JPH0629257B2 - Phenyl pyrimidine derivative - Google Patents
Phenyl pyrimidine derivativeInfo
- Publication number
- JPH0629257B2 JPH0629257B2 JP59206908A JP20690884A JPH0629257B2 JP H0629257 B2 JPH0629257 B2 JP H0629257B2 JP 59206908 A JP59206908 A JP 59206908A JP 20690884 A JP20690884 A JP 20690884A JP H0629257 B2 JPH0629257 B2 JP H0629257B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- compound
- pyrimidine derivative
- phenyl pyrimidine
- compound represented
- 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.)
- Expired - Lifetime
Links
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、液晶表示装置に使われる液晶化合物を合成す
るための重要な中間体化合物に関する。The present invention relates to an important intermediate compound for synthesizing a liquid crystal compound used in a liquid crystal display device.
従来、液晶化合物として、式 （式中、ＸはＨ、Cl、CNを、ＹはCl、C2H5を、＊印は不
斉炭素原子を示す。）で示される化合物や、 （Ferroellectrics，24(1980)309，Mol.Cryst.，Liq.Cr
yst.，Letter82(1982)61) また （上記三化合物においてｎは９又は１０である）がB.I.
Ostrovskiiらによつて造られている。Conventionally, as a liquid crystal compound, (Wherein X represents H, Cl, CN, Y represents Cl, C 2 H 5 , and * represents an asymmetric carbon atom), (Ferroellectrics, 24 (1980) 309, Mol.Cryst., Liq.Cr
yst., Letter 82 (1982) 61) See also (In the above three compounds, n is 9 or 10) is BI
Built by Ostrovskii et al.
しかしながら、これら公知の液晶化合物は広い温度範囲
でカイラルスメクチツク相を呈するものが少なく、ま
た、あつたとしても安定性の点において問題があつた。However, few of these known liquid crystal compounds exhibit a chiral smectic phase in a wide temperature range, and even if they are used, there is a problem in stability.
本発明の目的は、従来の技術における問題点を解決する
ために、即ち、安定性に優れ、広い温度範囲でカイラル
スメクチツク相を呈する各種液晶化合物を提供するのに
まさに要となる光学活性な中間化合物を提供することに
ある。The object of the present invention is to solve the problems in the prior art, that is, to provide various liquid crystal compounds which are excellent in stability and exhibit a chiral smectic phase in a wide temperature range, and which are very important for providing optically active compounds. To provide various intermediate compounds.
本発明の目的化合物は、次のようにして合成される。即
ち、式(I) （式中、Ｒは低級アルキル基、ＺはＯ−Tos，Ｏ−Mes，
Ｏ−THP，Ｏ−Si(CH3)2t−Bu，Ｏ−Benzyl，Ｏ−Benzoy
l，Ｏ，Acyl，ｍは正の整数、＊印は不斉炭素原子を示
す。）で示される化合物をリチユウムアルミニウムハイ
ドライドで還元し、式(II) （式中、Ｚ、＊印、ｍは前記と同じ。）で示される化合
物を得る。The target compound of the present invention is synthesized as follows. That is, formula (I) (In the formula, R is a lower alkyl group, Z is O-Tos, O-Mes,
O-THP, O-Si ( CH 3) 2 t-Bu, O-Benzyl, O-Benzoy
l, O, Acyl and m are positive integers, and * indicates an asymmetric carbon atom. ) Is reduced with lithium aluminum hydride to give a compound of formula (II) (In the formula, Z, * mark, and m are the same as above.).
かくして得られた式(II)で示される化合物は、そのまま
で、もしくは、第一級水酸基を、反応性を有する基（例
えば、ハロゲン、−Ｏ−Tos，−Ｏ−Mesなど）に変えて
式(III) （式中、Ａはハロゲン、ＯＨなどを示し、ｎは正の整数
を示す。） で示される化合物とを反応させる。The compound represented by the formula (II) thus obtained may be used as it is, or by changing the primary hydroxyl group to a reactive group (for example, halogen, —O—Tos, —O—Mes, etc.). (III) (In the formula, A represents halogen, OH, and the like, and n represents a positive integer.).
かくすることによつて、式(IV)で示される本発明目的化
合物を得ることができる。Thus, the compound of the present invention represented by the formula (IV) can be obtained.
（式中、Ｚ、ｍ、ｎ、＊印は前記と同じ。） ここにおいて、式(I)で示される化合物を還元して得ら
れた式(II)で示される化合物をそのままで式(III)で示
される化合物と反応させるときは、式(III)で示される
化合物のＡはハロゲンであり、式(II)で示される化合物
の第一級水酸基を反応性を有する基に変換したときは、
式(III)で示される化合物のＡは水酸基である。反応
は、適宜溶媒中で、アルカリ金属、アルカリ金属水素化
物、アルカリ金属炭酸塩などの存在下で好適に進められ
る。用いられる溶媒としては、ベンゼン、トルエン、ジ
メチルスルホキシド、ジメチルホルムアミド、ジ（低級
アルキル）グリコールエーテルなどがあげらる。反応温
度は室温から２５０℃であるが、好ましくは５０〜１０
０℃である。 (In the formula, Z, m, n and * are the same as above.) Here, the compound represented by the formula (II) obtained by reducing the compound represented by the formula (I) is used as it is in the formula (III When the compound represented by the formula (III) is reacted with A, the compound A represented by the formula (III) is halogen, and when the primary hydroxyl group of the compound represented by the formula (II) is converted into a reactive group. ,
A of the compound represented by the formula (III) is a hydroxyl group. The reaction is suitably carried out in an appropriate solvent in the presence of an alkali metal, an alkali metal hydride, an alkali metal carbonate or the like. Examples of the solvent used include benzene, toluene, dimethylsulfoxide, dimethylformamide, di (lower alkyl) glycol ether and the like. The reaction temperature is room temperature to 250 ° C, preferably 50 to 10
0 ° C.
このほかに、本発明目的化合物の合成方法としては、次
の化学反応式で示すものがあげられる。In addition to this, as a method for synthesizing the object compound of the present invention, the method represented by the following chemical reaction formula can be mentioned.
（式中、Ｚ、Ａ、ｍ、ｎ、＊印は前記と同じ。） 式(II)で示される化合物において、ｍが１のものは３−
ヒドロキシ吉草酸の低級アルキルエステルから造られ、
ｍが２以上のものについては、得られた２−ヒドロキシ
ペンタノールを原料として、マロン酸エステル合成法、
アセト酢酸エステル合成法、グリニヤール試薬を用いる
方法などを使つて合成することができる。 (In the formula, Z, A, m, n, and * are the same as above.) In the compound represented by the formula (II), when m is 1 is 3-
Made from lower alkyl ester of hydroxyvaleric acid,
When m is 2 or more, the obtained 2-hydroxypentanol is used as a raw material to synthesize a malonic acid ester,
Acetoacetic acid ester synthesis method, a method using a Grignard reagent and the like can be used for the synthesis.
また、本発明目的化合物は、１個の不斉炭素原子を持つ
ているので、光学的対掌体が存在している。原料として
使用する式(I)で示される化合物において、その光学活
性体のいずれを選択するかによつて、該対掌体のどちら
ができるかが定まる。In addition, since the compound of the present invention has one asymmetric carbon atom, it has an optical antipode. In the compound represented by the formula (I) used as a raw material, which enantiomer is formed depends on which of the optically active forms is selected.
以下、本発明を具体的に説明するため実施例を記述す
る。Hereinafter, examples will be described in order to specifically describe the present invention.
実施例 光学活性な５−ｎ−ウンデシル−２−〔４−（３−ピラ
ニルオキシ−ペンチルオキシ）フエニル〕ピリミジンの
製造： 冷却管、温度計、滴下ロート、塩化カルシウム管を備え
た３０mlの三ツ口フラスコに水素化ナトリウム（abt.50
％ｏｉｌsuspension）0.76ｇ、乾燥ジメチルホルムアミ
ド５mlを入れた。次に、乾燥ジメチルホルムアミド５ml
に４−（５−ｎ−ウンデシル−２−ピリミジニル）フエ
ノール4.33ｇを溶かした溶液をゆつくり滴下した。８０
℃で３０分反応したのち、ｐ−トルエンスルホン酸３−
ピラニルオキシペンチルエステル4.3ｇ（この化合物は
Ｌ(+)−３−ヒドロキシ吉草酸メチルエステル〔▲
〔α〕20 D▼＝＋28.1（Ｃ＝ｌ，CHCl3）〕より合成し
た。） を乾燥ジメチルホルムアミド５mlに溶かした溶液を滴下
した。混合物を８０〜８５℃で８時間反応後、冷却し、
氷水中に流し込み、エーテル抽出した。エーテル層を１
０％水酸化ナトリウム溶液、水で洗浄後、乾燥し、エー
テルを留去して、光学活性な５−ｎ−ウンデシル−２−
〔４（３−ピラニルオキシ−ペンチルオキシ）フエニ
ル〕ピリミジン6.39ｇの粗生成物を得た。Example Preparation of optically active 5-n-undecyl-2- [4- (3-pyranyloxy-pentyloxy) phenyl] pyrimidine: In a 30 ml three-necked flask equipped with a cooling tube, thermometer, dropping funnel and calcium chloride tube. Sodium hydride (abt.50
% Oil suspension) (0.76 g) and dry dimethylformamide (5 ml) were added. Next, 5 ml of dry dimethylformamide
A solution having 4.33 g of 4- (5-n-undecyl-2-pyrimidinyl) phenol dissolved therein was slowly added dropwise. 80
After reacting at 30 ° C for 30 minutes, p-toluenesulfonic acid 3-
4.3 g of pyranyloxypentyl ester (This compound is L (+)-3-hydroxyvaleric acid methyl ester [▲
[Α] 20 D ▼ = + 28.1 (C = 1, CHCl 3 )]. ) Was dissolved in 5 ml of dry dimethylformamide and added dropwise. The mixture was reacted at 80-85 ° C for 8 hours, then cooled,
It was poured into ice water and extracted with ether. 1 ether layer
After washing with 0% sodium hydroxide solution and water, it was dried and the ether was distilled off to give optically active 5-n-undecyl-2-
[4 (3-Pyranyloxy-pentyloxy) phenyl] pyrimidine 6.39 g of crude product was obtained.
Claims (1)
2t−Bu，Ｏ−Benzyl，Ｏ−Benzoyl，ｍは１〜１６、ｎ
は１〜２０の整数を、＊印は不斉炭素原子を示す。）1. A formula A phenylpyrimidine derivative represented by: (In the formula, Z is O-Tos, O-Mes, O-THP, O-Si (CH 3 ).
2 t-Bu, O-Benzyl, O-Benzoyl, m is 1-16, n
Represents an integer of 1 to 20, and * represents an asymmetric carbon atom. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59206908A JPH0629257B2 (en) | 1984-10-01 | 1984-10-01 | Phenyl pyrimidine derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59206908A JPH0629257B2 (en) | 1984-10-01 | 1984-10-01 | Phenyl pyrimidine derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6185368A JPS6185368A (en) | 1986-04-30 |
| JPH0629257B2 true JPH0629257B2 (en) | 1994-04-20 |
Family
ID=16531061
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59206908A Expired - Lifetime JPH0629257B2 (en) | 1984-10-01 | 1984-10-01 | Phenyl pyrimidine derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0629257B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4725688A (en) * | 1984-06-07 | 1988-02-16 | Seiko Instruments Inc. | Liquid crystal compound |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58121225A (en) * | 1982-01-04 | 1983-07-19 | メルク・パテント・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング | Bbc brown boveri & cie |
| JPS6084232A (en) * | 1983-09-10 | 1985-05-13 | メルク・パテント・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング | Anisotropic compound and liquid crystal mixture |
-
1984
- 1984-10-01 JP JP59206908A patent/JPH0629257B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58121225A (en) * | 1982-01-04 | 1983-07-19 | メルク・パテント・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング | Bbc brown boveri & cie |
| JPS6084232A (en) * | 1983-09-10 | 1985-05-13 | メルク・パテント・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツング | Anisotropic compound and liquid crystal mixture |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6185368A (en) | 1986-04-30 |
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