WO2022215460A1 - Procédé de production de 2,2'-bis(2-hydroxyéthoxy)-1,1'-binaphtalène - Google Patents

Procédé de production de 2,2'-bis(2-hydroxyéthoxy)-1,1'-binaphtalène Download PDF

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Publication number
WO2022215460A1
WO2022215460A1 PCT/JP2022/011612 JP2022011612W WO2022215460A1 WO 2022215460 A1 WO2022215460 A1 WO 2022215460A1 JP 2022011612 W JP2022011612 W JP 2022011612W WO 2022215460 A1 WO2022215460 A1 WO 2022215460A1
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Prior art keywords
hydroxyethoxy
bis
binaphthalene
solution
crystals
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PCT/JP2022/011612
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English (en)
Japanese (ja)
Inventor
浩二 松本
祥多 曾我部
幸寛 杉町
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田岡化学工業株式会社
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Priority to CN202280012863.3A priority Critical patent/CN116848081A/zh
Publication of WO2022215460A1 publication Critical patent/WO2022215460A1/fr

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    • 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
    • C07C41/34—Separation; Purification; Stabilisation; Use of additives
    • C07C41/40—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/48—Preparation of compounds having groups
    • C07C41/58—Separation; Purification; Stabilisation; Use of additives
    • 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
    • C07C43/23—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing hydroxy or O-metal groups

Definitions

  • the present invention provides 2,2′-bis(2-hydroxyethoxy)-1,1′-binaphthalene, which is suitable as a monomer for forming resins (optical resins) constituting optical members typified by optical lenses and optical films. It relates to an improved manufacturing method.
  • Resin materials such as polycarbonates, polyesters, polyacrylates, polyurethanes, and epoxies that use binaphthalenes such as 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene as raw material monomers have optical properties, heat resistance, etc. In recent years, it has attracted attention as a new optical material for optical lenses, sheets, etc., due to its excellent properties.
  • a method for obtaining 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene is a method of reacting 1,1'-bi-2-naphthol with alkylene oxide, halogenoalkanol, or alkylene carbonate.
  • Patent Document 1 discloses, as Synthesis Example 1, 1,1′-bi-2-naphthol and an excess amount of ethylene carbonate in potassium hydroxide. The reaction mixture reacted in the presence of a catalyst was dissolved in methyl isobutyl ketone, washed with water, and then the solvent was removed at 150° C.
  • Patent Document 2 discloses that, as Example 1, 1,1'-bi-2-naphthol and an excess amount of ethylene carbonate are reacted in a toluene solvent under a potassium carbonate catalyst. After washing the resulting reaction mixture with a 1% aqueous sodium hydroxide solution and water, the solvent is removed using a rotary evaporator under reduced pressure to obtain 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene. disclosed. However, in these methods, by distilling off the solvent from the reaction mixture, the target product is obtained as a resinous concentrated residue, which is difficult to remove.
  • Patent Document 3 Japanese Patent Application Laid-Open No. 2015-168658
  • An object of the present invention is to provide a more suitable method for producing 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene when implemented on an industrial scale.
  • the present inventors have made intensive studies to solve the above problems, and found that 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene, aromatic hydrocarbons and methanol are mixed in a specific ratio.
  • the above problem can be solved by precipitating crystals of 2,2′-bis(2-hydroxyethoxy)-1,1′-binaphthalene from a solution with the solvent contained in 2,
  • 2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene can be efficiently produced on an industrial scale.
  • the present invention includes the following inventions.
  • the present invention does not require a mother liquor, it is possible to avoid the influence of impurities contained in the mother liquor. Therefore, for example, when it is desired to further improve the purity of 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene obtained by the method of Patent Document 3, the production method of the present invention can be applied.
  • the purity of 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene obtained by the method of Patent Document 3 is determined by (performing so-called recrystallization by the production method of the present invention). , can be improved easily and efficiently.
  • the solution of the present invention contains 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene, an aromatic hydrocarbon and methanol in specific proportions. Moreover, 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene contained in the solution is preferably completely dissolved.
  • 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene used in the present invention is obtained, for example, by a conventionally known method (for example, the methods described in Patent Documents 1 to 3 above), It is preferably prepared by the reaction of 1,1'-bi-2-naphthol and ethylene carbonate in that the effects of the present invention are readily exhibited.
  • aromatic hydrocarbons used in the solution of the present invention include benzene, toluene, xylene, and mesitylene. Among these aromatic hydrocarbons, toluene or xylene is preferred. These aromatic hydrocarbons may be used alone or in combination of two or more.
  • 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene is crystallized, if only aromatic hydrocarbons are used, the description in Patent Document 3 and the section of Examples described later also indicate that As shown, it is necessary to use methanol together because it interferes with stirring during crystallization. Also, when other alcohols are used instead of methanol, stirring during crystallization becomes difficult as in the case of using only aromatic hydrocarbons, as shown in the section of Examples described later.
  • the solution of the present invention may contain organic solvents other than aromatic hydrocarbons and methanol.
  • organic solvents that may be included include, for example, aliphatic hydrocarbons, esters, ethers, ketones, and the like.
  • the aliphatic hydrocarbons include hexane, cyclohexane, and heptane
  • examples of the esters include ethyl acetate, isopropyl acetate, and isobutyl acetate
  • examples of the ethers include tetrahydrofuran, dioxane, and the like.
  • examples of the ketones include acetone, 2-butanone, 4-methyl-2-pentanone and cyclohexanone.
  • the amount thereof is, for example, 50 parts by weight or less, preferably 30 parts by weight or less, relative to 100 parts by weight of the total amount of the aromatic hydrocarbons and methanol in the solution.
  • the total amount of aromatic hydrocarbons and methanol is, for example, 100 to 2000 per 100 parts by weight of 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene. parts by weight, preferably 150 to 1500 parts by weight, more preferably 150 to 1000 parts by weight.
  • 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene is preferably completely dissolved.
  • the temperature for complete dissolution is usually 40°C or higher and lower than the boiling point of the solvent, preferably 50 to 65°C.
  • Crystals of 2,2'-bis(2-hydroxyethoxy)-1,1′-binaphthalene are precipitated from the solution of the present invention by a method such as cooling the solution, thereby reducing stirring during crystallization. Crystals of 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene can be produced without difficulty.
  • the method for producing 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene will be described in detail below.
  • Crystals of 2,2′-bis(2-hydroxyethoxy)-1,1′-binaphthalene are obtained by heating the solution of the present invention to 15° C. or lower than the temperature of the solution of the present invention described above, specifically, usually It can be precipitated by cooling to 25-45°C, preferably 30-40°C. In addition, cooling is normally performed by standing to cool or slow cooling. Also, if necessary, crystals can be precipitated by adding seed crystals at a predetermined temperature. After crystal precipitation, if necessary, the same temperature may be maintained for a certain period of time to grow crystals, or further cooling may be performed.
  • the crystallization solution containing crystals of 2,2'-bis(2-hydroxyethoxy)-1,1'-binaphthalene thus prepared is then subjected to solid-liquid separation to recover the crystals. do.
  • the solid-liquid separation operation include filtration using a centrifugal separator, a filter press, a Nutsche, etc. Industrially, a centrifugal separator is preferred. Thereafter, the collected crystals may be washed with a solvent or the like, or dried, if necessary. Further, if necessary, further purification such as adsorption and recrystallization may be performed.
  • the present invention will be specifically described below with reference to Examples, etc., but the present invention is not limited to these.
  • various measurements were implemented by the following method.
  • the yield is (RS)-2,2'-bis(2-hydroxy Ethoxy)-1,1'-binaphthalene is a solid yield
  • HPLC purity is an area percentage value of HPLC measured under the following conditions.
  • Example 1 50 g (0.175 mol) of (RS)-1,1′-bi-2-naphthol, 35 g (0.401 mol) of ethylene carbonate, potassium carbonate were placed in a glass reactor equipped with stirrer, condenser, and thermometer. 2.5 g and 50 g of toluene were charged and stirred at 110° C. for 8 hours to obtain a reaction mixture containing (RS)-2,2′-bis(2-hydroxyethoxy)-1,1′-binaphthalene. After adding 180 g of toluene to the obtained reaction mixture and diluting it, the organic solvent layer containing the reaction mixture was kept at 85° C.
  • Example 2 In Example 1, except that the amount of toluene added to the reaction mixture was 246 g. A crystallization solution was obtained. This crystallization solution was cooled to 45° C., held at the same temperature for 1 hour to precipitate crystals, and further cooled to 2° C. to obtain a crystallization mixture. The resulting crystallization mixture was stirrable. The precipitated crystals were separated by filtration, washed twice with 35 g of toluene, and dried at 80° C. under reduced pressure to give white (RS)-2,2′-bis(2-hydroxyethoxy)-1,1′-binaphthalene. 53 g of crystals were obtained (yield: 81%, HPLC purity: 99%).
  • Example 3 In Example 1, except that the amount of toluene added to the reaction mixture was 16 g, dehydration was performed under reflux in the same manner as in Example 1, then the organic solvent layer was cooled to 62° C., 263 g of methanol was added, A crystallization solution was obtained. This crystallization solution was cooled to 31° C., held at the same temperature for 1 hour to precipitate crystals, and further cooled to 2° C. to obtain a crystallization mixture. The resulting crystallization mixture was stirrable. The precipitated crystals were separated by filtration, washed twice with 35 g of toluene, and dried at 80° C. under reduced pressure to give white (RS)-2,2′-bis(2-hydroxyethoxy)-1,1′-binaphthalene. 52 g of crystals were obtained (yield: 79%, HPLC purity: 99%).
  • Example 4 In Example 1, except that the amount of toluene added to the reaction mixture was 16 g. A crystallization solution was obtained. This crystallization solution was cooled to 39° C., held at the same temperature for 1 hour to precipitate crystals, and further cooled to 2° C. to obtain a crystallization mixture. The resulting crystallization mixture was stirrable. The precipitated crystals were separated by filtration, washed twice with 35 g of toluene, and dried at 80° C. under reduced pressure to give white (RS)-2,2′-bis(2-hydroxyethoxy)-1,1′-binaphthalene. 56 g of crystals were obtained (yield: 85%, HPLC purity: 99%).
  • Example 5 In Example 1, except that the amount of toluene added to the reaction mixture was 896 g, dehydration was performed under reflux in the same manner as in Example 1, then the organic solvent layer was cooled to 60°C, 39 g of methanol was added, A crystallization solution was obtained. This crystallization solution was cooled to 30° C., held at the same temperature for 1 hour to precipitate crystals, and further cooled to 2° C. to obtain a crystallization mixture. The resulting crystallization mixture was stirrable. The precipitated crystals were separated by filtration, washed twice with 35 g of toluene, and dried at 80° C. under reduced pressure to give white (RS)-2,2′-bis(2-hydroxyethoxy)-1,1′-binaphthalene. 37 g of crystals were obtained (yield: 57%, HPLC purity: 99%).
  • Example 1 ⁇ Comparative Example 1> In Example 1, except that the amount of toluene added to the reaction mixture was changed to 1264 g, the operations up to the step of dehydration under reflux were carried out in the same manner as in Example 1, and then the organic solvent layer was cooled to 30°C, crystals were formed. precipitated at once, making stirring difficult.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne une solution de 2,2'-bis(2-hydroxyéthoxy)-1,1'-binaphtalène qui comprend du 2,2'-bis(2-hydroxyéthoxy)-1,1'-binaphtalène, un hydrocarbure aromatique et du méthanol, la proportion entre l'hydrocarbure aromatique et le méthanol étant (hydrocarbure aromatique):méthanol = 99:1 à 10:90 en poids ; et un procédé de production de 2,2'-bis(2-hydroxyéthoxy)-1,1'-binaphtalène qui comprend l'étape consistant à isoler de la solution par cristallisation le 2,2'-bis(2-hydroxyéthoxy)-1,1'-binaphtalène.
PCT/JP2022/011612 2021-04-08 2022-03-15 Procédé de production de 2,2'-bis(2-hydroxyéthoxy)-1,1'-binaphtalène WO2022215460A1 (fr)

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CN202280012863.3A CN116848081A (zh) 2021-04-08 2022-03-15 2,2’-双（2-羟基乙氧基）-1,1’-联萘的制造方法

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JP2021-066055 2021-04-08
JP2021066055 2021-04-08

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010018753A (ja) * 2008-07-14 2010-01-28 Nippon Kayaku Co Ltd （メタ）アクリレート化合物及びそれを含有する活性エネルギー線硬化型樹脂組成物並びにその硬化物
JP2011153248A (ja) * 2010-01-28 2011-08-11 Dic Corp 硬化性樹脂組成物、その硬化物、及びプラスチックレンズ
JP2014227388A (ja) * 2013-05-24 2014-12-08 田岡化学工業株式会社 ビナフタレン化合物の製造方法
JP2015168658A (ja) * 2014-03-10 2015-09-28 田岡化学工業株式会社 ２，２’−ビス（２−ヒドロキシエトキシ）−１，１’−ビナフタレンの製造方法
JP2020534350A (ja) * 2017-08-30 2020-11-26 ロイター ヒェミッシャー アパラ—テバウ エー．カー． ビナフチル化合物

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010018753A (ja) * 2008-07-14 2010-01-28 Nippon Kayaku Co Ltd （メタ）アクリレート化合物及びそれを含有する活性エネルギー線硬化型樹脂組成物並びにその硬化物
JP2011153248A (ja) * 2010-01-28 2011-08-11 Dic Corp 硬化性樹脂組成物、その硬化物、及びプラスチックレンズ
JP2014227388A (ja) * 2013-05-24 2014-12-08 田岡化学工業株式会社 ビナフタレン化合物の製造方法
JP2015168658A (ja) * 2014-03-10 2015-09-28 田岡化学工業株式会社 ２，２’−ビス（２−ヒドロキシエトキシ）−１，１’−ビナフタレンの製造方法
JP2020534350A (ja) * 2017-08-30 2020-11-26 ロイター ヒェミッシャー アパラ—テバウ エー．カー． ビナフチル化合物

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