JPS62238265A - Phenylpyridine derivative - Google Patents
Phenylpyridine derivativeInfo
- Publication number
- JPS62238265A JPS62238265A JP61080726A JP8072686A JPS62238265A JP S62238265 A JPS62238265 A JP S62238265A JP 61080726 A JP61080726 A JP 61080726A JP 8072686 A JP8072686 A JP 8072686A JP S62238265 A JPS62238265 A JP S62238265A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- liquid crystal
- formula
- reacting
- chiral smectic
- 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
- 150000005359 phenylpyridines Chemical class 0.000 title claims abstract 3
- 239000000126 substance Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 45
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 23
- 239000004990 Smectic liquid crystal Substances 0.000 abstract description 13
- -1 alkyloxy alkali metal salt Chemical class 0.000 abstract description 9
- 125000000217 alkyl group Chemical group 0.000 abstract description 6
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 3
- IWAKWOFEHSYKSI-YFKPBYRVSA-N (2s)-1-chloro-2-methylbutane Chemical compound CC[C@H](C)CCl IWAKWOFEHSYKSI-YFKPBYRVSA-N 0.000 abstract description 2
- 150000007514 bases Chemical class 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 230000002140 halogenating effect Effects 0.000 abstract description 2
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 230000007704 transition Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 239000005262 ferroelectric liquid crystals (FLCs) Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- OXPDQFOKSZYEMJ-UHFFFAOYSA-N 2-phenylpyrimidine Chemical compound C1=CC=CC=C1C1=NC=CC=N1 OXPDQFOKSZYEMJ-UHFFFAOYSA-N 0.000 description 3
- CBGGBVLOBRXQAF-UHFFFAOYSA-N 4-(6-chloropyridin-3-yl)phenol Chemical compound C1=CC(O)=CC=C1C1=CC=C(Cl)N=C1 CBGGBVLOBRXQAF-UHFFFAOYSA-N 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 3
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 239000012312 sodium hydride Substances 0.000 description 3
- 229910000104 sodium hydride Inorganic materials 0.000 description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 235000002597 Solanum melongena Nutrition 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- HPEVJTNZYIMANV-JTQLQIEISA-N [(2s)-2-methylbutyl] 4-methylbenzenesulfonate Chemical compound CC[C@H](C)COS(=O)(=O)C1=CC=C(C)C=C1 HPEVJTNZYIMANV-JTQLQIEISA-N 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- KJIOQYGWTQBHNH-UHFFFAOYSA-N undecanol Chemical compound CCCCCCCCCCCO KJIOQYGWTQBHNH-UHFFFAOYSA-N 0.000 description 2
- XKVLZBNEPALHIO-YFKPBYRVSA-N (2s)-1-bromo-2-methylbutane Chemical compound CC[C@H](C)CBr XKVLZBNEPALHIO-YFKPBYRVSA-N 0.000 description 1
- NRLWLQUJUTWEJD-LURJTMIESA-N (3s)-1-chloro-3-methylpentane Chemical compound CC[C@H](C)CCCl NRLWLQUJUTWEJD-LURJTMIESA-N 0.000 description 1
- HKKQSNCJIFHCQD-ZETCQYMHSA-N (4S)-1-chloro-4-methylhexane Chemical compound CC[C@H](C)CCCCl HKKQSNCJIFHCQD-ZETCQYMHSA-N 0.000 description 1
- KYUQEUPBPQEGMO-VIFPVBQESA-N (6S)-1-chloro-6-methyloctane Chemical compound C[C@H](CCCCCCl)CC KYUQEUPBPQEGMO-VIFPVBQESA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ZFFBIQMNKOJDJE-UHFFFAOYSA-N 2-bromo-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(Br)C(=O)C1=CC=CC=C1 ZFFBIQMNKOJDJE-UHFFFAOYSA-N 0.000 description 1
- UVGUYKDDJYXGTR-UHFFFAOYSA-N CCCCCCCCCCCCC(=C(C(=CC1=CC=CC=C1)C(C)CC)C(=O)O)C2=CC=C(C=C2)N Chemical compound CCCCCCCCCCCCC(=C(C(=CC1=CC=CC=C1)C(C)CC)C(=O)O)C2=CC=C(C=C2)N UVGUYKDDJYXGTR-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- PHSPJQZRQAJPPF-UHFFFAOYSA-N N-alpha-Methylhistamine Chemical compound CNCCC1=CN=CN1 PHSPJQZRQAJPPF-UHFFFAOYSA-N 0.000 description 1
- 239000004988 Nematic liquid crystal Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- MDLIEARNNGUFNL-NSHDSACASA-N [(3s)-3-methylpentyl] 4-methylbenzenesulfonate Chemical compound CC[C@H](C)CCOS(=O)(=O)C1=CC=C(C)C=C1 MDLIEARNNGUFNL-NSHDSACASA-N 0.000 description 1
- DMQYHXJZYZZOTR-AWEZNQCLSA-N [(6s)-6-methyloctyl] 4-methylbenzenesulfonate Chemical compound CC[C@H](C)CCCCCOS(=O)(=O)C1=CC=C(C)C=C1 DMQYHXJZYZZOTR-AWEZNQCLSA-N 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229940057402 undecyl alcohol Drugs 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Liquid Crystal (AREA)
- Pyridine Compounds (AREA)
- Liquid Crystal Substances (AREA)
Abstract
Description
【発明の詳細な説明】
（産業−にの利用分野）
本発明は、液晶化合物ないしは液晶材料として使用でき
る新規な化合物の提供に係るものであって、それ自体で
又は他の液晶化合物とのブレンド１こより性能の改善を
はかるなどして液晶表示素子の作成に利用できる。Detailed Description of the Invention (Industrial Field of Application) The present invention relates to the provision of a new compound that can be used as a liquid crystal compound or liquid crystal material, either by itself or in a blend with other liquid crystal compounds. This method can be used to improve the performance of liquid crystal display devices.
（軸間の技術）
液晶による表示素子において使用されている液晶化合物
は、ネマチック相をとる液晶が大半である。しかし、電
気光学的応答速度の点において発光型表示素子にくらべ
ると遥かに及ばず改善が試みられている。近年、応答速
度が速いことで注目されている液晶化合物に１強誘電性
液晶化合物がある０強誘電性液晶化合物としてはじめて
開発されたのは、ドデシルベンジリデン−ｐ−アミノ−
２−メチルブチルシンナメートであって、１９７５年に
合成された。(Interaxial technology) Most liquid crystal compounds used in liquid crystal display elements are liquid crystals that take a nematic phase. However, in terms of electro-optical response speed, it is far inferior to that of light-emitting display elements, and attempts are being made to improve it. In recent years, ferroelectric liquid crystal compounds have attracted attention due to their fast response speed.The first ferroelectric liquid crystal compound developed was dodecylbenzylidene-p-amino-
2-Methylbutylcinnamate, synthesized in 1975.
この化合物は、カイラルスメクチックＣ相をとるけれど
も、その転移温度が高いこと、従って。Although this compound adopts a chiral smectic C phase, its transition temperature is therefore high.
室温を含む低い温度での使用は不可能であり、そのほか
に、シップ塩基を含む化合物であるため化学的安定性に
欠けるという問題を持っている。その後、数多くの強誘
電性液晶化合物が合成され、その性質の究明が行われて
いるけれども、室温を含む幅広い温度範囲で、カイラル
スメクチックＣ相をとる液晶化合物は知られていない。It is impossible to use it at low temperatures, including room temperature, and it also has the problem of lacking chemical stability because it is a compound containing a ship base. Since then, many ferroelectric liquid crystal compounds have been synthesized and their properties have been investigated, but no liquid crystal compound is known that takes a chiral smectic C phase over a wide temperature range including room temperature.
液晶相の移転温度の低下又は、温度範囲の拡大のためネ
マチック液晶の分野で採用されている−般的な方法に、
いくつかの液晶化合物を混合する方法がある。A common method employed in the field of nematic liquid crystals to lower the transition temperature or expand the temperature range of the liquid crystal phase is:
There are methods of mixing several liquid crystal compounds.
強誘電性液晶の分野においても同様の方法が検討されて
いて、試行錯誤の域を出ていない。どのような骨格を選
べば、他の液晶との相溶性が高まるか、どのような置換
基を導入すれば如何なる液晶相をとって、他の液晶の相
転移温度にどのような影響を及ぼすかといったことは、
化合物一つ一つについてデス１−シてみなければ全く判
らないといっても過言ではない。Similar methods are being considered in the field of ferroelectric liquid crystals, and are still a matter of trial and error. What kind of skeleton should be selected to increase compatibility with other liquid crystals, what kind of substituents should be introduced to form a liquid crystal phase, and what effect will it have on the phase transition temperature of other liquid crystals? That means,
It is no exaggeration to say that you will not understand anything unless you examine each compound one by one.
本発明に係る液晶化合物と同様の骨格を持つ液晶化合物
に関する研究がなされたことが、Ａｄｖ。Adv that research has been conducted on liquid crystal compounds having the same skeleton as the liquid crystal compound according to the present invention.
Ｌｉｑ、 Ｃｒｙｓｔ、 Ｒｓｓ、 Ａｐｐｌ、
。Liq, Cryst, Rss, Appl,
.
Ｐｒｏｃ、 Ｌｉｑ、 Ｃｒｙｓｔ、 Ｃｏｎｆ
。Proc, Liq, Crystal, Conf
.
Ｓｏｃ、 Ｃｏｕｎｔｒｉｅｓ、３ｒｄ １９７９
゜２．１００７−１．３に明らかにされている。これに
よると、得られた化合物は全て直鎖状のアルキル１＆を
ピリジン環側に置換しており、直鎖のアルキルＪ＆又は
アルコキシ基がフェニル核上に置換している化合物に過
ぎない。Soc, Countries, 3rd 1979
2.1007-1.3. According to this, all of the obtained compounds have a linear alkyl 1& substituted on the pyridine ring side, and are simply compounds in which a linear alkyl J& or an alkoxy group is substituted on the phenyl nucleus.
酸素原子を介して各々の環に結合している方が。The one that is bonded to each ring via an oxygen atom.
駆動性能において優れていることが他の化合物に関する
実験から判っている。又、不斉炭素原ｆ−の存在によっ
てカイラルスメクチックＣ相をとるであろうことが期待
された。しかしながら、以下の記述からも明らかになる
が、カイラルスメクチックＣ相はとらず、スメクチック
Ａ相をとったに過ぎなかった。液晶化合物の構造と相と
の関係が区々であることがわかる。Experiments with other compounds have shown that this compound has excellent drive performance. Furthermore, it was expected that a chiral smectic C phase would be formed due to the presence of the asymmetric carbon atom f-. However, as will be clear from the description below, the chiral smectic C phase was not formed, but only the smectic A phase was formed. It can be seen that the relationship between the structure and phase of liquid crystal compounds is different.
（発明が解決しようとする問題点）
本発明の目的は、強誘電性カイラルスメクチック液晶と
ブレンドでき、それによって全体として均一化されたド
メインを得、且つ、カイラルスメクチックＣ相をとる温
度範囲を広くすることができる性能を有する化合物を提
供することにある。(Problems to be Solved by the Invention) An object of the present invention is to be able to blend with a ferroelectric chiral smectic liquid crystal, thereby obtaining homogeneous domains as a whole, and widening the temperature range in which the chiral smectic C phase takes place. The objective is to provide a compound that has the ability to
（問題点を解決するだめの手段） 本発明化合物は次のようにして合成される。(Failure to solve the problem) The compound of the present invention is synthesized as follows.
即ち、
（Ｗ）
（式中Ｒは分子鎖中に不斉炭素原子をもつ光学的に活性
なアルキル基、ｋは直鎖状アルキル基、Ｘはハロゲン原
子、Ａはハロゲン原子又はスルホン式（Ｉ）で示される
５−（４’−ハイドロキシフェニル）ビリジノン−２を
、ジエチルアニリン、ジメチルアニリン、１−リエチル
アミン、ピリジンなどの塩基性化合物の存在下、溶媒の
存在又は不存在で、オキシ塩化燐、三塩化燐、三臭化燐
、五塩化燐、塩化チオニルなどのハロゲン化剤と反応さ
せ式（■）で示される化合物を得る。（反応１）得られ
た式（ＩＩ）で示される化合物を、ジメチルホルムアミ
ド、アセトアミド、トルエン、キシレン、テトラヒドロ
フラン、ジオキサン、ジメチルスルホキシド、ジグリム
などの適宜溶媒中、Ｒ−Ｏ−Ｍで示されるアルキルオキ
シアルカリ金属塩と反応させる。ここにおいてアルキル
オキシとしては、ブチルオキシ、ペンチルオキシ、ヘキ
シルオキシ、ヘプチルオキシ、オクチルオキシ、ノニル
オキシ、デシルオキシ、ウンデシルオキシ。That is, (W) (wherein R is an optically active alkyl group having an asymmetric carbon atom in the molecular chain, k is a linear alkyl group, X is a halogen atom, A is a halogen atom or a sulfone formula (I ) in the presence of a basic compound such as diethylaniline, dimethylaniline, 1-ethylamine, or pyridine, in the presence or absence of a solvent, to phosphorus oxychloride. , react with a halogenating agent such as phosphorus trichloride, phosphorus tribromide, phosphorus pentachloride, or thionyl chloride to obtain a compound represented by formula (■). (Reaction 1) Obtained compound represented by formula (II) is reacted with an alkyloxy alkali metal salt represented by R-O-M in an appropriate solvent such as dimethylformamide, acetamide, toluene, xylene, tetrahydrofuran, dioxane, dimethylsulfoxide, diglyme, etc. Here, alkyloxy is butyloxy. , pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy.
ドデシルオキシなどの直鎖状アルキルオキシが挙げられ
、アルカリ金属としてはす１−リウム、カリウムなどで
ある。かくて１式（Ｉｌｌ）で示される化合物を得る。Examples include linear alkyloxy such as dodecyloxy, and alkali metals include 1-lium, potassium, and the like. In this way, a compound represented by formula 1 (Ill) is obtained.
（反応２）
得られた式（ｎ［）で示される化合物を、適宜溶媒中、
ナトリウム、カリウムなどのアルカリ金属又は、炭酸カ
リウム、炭酸ソーダ、水素化ナトリラム、ナトリウムア
ミド、カリウムアミドなどのアルカリ金属塩の共存下、
分子鎖中に不斉炭素原子を有する光学活性なアルキルハ
ライド、例えば。(Reaction 2) The obtained compound represented by formula (n[) is mixed in an appropriate solvent,
In the coexistence of an alkali metal such as sodium or potassium or an alkali metal salt such as potassium carbonate, soda carbonate, sodium hydride, sodium amide, potassium amide, etc.
Optically active alkyl halides having asymmetric carbon atoms in the molecular chain, for example.
（Ｓ）−２−メチルブチルクロリド、（Ｓ） −２−メ
チルブチルプロミド、（Ｓ）−３−メチルペンチルクロ
リド、（Ｓ）−４−メチルへキシルク〆ロリド、（Ｓ）
−５−メチルへブチルクロリド。(S)-2-methylbutyl chloride, (S)-2-methylbutyl bromide, (S)-3-methylpentyl chloride, (S)-4-methylhexyl chloride, (S)
-5-Methylhebutyl chloride.
（Ｓ）−６−メチルオクチルクロリドなどを、あるいは
、光学活性なアルキルスルホン酸エステル例えば（Ｓ）
−２−メチルブチルＰ−トルエンスルホネート、（Ｓ）
−３−メチルペンチルｐ−トルエンスルホネート、（Ｓ
）−４−メチルヘキシルＩ】−トルエンスルホネート、
（Ｓ）−５−メチルオクチルｐ−トルエンスルホネート
、（Ｓ）−６−メチルオクチルｐ−トルエンスルホネー
トなどを反応させ、式（ＴＶ）で示される化合物を得る
。(S)-6-methyloctyl chloride, etc., or an optically active alkyl sulfonic acid ester such as (S)
-2-Methylbutyl P-toluenesulfonate, (S)
-3-methylpentyl p-toluenesulfonate, (S
)-4-methylhexyl I]-toluenesulfonate,
(S)-5-methyloctyl p-toluenesulfonate, (S)-6-methyloctyl p-toluenesulfonate, etc. are reacted to obtain a compound represented by formula (TV).
反応２で用いられた溶媒が好適に使用される。The solvent used in reaction 2 is preferably used.
（反応３）
更にまた１本発明化合物は別の方法で造ることもできる
。即ち、式（１）で示されろ化合物を反応３と同様にし
て式（Ｖ）で示される化合物を１１）る。（反応４）
１；）られた式（Ｖ）で示される化合物を反応］−と同
様にして式（ＶＩ）で示される化合物を得る。(Reaction 3) Furthermore, a compound of the present invention can also be produced by another method. That is, the compound represented by formula (1) is converted to a compound represented by formula (V) in the same manner as in reaction 3 (11). (Reaction 4) A compound represented by formula (VI) is obtained in the same manner as in 1;).
（反応５）
得られた式（ＶＩ）で示される化合物を反応２と同様に
して式（ｒＶ）で示される化合物を得る。(Reaction 5) The obtained compound represented by formula (VI) is treated in the same manner as in reaction 2 to obtain a compound represented by formula (rV).
（反応６）
憂
ＲとＲが相互に入れ替わった化合物は１反応２と反応３
において使用する原料を交換して１反応させることによ
って造られる。反応４と反応６も同様である。(Reaction 6) Compounds in which R and R are interchanged are Reaction 2 and Reaction 3.
It is produced by exchanging the raw materials used in 1 and performing one reaction. The same applies to reactions 4 and 6.
かくて本発明化合物は、本出願人らの出願に係るフェニ
ルピリミジン系強誘電性カイラルスメクチック化合物と
ブレンドされると、均一性の良いドメインを与える。即
ち、電低光学素子に使用するとシャープなコントラス１
−を与えることが判った。同時にまた。フェニルピリミ
ジン系強誘電性カイラルスメクチック化合物の結晶化温
度をより低温側へ下げ、結果としてカイラルスメクチッ
クＣ相の温度範囲を拡大する働きをすることが判った。Thus, when the compound of the present invention is blended with the phenylpyrimidine-based ferroelectric chiral smectic compound of the applicant's application, it provides domains with good uniformity. In other words, when used in low voltage optical elements, sharp contrast 1
It was found that -. At the same time again. It has been found that the crystallization temperature of a phenylpyrimidine-based ferroelectric chiral smectic compound is lowered to a lower temperature, and as a result, the temperature range of the chiral smectic C phase is expanded.
ここにおいて、フェニルピリミジン系強誘電性カイラル
スメクチック化合物としては、特願昭５９−２１．５３
６７、同５９−１４１７００、Ｉ’ｉ’１１５９−１１
７２０９、同５９−１４４０２．同５９−２５０１７１
、同６０−４２１１．６、同６ｏ−４２１１７、同６０
−５６６５２に明らかにされている。Here, as the phenylpyrimidine-based ferroelectric chiral smectic compound, Japanese Patent Application No. 59-21.53
67, 59-141700, I'i'1159-11
7209, 59-14402. 59-250171
, 60-4211.6, 6o-42117, 60
-56652.
以下、実施例を記述して更に本発明を詳述する。Hereinafter, the present invention will be further explained in detail by describing examples.
実施例＼
（１）２−クロロ−５−（４’−ハイドロキシフェニル
）ピリジンの合成：
５−（４’−ハイドロキシフェニル）ビリジノン−２を
２．０ｇ、オキシ塩化燐１０ｍ１及びジエチルアニリン
１．５ｍｌを加えて、１５時間還流した。反応後、過剰
のオキシ塩化燐を留去し、残渣を氷水で分解した。析出
結晶を濾取し、乾燥して２．２１ｇの２−クロロ−５−
（４’−ハイドロキシフェニル）ピリジンを得た。Example (1) Synthesis of 2-chloro-5-(4'-hydroxyphenyl)pyridine: 2.0 g of 5-(4'-hydroxyphenyl)pyridinone-2, 10 ml of phosphorus oxychloride, and 1.5 ml of diethylaniline. was added and refluxed for 15 hours. After the reaction, excess phosphorus oxychloride was distilled off, and the residue was decomposed with ice water. The precipitated crystals were collected by filtration and dried to give 2.21 g of 2-chloro-5-
(4'-hydroxyphenyl)pyridine was obtained.
ＩＲｙ’ （ｃ；）：１６１０．１５２０．１２３５
、 ９８０．８２５
→←謄→−具
（２） ５− （４’−ハイドロキシフェニル）−２
−ウンデシロキシピリジンの合成：
３００ｍ１ナスフラスコに５０％水素化ナトリウム４．
２ｇ （０，０８８ｍｏ １）、ｆ、燥したジメチルホ
ルムアミド１６０ ｍ ｌ及びローウンデシルアルコー
ル１５．ｏｇを入れ、室温で約１時間攪拌後、２−クロ
ロ−５−（４−ハイドロキシフェニル）ピリジン９．０
ｇを加え、８０℃で８時間攪拌を行った。反応終了後、
氷水に注ぎ、酢酸エチルで抽出し、５％水酸化カリウム
水溶液１００ｍ１で洗浄し、硫酸マグネシウムで乾燥後
、溶媒を留去した。残渣をシリカゲルカラムクロマトグ
ラフィーで精製し５題記化合物０．６２ｇを得た。IRy'(c;): 1610.1520.1235
, 980.825 →←transfer→-tool (2) 5- (4'-hydroxyphenyl)-2
-Synthesis of undecyloxypyridine: 4. 50% sodium hydride in a 300ml eggplant flask.
2 g (0,088 mo 1), f, 160 ml dry dimethylformamide and raw undecyl alcohol 15. After stirring at room temperature for about 1 hour, 9.0% of 2-chloro-5-(4-hydroxyphenyl)pyridine was added.
g was added thereto, and the mixture was stirred at 80°C for 8 hours. After the reaction is complete,
The mixture was poured into ice water, extracted with ethyl acetate, washed with 100 ml of a 5% aqueous potassium hydroxide solution, dried over magnesium sulfate, and then the solvent was distilled off. The residue was purified by silica gel column chromatography to obtain 0.62 g of the title compound 5.
ＩＲ＾、、（ｃｉｌ） ： ３３００〜２６００．１６
１５．１５９０．１１２０．８４Ｏ
ＮＭＲ（６０ＭＩＩｚ、ＣＤＣ１，）δ （ｐｐ−）
：０．６−２．０ （ｍ、 ２１Ｈ）３．６３
（ｔ、２Ｈ）
６．７−７、 ９ （ｍ、 ６Ｈ）８．５
（ｄ、 ＬＨ）門８丹＋−一
（、、Ｅ）（Ｓ）−５−［４’−（２−メチルブチルオ
キシ）フェニル］−２−ｎ−ウンデシルオキシピリジン
の合成：
５０ｍ１ナスフラスコに５０％水素化ナトリウム０．０
４ｇ （０，ＯＯ０８５ｍｏ １）、乾燥ジメチルホル
ムアミド１０ｍ１及び５−（４’−ハイドロキシフェニ
ル）−２−ｎ−ウンデシルオキシピリジン０．２５ｇ
（０，ＯＯ０７６ｍｏｌ）を入れ、８０℃で１時間攪拌
後、（Ｓ）−２−メチルブチルＰ−トルエンスルホネー
ト０．１９ｇ（０，０００７９ｍｏ ｌ）を乾燥ジメチ
ルホルムアミド２ｍｌに溶かして加え、８０℃で１０時
間攪拌した。反応終了後、氷水にあけ、酢酸エチルで抽
出（５０ｍｌＸ３） し、５％水酸化ナトリウム水溶液
（５０ｍｌＸ３）、飽和食塩水（１００ｍｌＸ４）で順
に洗浄し、硫酸マグ不ソウムで乾燥後のち、）８媒を留
去して緑色油状物０．２８ｇを得た。これを薄層クロマ
［グラフィ＝（ＭＥＲＣＫ、Ｓ＋ＬＩＣＡＧＥＩ、 ６
０．１−２５４１１で分離精製し、題記化合物０．２ｇ
を得た。IR^,, (cil): 3300-2600.16
15.1590.1120.84O NMR (60MIIz, CDC1,) δ (pp-)
:0.6-2.0 (m, 21H) 3.63
(t, 2H) 6.7-7, 9 (m, 6H) 8.5
(d, LH) Synthesis of gate 8tan+-1(,,E)(S)-5-[4'-(2-methylbutyloxy)phenyl]-2-n-undecyloxypyridine: 50ml eggplant flask 50% sodium hydride 0.0
4g (0,OO085mo 1), 10ml of dry dimethylformamide and 0.25g of 5-(4'-hydroxyphenyl)-2-n-undecyloxypyridine
(0,OO076 mol) and stirred at 80°C for 1 hour, then added 0.19 g (0,00079 mol) of (S)-2-methylbutyl P-toluenesulfonate dissolved in 2 ml of dry dimethylformamide, and stirred at 80°C for 1 hour. Stir for hours. After the reaction is complete, pour into ice water, extract with ethyl acetate (50 ml x 3), wash sequentially with 5% sodium hydroxide aqueous solution (50 ml x 3) and saturated brine (100 ml x 4), dry over magnesium sulfate, and extract with ethyl acetate (50 ml x 3). was distilled off to obtain 0.28 g of a green oil. This is thin layer chroma [graphie=(MERCK, S+LICAGEI, 6
Separation and purification of 0.1-25411 yielded 0.2 g of the title compound.
I got it.
Ｉ Ｒ（ｎｕ ｊ ｏ Ｉ）ｉ）ｍａｘ （ｃｍ−’）
：１ Ｇ １０．１４９０．１４７０．１３８０，１２
５５．８２ＯＮＭＲ（ＣＤＣｌ２ ） δ（ｐｐｍ）：
０．６〜２．３ （ｍ、３０Ｈ）
３．７７ （ｄ、２８）
４．２７ （ｔ、２Ｈ）
６．６８ （ａ、ＩＨ）
６．８８ （ｄ、２Ｈ）
７．３５ （ｍ、３Ｈ）
７．６３ （ｔ、ＩＨ）
８．２３ （ｄ、ＩＨ）
得られた題記化合物は、下のような転移温度を示した。I R(nu j o I)i)max (cm-')
:1 G 10.1490.1470.1380,12
55.82ONMR (CDCl2) δ (ppm):
0.6-2.3 (m, 30H) 3.77 (d, 28) 4.27 (t, 2H) 6.68 (a, IH) 6.88 (d, 2H) 7.35 (m, 3H) 7.63 (t, IH) 8.23 (d, IH) The obtained title compound showed the following transition temperature.
また、２の化合物を下に示した比率でピリミジン系液晶
組成物とブレンドし、転移温度を見た。In addition, compound No. 2 was blended with a pyrimidine-based liquid crystal composition in the ratio shown below, and the transition temperature was observed.
ＣｚＬＣＨＣＨｚＯＧＱＯＣ＋ ＋Ｈｚｚ−ｒｉ
２５重量％？Ｈ′
ＣｚＨｓＣＨ（Ｃ）Ｉｚ）ｓＯＧｆｉＯｃｓＬｔ−ｎ
３ｏ重量％−３，２’Ｃ
ところで、上記組成のピリミジン系液晶化合物３種のみ
の転移温度は、
１４１Ｃフ４．９’０ フｅ、ｏ’ｃＣｒｙ
Ｓｃ” Ｓ、 ＋５゜１０’Ｑ
であり、実施例の化合物を２のピリミジン系液晶組成物
にブレンドすることにより、液晶からＳｃ“相への転移
温度を大きく下げることが出来る。CzLCHCHzOGQOC+ +Hzz-ri
25% by weight? H' CzHsCH(C)Iz)sOGfiOcsLt-n
3o wt % - 3,2'C By the way, the transition temperature of only the three types of pyrimidine liquid crystal compounds having the above composition is 141C f4.9'0 f e, o'cCry
Sc''S, +5°10'Q, and by blending the compound of Example into the pyrimidine liquid crystal composition of 2, the transition temperature from liquid crystal to Sc'' phase can be significantly lowered.
参考例
イ）３−シアノ−５−（４’−ハイドロキシフェニル）
ビリジノン−２の合成：
１−ジメチルアミツー：’−（４’−ハイドロキシフェ
ニル）−３−ジメチルアミノプロペン−１過塩素酸塩（
このものはＨ，Ｚａｓｃｈｋｅ、Ｓ。Reference example a) 3-cyano-5-(4'-hydroxyphenyl)
Synthesis of pyridinone-2: 1-dimethylamitsu:'-(4'-hydroxyphenyl)-3-dimethylaminopropene-1 perchlorate (
This one is by H. Zaschke, S.
Ａｒｎｄｔ、Ｖ、Ｗａｇｎｓｒ、Ｈ，５ｃｈｕｂａｒｔ
Ｚ、Ｃｈａｍ、１７ ２９３ ２９４（１９７７）
の方法により合成した。）３．２ｇと２−シアノアセト
アミド０．８４ｇを乾燥エタノール２０ｍ１に懸濁し、
２８％ソジウムメチラートメタノール溶液５８８ｇを加
え、６時間還流下に反応を行った０反応液を氷水に注ぎ
、希塩酸で酸性として析出結晶を濾取した。水洗後、乾
燥して題記化合物１．９８ｇを得た。Arndt, V., Wagner, H., 5chubart.
Z, Cham, 17 293 294 (1977)
It was synthesized by the method of ) and 0.84 g of 2-cyanoacetamide were suspended in 20 ml of dry ethanol,
588 g of 28% sodium methylate methanol solution was added and the reaction was carried out under reflux for 6 hours. The reaction solution was poured into ice water, acidified with dilute hydrochloric acid, and the precipitated crystals were collected by filtration. After washing with water and drying, 1.98 g of the title compound was obtained.
ＩＨ久、、（ｃｍ−’）：３３５０，３３００，２２４
０．１６７０．．１５３０．１２８０．１１８５０）５
−（４’−ハイドロキシフェニル）とリジノン−２の合
成：
５ｇの３−シアノ−５−（４’−ハイドロキシフェニル
）ビリジノン−２に８５％ｔｊＪ＆５０ｍ＋を加えて３
１時間加熱還流した後、反応液を氷水に注ぎ、析出結晶
を濾取、水洗、乾燥して題記化合物４．６９ｇを得た。IH Ku,, (cm-'): 3350, 3300, 224
0.1670. ．． 1530.1280.11850)5
Synthesis of -(4'-hydroxyphenyl) and lysinone-2: Add 85% tjJ & 50m+ to 5 g of 3-cyano-5-(4'-hydroxyphenyl)pyridinone-2 and prepare 3
After heating under reflux for 1 hour, the reaction solution was poured into ice water, and the precipitated crystals were collected by filtration, washed with water, and dried to obtain 4.69 g of the title compound.
■ＲＶ）、、、（ｃ＋ｍ−’）：３３００〜２４００．
１６７０．１６３０，１５２５．１２８０．８３５以
上■RV),,,(c+m-'): 3300-2400.
1670.1630, 1525.1280.835 or higher
Claims (1)
に活性なアルキル基を、Ｒは直鎖状アルキル基を示す。 これらは相互に入れ替わっていてもよい。） で示されるフェニルピリジン誘導体[Claims] Formulas include mathematical formulas, chemical formulas, tables, etc. (These may be interchanged.) Phenylpyridine derivatives represented by
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61080726A JPH0692370B2 (en) | 1986-04-08 | 1986-04-08 | Phenyl pyridine derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61080726A JPH0692370B2 (en) | 1986-04-08 | 1986-04-08 | Phenyl pyridine derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62238265A true JPS62238265A (en) | 1987-10-19 |
| JPH0692370B2 JPH0692370B2 (en) | 1994-11-16 |
Family
ID=13726369
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61080726A Expired - Fee Related JPH0692370B2 (en) | 1986-04-08 | 1986-04-08 | Phenyl pyridine derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0692370B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4898455A (en) * | 1986-04-22 | 1990-02-06 | Hoffmann-La Roche Inc. | Pyridine liquid crystalline compounds |
-
1986
- 1986-04-08 JP JP61080726A patent/JPH0692370B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4898455A (en) * | 1986-04-22 | 1990-02-06 | Hoffmann-La Roche Inc. | Pyridine liquid crystalline compounds |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0692370B2 (en) | 1994-11-16 |
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