WO2023176736A1 - Nouveau composé 1,3-bis (1-méthyl-1-phényléthyl) benzène - Google Patents

Nouveau composé 1,3-bis (1-méthyl-1-phényléthyl) benzène Download PDF

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WO2023176736A1
WO2023176736A1 PCT/JP2023/009385 JP2023009385W WO2023176736A1 WO 2023176736 A1 WO2023176736 A1 WO 2023176736A1 JP 2023009385 W JP2023009385 W JP 2023009385W WO 2023176736 A1 WO2023176736 A1 WO 2023176736A1
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methyl
general formula
carbon atoms
bis
phenylethyl
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利恵 藤岡
邦昌 圓井
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本州化学工業株式会社
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
    • C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
    • C07C39/15—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings with all hydroxy groups on non-condensed rings, e.g. phenylphenol
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring

Definitions

  • the present invention relates to a novel 1,3-bis(1-methyl-1-phenylethyl)benzene compound.
  • Bisphenols are used as raw materials for curable materials such as epoxy compounds, (meth)acrylate compounds, cyanate compounds, and allyl ester compounds, raw materials for antioxidants, and raw materials for heat-sensitive recording materials.
  • curable materials such as epoxy compounds, (meth)acrylate compounds, cyanate compounds, and allyl ester compounds
  • raw materials for antioxidants such as antioxidants
  • raw materials for heat-sensitive recording materials such as 1,3-di[2-(4-hydroxyphenyl)-2-propyl]benzene is known (Patent Document 1, etc.).
  • Patent Document 1 1,3-di[2-(4-hydroxyphenyl)-2-propyl]benzene
  • An object of the present invention is to provide a novel bisphenol compound with a further improved refractive index.
  • the present inventors found that the 1,3-bis(1-methyl-1-phenylethyl)benzene compound represented by the general formula (1) is a conventionally known 1,
  • the present invention was completed based on the discovery that the refractive index is greatly improved compared to 3-bis(1-methyl-1-phenylethyl)benzene compound.
  • R 1 each independently represents an aryl group having 6 to 14 carbon atoms or an aralkyl group having 7 to 17 carbon atoms
  • R 2 each independently represents a hydrogen atom, a carbon number 6 to 14 aryl group or an aralkyl group having 7 to 17 carbon atoms
  • R 3 each independently represents -OH, -O-(CH 2 ) n -OH or -O-(CH 2 ) m -COOR 4 group, where each R 4 is independently a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms; , or an alkali metal atom, and n and m are integers of 1 to 4.
  • R 4 is independently a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms; , or an
  • each R 1 is independently an aryl group having 6 to 14 carbon atoms, a is 0, 1. 1,3-bis(1-methyl-1-phenylethyl)benzene compound described in . 3. 1. Represented by general formula (1A). 1,3-bis(1-methyl-1-phenylethyl)benzene compound described in . (In the formula, R 1 , R 2 and a have the same definition as in general formula (1).) 4. 3. R 1 in the general formula (1A) is each independently an aryl group having 6 to 14 carbon atoms, and a is 0; 1,3-bis(1-methyl-1-phenylethyl)benzene compound described in . 5. 1. Represented by general formula (1B).
  • each R 1 is independently an aryl group having 6 to 14 carbon atoms, and a is 0. 1,3-bis(1-methyl-1-phenylethyl)benzene compound described in . 7.
  • R 1 , R 2 , a, m and R 4 have the same definition as in general formula (1).
  • each R 1 is independently an aryl group having 6 to 14 carbon atoms, and a is 0. 1,3-bis(1-methyl-1-phenylethyl)benzene compound described in . 9.
  • the phenol compound represented by the general formula (1A) is reacted with the phenol compound represented by the general formula (2) and ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethyl-1,3-benzenedimethanol in the presence of an acid catalyst.
  • a method for producing a 1,3-bis(1-methyl-1-phenylethyl)benzene compound is reacted with the phenol compound represented by the general formula (2) and ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethyl-1,3-benzenedimethanol.
  • R 1 each independently represents an aryl group having 6 to 14 carbon atoms or an aralkyl group having 7 to 17 carbon atoms
  • R 2 each independently represents a hydrogen atom, a carbon number 6 to 14 aryl group or an aralkyl group having 7 to 17 carbon atoms, each a independently represents 0 or an integer of 1 to 3.
  • R 1 , R 2 and a have the same definition as in general formula (2).
  • 10. 1,3-bis(1-methyl-1-phenylethyl)benzene compound represented by general formula (1A) and an alkylene oxylating agent are reacted.
  • R 1 each independently represents an aryl group having 6 to 14 carbon atoms or an aralkyl group having 7 to 17 carbon atoms
  • R 2 each independently represents a hydrogen atom, a carbon number 6 to 14 aryl group or an aralkyl group having 7 to 17 carbon atoms, each a independently represents 0 or an integer of 1 to 3.
  • R 1 , R 2 and a have the same definition as in general formula (1A), and n each independently represents an integer from 1 to 4.
  • the alkylene oxylating agent is a carbonate represented by general formula (3).
  • n is the same as the definition of general formula (1B).
  • the diffraction angles 2 ⁇ are 7.9 ⁇ 0.2°, 10.8 ⁇ 0.2°, 16.3 ⁇ 0.2°, and 18.6 ⁇ 0.
  • R 1 each independently represents an aryl group having 6 to 14 carbon atoms or an aralkyl group having 7 to 17 carbon atoms
  • R 2 each independently represents a hydrogen atom, a carbon number 6 to 14 aryl group or an aralkyl group having 7 to 17 carbon atoms, each a independently represents 0 or an integer of 1 to 3.
  • m each independently represents an integer of 1 to 4
  • R 4 each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or an alkali metal atom.
  • X represents a halogen atom.
  • R 1 , R 2 , and a have the same definitions as in general formula (1A)
  • m each independently represents an integer of 1 to 4
  • R 4 each independently represents a hydrogen atom, the number of carbon atoms, 1 to 6 linear or branched alkyl groups or alkali metal atoms
  • the reaction is carried out using a chain aliphatic ketone having 3 to 8 carbon atoms or acetonitrile. The manufacturing method described in. 19. 17.
  • the reaction is carried out under reduced pressure.
  • the novel 1,3-bis(1-methyl-1-phenylethyl)benzene compound of the present invention has a refractive index higher than that of the conventionally known 1,3-bis(1-methyl-1-phenylethyl)benzene compound. As a result, it is possible to provide an optical material with a high refractive index, which is useful.
  • the novel 1,3-bis(1-methyl-1-phenylethyl)benzene compound of the present invention is a raw material for various materials such as derivatives such as epoxy compounds, (meth)acrylate compounds, cyanate compounds, and allyl ester compounds, and polyamides.
  • the production method of the present invention is very useful because the novel 1,3-bis(1-methyl-1-phenylethyl)benzene compound of the present invention can be produced with high purity and yield.
  • novel 1,3-bis(1-methyl-1-phenylethyl)benzene compounds of the present invention 1,3-bis[1-methyl-1-(4-(2-hydroxyethoxy)-3-phenyl) Phenyl)ethyl]benzene can be provided as a crystal of the present invention, and is very useful in industrial production because it has excellent handling and transportability.
  • FIG. 1 is a diagram showing a chart of differential scanning calorimetry (DSC) data of crystals of compound 1B-1 obtained in Example 2.
  • FIG. 2 is a diagram showing a chart of powder X-ray diffraction (PXRD) measurement of crystals of compound 1B-1 obtained in Example 2.
  • DSC differential scanning calorimetry
  • PXRD powder X-ray diffraction
  • R 1 each independently represents an aryl group having 6 to 14 carbon atoms or an aralkyl group having 7 to 17 carbon atoms
  • R 2 each independently represents a hydrogen atom, a carbon number 6 to 14 aryl group or an aralkyl group having 7 to 17 carbon atoms
  • each a independently represents 0 or an integer of 1 to 3
  • R 3 each independently represents -OH, -O-(CH 2 ) n -OH or -O-(CH 2 ) m -COOR 4 group, where each R 4 is independently a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms; , or an alkali metal atom, and n and m are integers of 1 to 4.
  • R 1 in the general formula (1) each independently represents an aryl group having 6 to 14 carbon atoms or an aralkyl group having 7 to 17 carbon atoms;
  • An aryl group or an aralkyl group having 7 to 13 carbon atoms is preferable, each independently an aryl group having 6 to 14 carbon atoms or an aralkyl group having 7 to 11 carbon atoms is more preferable, each independently having 7 to 13 carbon atoms.
  • Aryl groups having 6 to 14 carbon atoms are more preferred, and aryl groups each independently having 6 to 10 carbon atoms are particularly preferred.
  • aryl group having 6 to 14 carbon atoms examples include phenyl group, naphthyl group, anthryl group, phenanthryl group, etc. Among them, phenyl group and naphthyl group are preferable, and phenyl group is more preferable.
  • Examples of aralkyl groups having 7 to 17 carbon atoms include benzyl group, phenethyl group, 1-methyl-1-phenylethyl group, naphthalen-1-yl-methyl group, naphthalen-2-yl-methyl group, 1-methyl- Examples include 1-(1-naphthyl)ethyl group, 1-methyl-1-(2-naphthyl)ethyl group, anthracen-9-yl-methyl group, phenanthren-9-yl-methyl group, among others, benzyl group, 1-methyl-1-phenylethyl group, naphthalen-1-yl-methyl group, naphthalen-2-yl-methyl group are preferred, benzyl group, naphthalen-1-yl-methyl group, naphthalen-2-yl- A methyl group is more preferred, and a benzyl group is even more preferred.
  • R 1 in general formula (1) it is particularly preferable that both R 1 are
  • R 2 in the general formula (1) each independently represents a hydrogen atom, an aryl group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 17 carbon atoms, and among them, each independently represents a hydrogen atom, An aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 13 carbon atoms is preferable, and each independently a hydrogen atom, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 11 carbon atoms is more preferable. preferable.
  • the aryl group having 6 to 14 carbon atoms include phenyl group, naphthyl group, anthryl group, phenanthryl group, etc.
  • phenyl group and naphthyl group are preferable, and phenyl group is more preferable.
  • aralkyl groups having 7 to 17 carbon atoms include benzyl group, phenethyl group, 1-methyl-1-phenylethyl group, naphthalen-1-yl-methyl group, naphthalen-2-yl-methyl group, 1-methyl- Examples include 1-(1-naphthyl)ethyl group, 1-methyl-1-(2-naphthyl)ethyl group, anthracen-9-yl-methyl group, phenanthren-9-yl-methyl group, among others, benzyl group, 1-methyl-1-phenylethyl group, naphthalen-1-yl-methyl group, naphthalen-2-yl-methyl group are preferred, benzyl group, naphthalen-1-yl-methyl group, naphthalen-2-yl- A methyl group is more preferred, and
  • a in general formula (1) each independently represents 0 or an integer of 1 to 3, each independently preferably 0, 1 or 2, each independently more preferably 0 or 1, and 0 is More preferred.
  • a in the general formula (1) represents an integer of 1 to 3, it is preferable that at least one R 2 is bonded to the ortho position of R 3 .
  • R 3 in general formula (1) each independently represents a group of -OH, -O-(CH 2 ) n -OH, or -O-(CH 2 ) m -COOR 4 .
  • the compound in which R 3 in general formula (1) is -OH is a compound represented by general formula (1A) (compound 1A).
  • R 1 , R 2 and a have the same definition as in general formula (1).
  • a compound in which R 3 in general formula (1) is -O-(CH 2 ) n -OH is a compound represented by general formula (1B) (compound 1B).
  • R 1 , R 2 , a and n have the same definitions as in general formula (1).
  • Each n in the general formula (1B) independently represents an integer of 1 to 4, preferably an integer of 2 to 4, more preferably 2 or 3, and particularly preferably 2.
  • a compound in which R 3 in general formula (1) is -O-(CH 2 ) m -COOR 4 is a compound represented by general formula (1C) (compound 1C).
  • R 4 in the general formula (1C) each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, or an alkali metal atom; Atom or a linear or branched alkyl group having 1 to 4 carbon atoms, a lithium atom, a potassium atom, a sodium atom are preferable, each independently a hydrogen atom, a methyl group or an ethyl group is more preferable, and each independently A hydrogen atom or an ethyl group is particularly preferred.
  • Each m in the general formula (1C) independently represents an integer of 1 to 4, preferably 1 or 2, and particularly preferably 1.
  • ⁇ Method for producing the compound of the present invention-1> Regarding the 1,3-bis(1-methyl-1-phenylethyl)benzene compound represented by the general formula (1) of the present invention, there are no particular limitations on the starting materials and production method for its production.
  • the method for producing compound 1A involves reacting a phenol compound represented by general formula (2) with ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethyl-1,3-benzenedimethanol, as exemplified by the reaction formula below. Examples include manufacturing methods. (In the formula, R 1 , R 2 and a are the same as defined in general formula (1).)
  • the phenol compound represented by the general formula (2) includes, for example, 2-phenylphenol, 2-(1-naphthyl)phenol, 2-(2-naphthyl)phenol, 2-(9-anthracenyl) Phenol, 2-(9-phenanthryl)phenol, 2,6-diphenylphenol, 2-benzylphenol, 2-(1-methyl-1-phenylethyl)phenol, 2-(1-naphthylmethyl)phenol, 2-( 2-naphthylmethyl)phenol, 2-(9-anthracenylmethyl)phenol, 2-(9-phenanthrylmethyl)phenol, 2-phenyl-6-benzylphenol, 2-phenyl-6-(1-methyl -1-phenylethyl)phenol, 2-phenyl-6-(1-naphthylmethyl)phenol, 2-phenyl-6-(2-naphthylmethyl)phenol, 2-(1-naphthyl)-6-benzylphenol,
  • the amount of the phenol compound represented by general formula (2) is 5 to 5 to 1 mole of ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethyl-1,3-benzenedimethanol.
  • the amount is preferably in the range of 12 mols, more preferably 7 to 10 mols, and even more preferably 8 mols.
  • the above manufacturing method is preferably carried out in the presence of an acid catalyst.
  • Preferred acid catalysts include concentrated hydrochloric acid, sulfuric acid, hydrochloric acid gas, etc. Among them, it is more preferable to use hydrochloric acid gas until the reaction solution is saturated.
  • the reaction is usually carried out in the presence of a solvent. There are no particular limitations on the solvent as long as it does not inhibit the reaction. Since Compound 1A is easily soluble in various solvents, various solvents can be used. Among these, alcohols with good solubility in the phenolic compound represented by general formula (2) are preferred, alcohols having 1 to 10 carbon atoms are more preferred, methanol, ethanol, propanol, and isopropanol are even more preferred, and methanol is particularly preferred.
  • solvents can be used alone or in combination.
  • the amount of solvent used is not particularly limited as long as it does not interfere with the reaction, but it is usually in the range of 1 to 5 times the weight of ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethyl-1,3-benzenedimethanol. It is preferably used in a range of 1 to 3 times by weight, more preferably in a range of 1 to 2 times by weight.
  • the above manufacturing method may be carried out either in the air or in an inert gas atmosphere, but in order to suppress coloring of the reaction product, an inert gas atmosphere such as nitrogen or argon is preferable.
  • the reaction temperature is usually in the range of 20 to 40°C, preferably in the range of 25 to 30°C.
  • the reaction may be carried out under normal pressure conditions, increased pressure conditions, or reduced pressure conditions, but it is preferable to carry out the reaction under normal pressure conditions.
  • Compound 1A can be obtained from the reaction mixture by separating and purifying the obtained reaction mixture according to a conventional method. For example, in order to neutralize the acid catalyst, an alkaline aqueous solution such as a sodium hydroxide aqueous solution or an ammonia aqueous solution is added to the reaction completed liquid to neutralize the acid catalyst. The neutralized reaction mixture is allowed to stand, and if necessary, a solvent that separates from water is added to separate and remove the aqueous layer.
  • the target compound 1A can be obtained as a residual liquid.
  • Examples of the manufacturing method of compound 1B include a manufacturing method in which a compound represented by general formula (1A) and an alkylene oxylating agent are reacted.
  • a reaction formula when carbonates represented by general formula (3) are used as the alkylene oxylating agent is illustrated. (In the formula, R 1 , R 2 , a and n are the same as defined in general formula (1).)
  • the compound 1A represented by the general formula (1A) can be a compound obtained by the above production method-1.
  • alkylene oxylating agents include carbonates represented by general formula (3) such as ethylene carbonate, and halogenated alcohols such as 2-chloroethanol and 3-chloro-1-propanol, depending on the target compound. Can be used.
  • carbonates represented by the general formula (3) are used as the alkylene oxylating agent will be described below.
  • the raw material molar ratio of Compound 1A and carbonates is usually 1/2 to 1/5, preferably 1/2 to 1/4, and more preferably 1/2 to 1/5. It is in the range of /2 to 1/3.
  • a basic catalyst during the reaction, and generally known ones can be used as the basic catalyst. Specifically, quaternary ammonium salts such as tetraethylammonium bromide and tetramethylammonium chloride, alkali metal halides such as potassium hydroxide, potassium iodide, and sodium bromide, and triorganophosphines such as triphenylphosphine and tributylphosphine.
  • quaternary ammonium salts such as tetraethylammonium bromide and tetramethylammonium chloride
  • alkali metal halides such as potassium hydroxide, potassium iodide, and sodium bromide
  • triorganophosphines such as triphenylphosphine and tributylphosphine.
  • Examples include amine catalysts such as compounds, 1-methylimidazole, and alkali catalysts such as potassium carbonate, calcium carbonate, magnesium carbonate, magnesium hydroxide, calcium hydroxide, sodium hydroxide, sodium hydrogen carbonate, sodium methoxy, and sodium phenoxy.
  • alkali catalysts such as potassium carbonate, calcium carbonate, magnesium carbonate, magnesium hydroxide, calcium hydroxide, sodium hydroxide, sodium hydrogen carbonate, sodium methoxy, and sodium phenoxy.
  • These basic catalysts may be used alone or in combination of two or more types.
  • the amount of the basic catalyst used is 0.001 to 10% by weight, preferably 0.01 to 1% by weight, based on the compound 1A represented by the general formula (1A).
  • reaction solvent various known reaction-inactive solvents can be used.
  • reaction solvents include aromatic hydrocarbons such as toluene and xylene, ether solvents such as tetrahydrofuran, dioxane, and 1,2-dimethoxyethane, ketone solvents such as acetone and methyl isobutyl ketone, chloroform, and 1,2-dimethoxyethane.
  • Halogenated hydrocarbons such as dichloroethane, aliphatic alcohols such as butanol and ethylene glycol, and polar solvents such as dimethylformamide and dimethyl sulfoxide.
  • amount of the reaction solvent used is preferably in the range of 0.5 to 10 times, more preferably 0.5 to 5 times by weight, relative to Compound 1A.
  • the above manufacturing method may be carried out either in the air or in an inert gas atmosphere, but in order to suppress coloring of the reaction product, an inert gas atmosphere such as nitrogen or argon is preferable.
  • the reaction temperature is not particularly limited as long as the reaction proceeds, but the reaction is usually carried out under heating.
  • reaction time depends on the reaction temperature, the carbonates used, the amount and type of basic catalyst, etc., but is usually carried out for about 3 to 24 hours. In this reaction, the time when the generation of carbon dioxide gas has stopped can be used as a guideline for the end of the reaction.
  • Compound 1B can be obtained from the reaction mixture by separating and purifying the obtained reaction mixture according to a conventional method.
  • acid-containing water eg, hydrochloric acid, sulfuric acid
  • acetic acid e.g., propionic acid, etc. This neutralization step may be performed after the hydrolysis step described below is performed.
  • the hydrolysis step of carbonates by adding water.
  • the amount of water used is in the range of 1 to 10 times the amount of carbonate used in the above reaction by mole.
  • the temperature may be lower than the boiling point of the reaction liquid, but is usually in the range from room temperature to lower than the boiling point of the reaction liquid. Specifically, the lower limit is 10°C or higher, more preferably 20°C or higher.
  • the upper limit depends on the boiling point of the solvent used, it is preferably 150°C or less.
  • add a solvent that separates from water as needed wash the oil layer multiple times with water, separate and remove the water layer, and remove low-boiling substances such as the solvent by distilling it under reduced pressure from the obtained oil layer.
  • post-treatment operations such as washing with water, crystallization, filtration, distillation, separation by column chromatography, etc., and drying can be performed.
  • further purification by distillation, recrystallization, or column chromatography may be performed according to conventional methods.
  • Compound 1B-1 (sometimes referred to as Compound 1B-1) are extremely useful in industrial production because they can be handled as a solid with crystallinity and are easy to handle and transport. It is.
  • the peak top temperature of the endothermic peak of the crystal of 1,3-bis[1-methyl-1-(4-(2-hydroxyethoxy)-3-phenylphenyl)ethyl]benzene according to differential scanning calorimetry is as follows: It is in the range of 134 to 140°C, more preferably in the range of 135 to 139°C, and particularly preferably in the range of 136 to 139°C.
  • the crystal of 1,3-bis[1-methyl-1-(4-(2-hydroxyethoxy)-3-phenylphenyl)ethyl]benzene of the present invention has a powder X-ray diffraction peak pattern using Cu-K ⁇ rays.
  • the purity of the crystals of 1,3-bis[1-methyl-1-(4-(2-hydroxyethoxy)-3-phenylphenyl)ethyl]benzene of the present invention is 90% in area percentage by liquid chromatography analysis. It is preferably at least 93%, more preferably at least 95%, even more preferably at least 98%.
  • Crystals of Compound 1B-1 of the present invention can be obtained by precipitation from a solution of Compound 1B-1 dissolved in a chain aliphatic ketone solvent having 5 to 8 carbon atoms.
  • Compound 1B-1 used here can be obtained by the method described above.
  • compound 1B-1 When compound 1B-1 is precipitated from a solution dissolved in a chain aliphatic ketone solvent having 5 to 8 carbon atoms, it can also be precipitated by cooling the solution or distilling off the solvent of the solution, but depending on the number of carbon atoms
  • a chain or cyclic aliphatic hydrocarbon solvent having 5 to 10 carbon atoms is mixed with a solution of compound 1B-1 in a chain aliphatic ketone solvent having 5 to 8 carbon atoms, and if necessary, further compound
  • chain aliphatic ketone solvents having 5 to 8 carbon atoms include diethyl ketone (5 carbon atoms), methyl isobutyl ketone (6 carbon atoms), methyl amyl ketone (7 carbon atoms), and methylhexyl ketone (7 carbon atoms). 8), among which methyl isobutyl ketone and methyl amyl ketone are preferred.
  • the solution can be washed with water to remove water-soluble impurities such as salts before crystallization.
  • the amount of the chain aliphatic ketone solvent to be used is preferably 1 to 7 times the weight of Compound 1B-1, more preferably 1.5 to 6 times the weight of Compound 1B-1.
  • the amount is preferably 2 to 5 times the weight, and more preferably 2 to 5 times the weight.
  • chain or cyclic aliphatic hydrocarbon solvent having 5 to 10 carbon atoms pentane, hexane, heptane, octane, isooctane, cyclopentane, cyclohexane, etc. can be used. Cyclic aliphatic hydrocarbon solvents are preferred, with cyclopentane or cyclohexane being more preferred.
  • the amount of the aliphatic hydrocarbon solvent to be used is preferably 1 to 10 times the weight of Compound 1B-1, more preferably 1 to 7 times the weight, and 1 to 7 times the weight of Compound 1B-1.
  • the amount is in the range of 5 to 5 times by weight.
  • the temperature at which the chain or cyclic aliphatic hydrocarbon solvent having 5 to 10 carbon atoms is mixed with the solution of the chain aliphatic ketone having 5 to 8 carbon atoms of compound 1B-1 depends on the chain aliphatic ketone used. Although it depends on the solution, the temperature is preferably in the range of 60 to 120°C, more preferably in the range of 60 to 100°C, even more preferably in the range of 60 to 90°C.
  • the temperature at which crystals of Compound 1B-1 start to precipitate is preferably in the range of 10 to 50°C, more preferably in the range of 15 to 40°C.
  • the crystals obtained by the above method may be isolated by a conventional method, for example, the crystals can be isolated by centrifugal filtration. Moreover, it is preferable to further wash the crystals with a solvent. The used solvent can be removed by drying the obtained crystals.
  • the method for producing compound 1C is to react a compound represented by general formula (1A) with a halogenated carboxylic acid represented by general formula (4) or an ester thereof, to achieve the desired Examples include a manufacturing method for obtaining a compound represented by the general formula (1C).
  • R 1 , R 2 , R 4 , a and m are the same as defined in general formula (1), and X represents a halogen atom.
  • a compound obtained by the above production method-1 can be used as the compound 1A represented by the general formula (1A).
  • X in general formula (4) is a halogen atom, preferably a chlorine atom, a bromine atom, or an iodine atom.
  • the amount of the halogenated carboxylic acid represented by the general formula (4) or its ester is not particularly limited as long as the molar ratio of the charged compound to compound 1A is at least the theoretical value (2.0); It is usually used in an amount of 2 mol or more, preferably 2.1 to 3.0 mol, more preferably 2.2 to 2.8 mol, per 1 mol of Compound 1A.
  • a base to increase nucleophilicity and react with the halogenated carboxylic acid represented by general formula (4) or its ester.
  • bases include, but are not particularly limited to, alkali metal carbonates such as lithium carbonate, sodium carbonate, and potassium carbonate; alkali metal hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate; lithium hydroxide; sodium hydroxide;
  • alkali metal hydroxides such as potassium hydroxide
  • organic bases such as triethylamine and pyridine can be suitably used. Among these, sodium carbonate and potassium carbonate are preferred.
  • the amount of the base used is preferably 2.0 to 2.5 mol, more preferably 2.05 to 2.15 mol, per 1 mol of compound 1A. Furthermore, in the above production method-3, in order to improve reaction efficiency, it is preferable to carry out the reaction in the presence of an iodide salt such as an alkali metal iodide or ammonium iodide. Specific examples include potassium iodide, sodium iodide, tetraalkylammonium iodide, tetraaryl ammonium iodide, and tetraaryl alkylammonium iodide. These may be used alone or in combination of two or more.
  • an iodide salt such as an alkali metal iodide or ammonium iodide.
  • the amount of iodide salt to be used is preferably 0.02 to 0.2 times the weight of Compound 1A, more preferably 0.02 to 0.1 times the weight, and 0.02 to 0.05 times the weight of the compound 1A. A range of times the weight is more preferable.
  • an aprotic polar solvent As the solvent that can be used in the above production method-3, it is preferable to use an aprotic polar solvent. Specifically, for example, acetone (number of carbon atoms: 3), methyl ethyl ketone (number of carbon atoms: 4), diethyl ketone (number of carbon atoms: 5), methyl isobutyl ketone (number of carbon atoms: 6), methyl amyl ketone (number of carbon atoms: 7) ), chain aliphatic ketones with 3 to 8 carbon atoms such as methylhexyl ketone (8 carbon atoms), chain nitrile solvents with 2 to 6 carbon atoms such as acetonitrile and propanenitrile, diethyl ether, tetrahydrofuran, etc.
  • acetone number of carbon atoms: 3
  • methyl ethyl ketone number of carbon atoms: 4
  • Examples include ether solvents, ester solvents such as ethyl acetate, dimethylformamide, dimethyl sulfoxide, and the like.
  • chain aliphatic ketones having 3 to 8 carbon atoms or acetonitrile are preferred, chain aliphatic ketones having 3 to 8 carbon atoms are more preferred, and chain aliphatic ketones having 3 to 6 carbon atoms are preferred.
  • More preferred is methyl isobutyl ketone.
  • methyl isobutyl ketone When 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.
  • These solvents may be used alone or in combination of two or more.
  • the amount of solvent used in the reaction is preferably 1.5 to 5 times the weight of Compound 1A, more preferably 1.5 to 3.5 times the weight, and 1.5 to 2.5 times the weight of Compound 1A. A double range is more preferred.
  • the above manufacturing method may be carried out either in the air or in an inert gas atmosphere, but in order to suppress coloring of the reaction product, an inert gas atmosphere such as nitrogen or argon is preferable.
  • the reaction temperature is usually in the range of 50 to 160°C.
  • the reaction pressure may be normal pressure, reduced pressure, or increased pressure. It is preferable to carry out the reaction under normal pressure or reduced pressure. In the reaction under pressure, for example, the reaction can be carried out under pressure in which an inert gas such as nitrogen is passed through the reaction.
  • the reaction can be carried out while introducing an inert gas into the reaction system and discharging the gas from the reaction system.
  • 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.
  • the inert gas for the reaction include nitrogen gas, argon gas, helium gas, etc. From an economical standpoint, nitrogen gas is most preferred. From the viewpoint of shortening the reaction time, it is more preferable to conduct 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 70 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.
  • reaction time varies depending on the reaction conditions such as reaction temperature, but it is usually completed in about 1 to 30 hours. Completion of the reaction can be confirmed by liquid chromatography or gas chromatography analysis.
  • the reaction is preferably terminated when no increase in the target compound represented by general formula (1C) is observed.
  • Compound 1C can be obtained from the reaction mixture by separating and purifying the obtained reaction mixture according to a conventional method. For example, post-treatment operations such as water washing, crystallization, filtration, distillation, separation by column chromatography, etc. can be performed. In order to further increase the purity, further purification by distillation, recrystallization, or column chromatography may be performed according to conventional methods.
  • metal salts in which R 4 in the general formula (1C) is an alkali metal are ester compounds in which R 4 in the general formula (1C) is an alkyl group. It can be produced by carrying out a hydrolysis reaction using a base such as an alkali metal hydroxide such as lithium oxide, sodium hydroxide, or potassium hydroxide.
  • carboxylic acid compounds in which R 4 in the general formula (1C) is a hydrogen atom are prepared by acidifying the reaction solution containing the metal salt using a strong acid such as hydrochloric acid. It can also be manufactured by At that time, metal salts such as lithium salts, sodium salts, potassium salts, etc. may be temporarily separated.
  • the moisture content of the compound 1A be in the range of 0.01% by weight or more and 3.0% by weight or less.
  • the upper limit of this moisture content is more preferably 2.0% by weight or less, even more preferably 1.5% by weight or less, and particularly preferably 1.0% by weight or less.
  • the 1,3-bis(1-methyl-1-phenylethyl)benzene compounds of the above compounds 1A to 1C represented by the general formula (1) of the present invention are the conventionally known 1,3-bis(1-methyl -1-Phenylethyl) exhibits a higher refractive index compared to the benzene compound. Therefore, by using this compound, it is possible to provide an optical material with an even higher refractive index, which is useful.
  • ⁇ Analysis method> Reaction composition, purity analysis (Analysis values are area percentages) Measuring device: High performance liquid chromatography analyzer (manufactured by Shimadzu Corporation) Pump: LC-20AD Column oven: CTO-20A Detector: SPD-20A Column: HALO-C18 Oven temperature: 50°C Flow rate: 0.7mL/min Mobile phase: (A) methanol, (B) 0.2 vol% acetic acid aqueous solution Gradient conditions: (A) volume % (time from start of analysis) 50% (0 min) ⁇ 100% (10 min) ⁇ 100% (15 min) Detection wavelength: 280nm 2.
  • NMR analysis Measuring device Fourier transform nuclear magnetic resonance AVANCE III HD 400 (manufactured by BRUKER) The measurement sample was dissolved in deuterated chloroform (CDCl 3 ), and 13 C-NMR and 1 H-NMR spectra were measured. 3.
  • Refractive index measuring device Refractometer (manufactured by Kyoto Electronics Industry Co., Ltd.: RA-500) Tetrahydrofuran solutions (concentrations of 30%, 20%, and 10% solutions) of measurement samples were prepared, and the refractive index was measured using a refractometer.
  • X-ray diffraction method 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.
  • Example 2 Production of 1,3-bis[1-methyl-1-(4-(2-hydroxyethoxy)-3-phenylphenyl)ethyl]benzene (compound 1B-1) 52.6 g (0.31 mol) of 2-phenylphenol and 11.8 g of methanol were placed in a 500 mL four-necked flask equipped with a reflux device, and after completely replacing the inside of the flask with nitrogen gas, the mixture was heated to an internal temperature of 35°C. The inside of the flask was completely replaced with hydrochloric acid gas.
  • DSC Differential scanning calorimetry
  • FIG. 1 A peak whose relative integrated intensity is 30 or more based on the diffraction angle 2 ⁇ (°) of the diffraction peak that appears in the powder X-ray diffraction (PXRD) measurement of the obtained crystal of Compound 1B-1 and the peak with the largest integrated intensity. are shown in Table 1.
  • a PXRD measurement chart is shown in FIG.
  • the refractive index measured by the above analysis method was 1.593.
  • the onset temperature of the endothermic peak was 72.0°C.
  • the yield of the obtained solid was 47 mol % based on 1,3-bis[1-methyl-1-(4-hydroxy-3-phenylphenyl)ethyl]benzene.
  • Compound 1C-1 was separated from the reaction solution by preparative liquid chromatography to obtain a pale yellow resinous solid. NMR analysis confirmed that the obtained solid was the target compound, Compound 1C-1.
  • Table 2 shows the refractive indexes of conventionally known 1,3-bis(1-methyl-1-phenylethyl)benzene compounds (compounds ⁇ , ⁇ , and ⁇ ) according to the above analysis method.
  • the novel 1,3-bis(1-methyl-1-phenylethyl)benzene compound of the present invention represented by the general formula (1) is a compound of the conventionally known 1,3-bis(1-methyl-1-phenylethyl) ) It was revealed that it exhibits a higher refractive index compared to benzene compounds.
  • various derivatives, engineering plastics, and super engineering plastics using the novel 1,3-bis(1-methyl-1-phenylethyl)benzene compound of the present invention represented by general formula (1) have a high refractive index. It is expected.

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

La présente invention aborde le problème de la production d'un nouveau composé bisphénol qui a un indice de réfraction amélioré supplémentaire. L'invention concerne un composé 1,3-bis (1-méthyl-1-phényléthyl) benzène représenté par la formule générale (1).
PCT/JP2023/009385 2022-03-14 2023-03-10 Nouveau composé 1,3-bis (1-méthyl-1-phényléthyl) benzène WO2023176736A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4746716A (en) * 1985-12-27 1988-05-24 Ppg Industries, Inc. Compositions for producing polymers of high refractive index and low yellowness
JPH11171810A (ja) * 1997-12-08 1999-06-29 Jsr Corp フェノール化合物およびその製造方法
JP2001058968A (ja) * 1999-06-14 2001-03-06 Honshu Chem Ind Co Ltd １，３−ジ（２−ｐ−ヒドロキシフェニル−２−プロピル）ベンゼンの製造方法
JP2013056967A (ja) * 2011-09-07 2013-03-28 Dic Corp 活性エネルギー線硬化型樹脂組成物、これを用いたコーティング剤
WO2016129350A1 (fr) * 2015-02-12 2016-08-18 Dic株式会社 Résine de (méth)acrylate d'uréthane, composition de résine durcissable, produit durci correspondant, et lentille en plastique

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4746716A (en) * 1985-12-27 1988-05-24 Ppg Industries, Inc. Compositions for producing polymers of high refractive index and low yellowness
JPH11171810A (ja) * 1997-12-08 1999-06-29 Jsr Corp フェノール化合物およびその製造方法
JP2001058968A (ja) * 1999-06-14 2001-03-06 Honshu Chem Ind Co Ltd １，３−ジ（２−ｐ−ヒドロキシフェニル−２−プロピル）ベンゼンの製造方法
JP2013056967A (ja) * 2011-09-07 2013-03-28 Dic Corp 活性エネルギー線硬化型樹脂組成物、これを用いたコーティング剤
WO2016129350A1 (fr) * 2015-02-12 2016-08-18 Dic株式会社 Résine de (méth)acrylate d'uréthane, composition de résine durcissable, produit durci correspondant, et lentille en plastique

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