JPWO2018008683A1 - Method for producing 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane compound - Google Patents
Method for producing 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane compound Download PDFInfo
- Publication number
- JPWO2018008683A1 JPWO2018008683A1 JP2018526418A JP2018526418A JPWO2018008683A1 JP WO2018008683 A1 JPWO2018008683 A1 JP WO2018008683A1 JP 2018526418 A JP2018526418 A JP 2018526418A JP 2018526418 A JP2018526418 A JP 2018526418A JP WO2018008683 A1 JPWO2018008683 A1 JP WO2018008683A1
- Authority
- JP
- Japan
- Prior art keywords
- hydroxyphenyl
- tetrakis
- ethane
- ethane compound
- tetrahydrofuran
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- -1 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane compound Chemical class 0.000 title claims abstract description 40
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- WEVYAHXRMPXWCK-UHFFFAOYSA-N methyl cyanide Natural products CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 59
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 50
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 150000002989 phenols Chemical class 0.000 claims abstract description 25
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229940015043 glyoxal Drugs 0.000 claims abstract description 15
- 239000003377 acid catalyst Substances 0.000 claims abstract description 11
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000000605 extraction Methods 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims 1
- 239000012074 organic phase Substances 0.000 description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 15
- 239000008346 aqueous phase Substances 0.000 description 13
- 239000002244 precipitate Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- HDPBBNNDDQOWPJ-UHFFFAOYSA-N 4-[1,2,2-tris(4-hydroxyphenyl)ethyl]phenol Chemical group C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)C(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 HDPBBNNDDQOWPJ-UHFFFAOYSA-N 0.000 description 8
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical class CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000006386 neutralization reaction Methods 0.000 description 5
- 125000005843 halogen group Chemical group 0.000 description 4
- 125000000962 organic group Chemical group 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- 229910052799 carbon Chemical group 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 1
- IXQGCWUGDFDQMF-UHFFFAOYSA-N 2-Ethylphenol Chemical class CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 1
- UBVXRQAPDRCBOE-UHFFFAOYSA-N 2-[1,2,2-tris(2-hydroxyphenyl)ethyl]phenol Chemical compound OC1=CC=CC=C1C(C=1C(=CC=CC=1)O)C(C=1C(=CC=CC=1)O)C1=CC=CC=C1O UBVXRQAPDRCBOE-UHFFFAOYSA-N 0.000 description 1
- MYKVTURBDFXUAB-UHFFFAOYSA-N 2-[1,2,2-tris(4-hydroxyphenyl)ethyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)C(C=1C(=CC=CC=1)O)C1=CC=C(O)C=C1 MYKVTURBDFXUAB-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- DDDZRVXTROKLFQ-UHFFFAOYSA-N 3-[1,2,2-tris(3-hydroxyphenyl)ethyl]phenol Chemical compound Oc1cccc(c1)C(C(c1cccc(O)c1)c1cccc(O)c1)c1cccc(O)c1 DDDZRVXTROKLFQ-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 210000003000 inclusion body Anatomy 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229940044654 phenolsulfonic acid Drugs 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
Classifications
-
- 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
- C07C37/16—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 by condensation involving hydroxy groups of phenols or alcohols or the ether or mineral ester group derived therefrom
-
- 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
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
- C07C37/72—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by liquid-liquid treatment
-
- 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
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B61/00—Other general methods
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
酸触媒の存在下に反応溶媒中でフェノール類とグリオキザールとを反応させて１，１，２，２−テトラキス（４−ヒドロキシフェニル）エタン化合物およびその異性体並びにフェノール類を含む混合物を得、得られた混合物から１，１，２，２−テトラキス（４−ヒドロキシフェニル）エタン化合物をテトラヒドロフランまたはアセトニトリルを用いて抽出することを有する、１，１，２，２−テトラキス（４−ヒドロキシフェニル）エタン化合物の製造方法。Phenols and glyoxal are reacted in a reaction solvent in the presence of an acid catalyst to obtain a 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane compound, its isomer and a mixture containing phenols. 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane compound having a 1,2,2,2-tetrakis (4-hydroxyphenyl) ethane compound extracted with tetrahydrofuran or acetonitrile Compound production method.
Description
本発明は、１，１，２，２−テトラキス（４−ヒドロキシフェニル）エタン化合物の製造方法に関する。より詳細に、本発明は、高純度の１，１，２，２−テトラキス（４−ヒドロキシフェニル）エタン化合物を高収率にて製造する方法に関する。
本願は、２０１６年７月７日に、日本に出願された特願２０１６−１３５２７０号に基づき優先権を主張し、その内容をここに援用する。The present invention relates to a method for producing a 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane compound. More specifically, the present invention relates to a method for producing a high purity 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane compound in a high yield.
This application claims priority on July 7, 2016 based on Japanese Patent Application No. 2016-135270 for which it applied to Japan, and uses the content here.
テトラキスフェノールエタン化合物は、エポキシ樹脂などの熱硬化性樹脂の原料、エポキシ樹脂用硬化剤、フォトレジスト感光剤用バラスト剤、フェノール樹脂改質剤及び酸化防止剤、などとして有用である。また、包摂化合物のホスト化合物としての利用も注目されている。 Tetrakisphenol ethane compounds are useful as raw materials for thermosetting resins such as epoxy resins, curing agents for epoxy resins, ballast agents for photoresist photosensitive agents, phenolic resin modifiers and antioxidants. Also, the use of inclusion compounds as host compounds has attracted attention.
テトラキスフェノールエタン化合物の製造方法が種々提案されている。例えば、特許文献１は、酸性触媒の存在下、フェノール類とグリオキザールとを縮合させたのち、濃縮して揮発性成分を留去させ、次いで残留物を、その中に含まれる低分子化合物及び高次縮合物を溶解し、かつテトラキスフェノールエタンに対して貧溶媒的に作用する有機溶剤で処理することを特徴とする高純度テトラキスフェノールエタンの製造方法を開示している。有機溶剤として、アセトン又はテトラヒドロフラン若しくはそれらの混合物を推奨している。 Various methods for producing tetrakisphenolethane compounds have been proposed. For example, Patent Document 1 discloses a method in which phenols and glyoxal are condensed in the presence of an acidic catalyst, and then concentrated to distill off a volatile component. Disclosed is a method for producing high-purity tetrakisphenol ethane, which comprises dissolving the next condensate and treating with an organic solvent that acts as a poor solvent for tetrakisphenol ethane. As the organic solvent, acetone or tetrahydrofuran or a mixture thereof is recommended.
特許文献２は、酸触媒の存在下、フェノール類とグリオキザールとを反応させてテトラキスフェノールエタンを製造するに当り、フェノール類に対して５重量％以上のアセトンを共存させ、かつ６０℃以下の温度で反応を行うことを特徴とするテトラキスフェノールエタンの製造方法を開示している。
特許文献３は、フェノール類とグリオキザール又はグリオキザール誘導体とを、過塩素酸塩及び酸触媒の存在下に反応させること特徴とする１，１，２，２−テトラキス（４−ヒドロキシフェニル）エタン化合物の製造方法を開示している。In Patent Document 2, in the production of tetrakisphenolethane by reacting phenols and glyoxal in the presence of an acid catalyst, 5% by weight or more of acetone is present in the phenols, and the temperature is 60 ° C. or less. Discloses a process for producing tetrakisphenolethane, which is characterized in that the reaction is carried out.
Patent Document 3 discloses a 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane compound obtained by reacting a phenol with glyoxal or a glyoxal derivative in the presence of a perchlorate and an acid catalyst. A manufacturing method is disclosed.
特許文献４は、ジオキシエタン化合物とフェノール類とを反応させることにより、１，１，２，２−テトラキス（４−ヒドロキシフェニル）エタン化合物及びその類縁体を、高収率かつ高い生産効率で製造する方法を開示している。
これらの方法では、反応液にアセトンなどの貧溶媒を加えて目的物質を析出させて、次いで蒸留などによって精製している。上記のような方法で得られるテトラキスフェノールエタン化合物は、１，１，２，２−テトラキス（４−ヒドロキシフェニル）エタン化合物以外に、１，１，２−トリス（４−ヒドロキシフェニル）−２−（２−ヒドロキシフェニル）エタン化合物等のような異性体を多数含んでいる。特に有用な物質は、１，１，２，２−テトラキス（４−ヒドロキシフェニル）エタン化合物であるので、他の異性体を除去し、高収率で高純度化することが望まれる。Patent Document 4 manufactures a 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane compound and its analogs with high yield and high production efficiency by reacting a dioxyethane compound with a phenol. A method is disclosed.
In these methods, a poor solvent such as acetone is added to the reaction solution to precipitate the target substance, and then purified by distillation or the like. The tetrakisphenol ethane compound obtained by the above method is not only 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane compound but also 1,1,2-tris (4-hydroxyphenyl) -2- It contains many isomers such as (2-hydroxyphenyl) ethane compounds. Since a particularly useful substance is a 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane compound, it is desired to remove other isomers and to achieve high purity and high purity.
本発明の課題は、高純度の１，１，２，２−テトラキス（４−ヒドロキシフェニル）エタン化合物を高収率にて製造する方法を提供することである。 An object of the present invention is to provide a method for producing a high-purity 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane compound in a high yield.
上記課題を解決するために検討した結果、以下の形態を包含する本発明を完成するに至った。 As a result of studies to solve the above problems, the present invention including the following modes has been completed.
〔１〕 １，１，２，２−テトラキス（４−ヒドロキシフェニル）エタン化合物およびその異性体並びにフェノール類を含む混合物から１，１，２，２−テトラキス（４−ヒドロキシフェニル）エタン化合物をテトラヒドロフランまたはアセトニトリルを用いて抽出することを有する、１，１，２，２−テトラキス（４−ヒドロキシフェニル）エタン化合物の製造方法。 [1] 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane compound and its isomer and a mixture containing phenols are converted into 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane compound in tetrahydrofuran. Or the manufacturing method of a 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane compound which has extracting using acetonitrile.
〔２〕 酸触媒の存在下に反応溶媒中でフェノール類とグリオキザールとを反応させて１，１，２，２−テトラキス（４−ヒドロキシフェニル）エタン化合物およびその異性体並びにフェノール類を含む混合物を得ることをさらに有する〔１〕に記載の製造方法。
〔３〕 反応溶媒がアセトン、テトラヒドロフランまたはアセトニトリルである、〔２〕に記載の製造方法。
〔４〕 フェノール類の仕込量を基準にした反応率が２０〜７０％である、〔２〕または〔３〕に記載の製造方法。
〔５〕 抽出時のテトラヒドロフランまたはアセトニトリルの量が、１，１，２，２−テトラキス（４−ヒドロキシフェニル）エタン化合物およびその異性体の合計量１モルに対して１．０〜７．０Ｌである、〔１〕〜〔４〕のいずれかひとつに記載の製造方法。[2] Phenols and glyoxal are reacted in a reaction solvent in the presence of an acid catalyst to produce a 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane compound, its isomer and a mixture containing phenols. The production method according to [1], further comprising obtaining.
[3] The production method according to [2], wherein the reaction solvent is acetone, tetrahydrofuran or acetonitrile.
[4] The production method according to [2] or [3], wherein a reaction rate based on a charged amount of phenols is 20 to 70%.
[5] The amount of tetrahydrofuran or acetonitrile at the time of extraction is 1.0 to 7.0 L with respect to 1 mol of the total amount of 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane compound and its isomer. The manufacturing method according to any one of [1] to [4].
本発明の製造方法によれば、高純度の１，１，２，２−テトラキス（４−ヒドロキシフェニル）エタン化合物を高収率にて製造することができる。
本発明の製造方法は、抽出にて１，１，２，２−テトラキス（４−ヒドロキシフェニル）エタン化合物を高い選択率で分離でき、且つ酸触媒の中和反応で生成する塩を抽出時の洗浄で除去することができるので、従来の方法に比べて、濾過または蒸留の工程が少ない。According to the production method of the present invention, a high-purity 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane compound can be produced in a high yield.
In the production method of the present invention, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane compound can be separated with high selectivity by extraction, and the salt produced by the neutralization reaction of the acid catalyst is extracted. Since it can be removed by washing, there are fewer steps of filtration or distillation compared to conventional methods.
本発明の１，１，２，２−テトラキス（４−ヒドロキシフェニル）エタン化合物の製造方法は、１，１，２，２−テトラキス（４−ヒドロキシフェニル）エタン化合物およびその異性体並びにフェノール類を含む混合物から１，１，２，２−テトラキス（４−ヒドロキシフェニル）エタン化合物をテトラヒドロフランまたはアセトニトリルを用いて抽出することを有する。 The method for producing 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane compound of the present invention comprises 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane compound and its isomers and phenols. Extracting the 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane compound from the containing mixture with tetrahydrofuran or acetonitrile.
１，１，２，２−テトラキス（４−ヒドロキシフェニル）エタン化合物は、１，１，２，２−テトラキス（４−ヒドロキシフェニル）エタンまたはそれのフェニル基構成炭素原子に直接に結合する水素原子が他の基で置換されてなるものである。より具体的には式（１）で表される化合物を包含する。
前記Ｒのハロゲノ基としては、フルオロ基、クロロ基、ブロモ基等が挙げられる。また、有機基としては、メチル基、エチル基、プロピル基、イソプロピル基等のアルキル基；メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基等のアルコキシ基；フェニル基、４−メチルフェニル基等の置換基を有していてもよいフェニル基等が挙げられる。The 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane compound is a hydrogen atom directly bonded to 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane or a carbon atom constituting the phenyl group thereof. Is substituted with another group. More specifically, the compound represented by Formula (1) is included.
Examples of the halogeno group for R include a fluoro group, a chloro group, and a bromo group. Examples of the organic group include alkyl groups such as methyl group, ethyl group, propyl group, and isopropyl group; alkoxy groups such as methoxy group, ethoxy group, propoxy group, and isopropoxy group; phenyl group, 4-methylphenyl group, and the like. Examples thereof include a phenyl group which may have a substituent.
１，１，２，２−テトラキス（４−ヒドロキシフェニル）エタン化合物の異性体は、フェニル基に結合する水酸基の位置が異なる物質である。例えば、１，１，２，２−テトラキス（２−ヒドロキシフェニル）エタン、１，１，２，２−テトラキス（３−ヒドロキシフェニル）エタン、１，１，２−トリス（４−ヒドロキシフェニル）−２−（２−ヒドロキシフェニル）エタンなどを挙げることができる。
混合物に含まれる１，１，２，２−テトラキス（４−ヒドロキシフェニル）エタン化合物およびそれの異性体の合計量は、混合物に対して、好ましくは１５〜３５質量％、より好ましくは１８〜３２質量％である。The isomers of 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane compounds are substances having different positions of hydroxyl groups bonded to phenyl groups. For example, 1,1,2,2-tetrakis (2-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (3-hydroxyphenyl) ethane, 1,1,2-tris (4-hydroxyphenyl)- 2- (2-hydroxyphenyl) ethane and the like can be mentioned.
The total amount of 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane compound and isomers thereof contained in the mixture is preferably 15 to 35% by mass, more preferably 18 to 32, based on the mixture. % By mass.
フェノール類は、フェノールまたはフェノールのベンゼン環構成炭素原子に直接に結合する水素原子が他の基で置換されてなるものである。より具体的には式（２）で表される化合物を包含する。
前記Ｒのハロゲノ基としては、フルオロ基、クロロ基、ブロモ基等が挙げられる。また、有機基としては、メチル基、エチル基、プロピル基、イソプロピル基等のアルキル基；メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基等のアルコキシ基；フェニル基、４−メチルフェニル基等の置換基を有していてもよいフェニル基等が挙げられる。
混合物に含まれるフェノール類の量は、混合物に対して、好ましくは６５〜８５質量％、より好ましくは６８〜８２質量％である。混合物に含まれるフェノール類の量が上記範囲にあると、テトラヒドロフランまたはアセトニトリルに対する１，１，２，２−テトラキス（４−ヒドロキシフェニル）エタン化合物の溶解度が高くなり、抽出効率が高くなる。Phenols are those in which the hydrogen atom directly bonded to the carbon atom constituting the benzene ring of phenol or phenol is substituted with another group. More specifically, the compound represented by Formula (2) is included.
Examples of the halogeno group for R include a fluoro group, a chloro group, and a bromo group. Examples of the organic group include alkyl groups such as methyl group, ethyl group, propyl group, and isopropyl group; alkoxy groups such as methoxy group, ethoxy group, propoxy group, and isopropoxy group; phenyl group, 4-methylphenyl group, and the like. Examples thereof include a phenyl group which may have a substituent.
The amount of phenols contained in the mixture is preferably 65 to 85% by mass, more preferably 68 to 82% by mass, based on the mixture. When the amount of phenols contained in the mixture is in the above range, the solubility of 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane compound in tetrahydrofuran or acetonitrile is increased, and the extraction efficiency is increased.
１，１，２，２−テトラキス（４−ヒドロキシフェニル）エタン化合物およびその異性体並びにフェノール類を含む混合物は、例えば、１，１，２，２−テトラキス（４−ヒドロキシフェニル）エタン化合物およびその異性体の混合物とフェノール類とを混ぜ合わせることによって得ることができる。あるいは、酸触媒の存在下に反応溶媒中でフェノール類とグリオキザールとを反応させることによっても得ることができる。 A mixture containing 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane compound and its isomers and phenols includes, for example, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane compound and its mixture It can be obtained by mixing a mixture of isomers with phenols. Alternatively, it can also be obtained by reacting phenols with glyoxal in a reaction solvent in the presence of an acid catalyst.
酸触媒の存在下に反応溶媒中でフェノール類とグリオキザールとを反応させる方法は、例えば、特許文献１、特許文献２などに開示される方法である。本発明においては、特に、反応溶媒には、アセトン、テトラヒドロフランまたはアセトニトリルを採用することが好ましい。また、酸触媒としては、例えばシュウ酸、フェノールスルホン酸、ｐ−トルエンスルホン酸などの有機酸、強酸性イオン交換樹脂などの樹脂酸、硫酸、塩酸、過塩素酸などの無機酸が挙げられる。
また、フェノール類の仕込量を基準にした反応率は、好ましくは２０〜７０％、より好ましくは４０〜６０％である。反応によって得られる混合物中にフェノール類が残存することによって、テトラヒドロフランまたはアセトニトリルに対する１，１，２，２−テトラキス（４−ヒドロキシフェニル）エタン化合物の溶解度が高くなり、抽出効率が高くなる。
反応によって得られる混合物中のフェノール類の残存量が上記の範囲より少ない場合は新たにフェノール類を混合物に加えることが好ましい。反応によって得られる混合物に酸触媒が残っている場合には塩基物質を添加して中和することができる。A method of reacting phenols and glyoxal in a reaction solvent in the presence of an acid catalyst is, for example, a method disclosed in Patent Document 1, Patent Document 2, and the like. In the present invention, it is particularly preferable to employ acetone, tetrahydrofuran or acetonitrile as the reaction solvent. Examples of the acid catalyst include organic acids such as oxalic acid, phenolsulfonic acid, and p-toluenesulfonic acid, resin acids such as strongly acidic ion exchange resins, and inorganic acids such as sulfuric acid, hydrochloric acid, and perchloric acid.
Moreover, the reaction rate based on the amount of phenols charged is preferably 20 to 70%, more preferably 40 to 60%. When phenols remain in the mixture obtained by the reaction, the solubility of 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane compound in tetrahydrofuran or acetonitrile increases, and the extraction efficiency increases.
When the residual amount of phenols in the mixture obtained by the reaction is less than the above range, it is preferable to newly add phenols to the mixture. When the acid catalyst remains in the mixture obtained by the reaction, it can be neutralized by adding a basic substance.
テトラヒドロフランまたはアセトニトリル、好ましくはテトラヒドロフランを用いての抽出は、その操作法によって特に限定されない。例えば、実験室レベルの抽出においては、前記混合物にテトラヒドロフランまたはアセトニトリルと、それに相溶しない溶媒、例えば、水とを添加し、撹拌し、次いで静置して有機相と水相とに分離させ、１，１，２，２−テトラキス（４−ヒドロキシフェニル）エタン化合物を多く含む有機相を残すという操作を含む。抽出時の温度は、好ましくは３０〜８０℃、より好ましくは６０〜７０℃である。抽出時のテトラヒドロフランまたはアセトニトリルの量は、１，１，２，２−テトラキス（４−ヒドロキシフェニル）エタン化合物およびその異性体の合計量１モルに対して、好ましくは０．５〜８．０Ｌ、より好ましくは１．０〜７．０Ｌ、更により好ましくは１．５〜６．５Ｌである。
上記の抽出を行うことにより、酸触媒の中和反応で生成する塩を抽出時の洗浄で除去することができるので、従来の方法に比べて、濾過または蒸留の工程を減らすことができる。Extraction with tetrahydrofuran or acetonitrile, preferably tetrahydrofuran, is not particularly limited by the operation method. For example, in laboratory-level extraction, tetrahydrofuran or acetonitrile and an incompatible solvent such as water are added to the mixture, stirred, and then allowed to stand to separate the organic and aqueous phases, This includes an operation of leaving an organic phase containing a large amount of 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane compound. The temperature at the time of extraction is preferably 30 to 80 ° C, more preferably 60 to 70 ° C. The amount of tetrahydrofuran or acetonitrile at the time of extraction is preferably 0.5 to 8.0 L with respect to 1 mol of the total amount of 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane compound and its isomer, More preferably, it is 1.0-7.0L, More preferably, it is 1.5-6.5L.
By performing the above extraction, the salt produced by the neutralization reaction of the acid catalyst can be removed by washing at the time of extraction, so that the filtration or distillation step can be reduced as compared with the conventional method.
得られた有機相を冷やすと、固形分が析出するので、それを濾過で、取り出す。析出時の温度は、好ましくは−５〜１０℃、より好ましくは０〜５℃である。
このようにして得られる析出物は、１，１，２，２−テトラキス（４−ヒドロキシフェニル）エタン化合物を高率で含有し、異性体が殆んど含まれていない。この析出物は１，１，２，２−テトラキス（４−ヒドロキシフェニル）エタン化合物からなるホストと、テトラヒドロフランまたはアセトニトリルからなるゲストとからなる包摂体であると推測する。When the obtained organic phase is cooled, a solid content is precipitated, which is taken out by filtration. The temperature during precipitation is preferably -5 to 10 ° C, more preferably 0 to 5 ° C.
The precipitate obtained in this way contains a 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane compound at a high rate and contains almost no isomer. This deposit is presumed to be an inclusion body composed of a host composed of a 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane compound and a guest composed of tetrahydrofuran or acetonitrile.
析出物から必要に応じて溶媒を除去すると、ゲストであるテトラヒドロフランまたはアセトニトリルが除かれて、ホストである１，１，２，２−テトラキス（４−ヒドロキシフェニル）エタン化合物が得られる。 When the solvent is removed from the precipitate as necessary, the guest, tetrahydrofuran or acetonitrile, is removed, and the host, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane compound, is obtained.
以下、実施例で本発明を更に詳細に説明するが、本発明はこれら実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.
［実施例１］
３００ｍＬの四つ口フラスコに、フェノール９４．１ｇ、テトラヒドロフラン１５ｇおよび濃度３９％グリオキザール１４．９ｇを加えた。この溶液に濃度９８％硫酸１９．６ｇを０℃〜５℃の温度範囲にて滴下し、同温度範囲で１６時間撹拌し、次いで３０℃にて３時間撹拌して反応させた。その後、室温まで冷却した。フェノール仕込量を基準にした反応率は４０％であった。これに、水３０ｍｌおよびテトラヒドロフラン１００ｍｌを加え、濃度２８％ＮａＯＨ水溶液５７．１ｇを加えて中和した。その後、６０〜６５℃の温度範囲にて３０分間撹拌した。次いで、静置して水相と有機相とに分離させた。水相を取り除き、有機相を取り出して、分析した。有機相にテトラキスフェノールエタン１９．９ｇが含まれていた。
この有機相を、５℃まで冷却し、１時間保持して、固形分を析出させた。析出物を濾過し、５℃のテトラヒドロフラン６０ｍｌにて洗浄した。洗浄された析出物を真空下にて溶媒除去した。１，１，２，２−テトラキス（４−ヒドロキシフェニル）エタン９５重量％および異性体１．５重量％含有のテトラキスフェノールエタン１６．４ｇを得た。[Example 1]
To a 300 mL four-necked flask, 94.1 g of phenol, 15 g of tetrahydrofuran and 14.9 g of 39% concentration glyoxal were added. To this solution, 19.6 g of 98% sulfuric acid was added dropwise in the temperature range of 0 ° C. to 5 ° C., stirred for 16 hours in the same temperature range, and then stirred for 3 hours at 30 ° C. for reaction. Then, it cooled to room temperature. The reaction rate based on the amount of phenol charged was 40%. 30 ml of water and 100 ml of tetrahydrofuran were added thereto, and 57.1 g of a 28% strength aqueous NaOH solution was added for neutralization. Then, it stirred for 30 minutes in the temperature range of 60-65 degreeC. Subsequently, it was left to separate into an aqueous phase and an organic phase. The aqueous phase was removed and the organic phase was removed and analyzed. The organic phase contained 19.9 g of tetrakisphenolethane.
The organic phase was cooled to 5 ° C. and held for 1 hour to precipitate a solid content. The precipitate was filtered and washed with 60 ml of tetrahydrofuran at 5 ° C. The washed precipitate was solvent removed under vacuum. 16.4 g of tetrakisphenolethane containing 95% by weight of 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane and 1.5% by weight of the isomer was obtained.
［実施例２］
３００ｍＬの四つ口フラスコに、フェノール９４．１ｇ、アセトン１５ｇおよび濃度３９％グリオキザール１４．９ｇを加えた。この溶液に濃度９８％硫酸１９．６ｇを０℃〜５℃の温度範囲にて滴下し、同温度範囲で１６時間撹拌し、次いで３０℃にて３時間撹拌して反応させた。その後、室温まで冷却した。フェノール仕込量を基準にした反応率は４０％であった。これに、水３０ｍｌおよびテトラヒドロフラン１００ｍｌを加え、濃度２８％ＮａＯＨ水溶液５７．１ｇを加えて中和した。その後、６０〜６５℃の温度範囲にて３０分間撹拌した。次いで静置して水相と有機相とに分離させた。水相を取り除き、有機相を取り出して、分析した。有機相にテトラキスフェノールエタン２３．９ｇが含まれていた。
この有機相を、５℃まで冷却し、１時間保持して、固形分を析出させた。析出物を濾過し、５℃のテトラヒドロフラン６０ｍｌにて洗浄した。洗浄された析出物を真空下にて溶媒除去した。１，１，２，２−テトラキス（４−ヒドロキシフェニル）エタン９５重量％および異性体３重量％含有のテトラキスフェノールエタン２０．７ｇを得た。[Example 2]
To a 300 mL four-necked flask, 94.1 g of phenol, 15 g of acetone and 14.9 g of 39% concentration of glyoxal were added. To this solution, 19.6 g of 98% sulfuric acid was added dropwise in the temperature range of 0 ° C. to 5 ° C., stirred for 16 hours in the same temperature range, and then stirred for 3 hours at 30 ° C. for reaction. Then, it cooled to room temperature. The reaction rate based on the amount of phenol charged was 40%. 30 ml of water and 100 ml of tetrahydrofuran were added thereto, and 57.1 g of a 28% strength aqueous NaOH solution was added for neutralization. Then, it stirred for 30 minutes in the temperature range of 60-65 degreeC. Next, the mixture was allowed to stand to separate into an aqueous phase and an organic phase. The aqueous phase was removed and the organic phase was removed and analyzed. The organic phase contained 23.9 g of tetrakisphenol ethane.
The organic phase was cooled to 5 ° C. and held for 1 hour to precipitate a solid content. The precipitate was filtered and washed with 60 ml of tetrahydrofuran at 5 ° C. The washed precipitate was solvent removed under vacuum. 20.7 g of tetrakisphenolethane containing 95% by weight of 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane and 3% by weight of the isomer was obtained.
［実施例３］
３００ｍＬの四つ口フラスコに、フェノール９４．１ｇ、アセトニトリル１５ｇおよび濃度３９％グリオキザール１４．９ｇを加えた。この溶液に濃度９８％硫酸１９．６ｇを０℃〜５℃の温度範囲にて滴下し、同温度範囲で１６時間撹拌し、次いで３０℃にて３時間撹拌して反応させた。その後、室温まで冷却した。フェノール仕込量を基準にした反応率は４０％であった。これに、水３０ｍｌおよびテトラヒドロフラン１００ｍｌを加え、濃度２８％ＮａＯＨ水溶液５７．１ｇを加えて中和した。その後、６０〜６５℃の温度範囲にて撹拌した。次いで静置して水相と有機相とに分離させた。水相を取り除き、有機相を取り出して、分析した。有機相にテトラキスフェノールエタン２１．９ｇが含まれていた。
この有機相を、５℃まで冷却し、１時間保持して、固形分を析出させた。析出物を濾過し、５℃のテトラヒドロフラン６０ｍｌにて洗浄した。洗浄された析出物を真空下にて溶媒除去した。１，１，２，２−テトラキス（４−ヒドロキシフェニル）エタン９６重量％および異性体２．０重量％含有のテトラキスフェノールエタン１８．５ｇを得た。[Example 3]
To a 300 mL four-necked flask, 94.1 g of phenol, 15 g of acetonitrile, and 14.9 g of 39% concentration glyoxal were added. To this solution, 19.6 g of 98% sulfuric acid was added dropwise in the temperature range of 0 ° C. to 5 ° C., stirred for 16 hours in the same temperature range, and then stirred for 3 hours at 30 ° C. for reaction. Then, it cooled to room temperature. The reaction rate based on the amount of phenol charged was 40%. 30 ml of water and 100 ml of tetrahydrofuran were added thereto, and 57.1 g of a 28% strength aqueous NaOH solution was added for neutralization. Then, it stirred in the temperature range of 60-65 degreeC. Next, the mixture was allowed to stand to separate into an aqueous phase and an organic phase. The aqueous phase was removed and the organic phase was removed and analyzed. The organic phase contained 21.9 g of tetrakisphenol ethane.
The organic phase was cooled to 5 ° C. and held for 1 hour to precipitate a solid content. The precipitate was filtered and washed with 60 ml of tetrahydrofuran at 5 ° C. The washed precipitate was solvent removed under vacuum. 18.5 g of tetrakisphenolethane containing 96% by weight of 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane and 2.0% by weight of the isomer was obtained.
［実施例４］
３００ｍＬの四つ口フラスコに、フェノール９４．１ｇ、アセトニトリル２０ｇおよび濃度３９％グリオキザール１４．９ｇを加えた。この溶液に濃度９５％硫酸２０．６ｇを０℃〜５℃の温度範囲にて滴下し、同温度範囲で７時間撹拌し、次いで室温下にて１６時間撹拌して反応させた。フェノール仕込量を基準にした反応率は４０％であった。これに、水３０ｍｌおよびアセトニトリル３２５ｍｌを加え、濃度２８％ＮａＯＨ水溶液５７．１ｇを加えて中和した。その後、７０〜７５℃の温度範囲にて撹拌した。次いで静置して水相と有機相とに分離させた。水相を取り除き、有機相を取り出して、分析した。有機相にテトラキスフェノールエタン１９．７ｇが含まれていた。
この有機相を、５℃まで冷却し、１時間保持して、固形分を析出させた。析出物を濾過し、５℃のアセトニトリル６０ｍｌにて洗浄した。洗浄された析出物を真空下にて溶媒除去した。１，１，２，２−テトラキス（４−ヒドロキシフェニル）エタン９３重量％および異性体１．０重量％含有のテトラキスフェノールエタン１２．１ｇを得た。[Example 4]
To a 300 mL four-necked flask, 94.1 g of phenol, 20 g of acetonitrile, and 14.9 g of 39% concentration glyoxal were added. To this solution, 20.6 g of 95% sulfuric acid was added dropwise in the temperature range of 0 ° C. to 5 ° C., stirred for 7 hours in the same temperature range, and then stirred for 16 hours at room temperature for reaction. The reaction rate based on the amount of phenol charged was 40%. To this, 30 ml of water and 325 ml of acetonitrile were added, and neutralized by adding 57.1 g of a 28% strength aqueous NaOH solution. Then, it stirred in the temperature range of 70-75 degreeC. Next, the mixture was allowed to stand to separate into an aqueous phase and an organic phase. The aqueous phase was removed and the organic phase was removed and analyzed. The organic phase contained 19.7 g of tetrakisphenol ethane.
The organic phase was cooled to 5 ° C. and held for 1 hour to precipitate a solid content. The precipitate was filtered and washed with 60 ml of acetonitrile at 5 ° C. The washed precipitate was solvent removed under vacuum. 12.1 g of tetrakisphenolethane containing 93% by weight of 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane and 1.0% by weight of the isomer was obtained.
［比較例１］
３００ｍＬの四つ口フラスコに、フェノール６３ｇ、アセトン７．８ｇおよび濃度３９％グリオキザール１４．９ｇを加えた。この溶液に濃度９８％硫酸１１．６ｇを１３℃〜１７℃の温度範囲にて滴下し、４０℃で１６時間撹拌し、その後、室温まで冷却した。これに、濃度２８％ＮａＯＨ水溶液３２．６ｇを加えて中和した。その後、アセトン４０ｇを添加した。析出物を濾過し、アセトン／水（２：３）１００ｍｌで洗浄した。洗浄された析出物をメタノール８７．５ｇに加えて加熱し溶解させ、不溶物を熱時濾過した。得られた溶液に水３５ｇを添加し、メタノールを留去し、次いで冷却して析出させた。析出物を濾過し、水／アセトン（１：１）３０ｍｌで洗浄した。１，１，２，２−テトラキス（４−ヒドロキシフェニル）エタン８９．０重量％および異性体６．７重量％含有のテトラキスフェノールエタン１８ｇを得た。[Comparative Example 1]
In a 300 mL four-necked flask, 63 g of phenol, 7.8 g of acetone, and 14.9 g of 39% concentration glyoxal were added. To this solution, 11.6 g of 98% sulfuric acid having a concentration of 98% was dropped in a temperature range of 13 ° C to 17 ° C, stirred at 40 ° C for 16 hours, and then cooled to room temperature. This was neutralized by adding 32.6 g of a 28% strength aqueous NaOH solution. Thereafter, 40 g of acetone was added. The precipitate was filtered and washed with 100 ml of acetone / water (2: 3). The washed precipitate was added to 87.5 g of methanol and heated to dissolve, and the insoluble matter was filtered while hot. 35 g of water was added to the resulting solution, methanol was distilled off, and then cooled to precipitate. The precipitate was filtered and washed with 30 ml of water / acetone (1: 1). 18 g of tetrakisphenolethane containing 89.0% by weight of 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane and 6.7% by weight of the isomer was obtained.
［比較例２］
３００ｍＬの四つ口フラスコに、フェノール９４．１ｇ、メチルエチルケトン１５ｇおよび濃度３９％グリオキザール１４．９ｇを加えた。この溶液に濃度９８％硫酸１９．６ｇを０℃〜５℃の温度範囲にて滴下し、同温度範囲で１６時間撹拌し、３０℃にて３時間撹拌して反応させた。室温まで冷却し、水３０ｍｌおよびメチルエチルケトン５０ｍｌを加え、濃度２８％ＮａＯＨ水溶液５７．１ｇを加えて中和した。その後、６０〜６５℃にて撹拌した。次いで静置して水相と有機相とに分離させた。水相を取り除き、有機相を取り出して、分析した。有機相にテトラキスフェノールエタン１７．９ｇが含まれていた。
この有機相を、５℃まで冷却し、１時間保持したが、固形分は析出しなかった。[Comparative Example 2]
To a 300 mL four-necked flask, 94.1 g of phenol, 15 g of methyl ethyl ketone, and 14.9 g of 39% concentration glyoxal were added. To this solution, 19.6 g of 98% sulfuric acid was added dropwise in the temperature range of 0 ° C. to 5 ° C., stirred for 16 hours in the same temperature range, and stirred for 3 hours at 30 ° C. for reaction. After cooling to room temperature, 30 ml of water and 50 ml of methyl ethyl ketone were added, and neutralized by adding 57.1 g of a 28% strength aqueous NaOH solution. Then, it stirred at 60-65 degreeC. Next, the mixture was allowed to stand to separate into an aqueous phase and an organic phase. The aqueous phase was removed and the organic phase was removed and analyzed. The organic phase contained 17.9 g of tetrakisphenol ethane.
The organic phase was cooled to 5 ° C. and held for 1 hour, but no solid content was precipitated.
［比較例３］
３００ｍＬの四つ口フラスコに、フェノール９４．１ｇ、酢酸エチル２０ｇおよび濃度４０％グリオキザール１４．５ｇを加えた。この溶液に濃度９５％硫酸２０．６ｇを０℃〜５℃の温度範囲にて滴下し、同温度範囲で２３時間撹拌した。その後、室温まで昇温し、水３０ｍｌおよび酢酸エチル４０ｍｌを加え、濃度２８％ＮａＯＨ水溶液５７．１ｇを加えて中和した。その後、６０〜６５℃の温度範囲で撹拌した。次いで静置して水相と有機相とに分離させた。水相を取り除き、有機相を取り出して、分析した。有機相にテトラキスフェノールエタン１９．５ｇが含まれていた。
この有機相を、５℃まで冷却し、１時間保持したが、固形分は析出しなかった。[Comparative Example 3]
To a 300 mL four-necked flask, 94.1 g of phenol, 20 g of ethyl acetate and 14.5 g of 40% strength glyoxal were added. To this solution, 20.6 g of 95% sulfuric acid was added dropwise in a temperature range of 0 ° C. to 5 ° C., and stirred for 23 hours in the same temperature range. Thereafter, the temperature was raised to room temperature, 30 ml of water and 40 ml of ethyl acetate were added, and neutralized by adding 57.1 g of a 28% strength aqueous NaOH solution. Then, it stirred in the temperature range of 60-65 degreeC. Next, the mixture was allowed to stand to separate into an aqueous phase and an organic phase. The aqueous phase was removed and the organic phase was removed and analyzed. The organic phase contained 19.5 g of tetrakisphenol ethane.
The organic phase was cooled to 5 ° C. and held for 1 hour, but no solid content was precipitated.
高純度の１，１，２，２−テトラキス（４−ヒドロキシフェニル）エタン化合物を高収率にて製造する方法を提供することができる。 A method for producing a high-purity 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane compound in a high yield can be provided.
Claims (5)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016135270 | 2016-07-07 | ||
| JP2016135270 | 2016-07-07 | ||
| PCT/JP2017/024651 WO2018008683A1 (en) | 2016-07-07 | 2017-07-05 | Method for producing 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPWO2018008683A1 true JPWO2018008683A1 (en) | 2019-03-07 |
| JP6665292B2 JP6665292B2 (en) | 2020-03-13 |
Family
ID=60912158
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2018526418A Expired - Fee Related JP6665292B2 (en) | 2016-07-07 | 2017-07-05 | Method for producing 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane compound |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP6665292B2 (en) |
| WO (1) | WO2018008683A1 (en) |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2897850B2 (en) * | 1991-04-26 | 1999-05-31 | 旭有機材工業株式会社 | Method for producing high-purity tetrakisphenolethane |
| JP4023539B2 (en) * | 2001-09-20 | 2007-12-19 | 江崎グリコ株式会社 | Extraction method and purification method of active substance |
| JP4438465B2 (en) * | 2004-03-18 | 2010-03-24 | 日本曹達株式会社 | Method for producing tetrakis (4-hydroxyphenyl) ethane compound |
| JP6502151B2 (en) * | 2015-04-09 | 2019-04-17 | Ｊｆｅケミカル株式会社 | Method for producing tetrakisphenol ethanes |
-
2017
- 2017-07-05 JP JP2018526418A patent/JP6665292B2/en not_active Expired - Fee Related
- 2017-07-05 WO PCT/JP2017/024651 patent/WO2018008683A1/en active Application Filing
Also Published As
| Publication number | Publication date |
|---|---|
| WO2018008683A1 (en) | 2018-01-11 |
| JP6665292B2 (en) | 2020-03-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2014123005A1 (en) | Novel aryl compound and method for producing same | |
| JP5341747B2 (en) | Synthesis of curcumin | |
| JP2006160663A (en) | Method for producing 1,1'-bis(2-hydroxynaphthyl) | |
| JP4181791B2 (en) | Hydroxymethyl-substituted polyfunctional phenols | |
| JP6665292B2 (en) | Method for producing 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane compound | |
| JP4438465B2 (en) | Method for producing tetrakis (4-hydroxyphenyl) ethane compound | |
| JP5899110B2 (en) | Method for producing diaryl derivative, novel binaphthyl derivative, method for producing arene derivative, and novel arene derivative | |
| JP2003300922A (en) | Trimethylolated triphenol | |
| JP2009107991A (en) | New hydroxymethyl-substituted or alkoxymethyl-substituted bisphenol compound | |
| JP5727830B2 (en) | Sulfonium compounds | |
| JP4029017B2 (en) | Method for producing bisphenol compound | |
| JP2005089363A (en) | Method for isolating and refining adamantane derivative formed and method for recovering raw material | |
| JP6502151B2 (en) | Method for producing tetrakisphenol ethanes | |
| JP4685409B2 (en) | Method for producing 2,5-bis (aminomethyl) -1,4-dithiane compound | |
| KR20140067368A (en) | Process for preparing eperisone hydrochloride | |
| JP2012153642A (en) | Sulfonium compound | |
| JP7030242B2 (en) | Epoxy reactive diluent and its manufacturing method | |
| JP6439219B2 (en) | Production method of fluorine-containing phenol | |
| JP2015048325A (en) | Novel hydroxymethyl-substituted or alkoxymethyl-substituted trisphenol compound | |
| JP2016169165A (en) | Method for producing 2,6-difluorobenzoylformate compound | |
| JP2012201611A5 (en) | ||
| KR101511235B1 (en) | Method of refining high purity 2,6-diamino-9,10-dihydroanthracene | |
| JPH0436254A (en) | Production of dehydroxydiphenylmethane | |
| JP2018095591A (en) | Sulphonium compound and thermal polymerization initiator | |
| JP4145082B2 (en) | Substituted phenols |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20181029 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20191126 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20191223 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20200114 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20200128 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20200212 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20200219 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6665292 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| LAPS | Cancellation because of no payment of annual fees |