H), 12. 4(s, 2H).
  • a PXRD measurement chart of the obtained target object is shown in FIG. It was revealed from the peak pattern that the solid of the target compound was a crystalline substance.
  • Example 2 30.1 g (0.08 mol) of 9,9'-biphenanthrene-10,10'-diol, 75.4 g of methyl isobutyl ketone, 22.6 g of potassium carbonate, and 1.7 g of potassium iodide were placed in a four-necked flask. , nitrogen substitution was performed. Thereafter, the temperature was raised to 100° C., and 28.4 g of methyl isobutyl ketone was distilled out under reduced pressure. Thereafter, 24.0 g (0.20 mol) of ethyl chloroacetate was added over 1 hour while maintaining the temperature of the reaction solution at 90°C. Thereafter, the temperature inside the flask was maintained at 90° C.
  • the amount of the target compound contained in the reaction solution was 96.0%, and the amount of the monoetherified product, which was a reaction intermediate, was 0.3%.
  • 45 g of methyl isobutyl ketone and 120 g of water were added while maintaining the temperature at 70°C, and after washing with water at 80°C, the aqueous layer was extracted.
  • 32 g of water was added, water washing was performed at 80°C, and the aqueous layer was extracted. Thereafter, the liquid temperature was raised to 87° C., and 92 g of normal heptane was added over 0.5 hours.
  • the liquid temperature during the addition of normal heptane was 75-82°C, and solid precipitation occurred.
  • the mixture was cooled from 80° C. to 25° C., and after continued cooling and stirring at 25° C. overnight, the solid matter was filtered off.
  • the solid matter separated by filtration was washed with 16 g of normal heptane.
  • 184 g of methyl isobutyl ketone was added to 42.6 g of the obtained solid, and the temperature was raised to 86° C. to dissolve it. Thereafter, 100 g of water was added and the mixture was washed with water at 80 to 85°C, and the aqueous layer was extracted. This operation was repeated once.
  • DSC Differential scanning calorimetry
  • Example 3 Production of 10,10'-bis(ethoxycarbonylmethoxy)-9,9'-biphenanthryl (compound represented by formula (1a-1-2)) 9,9'-biphenanthrene-10,10'-diol 300 .0g (0.78 mol), 750.0g of methyl isobutyl ketone, 225.3g of potassium carbonate, and 15.0g of potassium iodide were placed in a four-necked flask, and the atmosphere was replaced with nitrogen. Thereafter, the temperature was raised to 90° C. to 100° C., and 300.0 g of the liquid in the flask was distilled out under reduced pressure using a vacuum pump.
  • the liquid temperature during the addition of normal heptane was between 75 and 82°C, and solid precipitation occurred.
  • the mixture was cooled from 80° C. to 25° C., and after continued cooling and stirring at 25° C. overnight, the solid matter was filtered off.
  • the solid matter separated by filtration was washed with 150.0 g of normal heptane. 423.7 g of the obtained solid, 1483 g of methyl isobutyl ketone, and 220.0 g of water were placed in a four-necked flask, and the mixture was heated to 86° C. to dissolve.
  • the prepared solution was filtered using filter paper (No. 5C) to remove insoluble matter.
  • the melting point of the obtained target product according to the above analysis method was 159°C.
  • Differential scanning calorimetry (DSC) data is shown in FIG.
  • the results of this analysis revealed that the target product obtained was Crystal I.
  • a PXRD measurement chart of the obtained target object is shown in FIG.
  • the target compound obtained from the peak pattern was found to be crystal ⁇ .
  • the diffraction angle 2 ⁇ (°) of the diffraction peak that appeared the relative integrated intensity based on the peak with the strongest integrated intensity, and the relative intensity based on the peak with the strongest intensity, extract peaks with relative integrated intensity of 10 or more.
  • Table 4 The results are shown in Table 4.
  • Example 4 Production of 10,10'-bis(ethoxycarbonylmethoxy)-9,9'-biphenanthryl (compound represented by formula (1a-1-2)) 9,9'-biphenanthrene-10,10'-diol 100 .0 g (0.26 mol), 250.0 g of methyl isobutyl ketone, 75.1 g of potassium carbonate, and 5.0 g of potassium iodide were placed in a four-necked flask, and the atmosphere was replaced with nitrogen. Thereafter, the temperature was raised to 90° C. to 100° C., and 97.9 g of the liquid in the flask was distilled out under reduced pressure using a vacuum pump.
  • Example 5 3.5 g of the solid obtained in the first filtration operation in Example 4 and 20.1 g of acetone were placed in a 100 ml test tube and heated to 53° C. to dissolve. Then, 7.0 g of water was slowly added. The liquid temperature during water addition was 45 to 53°C, and solids precipitated during the addition. After the addition of water was completed, the liquid was cooled to 34° C., and the precipitated solid matter was filtered off. The solid matter separated by filtration was washed with water. The filtered solid was dried at 60° C. under reduced pressure to obtain 10,10′-bis(ethoxycarbonylmethoxy)-9,9′-biphenanthrile (compound represented by formula (1a-1-2)).
  • Example 6 4.0 g of the solid obtained in the first filtration operation in Example 4 and 25.0 g of acetone were placed in a 100 mL test tube and heated to 53° C. to dissolve. Thereafter, the liquid was cooled to 34° C., and the solid matter precipitated during cooling was filtered off. The solid matter separated by filtration was washed with acetone. The filtered solid matter was dried at 60° C. under reduced pressure, and 10,10′-bis(ethoxycarbonylmethoxy)-9,9′-biphenanthrile (compound represented by formula (1a-1-2)) was dissolved in 1. I got 2g. The melting point of the obtained target product according to the above analysis method was 156°C.
  • the diffraction angle 2 ⁇ (°) of the diffraction peak that appeared the relative integrated intensity based on the peak with the strongest integrated intensity, and the relative intensity based on the peak with the strongest intensity, extract peaks with relative integrated intensity of 10 or more.
  • Example 7 8.2 g of the solid obtained in the first filtration operation in Example 4 and 10.0 g of toluene were placed in a 100 mL test tube and heated to 85° C. to dissolve. Thereafter, the liquid was cooled to 34° C., and the solid matter precipitated during cooling was filtered off. The solid matter separated by filtration was washed with toluene. The filtered solid was dried at 80° C. under reduced pressure to obtain 10,10'-bis(ethoxycarbonylmethoxy)-9,9'-biphenanthrile (compound represented by formula (1a-1-2)). I got 7g. The melting point of the obtained target product according to the above analysis method was 156°C.
  • the diffraction angle 2 ⁇ (°) of the diffraction peak that appeared the relative integrated intensity based on the peak with the strongest integrated intensity, and the relative intensity based on the peak with the strongest intensity, extract peaks with relative integrated intensity of 10 or more.
  • Example 8 5.0 g of the solid obtained in the first filtration operation in Example 4 and 10.1 g of toluene were placed in a 100 mL test tube and heated to 85° C. to dissolve. Then, 10.4 g of methanol was slowly added. The liquid temperature during methanol addition was 53 to 57°C. Thereafter, the liquid was cooled to 34° C., and the solid matter precipitated during cooling was filtered off. The solid matter separated by filtration was washed with methanol. The filtered solid matter was dried at 80° C. under reduced pressure, and 10,10′-bis(ethoxycarbonylmethoxy)-9,9′-biphenanthrile (compound represented by formula (1a-1-2)) was obtained in 3.
  • Example 9 3.5 g of the solid obtained in the first filtration operation in Example 4 and 20.2 g of acetone were placed in a 100 mL test tube and heated to 53° C. to dissolve. Then, 7.3 g of normal heptane was slowly added. The liquid temperature during the addition of normal heptane was 46 to 53°C. Thereafter, the liquid was cooled to 34° C., and the solid matter precipitated during cooling was filtered off. The solid matter separated by filtration was washed with normal heptane. The filtered solid matter was dried at 60° C.
  • Example 10> 4.0 g of the solid obtained in the first filtration operation in Example 4 and 20.1 g of methyl isobutyl ketone were placed in a 100 mL test tube and heated to 80° C. to dissolve. Thereafter, the liquid was cooled to 34° C., and the solid matter precipitated during cooling was filtered off. The solid matter separated by filtration was washed with methyl isobutyl ketone. The filtered solid was dried at 80° C. under reduced pressure to obtain 10,10′-bis(ethoxycarbonylmethoxy)-9,9′-biphenanthrile (compound represented by formula (1a-1-2)). I got 1g. The melting point of the obtained target product according to the above analysis method was 156°C.
  • the diffraction angle 2 ⁇ (°) of the diffraction peak that appeared the relative integrated intensity based on the peak with the strongest integrated intensity, and the relative intensity based on the peak with the strongest intensity, extract peaks with relative integrated intensity of 10 or more.
  • Example 11 4.1 g of the solid obtained in the first filtration operation in Example 4 and 20.3 g of methyl isobutyl ketone were placed in a 100 mL test tube and heated to 80° C. to dissolve. Then, 8.1 g of methanol was slowly added. The liquid temperature during methanol addition was 55 to 62°C, and then the liquid was cooled to 34°C, and the solids precipitated during cooling were filtered off. The solid matter separated by filtration was washed with methanol. The filtered solid was dried at 80° C. under reduced pressure to obtain 10,10′-bis(ethoxycarbonylmethoxy)-9,9′-biphenanthrile (compound represented by formula (1a-1-2)).
  • the melting point of the obtained target product according to the above analysis method was 156°C.
  • the results of this analysis revealed that the target product obtained was Crystal I.
  • a PXRD measurement chart of the obtained target object is shown in FIG.
  • the target compound obtained from the peak pattern was found to be crystal ⁇ .
  • the relative integrated intensity based on the peak with the strongest integrated intensity, and the relative intensity based on the peak with the strongest intensity extract peaks with relative integrated intensity of 10 or more. The results are shown in Table 12.
  • Example 12 4.0 g of the crystals of 10,10'-bis(ethoxycarbonylmethoxy)-9,9'-biphenanthrile (compound represented by formula (1a-1-2)) obtained in Example 4 and methyl 18.0 g of isobutyl ketone was placed in a 100 mL test tube and heated to 82° C. to dissolve it. Thereafter, the mixture was rapidly cooled to 27°C in a 25°C water bath for 5 minutes, and the solid matter precipitated after cooling was filtered off. The solid matter separated by filtration was washed with methyl isobutyl ketone. The filtered solid matter was dried at 80° C.
  • Example 13 Production of crystal II and crystal ⁇ of 10,10'-bis(ethoxycarbonylmethoxy)-9,9'-biphenanthrile (compound represented by formula (1a-1-2)) 10 obtained in Example 5, 1.0 g of crystals (I ⁇ ) of 10'-bis(ethoxycarbonylmethoxy)-9,9'-biphenanthrile (compound represented by formula (1a-1-2)) was placed in a test tube, and heated using an aluminum block heater. The mixture was heated to 160°C and melted. Thereafter, it was cooled to 25°C. The melting point of the obtained solid according to the above analysis method was 167°C. Differential scanning calorimetry (DSC) data is shown in FIG. 16.
  • DSC Differential scanning calorimetry
  • a PXRD measurement chart of the obtained solid is shown in FIG.
  • the peak pattern revealed that the solid obtained was crystal ⁇ .
  • the relative integrated intensity based on the peak with the strongest integrated intensity, and the relative intensity based on the peak with the strongest intensity extract peaks with relative integrated intensity of 10 or more.
  • the results are shown in Table 14.
  • the crystals were sealed in a polyethylene bag with a zipper, the zipper was closed, and the moisture content was measured after being stored at room temperature in the atmosphere for one day, and found to be less than 0.1%. This revealed that this crystal had low hygroscopicity. These crystals with low hygroscopicity are very useful because of their excellent storage stability.

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Abstract

La présente invention aborde le problème de la fourniture d'un nouveau composé d'acide dicarboxylique qui a un indice de réfraction encore amélioré. La solution consiste à fournir un composé de biphénanthrène, représenté par la formule générale (1), ou un sel de métal alcalin de celui-ci.
PCT/JP2023/009059 2022-03-14 2023-03-09 Composé de biphénanthrène ou sel de métal alcalin de celui-ci WO2023176687A1 (fr)

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