JP2021024788A - Method for producing compound having binaphthalene skeleton, and compound having binaphthalene skeleton - Google Patents
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 150000001875 compounds Chemical class 0.000 title claims description 57
- ZDZHCHYQNPQSGG-UHFFFAOYSA-N 1-naphthalen-1-ylnaphthalene Chemical group C1=CC=C2C(C=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 ZDZHCHYQNPQSGG-UHFFFAOYSA-N 0.000 title description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000243 solution Substances 0.000 claims abstract description 19
- 239000007864 aqueous solution Substances 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 239000011541 reaction mixture Substances 0.000 claims abstract description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 39
- 241001550224 Apha Species 0.000 claims description 9
- 239000003513 alkali Substances 0.000 abstract description 13
- ZKBUCVUKEWAMGB-UHFFFAOYSA-N 2-[1-[2-(2-hydroxyethoxy)-6-phenylnaphthalen-1-yl]-6-phenylnaphthalen-2-yl]oxyethanol Chemical compound C1(=CC=CC=C1)C=1C=C2C=CC(=C(C2=CC=1)C1=C(C=CC2=CC(=CC=C12)C1=CC=CC=C1)OCCO)OCCO ZKBUCVUKEWAMGB-UHFFFAOYSA-N 0.000 abstract description 4
- -1 binaphthalene compound Chemical class 0.000 abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000006227 byproduct Substances 0.000 description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- 238000005259 measurement Methods 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 10
- 239000013078 crystal Substances 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 239000003960 organic solvent Substances 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 238000004040 coloring Methods 0.000 description 4
- 239000006103 coloring component Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 3
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000003111 delayed effect Effects 0.000 description 3
- 229940117389 dichlorobenzene Drugs 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000011403 purification operation Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- OVJPYIRGUFWANT-UHFFFAOYSA-N 2-[1-[2-(2-hydroxyethoxy)naphthalen-1-yl]naphthalen-2-yl]oxyethanol Chemical compound C1=CC=C2C(C3=C4C=CC=CC4=CC=C3OCCO)=C(OCCO)C=CC2=C1 OVJPYIRGUFWANT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 125000004062 acenaphthenyl group Chemical group C1(CC2=CC=CC3=CC=CC1=C23)* 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000001828 phenalenyl group Chemical group C1(C=CC2=CC=CC3=CC=CC1=C23)* 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-OUBTZVSYSA-N potassium-40 Chemical compound [40K] ZLMJMSJWJFRBEC-OUBTZVSYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000719 pyrrolidinyl group Chemical group 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
本発明は、ビナフタレン骨格を有する化合物の製造方法およびビナフタレン骨格を有する化合物に関する。 The present invention relates to a method for producing a compound having a vinaphthalene skeleton and a compound having a vinaphthalene skeleton.
２，２’−ビス（２−ヒドロキシエトキシ）−１，１’−ビナフタレンなどのビナフタレン類を原料モノマーとするポリカーボネート、ポリエステル、ポリアクリレート、ポリウレタン、エポキシなどの樹脂材料は、光学特性、耐熱性等に優れることから、近年、光学レンズや光学シートなどの新たな光学材料として注目されている。また、２，２’−ビス（２−ヒドロキシエトキシ）−１，１’−ビナフタレンの６，６’位を置換した化合物は光学特性がさらに優れることが記載されている（特許文献１）。特許文献１には２，２’−ビス（２−ヒドロキシエトキシ）−６，６’−ジフェニル−１，１’−ビナフタレンの合成方法が開示されている。該文献に記載の合成方法から得られた２，２’−ビス（２−ヒドロキシエトキシ）−６，６’−ジフェニル−１，１’−ビナフタレンは、高純度であることが記されているが、精製や洗浄を繰り返すことで高純度化しているため、生産収率が低いことに課題があった。 Resin materials such as polycarbonate, polyester, polyacrylate, polyurethane, and epoxy using binaphthalene such as 2,2'-bis (2-hydroxyethoxy) -1,1'-binaphthalene as a raw material monomer have optical properties, heat resistance, etc. In recent years, it has been attracting attention as a new optical material such as an optical lens and an optical sheet because of its excellent properties. Further, it is described that the compound in which the 6,6'position of 2,2'-bis (2-hydroxyethoxy) -1,1'-binaphthalene is substituted has further excellent optical properties (Patent Document 1). Patent Document 1 discloses a method for synthesizing 2,2'-bis (2-hydroxyethoxy) -6,6'-diphenyl-1,1'-binaphthalene. Although 2,2'-bis (2-hydroxyethoxy) -6,6'-diphenyl-1,1'-binaphthalene obtained from the synthetic method described in the document is described to have high purity. There is a problem that the production yield is low because the purity is increased by repeating purification and washing.
本発明は、高純度でかつ色相に優れるビナフタレン化合物を収率良く製造する方法を提供することを目的とする。 An object of the present invention is to provide a method for producing a vinaphthalene compound having high purity and excellent hue in high yield.
本発明者らは、以下の態様を有する本発明により、上記課題を解決できることを見出した。
《態様１》
下記式（１）で表される化合物とエチレンカーボネートとを反応させて、下記式（２）で表される化合物を製造する方法において、下記工程１および下記工程２を含む式（２）で表される化合物の製造方法。
工程１：式（１）で表される化合物とエチレンカーボネートとを、１：１．９〜１：２．９の使用量（モル比）で反応させる工程
工程２：上記工程１の反応終了後、得られた反応混合物溶液に３重量％以上のアルカリ水溶液を添加し、５０℃以上の温度で加熱攪拌する工程
The present inventors have found that the above problems can be solved by the present invention having the following aspects.
<< Aspect 1 >>
In a method for producing a compound represented by the following formula (2) by reacting a compound represented by the following formula (1) with an ethylene carbonate, the formula (2) including the following step 1 and the following step 2 is represented. A method for producing a compound to be produced.
Step 1: The compound represented by the formula (1) and ethylene carbonate are reacted in an amount (molar ratio) of 1: 1.9 to 1: 2.9. Step 2: After the reaction of Step 1 is completed. , A step of adding an alkaline aqueous solution of 3% by weight or more to the obtained reaction mixture solution and heating and stirring at a temperature of 50 ° C. or more.
《態様２》
式（１）および式（２）中のｎ１およびｎ２が１であり、ｎ３およびｎ４が０である態様１に記載の化合物の製造方法。
<< Aspect 2 >>
The method for producing a compound according to embodiment 1, wherein n1 and n2 in the formulas (1) and (2) are 1, and n3 and n4 are 0.
《態様３》
式（２）が下記式（２−Ａ）である態様１または態様２に記載の化合物の製造方法。
The method for producing a compound according to the first or second aspect, wherein the formula (2) is the following formula (2-A).
《態様４》
下記式（２−Ａ）で表される化合物０．５ｇをジメチルホルムアミド１０ｍｌに溶解させた溶液のＡＰＨＡが１００以下である下記式（２−Ａ）で表される化合物。
A compound represented by the following formula (2-A) in which 0.5 g of the compound represented by the following formula (2-A) is dissolved in 10 ml of dimethylformamide and the APHA is 100 or less.
本発明によれば、高純度でかつ色相に優れるビナフタレン化合物を収率良く得ることができる。 According to the present invention, a vinaphthalene compound having high purity and excellent hue can be obtained in good yield.
《ビナフタレン化合物の製造方法》
（工程１）
本発明では、下記式（１）で表される化合物と所定量のエチレンカーボネートとを反応させ、下記式（２）で表される化合物を得る。
<< Manufacturing method of binaphthalene compound >>
(Step 1)
In the present invention, a compound represented by the following formula (1) is reacted with a predetermined amount of ethylene carbonate to obtain a compound represented by the following formula (2).
式（１）および式（２）中のＸ１〜Ｘ４はそれぞれ独立に炭素原子数４〜３６のヘテロ原子を含んでいても良く、置換基を有していても良い芳香族基である。炭素原子数４〜３６、好ましくは炭素原子数５〜２４、より好ましくは炭素原子数６〜１８のヘテロ原子を含んでいても良く、置換基を有していても良い芳香族基として、フェニル基、ナフチル基、アントリル基、フェナントリル基、フェナレニル基、フルオレニル基、アセナフテチレニル基、アセナフテニル基、ビフェニレニル基、インダセニル基、ピリジル基、ピロリジニル基、チエニル基などが挙げられ、フェニル基、ナフチル基が特に好ましい。 Equation (1) and (2) X 1 to X 4 may also comprise independently heteroatom carbon atoms 4 to 36 in, a good aromatic group which may have a substituent .. Phenyl is an aromatic group that may contain a heteroatom having 4 to 36 carbon atoms, preferably 5 to 24 carbon atoms, more preferably 6 to 18 carbon atoms, and may have a substituent. Groups, naphthyl groups, anthryl groups, phenanthryl groups, phenalenyl groups, fluorenyl groups, acenaphthethylenyl groups, acenaphthenyl groups, biphenylenyl groups, indaceyl groups, pyridyl groups, pyrrolidinyl groups, thienyl groups and the like, and include phenyl groups and naphthyl groups. Is particularly preferable.
また、式（１）および式（２）中のｎ１およびｎ２はそれぞれ独立に１〜４の整数であり、好ましくは１〜２の整数であり、特に好ましくは１である。また、式（１）および式（２）中のｎ３およびｎ４はそれぞれ独立に０〜２の整数であり、好ましくは０〜１の整数であり、特に好ましくは０である。すなわち、式（２）で表される化合物は下記式（２−Ａ）で表される化合物であると特に好ましい。 Further, n1 and n2 in the formulas (1) and (2) are independently integers of 1 to 4, preferably integers of 1 to 2, and particularly preferably 1. Further, n3 and n4 in the formulas (1) and (2) are independently integers of 0 to 2, preferably integers of 0 to 1, and particularly preferably 0. That is, the compound represented by the formula (2) is particularly preferably a compound represented by the following formula (2-A).
本発明において、式（１）で表される化合物とエチレンカーボネートの使用量（モル比）は、１：１．９〜１：２．９であり、好ましくは１：２〜１：２．７であり、より好ましくは１：２．１〜１：２．５である。エチレンカーボネートの使用量が１：１．９より少ないと、反応時間が長くなることがある。また、式（１）で表される化合物が未反応のまま残ることや、式（１）で表される化合物１モルとエチレンカーボネート１モルが反応した副生物が多くなることにより、収率や純度が低下するので好ましくない。エチレンカーボネートの使用量が１：２．９より多いと、式（１）で表される化合物１モルとエチレンカーボネート３モル以上が反応した副生物が多くなることにより、収率や純度が低下し好ましくない。 In the present invention, the amount (molar ratio) of the compound represented by the formula (1) and ethylene carbonate used is 1: 1.9 to 1: 2.9, preferably 1: 2 to 1: 2.7. It is more preferably 1: 2.1 to 1: 2.5. If the amount of ethylene carbonate used is less than 1: 1.9, the reaction time may be long. In addition, the yield and yield are increased due to the fact that the compound represented by the formula (1) remains unreacted and that 1 mol of the compound represented by the formula (1) reacts with 1 mol of ethylene carbonate. It is not preferable because it reduces the purity. If the amount of ethylene carbonate used is more than 1: 2.9, the yield and purity will decrease due to the increase in the number of by-products in which 1 mol of the compound represented by the formula (1) reacts with 3 mol or more of ethylene carbonate. Not preferred.
本発明において、反応時に所定量の非反応性溶媒を共存させることが好ましい。非反応性溶媒とは反応を阻害しないものであれば特に限定されるものではなく、ベンゼン、トルエン、キシレン、メシチレンなどの芳香族炭化水素、ペンタン、ヘキサン、ヘプタンなどの脂肪族炭化水素、クロロベンゼン、ジクロロベンゼンなどのハロゲン化芳香族炭化水素、ジクロロメタン、１，２−ジクロロエタンなどのハロゲン化脂肪族炭化水素、ジメチルホルムアミド、ジメチルスルホキシドなどが挙げられる。好ましくはトルエン、ジメチルホルムアミドであり、より好ましくはジメチルホルムアミドである。所定量の非反応性溶媒が共存しない場合、攪拌困難となり反応が進行しないか、反応が著しく遅延する場合がある。この場合、反応を進行させるには温度を高くするか、所定量以上の多量の溶媒で希釈し、反応系内を溶解または攪拌可能なスラリー状態とする必要がある。しかしながら反応温度が高いと多量体などの副生物の増加により、収率や純度が低下することや着色により色相が悪化することがある。 In the present invention, it is preferable that a predetermined amount of non-reactive solvent coexists during the reaction. The non-reactive solvent is not particularly limited as long as it does not inhibit the reaction, and is not limited to aromatic hydrocarbons such as benzene, toluene, xylene and mesitylen, aliphatic hydrocarbons such as pentane, hexane and heptane, and chlorobenzene. Examples thereof include halogenated aromatic hydrocarbons such as dichlorobenzene, dichloromethane, halogenated aliphatic hydrocarbons such as 1,2-dichloroethane, dimethylformamide, and dimethylsulfoxide. Toluene and dimethylformamide are preferable, and dimethylformamide is more preferable. If a predetermined amount of non-reactive solvent does not coexist, stirring may become difficult and the reaction may not proceed or the reaction may be significantly delayed. In this case, in order to proceed the reaction, it is necessary to raise the temperature or dilute with a large amount of solvent of a predetermined amount or more to prepare a slurry state in which the inside of the reaction system can be dissolved or stirred. However, if the reaction temperature is high, the yield and purity may decrease due to the increase of by-products such as multimers, and the hue may deteriorate due to coloring.
本発明において、反応時に共存させる非反応性有機溶媒の使用量は式（１）で表される化合物に対して好ましくは０．１〜１０重量倍、より好ましくは０．３〜７重量倍、さらに好ましくは０．５〜５重量倍である。溶媒の使用量が０．１重量倍より少ないと式（１）で表される化合物や生成した式（２）で表される化合物が攪拌困難となることがある。溶媒の使用量が１０重量倍より多いと反応時間の遅延や容積効率が低下するなど、生産効率が悪化し経済的に不利である。また、長期の加熱操作は副反応物の増加や着色原因となることがある。本発明においては、好適には前記所定量のエチレンカーボネートと所定量の非反応性有機溶媒を用いて反応を行うことにより融点が高く、エチレンカーボネートや有機溶媒への溶解度が低い式（１）で表される化合物を溶液または攪拌可能なスラリー状態で最も効率よく反応を行うことができ、高収率でかつ高純度な式（２）で表される化合物を得ることができる。 In the present invention, the amount of the non-reactive organic solvent coexisting during the reaction is preferably 0.1 to 10 times by weight, more preferably 0.3 to 7 times by weight, based on the compound represented by the formula (1). More preferably, it is 0.5 to 5 times by weight. If the amount of the solvent used is less than 0.1 times by weight, it may be difficult to stir the compound represented by the formula (1) or the produced compound represented by the formula (2). If the amount of the solvent used is more than 10 times by weight, the reaction time is delayed and the volumetric efficiency is lowered, so that the production efficiency is deteriorated, which is economically disadvantageous. In addition, long-term heating operations may cause an increase in side reactants and coloring. In the present invention, the formula (1) preferably has a high melting point and low solubility in ethylene carbonate or an organic solvent by carrying out a reaction using the predetermined amount of ethylene carbonate and a predetermined amount of a non-reactive organic solvent. The reaction of the represented compound can be carried out most efficiently in a solution or a stirable slurry state, and a compound represented by the formula (2) with high yield and high purity can be obtained.
本発明において、式（１）で表される化合物と所定量のエチレンカーボネートとを反応させる方法は、特に限定されるものではないが、通常、式（１）で表される化合物、エチレンカーボネート、溶媒および触媒を反応容器に仕込み、空気中又は窒素、ヘリウムなどの不活性ガス雰囲気下、加熱攪拌することにより行うことができる。反応は液体クロマトグラフィーなどの分析手段で追跡することができる。 In the present invention, the method for reacting the compound represented by the formula (1) with a predetermined amount of ethylene carbonate is not particularly limited, but the compound represented by the formula (1), ethylene carbonate, is usually used. The solvent and catalyst can be charged into the reaction vessel and heated and stirred in the air or in an atmosphere of an inert gas such as nitrogen or helium. The reaction can be followed by analytical means such as liquid chromatography.
本発明において、反応温度は特に限定されるものではないが、通常、１５０℃以下、好ましくは１４０〜４０℃、より好ましくは１３０〜７０℃である。反応温度が高すぎると副反応物の増加による収率低下や色相悪化の原因となる場合がある。反応温度が低すぎると反応が速やかに進行しない場合がある。 In the present invention, the reaction temperature is not particularly limited, but is usually 150 ° C. or lower, preferably 140 to 40 ° C., and more preferably 130 to 70 ° C. If the reaction temperature is too high, it may cause a decrease in yield or a deterioration in hue due to an increase in side reactants. If the reaction temperature is too low, the reaction may not proceed rapidly.
本発明に用いられる触媒は、アルカリ触媒、酸触媒のいずれであってもよいが、反応の進行が速く、不純物が少なくなる点からアルカリ触媒が好ましい。アルカリ触媒としては、例えば水酸化カリウム、水酸化ナトリウム、水酸化バリウム、酸化マグネシウム、炭酸ナトリウム、炭酸カリウムなどが挙げられる。中でも水酸化カリウム、水酸化ナトリウム、炭酸カリウムが好ましい。酸触媒を使用する場合も特に限定されるものではなく、硫酸、パラトルエンスルホン酸、メタンスルホン酸などが挙げられる。触媒の使用量は特に限定されるものではないが、通常、式（１）で表される化合物１モルに対して好ましくは０．０１〜０．５モル、より好ましくは０．０５〜０．２モルである。触媒量が少ないと反応が進行しないか、反応が遅延することがある。触媒量が多いと副生物の増加による収率や純度の低下、着色原因となることがある。 The catalyst used in the present invention may be either an alkaline catalyst or an acid catalyst, but an alkaline catalyst is preferable because the reaction proceeds quickly and impurities are reduced. Examples of the alkaline catalyst include potassium hydroxide, sodium hydroxide, barium hydroxide, magnesium oxide, sodium carbonate, potassium carbonate and the like. Of these, potassium hydroxide, sodium hydroxide and potassium carbonate are preferable. The case where an acid catalyst is used is also not particularly limited, and examples thereof include sulfuric acid, paratoluenesulfonic acid, and methanesulfonic acid. The amount of the catalyst used is not particularly limited, but is usually preferably 0.01 to 0.5 mol, more preferably 0.05 to 0, based on 1 mol of the compound represented by the formula (1). 2 mol. If the amount of catalyst is small, the reaction may not proceed or the reaction may be delayed. If the amount of catalyst is large, the yield and purity may decrease due to the increase of by-products, which may cause coloring.
（工程２）
本発明において、式（１）で表される化合物と所定量のエチレンカーボネートとを反応させ得られた、式（２）で表される化合物を含む反応混合物溶液に、濃度３重量％以上のアルカリ水溶液を添加し、５０℃以上の温度で加熱攪拌する工程（以下、アルカリ精製工程と称する）を行う。
(Step 2)
In the present invention, an alkali having a concentration of 3% by weight or more is added to a reaction mixture solution containing the compound represented by the formula (2) obtained by reacting the compound represented by the formula (1) with a predetermined amount of ethylene carbonate. A step of adding an aqueous solution and heating and stirring at a temperature of 50 ° C. or higher (hereinafter referred to as an alkali purification step) is performed.
本発明において、式（２）で表される化合物を含む反応混合物溶液に添加するアルカリ水溶液の濃度は３重量％以上であり、６重量％が好ましく、８重量％以上がさらに好ましい。３重量％以上の濃度のアルカリ水溶液を添加し５０℃以上の温度で加熱攪拌することにより、式（１）で表される化合物１モルとエチレンカーボネート３モル以上が反応した副生物が分解し、式（２）で表される化合物となる。また、着色成分をアルカリ水溶液中に除去することができることから高純度で着色の少ない式（２）で表される化合物を得ることができる。アルカリ水溶液の濃度が３重量％より低いと副生物や着色成分を効率よく除去することできなくなり好ましくない。アルカリ濃度は３重量％以上であれば特に限定されるものではないが、アルカリの溶解度や取り扱い易さから、好ましくは５０重量％以下、より好ましくは３０重量％以下、さらに好ましくは１５重量％以下の濃度が好ましい。 In the present invention, the concentration of the alkaline aqueous solution added to the reaction mixture solution containing the compound represented by the formula (2) is 3% by weight or more, preferably 6% by weight, more preferably 8% by weight or more. By adding an alkaline aqueous solution having a concentration of 3% by weight or more and heating and stirring at a temperature of 50 ° C. or higher, by-products obtained by reacting 1 mol of the compound represented by the formula (1) with 3 mol or more of ethylene carbonate are decomposed. It is a compound represented by the formula (2). Further, since the coloring component can be removed in the alkaline aqueous solution, a compound represented by the formula (2) having high purity and less coloring can be obtained. If the concentration of the alkaline aqueous solution is lower than 3% by weight, by-products and coloring components cannot be efficiently removed, which is not preferable. The alkali concentration is not particularly limited as long as it is 3% by weight or more, but is preferably 50% by weight or less, more preferably 30% by weight or less, still more preferably 15% by weight or less, from the viewpoint of alkali solubility and ease of handling. Concentration is preferred.
アルカリ水溶液を加熱攪拌する温度は、５０℃以上であり、好ましくは６０℃以上、より好ましくは８０℃以上であり、好ましくは使用する溶媒の沸点以下の温度、より好ましくは１３０℃以下で行われる。温度が５０℃より低いと副生物が除去できないか、効率よく除去することができないため好ましくない。また、温度が１３０℃より高いと、不純物が増え純度が低下することや色相が悪化するため好ましくない。また、攪拌時間は特に限定されないが、好ましくは０．５〜１０時間であり、より好ましくは１〜９時間であり、さらに好ましくは２〜８時間である。 The temperature at which the alkaline aqueous solution is heated and stirred is 50 ° C. or higher, preferably 60 ° C. or higher, more preferably 80 ° C. or higher, preferably a temperature below the boiling point of the solvent used, more preferably 130 ° C. or lower. .. If the temperature is lower than 50 ° C., by-products cannot be removed or efficiently removed, which is not preferable. Further, if the temperature is higher than 130 ° C., impurities increase, the purity decreases, and the hue deteriorates, which is not preferable. The stirring time is not particularly limited, but is preferably 0.5 to 10 hours, more preferably 1 to 9 hours, and even more preferably 2 to 8 hours.
本発明のアルカリ水溶液に用いられるアルカリは、特に限定されるものではないが、水酸化リチウム、水酸化ナトリウム、水酸化カリウム、水酸化テトラメチルアンモニウム、水酸化テトラエチルアンモニウム、水酸化カルシウム、水酸化バリウム、炭酸ナトリウム、炭酸カリウムなどが挙げられる。好ましくは水酸化ナトリウム、水酸化カリウムである。アルカリの使用量は、特に制限されるものではないが、副生物の除去や着色成分の除去を効率よく行うためには、通常、式（１）で表される化合物１モルに対して０．１〜２０モルであると好ましく、０．２〜１０モルであるとより好ましく、０．３〜５モルであるとよりいっそう好ましい。アルカリ量が０．１モルより少ないと副生物を効率よく除去できない場合がある。また着色成分を効率よく除去することできない場合が有り好ましくない。アルカリ量が２０モルより多いと純度が低下することや色相が悪化することがあり好ましくない。 The alkali used in the alkaline aqueous solution of the present invention is not particularly limited, but is limited to lithium hydroxide, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, calcium hydroxide, and barium hydroxide. , Sodium carbonate, potassium carbonate and the like. Sodium hydroxide and potassium hydroxide are preferable. The amount of alkali used is not particularly limited, but in order to efficiently remove by-products and coloring components, it is usually 0 to 1 mol of the compound represented by the formula (1). It is preferably 1 to 20 mol, more preferably 0.2 to 10 mol, and even more preferably 0.3 to 5 mol. If the amount of alkali is less than 0.1 mol, by-products may not be removed efficiently. In addition, it may not be possible to efficiently remove the coloring component, which is not preferable. If the amount of alkali is more than 20 mol, the purity may be lowered and the hue may be deteriorated, which is not preferable.
本発明において、アルカリ精製工程は式（２）で表される化合物を含む反応混合物溶液にアルカリ水溶液を添加し加熱攪拌してもよいし、反応混合物溶液を有機溶媒で希釈した後にアルカリ水溶液を添加し加熱攪拌してもよい。通常、有機溶媒希釈後に実施される。希釈する有機溶媒は、特に限定されるものではないが、ベンゼン、トルエン、キシレン、メシチレンなどの芳香族炭化水素、ペンタン、ヘキサン、ヘプタンなどの脂肪族炭化水素、クロロベンゼン、ジクロロベンゼンなどのハロゲン化芳香族炭化水素、ジメチルホルムアミド、ジメチルスルホキシドなどなどが挙げられる。好ましくはトルエン、ジメチルホルムアミドであり、より好ましくはジメチルホルムアミドである。アルカリ精製操作後は、アルカリ水溶液を分液除去することができる。また、アルカリ精製操作後に水洗、吸着処理、濾過などの他の精製操作を付加してもよい。 In the present invention, the alkali purification step may be carried out by adding an alkaline aqueous solution to the reaction mixture solution containing the compound represented by the formula (2) and heating and stirring, or by diluting the reaction mixture solution with an organic solvent and then adding the alkaline aqueous solution. It may be heated and stirred. It is usually carried out after diluting the organic solvent. The organic solvent to be diluted is not particularly limited, but is limited to aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene, aliphatic hydrocarbons such as pentane, hexane and heptane, and halogenated aromatics such as chlorobenzene and dichlorobenzene. Examples thereof include group hydrocarbons, dimethylformamide, dimethylsulfoxide and the like. Toluene and dimethylformamide are preferable, and dimethylformamide is more preferable. After the alkali purification operation, the alkaline aqueous solution can be separated and removed. Further, other purification operations such as washing with water, adsorption treatment, and filtration may be added after the alkali purification operation.
一般的に、式（２）で表される化合物は、エチレンカーボネートが３モル以上付加した副生物が多いほど結晶化し難いが、本発明においてはこれらの副生物が少ないため容易に結晶化ができ、色相、純度とも良好な式（２）で表される化合物の結晶を得ることができる。 In general, the compound represented by the formula (2) is more difficult to crystallize as the number of by-products to which 3 mol or more of ethylene carbonate is added increases, but in the present invention, it can be easily crystallized because these by-products are small. It is possible to obtain crystals of a compound represented by the formula (2), which has good hue and purity.
本発明において、式（２）で表される化合物を晶析精製するなどしてさらに純度を高くしても良い。晶析精製に用いられる有機溶媒は、特に限定されるものではないが、トルエン、キシレン、メシチレンなどの芳香族炭化水素、ヘキサン、ヘプタンなどの脂肪族炭化水素、クロロベンゼン、ジクロロベンゼンなどのハロゲン化芳香族炭化水素、メタノール、エタノール、プロパノール、ブタノールなどのアルコール類、アセトン、メチルエチルケトン、メチルイソブチルケトンなどのケトン類、酢酸エチル、酢酸ブチルなどのエステル類、ジメチルホルムアミド、ジメチルスルホキシドなどが挙げられる。これら有機溶媒は単独または二種類以上の組み合わせで使用できる。これらの溶媒は新たに添加することも可能であるし、あるいは新たに添加することなく、前記アルカリ精製工程で用いた溶媒をそのまま用いても良い。有機溶媒の使用量は、特に限定されるものではないが、経済性の点から、通常、式（２）で表される化合物に対して、１重量倍以上、好ましくは１〜５０重量倍、更に好ましくは３〜２０重量倍程度である。 In the present invention, the purity may be further increased by crystallizing and purifying the compound represented by the formula (2). The organic solvent used for crystallization purification is not particularly limited, but is not limited to aromatic hydrocarbons such as toluene, xylene and mesitylene, aliphatic hydrocarbons such as hexane and heptane, and halogenated aromatics such as chlorobenzene and dichlorobenzene. Examples thereof include group hydrocarbons, alcohols such as methanol, ethanol, propanol and butanol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, esters such as ethyl acetate and butyl acetate, dimethylformamide and dimethyl sulfoxide. These organic solvents can be used alone or in combination of two or more. These solvents can be newly added, or the solvent used in the alkali purification step may be used as it is without being newly added. The amount of the organic solvent used is not particularly limited, but from the viewpoint of economy, it is usually 1% by weight or more, preferably 1 to 50 times by weight, that of the compound represented by the formula (2). More preferably, it is about 3 to 20 times by weight.
晶析精製は一般的な方法で実施可能であり特に限定されないが、通常、晶析を行う混合物中の結晶が溶解する温度、例えば６０℃以上、好ましくは８０℃以上に加熱した後、この溶液を適当な温度、例えば−１０〜３０℃に冷却することにより目的物の結晶を得ることができる。析出した結晶は濾過などにより回収され、必要により洗浄し、乾燥することにより単離できる。また必要に応じて、単離された結晶を精製してもよい。精製方法としては、再晶析（再結晶）や活性炭等の吸着剤を用いた不純物除去処理を挙げることができる。 Crystallization purification can be carried out by a general method and is not particularly limited, but usually, after heating to a temperature at which the crystals in the mixture to be crystallized dissolve, for example, 60 ° C. or higher, preferably 80 ° C. or higher, this solution is used. The desired crystal can be obtained by cooling the mixture to an appropriate temperature, for example, −10 to 30 ° C. The precipitated crystals can be recovered by filtration or the like, washed if necessary, and dried to isolate them. If necessary, the isolated crystals may be purified. Examples of the refining method include recrystallization (recrystallization) and impurity removal treatment using an adsorbent such as activated carbon.
《ビナフタレン化合物》
本発明において、前記式（２）で表される化合物の純度は、９５％以上が好ましく、９７％以上がより好ましく、９９％以上がさらに好ましい。本発明の純度について、％は高速液体クロマトグラフ（ＨＰＬＣ）測定における溶媒を除いた面積百分率値である。
《Vinaphthalene compound》
In the present invention, the purity of the compound represented by the formula (2) is preferably 95% or more, more preferably 97% or more, still more preferably 99% or more. For the purity of the present invention,% is the area percentage value excluding the solvent in high performance liquid chromatography (HPLC) measurement.
本発明において、前記式（２−Ａ）で表される化合物の溶液ＡＰＨＡは１００以下であると好ましく、８０以下であるとより好ましく、５０以下であるとさらに好ましい。溶液ＡＰＨＡが１００より高いと光学用樹脂原料として使用した場合、樹脂の色相やそれを使った光学部材に悪影響を及ぼすことがある。 In the present invention, the solution APHA of the compound represented by the formula (2-A) is preferably 100 or less, more preferably 80 or less, and further preferably 50 or less. If the solution APHA is higher than 100, when it is used as an optical resin raw material, it may adversely affect the hue of the resin and the optical member using the resin.
本発明において、溶液ＡＰＨＡは、前記式（２−Ａ）で表される化合物０．５ｇをジメチルホルムアミド１０ｍｌに溶解させた溶液を、測色計を用いて測定試料の透過測定を行うことにより測定する。 In the present invention, the solution APHA is measured by measuring the permeation of a measurement sample using a colorimeter by dissolving 0.5 g of the compound represented by the above formula (2-A) in 10 ml of dimethylformamide. To do.
以下、本発明を実施例により詳細に説明するが、本発明はその要旨を超えない限り、以下の実施例に限定されるものではない。 Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to the following Examples as long as the gist thereof is not exceeded.
なお、実施例において、各種測定は以下のように行った。
（１）高速液体クロマトグラフ（ＨＰＬＣ）測定
日立製高速液体クロマトグラフＬ−２３５０を用い、表１の測定条件で測定した。実施例中、特に断らない限り％はＨＰＬＣにおける溶媒を除いて補正した面積百分率値である。
In the examples, various measurements were performed as follows.
(1) High Performance Liquid Chromatography (HPLC) Measurement Using a high performance liquid chromatograph L-2350 manufactured by Hitachi, measurement was performed under the measurement conditions shown in Table 1. In the examples,% is the area percentage value corrected by excluding the solvent in HPLC unless otherwise specified.
（２）ＡＰＨＡ測定
測定試料０．５ｇをジメチルホルムアミド１０ｍｌに溶解させた溶液をφ２５ｍｍの試験管に入れ、日本電色製工業（株）製ＴＺ６０００を用いて測定した。
(2) APHA measurement A solution prepared by dissolving 0.5 g of a measurement sample in 10 ml of dimethylformamide was placed in a test tube having a diameter of 25 mm, and measurement was performed using TZ6000 manufactured by Nippon Denshoku Kogyo Co., Ltd.
［実施例１］
（工程１）
撹拌機、冷却器、温度計を備え付けたフラスコに６，６’−ジフェニル−１，１’−ビ−２−ナフトール（以下、ＢＮ−６Ｐｈと略記することがある）４０．００ｇ（０．０９１モル）、エチレンカーボネート１８．４７ｇ（０．２１０モル）、炭酸カリウム１．３１ｇ、ジメチルホルムアミド４０ｍｌを仕込み、１２０℃で９時間反応した。ＨＰＬＣで測定した結果、ＢＮ−６Ｐｈは０．１％、２，２’−ビス（２−ヒドロキシエトキシ）−６，６’−ジフェニル−１，１’−ビナフタレン（以下、ＢＮ２ＥＯ−６Ｐｈと略記することがある）は９５．１％、ＢＮ−６Ｐｈ１モルに対しエチレンカーボネートが３モル以上反応した副生物は３．０％だった。
[Example 1]
(Step 1)
6,6'-diphenyl-1,1'-bi-2-naphthol (hereinafter sometimes abbreviated as BN-6Ph) 40.00 g (0.091) in a flask equipped with a stirrer, a cooler, and a thermometer. Mol), 18.47 g (0.210 mol) of ethylene carbonate, 1.31 g of potassium carbonate and 40 ml of dimethylformamide were charged and reacted at 120 ° C. for 9 hours. As a result of measurement by HPLC, BN-6Ph is 0.1%, 2,2'-bis (2-hydroxyethoxy) -6,6'-diphenyl-1,1'-binaphthalene (hereinafter, abbreviated as BN2EO-6Ph). (May be) was 95.1%, and 3.0% of by-products in which 3 mol or more of ethylene carbonate reacted with 1 mol of BN-6 Ph.
（工程２）
工程１で得られた反応混合物溶液にジメチルホルムアミド６０ｍｌを加え希釈した後、１０重量％水酸化ナトリウム水溶液９ｍｌを加え１１０℃で４時間撹拌後、反応液を２Ｌの蒸留水中に撹拌しながら滴下し、ＢＮ２ＥＯ−６Ｐｈを結晶化させた。この結晶を回収し、２Ｌの蒸留水でスラリー洗浄を３回行った。回収した結晶を９０℃で７時間真空乾燥し、ＢＮ２ＥＯ−６Ｐｈの結晶を４６ｇ得た（収率：９６％、純度：９９．１％、ＢＮ−６Ｐｈ１モルに対しエチレンカーボネートが３モル以上反応した副生物：０．０％、ＡＰＨＡ：５０）。
(Step 2)
60 ml of dimethylformamide was added to the reaction mixture solution obtained in step 1 to dilute it, 9 ml of a 10 wt% sodium hydroxide aqueous solution was added, and the mixture was stirred at 110 ° C. for 4 hours, and then the reaction solution was added dropwise to 2 L of distilled water with stirring. , BN2EO-6Ph was crystallized. The crystals were recovered and slurry-washed with 2 L of distilled water three times. The recovered crystals were vacuum dried at 90 ° C. for 7 hours to obtain 46 g of BN2EO-6Ph crystals (yield: 96%, purity: 99.1%, and 3 mol or more of ethylene carbonate reacted with 1 mol of BN-6Ph. By-products: 0.0%, APHA: 50).
［実施例２］
（工程１）
撹拌機、冷却器、温度計を備え付けたフラスコにＢＮ−６Ｐｈ３５．００ｇ（０．０８０モル）、エチレンカーボネート１６．１６ｇ（０．１８４モル）、炭酸カリウム１．１５ｇ、トルエン３５ｍｌを仕込み、１１０℃で１１時間反応した。ＨＰＬＣで測定した結果、ＢＮ−６Ｐｈは０．１％、ＢＮ２ＥＯ−６Ｐｈは９１．５％、ＢＮ−６Ｐｈ１モルに対しエチレンカーボネートが３モル以上反応した副生物は４．２％だった。
[Example 2]
(Step 1)
A flask equipped with a stirrer, a cooler, and a thermometer was charged with 35.00 g (0.080 mol) of BN-6Ph, 16.16 g (0.184 mol) of ethylene carbonate, 1.15 g of potassium carbonate, and 35 ml of toluene, and charged at 110 ° C. Reacted for 11 hours. As a result of measurement by HPLC, BN-6Ph was 0.1%, BN2EO-6Ph was 91.5%, and 1 mol of BN-6Ph was reacted with 3 mol or more of ethylene carbonate by 4.2%.
（工程２）
得られた反応混合物溶液にトルエン５０ｍｌを加え希釈した後、１０重量％水酸化ナトリウム水溶液８ｍｌを加え１１０℃で４時間撹拌した。反応終了後、反応液を分液漏斗に移し中性なるまで蒸留水で洗浄した。反応液を濃縮した後、メチルエチルケトンで再結晶を一回行い、ＢＮ２ＥＯ−６Ｐｈの結晶を３９ｇ得た（収率：９３％、純度：９８．６％、ＢＮ−６Ｐｈ１モルに対しエチレンカーボネートが３モル以上反応した副生物：０．０％、ＡＰＨＡ：３０）。
(Step 2)
50 ml of toluene was added to the obtained reaction mixture solution for dilution, 8 ml of a 10 wt% sodium hydroxide aqueous solution was added, and the mixture was stirred at 110 ° C. for 4 hours. After completion of the reaction, the reaction solution was transferred to a separating funnel and washed with distilled water until it became neutral. After concentrating the reaction solution, recrystallization was performed once with methyl ethyl ketone to obtain 39 g of BN2EO-6Ph crystals (yield: 93%, purity: 98.6%, 3 mol of ethylene carbonate per 1 mol of BN-6Ph. By-products that reacted as described above: 0.0%, APHA: 30).
［比較例１］
特許文献１の実施例１．５に記載の方法（式（１）で表される化合物とエチレンカーボネートとを１：３の使用量（モル比）で反応させる条件であり、さらに、３重量％以上のアルカリ水溶液を添加し、５０℃以上の温度で加熱攪拌する工程を実施していないため、本発明の請求項１を満足しない）で反応後、ＨＰＬＣ測定をした結果、ＢＮ−６Ｂｒは０．１％、ＢＮ２ＥＯ−６Ｐｈは９２．８％、ＢＮ−６Ｐｈ１モルに対し、エチレンカーボネートが３モル以上反応した副生物は５．３％だった。その後、特許文献１の実施例１．５に記載の方法で洗浄、精製、乾燥を行い、ＢＮ２ＥＯ−６Ｐｈを得た（収率：６９％、純度：９９％、ＢＮ−６Ｐｈ１モルに対しエチレンカーボネートが３モル以上反応した副生物：０．５％、ＡＰＨＡ：１５０）。３重量％以上のアルカリ水溶液を添加し、５０℃以上の温度で加熱攪拌する工程を実施せず、洗浄や再結晶により副生物を除去するため、収率が低かった。
[Comparative Example 1]
It is a condition that the compound represented by the formula (1) and ethylene carbonate are reacted in an amount (molar ratio) of 1: 3 according to the method described in Example 1.5 of Patent Document 1, and further, 3% by weight. BN-6Br is 0 as a result of HPLC measurement after the reaction (which does not satisfy claim 1 of the present invention because the step of adding the above alkaline aqueous solution and heating and stirring at a temperature of 50 ° C. or higher has not been carried out). .1%, BN2EO-6Ph was 92.8%, and BN-6Ph was 1 mol, while 5.3% of by-products were reacted with 3 mol or more of ethylene carbonate. Then, it was washed, purified and dried by the method described in Example 1.5 of Patent Document 1 to obtain BN2EO-6Ph (yield: 69%, purity: 99%, ethylene carbonate per 1 mol of BN-6Ph). By-products that reacted in 3 mol or more: 0.5%, APHA: 150). The yield was low because by-products were removed by washing and recrystallization without performing the step of adding an alkaline aqueous solution of 3% by weight or more and heating and stirring at a temperature of 50 ° C. or higher.
本発明により、高純度かつ色相に優れるビナフタレン化合物が収率良く得られるため、光学用樹脂原料として好適に使用される。 According to the present invention, a vinaphthalene compound having high purity and excellent hue can be obtained in high yield, and thus is suitably used as a raw material for an optical resin.
Claims (4)
工程１：式（１）で表される化合物とエチレンカーボネートとを、１：１．９〜１：２．９の使用量（モル比）で反応させる工程
工程２：上記工程１の反応終了後、得られた反応混合物溶液に３重量％以上のアルカリ水溶液を添加し、５０℃以上の温度で加熱攪拌する工程
Step 1: The compound represented by the formula (1) and ethylene carbonate are reacted in an amount (molar ratio) of 1: 1.9 to 1: 2.9. Step 2: After the reaction of Step 1 is completed. , A step of adding an alkaline aqueous solution of 3% by weight or more to the obtained reaction mixture solution and heating and stirring at a temperature of 50 ° C. or more.
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| EP20763864.4A EP3932898A4 (en) | 2019-02-27 | 2020-02-21 | Compound having binaphthalene skeleton and method for producing compound having binaphthalene skeleton |
| PCT/JP2020/007001 WO2020175353A1 (en) | 2019-02-27 | 2020-02-21 | Compound having binaphthalene skeleton and method for producing compound having binaphthalene skeleton |
| CN202080016683.3A CN113474321B (en) | 2019-02-27 | 2020-02-21 | Compound having binaphthyl skeleton and method for producing compound having binaphthyl skeleton |
| TW109105967A TW202043185A (en) | 2019-02-27 | 2020-02-25 | Compound having binaphthalene skeleton and method for producing compound having binaphthalene skeleton |
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| WO2019043060A1 (en) * | 2017-08-30 | 2019-03-07 | Reuter Chemische Apparatebau Kg | Binaphthyl compounds |
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| WO2019043060A1 (en) * | 2017-08-30 | 2019-03-07 | Reuter Chemische Apparatebau Kg | Binaphthyl compounds |
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