JPH0193553A - Optically active high polymer liquid crystal intermediate - Google Patents
Optically active high polymer liquid crystal intermediateInfo
- Publication number
- JPH0193553A JPH0193553A JP25056787A JP25056787A JPH0193553A JP H0193553 A JPH0193553 A JP H0193553A JP 25056787 A JP25056787 A JP 25056787A JP 25056787 A JP25056787 A JP 25056787A JP H0193553 A JPH0193553 A JP H0193553A
- Authority
- JP
- Japan
- Prior art keywords
- liquid crystal
- formula
- polymer liquid
- reaction
- high polymer
- 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
- 239000005264 High molar mass liquid crystal Substances 0.000 title claims abstract description 30
- 150000001875 compounds Chemical class 0.000 claims abstract description 31
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims 3
- 238000006243 chemical reaction Methods 0.000 abstract description 25
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 16
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 4
- BUDQDWGNQVEFAC-UHFFFAOYSA-N Dihydropyran Chemical compound C1COC=CC1 BUDQDWGNQVEFAC-UHFFFAOYSA-N 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 125000000217 alkyl group Chemical group 0.000 abstract 2
- 101150034680 Lis-1 gene Proteins 0.000 abstract 1
- 101150084844 PAFAH1B1 gene Proteins 0.000 abstract 1
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 239000012071 phase Substances 0.000 description 12
- 239000002904 solvent Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 150000002009 diols Chemical class 0.000 description 8
- 239000012074 organic phase Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- 239000000543 intermediate Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 3
- ZRLDVMGSMOLUOJ-UHFFFAOYSA-N 2-hydroxypropyl 4-methylbenzenesulfonate Chemical compound CC(O)COS(=O)(=O)C1=CC=C(C)C=C1 ZRLDVMGSMOLUOJ-UHFFFAOYSA-N 0.000 description 3
- 239000004990 Smectic liquid crystal Substances 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 125000001412 tetrahydropyranyl group Chemical group 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- -1 Lithium aluminum hydride Chemical compound 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 230000003098 cholesteric effect Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 229940116333 ethyl lactate Drugs 0.000 description 2
- 230000005621 ferroelectricity Effects 0.000 description 2
- 239000012280 lithium aluminium hydride Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000011097 chromatography purification Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000005055 memory storage Effects 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- FVXBCDWMKCEPCL-UHFFFAOYSA-N nonane-1,1-diol Chemical compound CCCCCCCCC(O)O FVXBCDWMKCEPCL-UHFFFAOYSA-N 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000004309 pyranyl group Chemical group O1C(C=CC=C1)* 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000007070 tosylation reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Liquid Crystal Substances (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、不斉炭素を有する高分子液晶、特に強誘電性
高分子液晶の合成に用いる新規な光学活性高分子液晶中
間体に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel optically active polymer liquid crystal intermediate used in the synthesis of polymer liquid crystals having asymmetric carbon, particularly ferroelectric polymer liquid crystals.
［従来の技術］
最近、高分子液晶材料が高機癒性材料として注目されて
いる。この理由としては、高分子液晶が下記のような優
れた特質を持つためとされている。[Prior Art] Recently, polymeric liquid crystal materials have attracted attention as highly flexible materials. The reason for this is said to be that polymer liquid crystals have the following excellent properties.
■ 薄膜化が容易であり、低分子液晶では実現困難な液
晶素子の大面積化が可能となる。■ It is easy to make thin films, making it possible to enlarge the area of liquid crystal elements, which is difficult to achieve with low-molecular liquid crystals.
■ 延伸等の配向処りを施すことで良好な配向状態が得
られる。■ A good orientation state can be obtained by applying an orientation process such as stretching.
■ 高分子の液晶状態をガラス転位点以下においても保
持できるので、メモリ保存性が低分子液晶を使用する場
合に比べ格段に向上する。■ Since the liquid crystal state of polymers can be maintained even below the glass transition point, memory storage stability is significantly improved compared to when low-molecular liquid crystals are used.
しかしながら、高分子液晶の実用化にあたっての問題点
は、電界に対する応答速度が遅い点であると言われてい
た。たか、その電界に対する応答速度は、低分子液晶に
おけると同様に自発分極を持った強誘電性の高分子液晶
を使用することで、大幅に改善されると考えられる。However, it has been said that a problem in putting polymer liquid crystals into practical use is that their response speed to electric fields is slow. In addition, it is thought that the response speed to the electric field can be significantly improved by using a ferroelectric polymer liquid crystal that has spontaneous polarization similar to that of a low-molecular liquid crystal.
高分子液晶に強誘電性を発現させるためには、そのフレ
キシブルスペーサー（屈曲類）に光学活性基を導入する
ことが必要である。すでに、ネマチック相を有する高分
子液晶の屈曲類の一部の炭素を不斉炭素に置きかえるこ
とでコレステリック相を示すようになることは知られて
いる。ここにおいて、不斉炭素に置きかえる効果として
は、発現する液晶相の種類は変えずに、液晶相をとる温
度範囲だけが変わることか多い。［デイ−ヴイルーエン
、エル リーベルトおよびエル ストゼレキ−「ヨーロ
ピアン ポリマー ジャーナル１６巻 ３０７頁 １９
８０年Ｊ （Ｄ、 Ｖ、 Ｌｕｙｅｎ、 Ｌ、 Ｌｉ
ｅｂｅｌｔ ａｎｄ Ｌ、 ５ｔｒｚｅｌｅｃｋｉ、、
Ｅｕｒｏｐ、 Ｐｏｌｙｍ、 Ｊ、、 １６３０７
１９８０ ） ］
したがって、同様にスメクティック相を有する高分子液
晶の屈曲類の炭素の一部を不斉炭素に置きかえることで
カイラルスメクテイツクＣ相を有する高分子液晶を得る
ことが可能となると考えられる。In order to make a polymeric liquid crystal exhibit ferroelectricity, it is necessary to introduce an optically active group into its flexible spacer (bent type). It is already known that a polymer liquid crystal having a nematic phase can exhibit a cholesteric phase by replacing some of the carbons in the bends with asymmetric carbons. Here, the effect of replacing the asymmetric carbon is that the type of liquid crystal phase that develops does not change, but only the temperature range in which the liquid crystal phase is formed changes. [D. V. Luen, El Liebert and El Strzelecki, European Polymer Journal, Vol. 16, p. 307, 19
1980J (D, V, Luyen, L, Li
ebelt and L, 5trzelecki,,
Europ, Polym, J., 16307
1980)] Therefore, it is thought that it is possible to obtain a polymer liquid crystal having a chiral smectic C phase by replacing some of the bent carbons in a polymer liquid crystal having a smectic phase with asymmetric carbon. .
しかなから、この様な分子設計に基づいた強誘電性高分
子液晶はこれまてに得られていない。また、強誘電性を
発現する高分子液晶の液晶相の種類および該液晶相を示
す温度領域が、屈曲類の種類や屈曲類の長さあるいはメ
ソゲンと屈曲類の結合様式により著しく変化することを
考えれば、高分子液晶の合成の際の屈曲類の分子設計は
特に重要である。However, a ferroelectric polymer liquid crystal based on such molecular design has not been obtained so far. Furthermore, it has been shown that the type of liquid crystal phase of a polymer liquid crystal that exhibits ferroelectricity and the temperature range in which the liquid crystal phase is exhibited vary significantly depending on the type of bend, the length of the bend, and the bonding mode between the mesogen and the bend. Considering this, the molecular design of bent classes during the synthesis of polymeric liquid crystals is particularly important.
［発明か解決しようとする問題点］
本発明は、この様な従来技術の問題点を改善するために
なされたものであり、高分子液晶の屈曲類の長さおよび
構造を制御することかでき、該高分子液晶として縮合系
高分子液晶、その中ても特に主鎖型強誘電性高分子液晶
合成のために用いる新規な光学活性高分子液晶中間体を
提供することを目的とするものである。[Problems to be Solved by the Invention] The present invention was made in order to improve the problems of the prior art, and it is possible to control the length and structure of the bends of polymer liquid crystal. The purpose of the present invention is to provide a novel optically active polymer liquid crystal intermediate for use in the synthesis of condensed polymer liquid crystals, particularly main chain type ferroelectric polymer liquid crystals. be.
［問題点を解決するための手段］および［作用］即ち、
本発明は、下記の一般式（Ｉ）で表わされる光学活性化
合物からなることを特徴とする光学活性高分子液晶中間
体である。[Means for solving the problem] and [effect], that is,
The present invention is an optically active polymer liquid crystal intermediate characterized by comprising an optically active compound represented by the following general formula (I).
（式中、Ｘは水素原子またはメチル基、Ｙは水素原子ま
たはメチル基、Ｘ≠Ｙ、Ｚは水素原子またのときρ＝１
、またはＲは＋Ｃ１１２→「 、１≦ｍ≦１０のとき１
≦ρ≦５を表わす）
以下、本発明の詳細な説明する。(In the formula, X is a hydrogen atom or a methyl group, Y is a hydrogen atom or a methyl group, X≠Y, Z is a hydrogen atom or
, or R is +C112 → " , 1 when 1≦m≦10
≦ρ≦5) Hereinafter, the present invention will be described in detail.
本発明は、一般式（Ｉ）が前記構造式で表わされる光学
活性化合物である。一般式（Ｉ）において、Ｘ、Ｙ、Ｚ
、Ｒは、
ＸツーＨ，−ＣＬ、Ｙ雪−Ｈ，−ＣＨ，！。The present invention is an optically active compound whose general formula (I) is represented by the above structural formula. In general formula (I), X, Y, Z
, R is X2H, -CL, Y snow -H, -CH,! .
Ｒ−−Ｕ：Ｌ）ｎ １≦ｎ≦１８． ｆ −１または
Ｒ−４ＣＨ２）、 １≦１≦１０゜１≦２≦５
を表わす。R--U:L)n 1≦n≦18. f −1 or
R-4CH2), 1≦1≦10°1≦2≦5.
本発明において、一般式（Ｉ）で表わされる光学活性化
合物は、下記の反応式（Ｉ）〜（５）て示される方法等
て製造することかできる。In the present invention, the optically active compound represented by the general formula (I) can be produced by the methods shown in the following reaction formulas (I) to (5).
たたし、ＴｓＣｊ’ −ＣＩＩ＝＋ （Ｑとｓｏ、ｃｉ
）ＢｚＣｊ’ ＝ ＣトＣＨ＊Ｃ１’
トシル化体が（Ａ）ならば
Ｘ −−Ｈ，Ｙ −−ＣＨ３
トシル化体が（Ｂ）ならば
Ｘ −−ＣＨ３，Ｙ −−Ｈ
ｌ） ＫＯＪＩ
ベンジル化体が（Ｃ）ならば
Ｘ −−Ｃ１，、Ｙ −−Ｈ
ベンジル化体が（Ｄ）ならば
Ｘ −−Ｈ，Ｙ −−ＣＨ３
上記の反応において（Ａ）および（Ｃ）を選択的に得る
ためには、出発原料である乳酸エチルエステルの水酸基
をジヒドロピラン（ＤＨＰ）との反応により保護するこ
とが望ましい、（下記反応式（５））（テトラヒドロピ
ラニル基）
保護基であるテトラヒドロピラニル基は反応式（３）お
よび（４）の反応を行なった後、適当な触媒を用いては
ずせば良い。Tatami, TsCj' −CII=+ (Q and so, ci
)BzCj' = CtoCH*C1' If the tosylated product is (A), then X --H, Y --CH3 If the tosylated product is (B), then X --CH3, Y --H l) KOJI Benzyl If the compound is (C), then X --C1,, Y --H If the benzylated compound is (D), then In order to obtain a tetrahydropyranyl group, it is desirable to protect the hydroxyl group of the starting material lactic acid ethyl ester by reaction with dihydropyran (DHP) (reaction formula (5) below) (tetrahydropyranyl group). The pyranyl group may be removed using an appropriate catalyst after carrying out the reactions of reaction formulas (3) and (4).
また反応式（３）または（４）において、ジオールＨＯ
（Ｃ）Ｉｔ）ｎＯＨ，１１０＋−（−Ｃ１１２）、Ｏｈ
Ｈに対し、トシル化体あるいはベンジル化体を大過剰に
加えると、ジオールの両末端で反応が起こり、前記−数
式（Ｉ）で表わされる光学活性化合物におけるる。Also, in reaction formula (3) or (4), diol HO
(C)It)nOH,110+-(-C112),Oh
When the tosylated compound or benzylated compound is added in large excess to H, a reaction occurs at both ends of the diol, resulting in a reaction in the optically active compound represented by formula (I).
ただし、Ｘ ＝ −Ｈ，−ＣＨ３，Ｙ −−Ｈ，−ＣＨ
５−Ｘ≠Ｙ。However, X = -H, -CH3, Y -H, -CH
5-X≠Y.
Ｒ＝４ＣＨ２）−ｎ １ ≦ｎ ≦１８． ｆ！−
１または＋１−４ＣＩ□）、１≦１≦１０゜ｌ ≦２
≦５
このようにして得られた光学活性化合物は、両ン）との
縮合反応を行なうことかできるので、特に縮合系高分子
液晶、例えば、
また、本発明の光学活性高分子液晶中間体を用いること
により、高分子液晶の屈曲類の長さｎあるいはｍを容易
に、かつ系統的に変化させることかできるので高分子液
晶の分子設計か比較的容易になる。R=4CH2)-n 1 ≦n ≦18. f! −
1 or +1-4CI□), 1≦1≦10゜l≦2
≦5 The optically active compound obtained in this way can undergo a condensation reaction with both polymers, so it can be used particularly for condensed polymer liquid crystals, such as optically active polymer liquid crystal intermediates of the present invention. By using this method, the length n or m of the bends in the polymer liquid crystal can be easily and systematically changed, making molecular design of the polymer liquid crystal relatively easy.
次に、他の光学活性化合物の製造例を示す。Next, production examples of other optically active compounds will be shown.
下記の一般式（ｍ）で表わされる光学活性化合物の製造
法としては、下記の方法をあげることができる。一般式
（ＩＩＩ）で表わされる化合物は、前記一般式（Ｉ）の
化合物におけるＺ −−Ｈ。Examples of methods for producing the optically active compound represented by the following general formula (m) include the following methods. The compound represented by general formula (III) is Z --H in the compound of general formula (I).
Ｒ＝ （Ｃ１ｌ□）。、 ｆ ＝ １． Ｘ −−Ｈの
場合の例を示すものである。R= (C1l□). , f = 1. An example of the case of X --H is shown.
「
ＩＯ÷ＣＩｌ□ｈｏ−（：Ｌ−ＣＨ（Ｏｌｌ）
（ｍ ）一般式（Ｉ［［）で表わされる光学活性化
合物は、一般式（ＩＴ）で表わされるジオールと一般式
（Ｖ）で表わされる化合物との反応によって得られる。"IO÷CIl□ho-(:L-CH(Oll)
(m) The optically active compound represented by the general formula (I[[) is obtained by the reaction of the diol represented by the general formula (IT) and the compound represented by the general formula (V).
（反応式（６））
％式％
前記反応式（６）の反応は、溶媒を用いなくても進行す
るが、必要に応じて反応に直接関与しない溶媒、例えば
ジメチルホルムアミド、テトラヒドロフランのような溶
媒を用いても良い。(Reaction formula (6)) % formula % The reaction of reaction formula (6) proceeds without using a solvent, but if necessary, a solvent that does not directly participate in the reaction, such as dimethylformamide or tetrahydrofuran, may be used. You may also use
ジオール（ＩＶ）と化合物（Ｖ）のモル比は、（ＩＶ）
／ （Ｖ）≧１．０以トであることか望ましく、水酸化
カリウム（にＯＨ）の量はジオール（ＩＶ）と等モルに
することか望ましい０反応は、ジオール（ＩＶ）とＫＯ
）ｌを混合後加熱し、Ｋ ＯＩ＋が完全に溶解するまで
激しく攪拌し、その後化合物（Ｖ）を加え、４時間以上
加熱攪拌する。反応終了後冷水を加え、水相をｐＨ＝２
程度になるまて酸性化した後、クロロホルムにて有機相
を抽出し、溶媒を留去すると一般式（ｍ）で表わされる
光学活性化合物か得られる。本反応で得られる一般式（
ＩＩＩ）で表わされる光学活性化合物は、必要に応じて
クロマト精製をかけるのか良い。The molar ratio of diol (IV) and compound (V) is (IV)
/ (V) ≧ 1.0 or more, and the amount of potassium hydroxide (OH) is preferably equimolar with diol (IV). In the reaction, diol (IV) and KO
) After mixing, heat and stir vigorously until KOI+ is completely dissolved, then add compound (V), and heat and stir for 4 hours or more. After the reaction is complete, add cold water to adjust the aqueous phase to pH=2.
After acidifying to a certain degree, the organic phase is extracted with chloroform and the solvent is distilled off to obtain an optically active compound represented by the general formula (m). The general formula obtained in this reaction (
The optically active compound represented by III) may be subjected to chromatographic purification if necessary.
［実施例］ 以下、実施例を示し本発明をさらに具体的に説明する。[Example] Hereinafter, the present invention will be explained in more detail with reference to Examples.
実施例１
リチウムアルミニウムハイドライドをテトラヒドロフラ
ン中に分散させ、これを０°Ｃに冷却する。これにシー
（÷）−乳酸エチル１４０ｇ （Ｉ，１９モル）の３０
０ｍｆ！テトラヒドロフラン溶液を２時間かけて滴下し
た。反応物を室温にもどした後、５０℃で１２時間還流
した。残渣を濾過し、溶媒留去後、減圧蒸留して１．２
−プロパンジオール７１．２ｇを得た。（収率７６．０
％）
得られた１、２−プロパンジオール４４ｇ （０，５８
モル）を１７０ｍｊ）の乾燥とりシンに溶解する。この
溶液に水冷下で１０９ｇ （０，５７８ｇ）の塩化トシ
ルな３０分間かけて加えた。反応物を室温にもどしてか
ら６時間攪拌した後、ベンゼン２５０ｍＡ’を加え、生
じた沈殿をか過して除き、炉液に３７０ｍ１）の冷水を
加え、水相をｐＨ２程度に酸性化した。さらに、有機相
を１００ｍβのベンゼンて３回抽出し、２Ｎ塩酸１５０
ｆｆｌ！で２回洗浮した後、水洗し無水硫酸マクネシウ
ムて一晩乾燥した。溶媒を留去し、減圧蒸留を行なって
、１−トシロキシ−２−ヒドロキシプロパン８４．０ｇ
を得た。（収率６３．０％）次に、１，９−ノナンジオ
ール８．２ｇ （０，０５１モル）と３．３ｇ （０，
０５０モル）の８５％水酸化カリウムを混合し、１１０
℃て６時間攪拌すると水酸化カルラムは完全に溶解した
。これに１−トシロキシ−２−ヒドロキシプロパン５．
７５ｇ （０，０２５モル）を加え１１０℃で４時間攪
拌した０反応物に２０ａＲの水を加え、水相を塩酸でｐ
ｌ＝ ２程度になるように酸性化し、有機相をクロロホ
ルム１００ｍｊＪで３回抽出し、溶媒を留去して、下記
の一般式（Ｉ）のｎ ＝ ９． Ｘ ＝ −Ｈ。Example 1 Lithium aluminum hydride is dispersed in tetrahydrofuran and cooled to 0°C. To this, 140 g (I, 19 mol) of C(÷)-ethyl lactate was added to 30
0mf! A tetrahydrofuran solution was added dropwise over 2 hours. After the reaction mixture was returned to room temperature, it was refluxed at 50°C for 12 hours. The residue was filtered, the solvent was distilled off, and the residue was distilled under reduced pressure to give 1.2
- Obtained 71.2 g of propanediol. (Yield 76.0
%) 44 g of 1,2-propanediol obtained (0,58
mol) is dissolved in 170 mj) of dry torishin. To this solution was added 109 g (0,578 g) of tosyl chloride over 30 minutes under water cooling. After the reaction mixture was returned to room temperature and stirred for 6 hours, 250 mA' of benzene was added, the resulting precipitate was filtered off, and 370 ml of cold water was added to the furnace liquid to acidify the aqueous phase to about pH 2. Furthermore, the organic phase was extracted three times with 100 mβ benzene, and the organic phase was extracted with 150 mβ of 2N hydrochloric acid.
ffl! After washing twice with water, it was washed with water and dried overnight with anhydrous magnesium sulfate. The solvent was distilled off and vacuum distillation was performed to obtain 84.0 g of 1-tosyloxy-2-hydroxypropane.
I got it. (yield 63.0%) Next, 8.2 g (0,051 mol) of 1,9-nonanediol and 3.3 g (0,
050 mol) of 85% potassium hydroxide, 110 mol)
After stirring for 6 hours at ℃, the hydroxide columnum was completely dissolved. Add 1-tosyloxy-2-hydroxypropane5.
75g (0,025 mol) was added and stirred at 110°C for 4 hours. 20aR of water was added and the aqueous phase was purified with hydrochloric acid.
It was acidified so that l=2, the organic phase was extracted three times with 100 mjJ of chloroform, the solvent was distilled off, and n=9. X = −H.
Ｙ −−ＣＨｔ、の光学活性化合物３．９０ｇを得た。3.90 g of an optically active compound of Y--CHt was obtained.
（収率７１．５％）
？Ｈ・
（）１０４ＣＨＪ９０−ＣＩｌｚ−ＣＩ−ＯＨ）得られ
た光学活性化合物の物性を下記に示す。(yield 71.5%)? H. ()104CHJ90-CIlz-CI-OH) The physical properties of the obtained optically active compound are shown below.
［α］二’＝ ４４．２゜
（ｃ ＝ １．００．溶媒：イソプロピルアルコール）
ＮＭＲデータ
溶媒二重クロロホルム δｐｐｍ （ＴＭＳ）１．２
０ （ｄ、 ３Ｈ，メチル）
１．４５−１．６５ （ｍ、 ７Ｈ，メチレン）３．７
５ （Ｌ、 ４Ｈ，メチレン）
４．０５ （ｔ、 ２Ｈ，メチレン）
実施例２
実施例１の１．９−ノナンジオールのかわりに、１．４
−ブタンジオールを用い、１−トシロキシ−２−ヒドロ
キシプロパンと下記の反応条件で反応させる以外は実施
例１と同様にして、下記の光学活性化合物を得た。[α]2' = 44.2° (c = 1.00. Solvent: Isopropyl alcohol)
NMR data solvent double chloroform δppm (TMS) 1.2
0 (d, 3H, methyl) 1.45-1.65 (m, 7H, methylene) 3.7
5 (L, 4H, methylene) 4.05 (t, 2H, methylene) Example 2 Instead of 1.9-nonanediol in Example 1, 1.4
The following optically active compound was obtained in the same manner as in Example 1 except that -butanediol was used and reacted with 1-tosyloxy-2-hydroxypropane under the following reaction conditions.
Ｉ１・
（ＨＯ（ＣＨｄ４０−ＣＨｔ−ＣＩ−ＯＨ）得られた光
学活性化合物の物性を表１に示す。I1. (HO(CHd40-CHt-CI-OH) Table 1 shows the physical properties of the obtained optically active compound.
表 １
実施例３
実施例１の１．９−ノナンジオールのかわりに、１．５
−ベンタンジオールを用い、１−トシロキシ−２−ヒド
ロキシプロパンと下記の反応条件で反応させる以外は実
施例１と同様にして、下記の光学活性化合物を得た。Table 1 Example 3 Instead of 1.9-nonanediol in Example 1, 1.5
The following optically active compound was obtained in the same manner as in Example 1 except that -bentanediol was used and reacted with 1-tosyloxy-2-hydroxypropane under the following reaction conditions.
？１・
（）１０（ＣＩ２）ｓＯ−ＣＨｔ−Ｃｌト０１１ ）得
られた光学活性化合物の物性を表２に示す。? Table 2 shows the physical properties of the optically active compound obtained.
表 ２
実施例４
実施例１と同じ反応で、１，９−ノナンジオール８、Ｏ
ｇ（０，０５モル）に対し、８５％の水酸化カリウム３
．３ｇ（０，０５０モル） 、１−）−シロキシ−２−
ヒドロキシプロパンを４６ｇ （０，２０ｍｏｉ））に
すると、化合物（■）でｎ ＝ ９． Ｘ ＝ −ＩＩ
、 Ｙ −−ＣＨ３のものが得られた。Table 2 Example 4 In the same reaction as in Example 1, 1,9-nonanediol 8,O
g (0.05 mol), 85% potassium hydroxide 3
．． 3g (0,050 mol), 1-)-siloxy-2-
When 46 g (0.20 moi) of hydroxypropane is used, n = 9. X = -II
, Y --CH3 was obtained.
カラムクロマトにて精製した後のｆｆｉ量は３．００ｇ
（ｏ、ｏｔｔモル）であった、この化合物の比旋光度は
［α］二’＝＋８．．２°であった。（Ｃ＝ １．００
．溶媒ニジメチルホルムアミド）
実施例５
１４０ｇ （Ｉ，６７モル）のジヒドロピランに１１８
ｇ（Ｉ，０モル）の乳酸エチルエステルを加えた後、１
２Ｎ １１ｃｉ）を２０滴加えた。これを６０℃にて１
５時間攪拌した後、炭酸ナトリウム１０ｇを加え、さら
に２時間攪拌した。その後、減圧蒸留を行ない、乳酸エ
チルの水酸基をテトラヒドロピラニル基により保護を行
ない、 ｌ−ヒドロキシ−２−テトラヒドロビラニロキ
シプロパンを得た。（収率９０％）その後、実施例１と
同様に、テトラヒド口フラン中、リチウムアルミニウム
ハイドライドにより還元を行なった後、とりシン中にて
、塩化トシルにて１ヘシル化を行なった。各々の段階の
収率は還元反応て８５％、トシル化で８０％であった。The amount of ffi after purification with column chromatography is 3.00g
(o, ott mole), the specific optical rotation of this compound was [α]2'=+8. ．． It was 2°. (C=1.00
．． Solvent dimethylformamide) Example 5 140 g (I, 67 mol) of dihydropyran
After adding 1 g (I, 0 mol) of lactic acid ethyl ester, 1
20 drops of 2N 11ci) were added. 1 at 60℃
After stirring for 5 hours, 10 g of sodium carbonate was added, and the mixture was further stirred for 2 hours. Thereafter, vacuum distillation was performed to protect the hydroxyl group of ethyl lactate with a tetrahydropyranyl group to obtain l-hydroxy-2-tetrahydrobyranyloxypropane. (Yield 90%) Thereafter, in the same manner as in Example 1, reduction was performed with lithium aluminum hydride in tetrahydrofuran, and then 1-hesylation was performed with tosyl chloride in trisine. The yield of each step was 85% for the reduction reaction and 80% for the tosylation.
このようにして得られたトシル化体と１．９−ノナンジ
オールを、実施例１と同様にＫＯ］１をノナンジオール
に溶解させた後に反応を行ない、同様の処理を行なった
。生成物をメタノールに溶解させた後、アムベリスト（
ＡｓｂｅｒｙｓＬ） −１５１１と混合後３時間攪拌し
、−数式（Ｉ）のｎ＝９．Ｘ＝−Ｈ，Ｙｇ−ｅｌｆ３の
生成物を得た。（収率５０％）生成物のＮＭＲスペクト
ル、比旋光度は、実施例１と一致した。The tosylated product thus obtained and 1,9-nonanediol were reacted in the same manner as in Example 1, after dissolving KO]1 in nonanediol, and the same treatment was performed. After dissolving the product in methanol, Ambelist (
AsberysL) - After mixing with 1511, it was stirred for 3 hours, - n = 9 in formula (I). A product of X=-H, Yg-elf3 was obtained. (Yield 50%) The NMR spectrum and specific optical rotation of the product were consistent with Example 1.
実施例６
２５ｍｊ’のテトラヒドロフラン中にＮａＨ１，，２０
ｇ（０，０５モル）を懸濁させた。これに実施例５と同
じ方法で製造した１−ヒドロキシ−２−テトラヒドロビ
ラニロキシプロパン７．５０ｇ （０，０５＋＊ｏｊり
を加えた。混合物を３時間還流した後室温にもどしてか
ら塩化ベンジル５．７３ｇ （０，０５モル）の２０ｔ
ｊ）テトラヒドロフラン溶液を加えた。１時間還流抜水
を加え、有機相をエーテルで抽出した。これを水洗し炭
酸カルシウムで乾燥し、さらに蒸留を行ない。Example 6 NaH1,,20 in 25 mj' of tetrahydrofuran
g (0.05 mol) were suspended. To this was added 7.50 g of 1-hydroxy-2-tetrahydrobylanyloxypropane (0.05 + *oj) produced in the same manner as in Example 5. The mixture was refluxed for 3 hours, then returned to room temperature, and then added with benzyl chloride. 20t of 5.73g (0.05 mol)
j) Added tetrahydrofuran solution. Reflux water was added for 1 hour, and the organic phase was extracted with ether. This is washed with water, dried with calcium carbonate, and further distilled.
１−ベンジロキシ−２−テトラヒドロビラニロキシブロ
バン１０．０ｇ （（Ｉ，０４モル）を得た。（収率８
０％）これを２５１ｐのメタノール中に１．００ｇのア
ムベリストー１５１１と混合し３時間攪拌した後、アム
ベリス）−−１５Ｈを濾過した。蒸留により５．９８ｇ
（０，０：ｔ６モル）の１−ベンジロキシ−２−ヒｌ
（ロキシプロパンを得た。（収率９０％）
つぎに、テトラエチレングリコール４ｇ （０，０５モ
ル）に８５％水酸化カリウム３．３ｇ （０，０５モル
）を加え、１００℃で５時間攪拌した後、■−ベンジロ
キシ＝２−ヒドロキシプロパン４．１５ｇ （０，０２
５モル）を加え、さらに１００℃で３時間攪拌した。反
応終了後、２０−２の水を加え有機相をｐ＋＋＝２程度
に酸性化し、有機相をクロロホルムで抽出し、５■２の
３３％ＨＢ ｒを加え、４時間攪拌し脱ベンジル基を行
ない、生じた沈殿をか過した後溶媒を留去して一般式（
Ｉ）において、ｊ’ ＝ Ｌ、 ｎ ＝ ４． ｘ ＝
−Ｃｕｔ、 Ｙ＝−１１の化合物が１．５０ｇ （０
，０１１モル）得られた。10.0 g ((1,04 mol)) of 1-benzyloxy-2-tetrahydrobillanyloxybroban was obtained. (Yield: 8
0%) was mixed with 1.00 g of Amberisto 1511 in 251p of methanol and stirred for 3 hours, and then filtered. 5.98g by distillation
(0,0:t6 mol) of 1-benzyloxy-2-hyl
(Roxypropane was obtained. (Yield 90%) Next, 3.3 g (0.05 mol) of 85% potassium hydroxide was added to 4 g (0.05 mol) of tetraethylene glycol, and the mixture was stirred at 100°C for 5 hours. After that, ■-benzyloxy=2-hydroxypropane 4.15g (0,02
5 mol) was added thereto, and the mixture was further stirred at 100°C for 3 hours. After the reaction, 20-2 of water was added to acidify the organic phase to p++=2, the organic phase was extracted with chloroform, 5.2 of 33% HBr was added, and the mixture was stirred for 4 hours to remove the benzyl group. After filtering the formed precipitate, the solvent was distilled off to obtain the general formula (
In I), j' = L, n = 4. x =
-Cut, Y=-11 compound is 1.50g (0
,011 mol) was obtained.
？Ｈ・
（＋１０（Ｃ１１２−ＣＨ２−Ｃ１１２−Ｃ１１２３０
−ＣＨ−ＣＨ□−０１１）この化合物の比旋光度は［α
］ ：Ｓ＝＋５．ａｏ （Ｃ＝ １．００．溶媒：イソ
ビルアルコール）であった。? H・(+10(C112-CH2-C112-C11230
-CH-CH□-011) The specific rotation of this compound is [α
] :S=+5. ao (C=1.00.Solvent: Isovyl alcohol).
［発明の効果コ
本発明の光学活性高分子液晶中間体によれば、高分子液
晶の屈曲類の長さ、構造を容易に制御できる。すなわち
、高分子液晶の有する液晶相の種類（コレステリック相
とカイラルスメクデイックＣ相）および液晶相を示す温
度範囲を容易に制御することか町１七となる効果かある
。[Effects of the Invention] According to the optically active polymer liquid crystal intermediate of the present invention, the length and structure of the bends of the polymer liquid crystal can be easily controlled. That is, it is possible to easily control the type of liquid crystal phase (cholesteric phase and chiral smectic C phase) of the polymer liquid crystal and the temperature range in which the liquid crystal phase is exhibited.
Claims (1)
なることを特徴とする光学活性高分子液晶中間体。 一般式（ I ） ▲数式、化学式、表等があります▼ （式中、Ｘは水素原子またはメチル基、Ｙは水素原子ま
たはメチル基、Ｘ≠Ｙ、Ｚは水素原子または▲数式、化
学式、表等があります▼、Ｒは▲数式、化学式、表等が
あります▼、１≦ｎ≦１８ のときｌ＝１、またはＲは▲数式、化学式、表等があり
ます▼、１≦ｍ ≦１０のとき１≦ｌ≦５を表わす）[Scope of Claims] An optically active polymer liquid crystal intermediate comprising an optically active compound represented by the following general formula (I). General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, X is a hydrogen atom or methyl group, Y is a hydrogen atom or methyl group, X≠Y, Z is a hydrogen atom, or etc. ▼, R is ▲ there is a mathematical formula, chemical formula, table, etc. ▼, when 1≦n≦18, l=1, or R is ▲ there is a mathematical formula, chemical formula, table, etc. ▼, when 1≦m ≦10 1≦l≦5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62250567A JPH0813771B2 (en) | 1987-10-06 | 1987-10-06 | Optically active polymer liquid crystal intermediate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62250567A JPH0813771B2 (en) | 1987-10-06 | 1987-10-06 | Optically active polymer liquid crystal intermediate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0193553A true JPH0193553A (en) | 1989-04-12 |
| JPH0813771B2 JPH0813771B2 (en) | 1996-02-14 |
Family
ID=17209810
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62250567A Expired - Fee Related JPH0813771B2 (en) | 1987-10-06 | 1987-10-06 | Optically active polymer liquid crystal intermediate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0813771B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0435350A2 (en) | 1989-12-29 | 1991-07-03 | Canon Kabushiki Kaisha | Polymeric liquid-crystalline compound, liquid-crystal composition containing it, and liquid-crystal device |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2834820A (en) * | 1953-07-28 | 1958-05-13 | Universal Oil Prod Co | Solvent extraction of organic mixtures with mixed glycol ethers as solvents |
-
1987
- 1987-10-06 JP JP62250567A patent/JPH0813771B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2834820A (en) * | 1953-07-28 | 1958-05-13 | Universal Oil Prod Co | Solvent extraction of organic mixtures with mixed glycol ethers as solvents |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0435350A2 (en) | 1989-12-29 | 1991-07-03 | Canon Kabushiki Kaisha | Polymeric liquid-crystalline compound, liquid-crystal composition containing it, and liquid-crystal device |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0813771B2 (en) | 1996-02-14 |
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