JP4090555B2 - 2,3,6,7,10,11-Hexakisyloxytriphenylene compound and method for producing high purity 2,3,6,7,10,11-hexahydroxytriphenylene - Google Patents
2,3,6,7,10,11-Hexakisyloxytriphenylene compound and method for producing high purity 2,3,6,7,10,11-hexahydroxytriphenylene Download PDFInfo
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- JP4090555B2 JP4090555B2 JP06362298A JP6362298A JP4090555B2 JP 4090555 B2 JP4090555 B2 JP 4090555B2 JP 06362298 A JP06362298 A JP 06362298A JP 6362298 A JP6362298 A JP 6362298A JP 4090555 B2 JP4090555 B2 JP 4090555B2
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- 150000001875 compounds Chemical class 0.000 title claims description 36
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- QMLILIIMKSKLES-UHFFFAOYSA-N triphenylene-2,3,6,7,10,11-hexol Chemical group C12=CC(O)=C(O)C=C2C2=CC(O)=C(O)C=C2C2=C1C=C(O)C(O)=C2 QMLILIIMKSKLES-UHFFFAOYSA-N 0.000 title description 6
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 10
- KEPYGYIKTTWNCR-UHFFFAOYSA-N [SiH3]C(C([SiH3])=C1)=CC(C(C(C2=C3)=C4)=CC([SiH3])=C4[SiH3])=C1C2=CC([SiH3])=C3[SiH3] Chemical group [SiH3]C(C([SiH3])=C1)=CC(C(C(C2=C3)=C4)=CC([SiH3])=C4[SiH3])=C1C2=CC([SiH3])=C3[SiH3] KEPYGYIKTTWNCR-UHFFFAOYSA-N 0.000 claims 1
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 18
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 13
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 239000004973 liquid crystal related substance Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- -1 2,3,6,7,10,11-hexahydroxytriphenylene compound Chemical class 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- DCFKHNIGBAHNSS-UHFFFAOYSA-N chloro(triethyl)silane Chemical compound CC[Si](Cl)(CC)CC DCFKHNIGBAHNSS-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000005828 desilylation reaction Methods 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- YTKHQSUTXVUOGK-UHFFFAOYSA-N (3,6,7,10,11-pentaacetyloxytriphenylen-2-yl) acetate Chemical group C12=CC(OC(C)=O)=C(OC(C)=O)C=C2C2=CC(OC(C)=O)=C(OC(C)=O)C=C2C2=C1C=C(OC(C)=O)C(OC(=O)C)=C2 YTKHQSUTXVUOGK-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 125000005580 triphenylene group Chemical group 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000004104 aryloxy group Chemical group 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000000269 nucleophilic effect Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- MHYGQXWCZAYSLJ-UHFFFAOYSA-N tert-butyl-chloro-diphenylsilane Chemical compound C=1C=CC=CC=1[Si](Cl)(C(C)(C)C)C1=CC=CC=C1 MHYGQXWCZAYSLJ-UHFFFAOYSA-N 0.000 description 2
- BCNZYOJHNLTNEZ-UHFFFAOYSA-N tert-butyldimethylsilyl chloride Chemical compound CC(C)(C)[Si](C)(C)Cl BCNZYOJHNLTNEZ-UHFFFAOYSA-N 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 239000004985 Discotic Liquid Crystal Substance Substances 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- SLGBZMMZGDRARJ-UHFFFAOYSA-N Triphenylene Natural products C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 SLGBZMMZGDRARJ-UHFFFAOYSA-N 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000020335 dealkylation Effects 0.000 description 1
- 238000006900 dealkylation reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000002035 hexane extract Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- KAHVZNKZQFSBFW-UHFFFAOYSA-N n-methyl-n-trimethylsilylmethanamine Chemical compound CN(C)[Si](C)(C)C KAHVZNKZQFSBFW-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005092 sublimation method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Liquid Crystal Substances (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は液晶材料であるトリフェニレン誘導体合成における有用な合成中間体である高純度の２，３，６，７，１０，１１−ヘキサヒドロキシトリフェニレン化合物の製造方法とその方法に用いる新規なトリフェニレン化合物に関するものである。
【０００２】
【従来の技術】
近年、液晶表示素子はワードプロセッサー、パーソナルコンピューター、テレビなどに広く用いられるようになり、それに関連する素材、装置などの産業活動が活発に行われている。液晶表示材料の根本をなす素材である液晶化合物についても活発な開発研究が行われ、数多くの化合物が開発されてきた。これらの化合物は、表示素子に限らず種々の用途の開発に向け利用が考えられている。
【０００３】
従来からよく知られ、より利用されている液晶化合物は棒状のものであるが、最近では円盤状の液晶化合物、いわゆるディスコティク液晶化合物が注目を浴びている。その中の代表的なものの１つにトリフェニレン誘導体がある（例えば、特開平７−２５８１６７号、同７−２５８１７０号）。
【０００４】
トリフェニレン誘導体の合成原料として重要な化合物は、２，３，６，７，１０，１１−ヘキサヒドロキシトリフェニレン（以下、単にＨＨＴＰという）であるが、該化合物は不安定であること、特定の溶媒でないと溶け難いなどの理由で高純度で製造することは容易でなく液晶化合物に用いる場合の大きな問題であった。そのため、この問題を解決する方法として例えば特開平８−１１９８９４号（ヨウ化水素で脱アルキル化）、および特開平９−３０１９０６号（ヘキサアシル体の加水分解）が提案されている。いずれも問題点の多くを改善するが、前者においては強酸条件下で加熱するため反応装置がガラスに限定されること、後者においては加水分解がアルカリ条件下の反応であるため、アルカリ条件下で不安定な生成物（ＨＨＴＰ）をアルカリに曝すことになり着色等の問題が生ずる。そこで、より工業的製造において効果的な高純度ＨＨＴＰの製造法の開発が引続き望まれている。
【０００５】
【発明が解決しようとする課題】
したがって本発明の目的は、ＨＨＴＰの製造に伴う前記の問題点を解決することであり、特に高純度ＨＨＴＰの製造方法を提供することである。
【０００６】
【課題を解決するための手段】
上記課題を達成するために鋭意検討した結果、本発明者は、ＨＨＴＰを一旦ヘキサシリル化することにより、そのシリル化物の再結晶精製が容易で、その脱シリル化も非常に温和な条件下で起こること、そして、こうして脱シリル化して得られたＨＨＴＰの純度は極めて高いものとなることを見い出した。本発明はこの知見に基づきなされたものである。すなわち本発明の目的は、
（１）下記一般式（Ｉ）で表わされる２，３，６，７，１０，１１−ヘキサキスシリルオキシトリフェニレン化合物
【０００７】
【化２】
（式中Ｒ1 、Ｒ2 、Ｒ3 、Ｒ4 、Ｒ5 およびＲ6 はシリル基を表わす）、及び（２）前記一般式（Ｉ）で表わされる（１）項記載の２，３，６，７，１０，１１−ヘキサキスシリルトリフェニレンを脱シリル化することを特徴とする高純度２，３，６，７，１０，１１−ヘキサヒドロキシトリフェニレンの製造方法
により達成された。
【０００９】
【発明の実施の形態】
以下、本発明について詳しく説明する。一般式（Ｉ）におけるＲ1 〜Ｒ6 はシリル基を表わすが、これらは互いに同一でも異なった基でもよい。好ましくは下記一般式（II）で表わされるシリル基である。
【００１０】
【化３】
（式中、Ｒa 、Ｒb およびＲc はシリコンと安定な結合を形成しうる基を表わす。）
一般式（II）のＲa 、Ｒb およびＲc はシリコンと安定な結合を形成しうる基を表わすが、詳しくは例えばハロゲン原子、炭素原子もしくは酸素原子で結合する基を表わす。好ましくはフッ素原子、置換もしくは無置換のアルキル、アリール、アルコキシ又はアリールオキシ基を表わす。これら好ましい基について詳しく説明するとメチル、エチル、プロピル、シクロヘキシル、イソプロピル、ｔ−ブチル、アリル、クロロメチルもしくはベンジルなどのアルキル基（好ましくは炭素数１〜１５のもの）、フェニル、トリル、ビフェニルイル、などのアリール基（好ましくは炭素数６〜２０のもの）、メトキシ、エトキシ、イソプロポキシ、ｔ−ブトキシもしくはベンジルオキシなどのアルコキシ基（好ましくは炭素数１〜１５のもの）、フェノキシ、４−メチルフェノキシ、４−ｔ−ブチルフェノキシ、２，４，６−トリメチルフェノキシなどのアリールオキシ基（好ましくは炭素数６〜２０のもの）を表わす。
【００１２】
Ｒa 、Ｒb およびＲc のいずれか１つが隣接するシリル基上の置換基と直接又は間接に結合してもよい。
【００１３】
特に好ましいＲa 、Ｒb およびＲc はメチル、エチル、イソプロピル、ｔ−ブチル、又はフェニル基である。
【００１４】
次に本発明の一般式（Ｉ）で表わされる化合物の具体例を表１および表２に示すが、本発明はこれらに限定されるものではない。
【００１５】
【表１】
【表２】
次に一般式（Ｉ）で表わされる本発明の化合物の合成法を以下に説明する。代表的合成法を（スキーム１）、（スキーム２）および（スキーム３）に示した。（スキーム１）と（スキーム２）の出発原料である２，３，６，７，１０，１１−ヘキサヒドロキシトリフェニレン（ＨＨＴＰ）は、Ｊ．Ｍａｔｅｒ．Ｃｈｅｍ．，２，１２６１（１９９２）、イスラエル特許第７０５７２号、特開平８−１１９８９４号、同９−３０１９０６号などに記載の方法により合成できる（スキーム３）の出発原料である２，３，６，７，１０，１１−ヘキサアルコキシトリフェニレンは、Ｔｅｔｒａｈｅｄｒｏｎ，４７，７９１（１９９１）、Ｓｙｎｔｈｅｓｉｓ，１９９４，４７７，Ｊ．Ｐｈｙｓ．Ｃｈｅｍ．９９，１００５（１９９５）などに記載の方法により合成できる。
【００１８】
【化４】
【化５】
【化６】
一般式（Ｉ）で表わされる化合物の精製は一般には再結晶法や昇華法により行なわれる。その理由はシリル基上の置換基が小さい場合には、酸素−ケイ素結合が容易に加水分解されるので、よく用いられるシリカゲルカラムクロマトグラフィなどによる精製が困難であるからである。但し、シリル基上の置換基が立体的にかさ高い場合はかなり安定になり、シリカゲルカラムクロマトグラフィなどでの精製も可能になる場合もある。
【００２２】
一般式（Ｉ）で表わされる化合物に代表されるＨＨＴＰのＯ−シリル化体から脱シリル化により高純度のＨＨＴＰを得る反応としては、ＨＣｌ、ＨＢｒ、ＨＦ、Ｈ2 ＳＯ4 および酢酸などの酸に曝す方法、水、アルコールなど求核性のある溶媒と接触させ、室温又は加熱条件下におく方法又は、フッ化物と反応させる方法があげられる。立体的かさ高い基をもつシリル基を有する場合はより強い酸性条件下に曝したり、フッ化物と反応させることが好ましいが、立体的にかさ高くない基のシリル基の場合は求核性のある溶媒中で中性条件下で容易に脱シリル化が達成できる。
【００２３】
酸を使用する場合、その使用量は好ましくは存在するシリル基に対して等モル量以上になる濃度であるが、アルコールや水のような求核剤が存在する条件下では、触媒量でも十分である。反応温度は通常−２０℃から１５０℃であり、好ましくは０℃〜５０℃であり、反応時間は１分から５時間が好ましい。
【００２４】
ＨＨＴＰは難溶なため、通常反応液から析出するのでろ過乾燥により簡単に高純度ＨＨＴＰが得られる。
【００２５】
【実施例】
以下に実施例に基づき本発明を説明するが、本発明はこれらの実施例により何ら限定されるものではない。
【００２６】
実施例１（例示化合物（１）の合成）
２，３，６，７，１０，１１−ヘキサヒドロキシトリフェニレン（ＨＨＴＰ）５．２ｇ（純度９７％ ０．０１５ｍｏｌ）のテトラヒドロフラン（５０ｍｌ）溶液にＮ，Ｎ−ジメチルトリメチルシリルアミン１２．７ｇ（０．１１ｍｏｌ）を加え、室温下約３０分撹拌し、次に加熱還流すると徐々にジメチルアミンの発生が起きた。約３時間後、反応液をエバポレーターで濃縮し、ｎ−ヘキサン１５０ｍｌと酢酸エチル１５ｍｌ加えた。その溶液に活性炭を加え、しばらく放置後セライトを用いて吸引ろ過し、ろ液を濃縮すると結晶性の残留物を１０．９ｇ得た。このものはＮＭＲスペクトル的にはほぼ純粋であった。収率９３．５％。これをアセトニトリルを用いて再結晶すると純粋な例示化合物（１）を無色結晶として７．９ｇ（６７．７％、純度９９．５％）得ることができた。
（純度は高速液体クロマトグラフィー（ＨＰＬＣ）で測定した。）
融点１４６〜１４７℃
ＮＭＲ（核磁気共鳴）スペクトル（ＣＤＣｌ3 ）δ（ｐｐｍ）；０．３５（５４Ｈ，ｓ），７．７８（６Ｈ，ｓ）
例示化合物（１）は２２０〜２４０℃／〜０．２ｍｍＨｇで蒸留可能であったが、若干の分解が起きるようで、蒸留で得られるものの純度は低下した。
【００２７】
実施例２（例示化合物（２）の合成）
ＨＨＴＰ、５ｇ（０．０１５ｍｏｌ、純度９７％）のジメチルホルムアミド（５０ｍｌ）溶液にイミダゾール１４．７ｇ（０．２１６ｍｏｌ）加えて撹拌し、室温下トリエチルシリルクロリド１６．３ｇ（０．１０８ｍｏｌ）を加えた。室温下約１時間撹拌後、約６０℃に加熱して約１時間撹拌した。その後室温にもどしてイミダゾール４．２ｇ（０．０６２ｍｏｌ）とトリエチルシリルクロリド４．６ｇ（０．０３１ｍｏｌ）を更に加え、室温下一晩放置した。反応液にｎ−ヘキサンを加えて、撹拌・抽出（水は使わない）し、ジメチルホルムアミド層を分離した後、ｎ−ヘキサン層をアセトニトリルで洗浄し、ｎ−ヘキサン層に活性炭を添加放置した。セライトを用いてろ過後、ろ液を減圧濃縮すると茶色の油状物が１９．３ｇ得られた。この油状物は冷蔵庫中で結晶化する。
ＮＭＲスペクトルでは、この茶色の油状物はトリエチルシリルクロリド由来の不純物を含む例示化合物（２）（純度８１％）であった。
ＮＭＲスペクトル（ＣＤＣｌ3 ）δ（ｐｐｍ）；０．９０（３６Ｈ，ｑ，Ｊ＝７．４），１．０６（５４Ｈ，ｔ，Ｊ＝７．４），７．７５（６Ｈ，ｓ）
【００２８】
実施例３（例示化合物（３）の合成）
ＨＨＴＰ、１ｇ（６．２ｍｍｏｌ、純度９７％）のジメチルホルムアミド（５０ｍｌ）溶液にイミダゾール５．８ｇ（８６ｍｍｏｌ）を加え撹拌し、室温下ｔ−ブチルジメチルシリルクロリド６．５ｇ（４３ｍｍｏｌ）を加えた。若干の発熱がおき約１時間撹拌後一晩放置した。反応の進行がＴＬＣで不十分であることがわかったので１１５℃に加熱し、撹拌した。約３時間後イミダゾール１．７ｇ（２５ｍｍｏｌ）とｔ−ブチルジメチルシリルクロリド１．９ｇ（１２ｍｍｏｌ）を更に添加した。約３時間加熱撹拌後室温に戻し、水を加えることなくｎ−ヘキサン抽出を２回行なった。ジメチルホルムアミド層を分離後、ｎ−ヘキサン抽出液を合わせ水（１回）と飽和食塩水（１回）で洗浄後、硫酸マグネシウムで乾燥した。ろ過後、減圧濃縮し、残渣をアセトニトリルで再結晶することにより例示化合物（３）を５．１ｇ（収率８２％、純度９９．４％）得ることができた。
融点２９９〜３００℃
ＮＭＲスペクトル（ＣＤＣｌ3 ）δ（ｐｐｍ）；０．３０（３６Ｈ，ｓ），１．０６（５４Ｈ，ｓ），７．７６（６Ｈ，ｓ）
【００２９】
実施例４（例示化合物（４）の合成）
ＨＨＴＰ、２ｇ（６．２ｍｍｏｌ、純度９７％）のジメチルホルムアミド（５０ｍｌ）溶液の中にイミダゾール５．８ｇ（８６ｍｍｏｌ）を加え撹拌した。その中にｔ−ブチルジフェニルシリルクロリド、１１．９ｇ（４３ｍｍｏｌ）を加え、室温下約１時間、次に６０℃に加熱して約９時間撹拌した。一晩放置後更に約１１時間１１５℃で撹拌したが反応が完結したかったので、イミダゾール１．７ｇ（２５ｍｍｏｌ）とｔ−ブチルジフェニルシリルクロリド３．４ｇ（１２ｍｍｏｌ）を加え約７時間１１５℃で撹拌した。室温に戻した後水を加えることなくｎ−ヘキサンで３回抽出し、抽出液を合わせた後アセトニトリルで洗浄し、ｎ−ヘキサンを減圧留去することにより黒青色の結晶性化合物を約１３ｇ得た。これをアセトニトリルと酢酸エチル混合溶液で再結晶することにより、３．４ｇ（３１．４％）の例示化合物（４）（純度９９．６％）を得た。尚、ろ液にはまだ多量の例示化合物（４）が含まれていたが、それ以上の取り出しは試みなかった。
融点２３５〜２３７℃
ＮＭＲスペクトル（ＣＤＣｌ3 ）δ（ｐｐｍ）；０．９１（５４Ｈ，ｓ），６．８８（６Ｈ，ｓ），７．２０（２４Ｈ，ｔ，Ｊ＝７．５），７．３２（１２Ｈ，ｔ，Ｊ＝７．５），７．５４（２４Ｈ，ｄ，Ｊ＝７．５）
【００３０】
実施例５（ＨＨＴＰの合成）
実施例１で得た純度９９．５％の例示化合物（１）を２ｇ（２．６ｍｍｏｌ）をメタノール１０ｍｌに加え、加熱還流を約２時間行なった。その後メタノール等低沸点化合物を減圧留去し、得られたＨＨＴＰの結晶を真空ポンプで乾燥後、ＨＰＬＣで純度を測定した所、純度は９９％であった。
実施例６（ＨＨＴＰの合成）
実施例１で得た純度９９．５％の例示化合物（１）２．０ｇ（２．６ｍｍｏｌ）を酢酸エチルに溶かし、その中に４６〜４８％のフッ化水素酸を０．７ｍｌを加え室温下撹拌した。約２時間後析出した結晶をろ別し、乾燥した所純度９９．３％（ＨＰＬＣ純度）のＨＨＴＰを０．８０ｇ（収率９５．０％）得ることができた。
実施例７（ＨＨＴＰの合成）
実施例１で得た純度９９．５％の例示化合物（１）２．０ｇ（２．６ｍｍｏｌ）を酢酸（５０ｍｌ）中で約１時間加熱還流し室温に戻して析出した結晶をろ別・乾燥することにより純度９９．５％（ＨＰＬＣ純度）のＨＨＴＰを０．７８ｇ（収率９２．５％）得ることができた。
【００３１】
実施例８（ＨＨＴＰの合成）
実施例２で得た純度８１％の例示化合物（２）１０ｇを酢酸１００ｍｌに混ぜ、約１時間加熱還流し、室温に戻して析出した結晶をろ別乾燥することにより純度９９．２％（ＨＰＬＣ純度）のＨＨＴＰを２．４ｇ（収率９１％）得ることができた。
【００３２】
参考例１（２，３，６，７，１０，１１−ヘキサアセトキシトリフェニレンの合成）
２，３，６，７，１０，１１−ヘキサアシルオキシ化合物を合成する際はＨＨＴＰを経由することなく、本発明の化合物から直接アシル化により合成することが可能である。その参考例として２，３，６，７，１０，１１−ヘキサアセトキシトリフェニレンの合成例を以下に示す。
例示化合物（１）、２ｇ（純度９９．５％、２．６ｍｍｏｌ）をクロロホルム５０ｍｌに溶かし、その中にアセチルクロリド２．４ｇ（３１．２ｍｍｏｌ）を加え、約２時間加熱還流した。反応液を減圧濃縮し、得られた結晶（８．４ｇ）の成分をＨＰＬＣで分析した所、純度９８％の２，３，６，７，１０，１１−ヘキサアセトキシトリフェニレン（Ｊ．Ｃｈｅｍ．Ｓｏｃ．（ｃ），１９７１，１３９７）であった。
【００３３】
【発明の効果】
本発明の２，３，６，７，１０，１１−ヘキサキスシリルオキシトリフェニレン化合物は有機溶媒への溶解性がよく、再結晶精製が容易であり、その脱シリル化は定量的かつ容易に起きるため、高純度の２，３，６，７，１０，１１−ヘキサヒドロキシトリフェニレン（ＨＨＴＰ）を容易に調製することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a high-purity 2,3,6,7,10,11-hexahydroxytriphenylene compound which is a useful synthetic intermediate in the synthesis of a triphenylene derivative which is a liquid crystal material, and a novel triphenylene compound used in the method. Is.
[0002]
[Prior art]
In recent years, liquid crystal display elements have been widely used in word processors, personal computers, televisions, and the like, and industrial activities such as materials and devices related thereto have been actively conducted. A lot of compounds have been developed for active research and development of liquid crystal compounds that are the basis of liquid crystal display materials. These compounds are considered to be used not only for display elements but also for development of various applications.
[0003]
Conventionally well-known and more widely used liquid crystal compounds are rod-shaped, but recently, disc-shaped liquid crystal compounds, so-called discotic liquid crystal compounds, are attracting attention. One of typical examples is a triphenylene derivative (for example, JP-A-7-258167 and JP-A-7-258170).
[0004]
An important compound as a raw material for the synthesis of a triphenylene derivative is 2,3,6,7,10,11-hexahydroxytriphenylene (hereinafter simply referred to as HHTP), but the compound is unstable and is not a specific solvent. It is not easy to produce with high purity because it is difficult to dissolve, and it has been a big problem when used for liquid crystal compounds. Therefore, as methods for solving this problem, for example, Japanese Patent Application Laid-Open No. 8-119894 (dealkylation with hydrogen iodide) and Japanese Patent Application Laid-Open No. 9-301906 (Hydroacyl hydrolysis) have been proposed. Both improve many of the problems, but in the former, the reactor is limited to glass because of heating under strong acid conditions, and in the latter, hydrolysis is a reaction under alkaline conditions, so under alkaline conditions. Unstable products (HHTP) are exposed to alkali, causing problems such as coloring. Therefore, development of a method for producing high-purity HHTP that is more effective in industrial production is still desired.
[0005]
[Problems to be solved by the invention]
Accordingly, an object of the present invention is to solve the above-mentioned problems associated with the production of HHTP, and particularly to provide a method for producing high-purity HHTP.
[0006]
[Means for Solving the Problems]
As a result of diligent studies to achieve the above-mentioned problems, the present inventor, once hexasilylating HHTP, facilitates recrystallization purification of the silylated product, and desilylation also occurs under very mild conditions. In addition, it has been found that the purity of HHTP obtained by desilylation in this way is extremely high. The present invention has been made based on this finding. That is, the object of the present invention is to
(1) 2,3,6,7,10,11-hexakisyloxytriphenylene compound represented by the following general formula (I)
[Chemical 2]
(Wherein R 1 , R 2 , R 3 , R 4 , R 5 and R 6 represent a silyl group), and (2) 2, 3, as described in item (1), represented by the general formula (I) This was achieved by a method for producing high-purity 2,3,6,7,10,11-hexahydroxytriphenylene, characterized by desilylation of 6,7,10,11-hexakissilyltriphenylene.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
The present invention will be described in detail below. R 1 to R 6 in the general formula (I) represent a silyl group, and these may be the same or different from each other. A silyl group represented by the following general formula (II) is preferable.
[0010]
[Chemical 3]
(Wherein R a , R b and R c represent groups capable of forming a stable bond with silicon.)
In the general formula (II), R a , R b and R c represent groups capable of forming a stable bond with silicon, and in detail, for example, a group bonded by a halogen atom, a carbon atom or an oxygen atom. Preferably, it represents a fluorine atom, a substituted or unsubstituted alkyl, aryl, alkoxy or aryloxy group. When these preferable groups are described in detail, an alkyl group (preferably having 1 to 15 carbon atoms) such as methyl, ethyl, propyl, cyclohexyl, isopropyl, t-butyl, allyl, chloromethyl or benzyl, phenyl, tolyl, biphenylyl, Aryl groups such as those having 6 to 20 carbon atoms, alkoxy groups such as methoxy, ethoxy, isopropoxy, t-butoxy or benzyloxy (preferably having 1 to 15 carbon atoms), phenoxy, 4-methyl An aryloxy group (preferably having 6 to 20 carbon atoms) such as phenoxy, 4-t-butylphenoxy and 2,4,6-trimethylphenoxy is represented.
[0012]
Any one of R a , R b and R c may be bonded directly or indirectly to a substituent on the adjacent silyl group.
[0013]
Particularly preferred R a , R b and R c are methyl, ethyl, isopropyl, t-butyl or phenyl groups.
[0014]
Next, specific examples of the compound represented by the general formula (I) of the present invention are shown in Tables 1 and 2, but the present invention is not limited thereto.
[0015]
[Table 1]
[Table 2]
Next, a method for synthesizing the compound of the present invention represented by the general formula (I) will be described below. Representative synthetic methods are shown in (Scheme 1), (Scheme 2) and (Scheme 3). The starting materials of (Scheme 1) and (Scheme 2) are 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP). Mater. Chem. 1, 2 , 1261 (1992), Israel Patent No. 70572, JP-A Nos. 8-119894 and 9-301906, etc. (Scheme 3) which is a starting material of 2,3,6,7 , 10,11-hexaalkoxytriphenylene is described in Tetrahedron, 47 , 791 (1991), Synthesis, 1994 , 477, J. MoI. Phys. Chem. 99 , 1005 (1995) and the like.
[0018]
[Formula 4]
[Chemical formula 5]
[Chemical 6]
The compound represented by the general formula (I) is generally purified by a recrystallization method or a sublimation method. The reason is that, when the substituent on the silyl group is small, the oxygen-silicon bond is easily hydrolyzed, so that purification by commonly used silica gel column chromatography or the like is difficult. However, when the substituent on the silyl group is sterically bulky, it becomes quite stable and may be purified by silica gel column chromatography or the like.
[0022]
Examples of the reaction for obtaining high purity HHTP by desilylation from an O-silylated form of HHTP represented by the compound represented by the general formula (I) include acids such as HCl, HBr, HF, H 2 SO 4 and acetic acid. Exposure to water, contact with a nucleophilic solvent such as water, alcohol, and the like, and a method of leaving at room temperature or heating, or a reaction with fluoride. In the case of having a silyl group having a sterically bulky group, it is preferable to expose it to a stronger acidic condition or to react with a fluoride, but in the case of a silyl group having a sterically bulky group, it is nucleophilic. Desilylation can be easily achieved under neutral conditions in a solvent.
[0023]
When an acid is used, the amount used is preferably a concentration that is at least equimolar with respect to the silyl groups present, but under conditions where a nucleophile such as alcohol or water is present, a catalytic amount is sufficient. It is. The reaction temperature is usually −20 ° C. to 150 ° C., preferably 0 ° C. to 50 ° C., and the reaction time is preferably 1 minute to 5 hours.
[0024]
Since HHTP is hardly soluble, it usually precipitates from the reaction solution, so that high-purity HHTP can be easily obtained by filtration and drying.
[0025]
【Example】
EXAMPLES The present invention will be described below based on examples, but the present invention is not limited to these examples.
[0026]
Example 1 (Synthesis of Exemplified Compound (1))
To a solution of 5.2 g (purity 97% 0.015 mol) of 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP) in tetrahydrofuran (50 ml) was added 12.7 g (0.11 mol) of N, N-dimethyltrimethylsilylamine. ) And stirred at room temperature for about 30 minutes, and then heated to reflux to gradually generate dimethylamine. After about 3 hours, the reaction solution was concentrated with an evaporator, and 150 ml of n-hexane and 15 ml of ethyl acetate were added. Activated carbon was added to the solution, allowed to stand for a while and then suction filtered using Celite, and the filtrate was concentrated to obtain 10.9 g of a crystalline residue. This was almost pure in NMR spectrum. Yield 93.5%. When this was recrystallized using acetonitrile, 7.9 g (67.7%, purity 99.5%) of pure exemplary compound (1) as colorless crystals could be obtained.
(Purity was measured by high performance liquid chromatography (HPLC).)
Melting point: 146-147 ° C
NMR (nuclear magnetic resonance) spectrum (CDCl 3 ) δ (ppm); 0.35 (54H, s), 7.78 (6H, s)
Exemplified compound (1) was distillable at 220 to 240 ° C./˜0.2 mmHg, but it seemed that some decomposition occurred, and the purity of what was obtained by distillation was lowered.
[0027]
Example 2 (Synthesis of Exemplified Compound (2))
14.7 g (0.216 mol) of imidazole was added to a solution of HHTP, 5 g (0.015 mol, purity 97%) in dimethylformamide (50 ml) and stirred, and 16.3 g (0.108 mol) of triethylsilyl chloride was added at room temperature. . After stirring at room temperature for about 1 hour, the mixture was heated to about 60 ° C. and stirred for about 1 hour. After returning to room temperature, 4.2 g (0.062 mol) of imidazole and 4.6 g (0.031 mol) of triethylsilyl chloride were further added, and the mixture was allowed to stand overnight at room temperature. N-Hexane was added to the reaction solution, followed by stirring and extraction (without using water), and after separating the dimethylformamide layer, the n-hexane layer was washed with acetonitrile, and activated carbon was added to the n-hexane layer and left standing. After filtration using Celite, the filtrate was concentrated under reduced pressure to obtain 19.3 g of a brown oil. This oil crystallizes in the refrigerator.
In the NMR spectrum, this brown oil was Exemplified Compound (2) (purity 81%) containing impurities derived from triethylsilyl chloride.
NMR spectrum (CDCl 3 ) δ (ppm); 0.90 (36H, q, J = 7.4), 1.06 (54H, t, J = 7.4), 7.75 (6H, s)
[0028]
Example 3 (Synthesis of Exemplified Compound (3))
To a solution of HHTP, 1 g (6.2 mmol, purity 97%) in dimethylformamide (50 ml), 5.8 g (86 mmol) of imidazole was added and stirred, and 6.5 g (43 mmol) of t-butyldimethylsilyl chloride was added at room temperature. Some exotherm occurred and the mixture was stirred for about 1 hour and left overnight. Since the reaction progress was found to be insufficient by TLC, it was heated to 115 ° C. and stirred. After about 3 hours, 1.7 g (25 mmol) of imidazole and 1.9 g (12 mmol) of t-butyldimethylsilyl chloride were further added. After heating and stirring for about 3 hours, the temperature was returned to room temperature, and n-hexane extraction was performed twice without adding water. After separating the dimethylformamide layer, the n-hexane extracts were combined, washed with water (once) and saturated brine (once), and dried over magnesium sulfate. After filtration, the filtrate was concentrated under reduced pressure, and 5.1 g (yield 82%, purity 99.4%) of Exemplary Compound (3) could be obtained by recrystallizing the residue with acetonitrile.
Melting point 299-300 ° C
NMR spectrum (CDCl 3 ) δ (ppm); 0.30 (36H, s), 1.06 (54H, s), 7.76 (6H, s)
[0029]
Example 4 (Synthesis of Exemplified Compound (4))
In a solution of HHTP, 2 g (6.2 mmol, purity 97%) in dimethylformamide (50 ml), 5.8 g (86 mmol) of imidazole was added and stirred. Into this, 11.9 g (43 mmol) of t-butyldiphenylsilyl chloride was added, and the mixture was stirred at room temperature for about 1 hour, then heated to 60 ° C. and stirred for about 9 hours. After standing overnight, the mixture was further stirred for about 11 hours at 115 ° C., but the reaction was not completed, so 1.7 g (25 mmol) of imidazole and 3.4 g (12 mmol) of t-butyldiphenylsilyl chloride were added and about 7 hours at 115 ° C. Stir. After returning to room temperature, the mixture was extracted three times with n-hexane without adding water. The extracts were combined, washed with acetonitrile, and n-hexane was distilled off under reduced pressure to obtain about 13 g of a black-blue crystalline compound. It was. This was recrystallized with a mixed solution of acetonitrile and ethyl acetate to obtain 3.4 g (31.4%) of exemplary compound (4) (purity 99.6%). Although the filtrate still contained a large amount of the exemplified compound (4), no further extraction was attempted.
Melting point: 235-237 ° C
NMR spectrum (CDCl 3 ) δ (ppm); 0.91 (54H, s), 6.88 (6H, s), 7.20 (24H, t, J = 7.5), 7.32 (12H, t, J = 7.5), 7.54 (24H, d, J = 7.5)
[0030]
Example 5 (Synthesis of HHTP)
2 g (2.6 mmol) of the exemplary compound (1) having a purity of 99.5% obtained in Example 1 was added to 10 ml of methanol, and the mixture was heated to reflux for about 2 hours. Thereafter, low-boiling compounds such as methanol were distilled off under reduced pressure, and the resulting HHTP crystals were dried with a vacuum pump and the purity was measured by HPLC. The purity was 99%.
Example 6 (Synthesis of HHTP)
2.0 g (2.6 mmol) of the exemplary compound (1) having a purity of 99.5% obtained in Example 1 was dissolved in ethyl acetate, 0.7 ml of 46 to 48% hydrofluoric acid was added thereto, and room temperature was added. Stirring under. After about 2 hours, the precipitated crystals were separated by filtration, and dried to obtain 0.80 g (yield 95.0%) of HHTP having a purity of 99.3% (HPLC purity).
Example 7 (Synthesis of HHTP)
2.0 g (2.6 mmol) of Exemplified Compound (1) 99.5% obtained in Example 1 was heated to reflux in acetic acid (50 ml) for about 1 hour, returned to room temperature, and the precipitated crystals were filtered off and dried. As a result, 0.78 g (yield 92.5%) of HHTP having a purity of 99.5% (HPLC purity) could be obtained.
[0031]
Example 8 (Synthesis of HHTP)
10 g of the 81% pure exemplary compound (2) obtained in Example 2 was mixed with 100 ml of acetic acid, heated to reflux for about 1 hour, returned to room temperature, and the precipitated crystals were filtered and dried to obtain a purity of 99.2% (HPLC Purity) of HHTP was obtained (yield 91%).
[0032]
Reference Example 1 (Synthesis of 2,3,6,7,10,11-hexaacetoxytriphenylene)
When a 2,3,6,7,10,11-hexaacyloxy compound is synthesized, it can be synthesized by direct acylation from the compound of the present invention without passing through HHTP. As a reference example, a synthesis example of 2,3,6,7,10,11-hexaacetoxytriphenylene is shown below.
Illustrative compound (1), 2 g (purity 99.5%, 2.6 mmol) was dissolved in 50 ml of chloroform, 2.4 g (31.2 mmol) of acetyl chloride was added thereto, and the mixture was heated to reflux for about 2 hours. The reaction solution was concentrated under reduced pressure, and the components of the obtained crystals (8.4 g) were analyzed by HPLC. As a result, 98% purity 2,3,6,7,10,11-hexaacetoxytriphenylene (J. Chem. Soc) was obtained. (C), 1971 , 1397).
[0033]
【The invention's effect】
The 2,3,6,7,10,11-hexakisyloxytriphenylene compound of the present invention has good solubility in an organic solvent, is easy to recrystallize, and its desilylation occurs quantitatively and easily. Therefore, high purity 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP) can be easily prepared.
Claims (2)
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| JP06362298A JP4090555B2 (en) | 1998-03-13 | 1998-03-13 | 2,3,6,7,10,11-Hexakisyloxytriphenylene compound and method for producing high purity 2,3,6,7,10,11-hexahydroxytriphenylene |
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| WO2005090275A1 (en) * | 2004-03-19 | 2005-09-29 | Otsuka Chemical Co., Ltd. | Crystal of hexahydroxytriphenylene monohydrate and method for preparation thereof |
| WO2006038709A1 (en) * | 2004-10-05 | 2006-04-13 | National University Corporation Gunma University | Triphenylene compounds, process for production thereof, and organic electroluminescent devices made by using the same |
| KR101528827B1 (en) * | 2007-08-07 | 2015-06-16 | 와코 쥰야꾸 고교 가부시키가이샤 | Process for producing triphenylene compound and crystal obtained by the process |
| KR101350581B1 (en) | 2010-12-29 | 2014-01-16 | 주식회사 엘지화학 | New compounds and organic light emitting device using the same |
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