JP2000247956A - Tricyclic phenylpyridine derivative and liquid crystal composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new tricyclic phenylpyridine derivative which is useful as a component for practically excellent liquid crystals responding at high speeds in wide temperature ranges, has alkyl side chains not having oxygen functional groups, and contains a pyridine ring. SOLUTION: A tricyclic phenylpyridine derivative of formula I (R1 is a 1-12C alkyl; R2 is a 1-12C alkyl or H; ring A and ring B are each 1,4-phenylene, pyridin-2,5-diyl, provided that the ring B is 1,4-phenylene, when the ring A is pyridin-2,5-diyl). For example, 2-(4decylphenyl)-5-(4-octylphenyl)pyridine. The compound of formula I is obtained, for example, by reacting an alkylbromobenzene of formula II with buthyllithium or the like to form the lithio compound, reacting the lithio compound with trimethyl borate, reacting the obtained borate derivative with 2,5-dibromopyridine in the presence of a palladium catalyst, and then reacting the obtained bromophenylpyridine derivative with a Grignard reagent in the presence of a nickel catalyst.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の属する技術分野】本発明は、新規な有機化合
物、特には、液晶材料の成分として有用である新規な液
晶化合物に関し、さらにはこれを含有する液晶組成物に
関する。The present invention relates to a novel organic compound, particularly to a novel liquid crystal compound useful as a component of a liquid crystal material, and further to a liquid crystal composition containing the same.

【０００２】[0002]

【従来の技術】表示素子に用いられる液晶材料にはネマ
チック液晶材料や強誘電性液晶材料があるが、単一の化
合物で実用的な諸特性、すなわち液晶温度範囲、動作電
圧、応答性能等を満たすことは難しく、従来から複数の
化合物を混合することによって種々の物性を満たす液晶
組成物を得る努力がなされている。特に、広い温度範囲
で目的とする液晶相を発現させ、高速応答する優れた材
料が求められている。2. Description of the Related Art Liquid crystal materials used for display devices include nematic liquid crystal materials and ferroelectric liquid crystal materials. A single compound can provide practical characteristics such as a liquid crystal temperature range, an operating voltage, and a response performance. It is difficult to satisfy the requirements, and efforts have conventionally been made to obtain liquid crystal compositions satisfying various physical properties by mixing a plurality of compounds. In particular, there is a need for an excellent material that exhibits a desired liquid crystal phase in a wide temperature range and that responds at high speed.

【０００３】[0003]

【発明が解決しようとする課題】本発明者らは、上記現
状に鑑み鋭意研究を進めた結果、酸素官能基を持たない
アルキル側鎖を有し、ピリジン環を含む三環系化合物が
容易に製造でき、さらにこれを組成物に添加すると、応
答速度を変えることなく、目的とする液晶温度範囲を広
げること、すなわち、強誘電性液晶組成物では混合して
キラルスメクチックＣ相を広げ、ネマチック液晶組成物
ではネマチック相を広げることができることを見出し
た。DISCLOSURE OF THE INVENTION The present inventors have conducted intensive studies in view of the above situation, and have found that tricyclic compounds having an alkyl side chain having no oxygen functional group and containing a pyridine ring can be easily obtained. It can be manufactured and further added to the composition to widen the target liquid crystal temperature range without changing the response speed. That is, in the ferroelectric liquid crystal composition, the chiral smectic C phase is mixed to expand the nematic liquid crystal. It has been found that the composition can expand the nematic phase.

【０００４】本発明はかかる知見に基づきなされたもの
で、本発明の目的は広い温度範囲で高速応答する実用的
に優れた液晶組成物を構成する成分として有用な化合物
およびその化合物を成分として含む液晶組成物を提供す
ることにある。The present invention has been made based on such findings, and it is an object of the present invention to include a compound useful as a component constituting a practically excellent liquid crystal composition which responds rapidly over a wide temperature range, and a compound containing the compound. It is to provide a liquid crystal composition.

【０００５】[0005]

【課題を解決するための手段】本発明は、一般式（I）The present invention provides a compound represented by the general formula (I):

【０００６】[0006]

【化２】 Embedded image

【０００７】〔式中、R¹は炭素数１〜１２のアルキル基
を、R²は炭素数１〜１２のアルキル基または水素を、環
Aは1,4-フェニレン基またはピリジン-2,5-ジイル基（２
位にR¹）を示し、環Bは環Aが1,4-フェニレン基の場合、
1,4-フェニレン基、ピリジン-2,5-ジイル基（２位また
は5位にR²）を示し、環Aがピリジン-2,5-ジイル基（２
位にR¹）の場合、1,4-フェニレン基を示す。〕で表され
る三環系フェニルピリジン誘導体及び上記一般式（I）
で表される三環系フェニルピリジン誘導体を含有する液
晶組成物からなるものである。Wherein R ¹ is an alkyl group having 1 to 12 carbon atoms, R ² is an alkyl group having 1 to 12 carbon atoms or hydrogen,
A represents a 1,4-phenylene group or a pyridine-2,5-diyl group (2
R ¹ ) at the position, ring B is a ring A is a 1,4-phenylene group,
A 1,4-phenylene group, a pyridine-2,5-diyl group (R ^{2 at the 2-} or 5-position), and ring A is a pyridine-2,5-diyl group (2
In the case of R ¹ ), it represents a 1,4-phenylene group. And a tricyclic phenylpyridine derivative represented by the formula (I):
And a liquid crystal composition containing a tricyclic phenylpyridine derivative represented by the formula:

【０００８】[0008]

【発明の実施の形態】一般式（I）で表される化合物と
しては、具体的には次の化合物を例示することができ
る。2-(4-オクチルフェニル)-5-フェニルピリジン、2-
(4-オクチルフェニル)-5-(4-メチルフェニル)ピリジ
ン、2-(4-オクチルフェニル)-5-(4-エチルフェニル)ピ
リジン、2-(4-オクチルフェニル)-5-(4-プロピルフェニ
ル)ピリジン、2-(4-オクチルフェニル)-5-(4-ブチルフ
ェニル)ピリジン、2-(4-オクチルフェニル)-5-(4-ペン
チルフェニル)ピリジン、2-(4-オクチルフェニル)-5-(4
-ヘキシルフェニル)ピリジン、2-(4-オクチルフェニル)
-5-(4-ヘプチルフェニル)ピリジン、2-(4-オクチルフェ
ニル)-5-(4-オクチルフェニル)ピリジン、2-(4-オクチ
ルフェニル)-5-(4-ノニルフェニル)ピリジン、2-(4-オ
クチルフェニル)-5-(4-デシルフェニル)ピリジン、2-(4
-オクチルフェニル)-5-(4-ウンデシルフェニル)ピリジ
ン、2-(4-オクチルフェニル)-5-(4-ドデシルフェニル)
ピリジンBEST MODE FOR CARRYING OUT THE INVENTION As the compound represented by the general formula (I), the following compounds can be specifically exemplified. 2- (4-octylphenyl) -5-phenylpyridine, 2-
(4-octylphenyl) -5- (4-methylphenyl) pyridine, 2- (4-octylphenyl) -5- (4-ethylphenyl) pyridine, 2- (4-octylphenyl) -5- (4- Propylphenyl) pyridine, 2- (4-octylphenyl) -5- (4-butylphenyl) pyridine, 2- (4-octylphenyl) -5- (4-pentylphenyl) pyridine, 2- (4-octylphenyl ) -5- (4
-Hexylphenyl) pyridine, 2- (4-octylphenyl)
-5- (4-heptylphenyl) pyridine, 2- (4-octylphenyl) -5- (4-octylphenyl) pyridine, 2- (4-octylphenyl) -5- (4-nonylphenyl) pyridine, 2 -(4-octylphenyl) -5- (4-decylphenyl) pyridine, 2- (4
-Octylphenyl) -5- (4-undecylphenyl) pyridine, 2- (4-octylphenyl) -5- (4-dodecylphenyl)
Pyridine

【０００９】および、上記の化合物の4-オクチルフェニ
ル基が、4-メチルフェニル基、4-エチルフェニル基、4-
プロピルフェニル基、4-ブチルフェニル基、4-ペンチル
フェニル基、4-ヘキシルフェニル基、4-ヘプチルフェニ
ル基、4-ノニルフェニル基、4-デシルフェニル基、4-ウ
ンデシルフェニル基または4-ドデシルフェニル基に代わ
った化合物、およびIn the above compound, the 4-octylphenyl group is a 4-methylphenyl group, a 4-ethylphenyl group,
Propylphenyl group, 4-butylphenyl group, 4-pentylphenyl group, 4-hexylphenyl group, 4-heptylphenyl group, 4-nonylphenyl group, 4-decylphenyl group, 4-undecylphenyl group or 4-dodecyl Compounds that replace the phenyl group, and

【００１０】2-(4-オクチルフェニル)-5-(ピリジン-2-
イル)ピリジン、2-(4-オクチルフェニル)-5-(5-メチル
ピリジン-2-イル)ピリジン、2-(4-オクチルフェニル)-5
-(5-エチルピリジン-2-イル)ピリジン、2-(4-オクチル
フェニル)-5-(5-プロピルピリジン-2-イル)ピリジン、2
-(4-オクチルフェニル)-5-(5-ブチルピリジン-2-イル)
ピリジン、2-(4-オクチルフェニル)-5-(5-ペンチルピリ
ジン-2-イル)ピリジン、2-(4-オクチルフェニル)-5-(5-
ヘキシルピリジン-2-イル)ピリジン、2-(4-オクチルフ
ェニル)-5-(5-ヘプチルピリジン-2-イル)ピリジン、2-
(4-オクチルフェニル)-5-(5-オクチルピリジン-2-イル)
ピリジン、2-(4-オクチルフェニル)-5-(5-ノニルピリジ
ン-2-イル)ピリジン、2-(4-オクチルフェニル)-5-(5-デ
シルピリジン-2-イル)ピリジン、2-(4-オクチルフェニ
ル)-5-(5-ウンデシルピリジン-2-イル)ピリジン、2-(4-
オクチルフェニル)-5-(5-ドデシルピリジン-2-イル)ピ
リジン2- (4-octylphenyl) -5- (pyridine-2-yl
Yl) pyridine, 2- (4-octylphenyl) -5- (5-methylpyridin-2-yl) pyridine, 2- (4-octylphenyl) -5
-(5-ethylpyridin-2-yl) pyridine, 2- (4-octylphenyl) -5- (5-propylpyridin-2-yl) pyridine, 2
-(4-octylphenyl) -5- (5-butylpyridin-2-yl)
Pyridine, 2- (4-octylphenyl) -5- (5-pentylpyridin-2-yl) pyridine, 2- (4-octylphenyl) -5- (5-
Hexylpyridin-2-yl) pyridine, 2- (4-octylphenyl) -5- (5-heptylpyridin-2-yl) pyridine, 2-
(4-octylphenyl) -5- (5-octylpyridin-2-yl)
Pyridine, 2- (4-octylphenyl) -5- (5-nonylpyridin-2-yl) pyridine, 2- (4-octylphenyl) -5- (5-decylpyridin-2-yl) pyridine, 2- (4-octylphenyl) -5- (5-undecylpyridin-2-yl) pyridine, 2- (4-
(Octylphenyl) -5- (5-dodecylpyridin-2-yl) pyridine

【００１１】および、上記の化合物の4-オクチルフェニ
ル基が、4-メチルフェニル基、4-エチルフェニル基、4-
プロピルフェニル基、4-ブチルフェニル基、4-ペンチル
フェニル基、4-ヘキシルフェニル基、4-ヘプチルフェニ
ル基、4-ノニルフェニル基、4-デシルフェニル基、4-ウ
ンデシルフェニル基または4-ドデシルフェニル基に代わ
った化合物、およびAnd the 4-octylphenyl group of the above compound is a 4-methylphenyl group, a 4-ethylphenyl group,
Propylphenyl group, 4-butylphenyl group, 4-pentylphenyl group, 4-hexylphenyl group, 4-heptylphenyl group, 4-nonylphenyl group, 4-decylphenyl group, 4-undecylphenyl group or 4-dodecyl Compounds that replace the phenyl group, and

【００１２】2-(4-オクチルフェニル)-5-(ピリジン-5-
イル)ピリジン、2-(4-オクチルフェニル)-5-(2-メチル
ピリジン-5-イル)ピリジン、2-(4-オクチルフェニル)-5
-(2-エチルピリジン-5-イル)ピリジン、2-(4-オクチル
フェニル)-5-(2-プロピルピリジン-5-イル)ピリジン、2
-(4-オクチルフェニル)-5-(2-ブチルピリジン-5-イル)
ピリジン、2-(4-オクチルフェニル)-5-(2-ペンチルピリ
ジン-5-イル)ピリジン、2-(4-オクチルフェニル)-5-(2-
ヘキシルピリジン-5-イル)ピリジン、2-(4-オクチルフ
ェニル)-5-(2-ヘプチルピリジン-5-イル)ピリジン、2-
(4-オクチルフェニル)-5-(2-オクチルピリジン-5-イル)
ピリジン、2-(4-オクチルフェニル)-5-(2-ノニルピリジ
ン-5-イル)ピリジン、2-(4-オクチルフェニル)-5-(2-デ
シルピリジン-5-イル)ピリジン、2-(4-オクチルフェニ
ル)-5-(2-ウンデシルピリジン-5-イル)ピリジン、2-(4-
オクチルフェニル)-5-(2-ドデシルピリジン-5-イル)ピ
リジン2- (4-octylphenyl) -5- (pyridine-5-
Yl) pyridine, 2- (4-octylphenyl) -5- (2-methylpyridin-5-yl) pyridine, 2- (4-octylphenyl) -5
-(2-ethylpyridin-5-yl) pyridine, 2- (4-octylphenyl) -5- (2-propylpyridin-5-yl) pyridine, 2
-(4-octylphenyl) -5- (2-butylpyridin-5-yl)
Pyridine, 2- (4-octylphenyl) -5- (2-pentylpyridin-5-yl) pyridine, 2- (4-octylphenyl) -5- (2-
Hexylpyridin-5-yl) pyridine, 2- (4-octylphenyl) -5- (2-heptylpyridin-5-yl) pyridine, 2-
(4-octylphenyl) -5- (2-octylpyridin-5-yl)
Pyridine, 2- (4-octylphenyl) -5- (2-nonylpyridin-5-yl) pyridine, 2- (4-octylphenyl) -5- (2-decylpyridin-5-yl) pyridine, 2- (4-octylphenyl) -5- (2-undecylpyridin-5-yl) pyridine, 2- (4-
(Octylphenyl) -5- (2-dodecylpyridin-5-yl) pyridine

【００１３】および、上記の化合物の4-オクチルフェニ
ル基が、4-メチルフェニル基、4-エチルフェニル基、4-
プロピルフェニル基、4-ブチルフェニル基、4-ペンチル
フェニル基、4-ヘキシルフェニル基、4-ヘプチルフェニ
ル基、4-ノニルフェニル基、4-デシルフェニル基、4-ウ
ンデシルフェニル基または4-ドデシルフェニル基に代わ
った化合物、およびAnd the 4-octylphenyl group of the above compound is a 4-methylphenyl group, a 4-ethylphenyl group,
Propylphenyl group, 4-butylphenyl group, 4-pentylphenyl group, 4-hexylphenyl group, 4-heptylphenyl group, 4-nonylphenyl group, 4-decylphenyl group, 4-undecylphenyl group or 4-dodecyl Compounds that replace the phenyl group, and

【００１４】2-(2-オクチルピリジン-5-イル)-5-フェニ
ルピリジン、2-(2-オクチルピリジン-5-イル)-5-(4-メ
チルフェニル)ピリジン、2-(2-オクチルピリジン-5-イ
ル)-5-(4-エチルフェニル)ピリジン、2-(2-オクチルピ
リジン-5-イル)-5-(4-プロピルフェニル)ピリジン、2-
(2-オクチルピリジン-5-イル)-5-(4-ブチルフェニル)ピ
リジン、2-(2-オクチルピリジン-5-イル)-5-(4-ペンチ
ルフェニル)ピリジン、2-(2-オクチルピリジン-5-イル)
-5-(4-ヘキシルフェニル)ピリジン、2-(2-オクチルピリ
ジン-5-イル)-5-(4-ヘプチルフェニル)ピリジン、2-(2-
オクチルピリジン-5-イル)-5-(4-オクチルフェニル)ピ
リジン、2-(2-オクチルピリジン-5-イル)-5-(4-ノニル
フェニル)ピリジン、2-(2-オクチルピリジン-5-イル)-5
-(4-デシルフェニル)ピリジン、2-(2-オクチルピリジン
-5-イル)-5-(4-ウンデシルフェニル)ピリジン、2-(2-オ
クチルピリジン-5-イル)-5-(4-ドデシルフェニル)ピリ
ジン2- (2-octylpyridin-5-yl) -5-phenylpyridine, 2- (2-octylpyridin-5-yl) -5- (4-methylphenyl) pyridine, 2- (2-octyl) Pyridin-5-yl) -5- (4-ethylphenyl) pyridine, 2- (2-octylpyridin-5-yl) -5- (4-propylphenyl) pyridine, 2-
(2-octylpyridin-5-yl) -5- (4-butylphenyl) pyridine, 2- (2-octylpyridin-5-yl) -5- (4-pentylphenyl) pyridine, 2- (2-octyl (Pyridin-5-yl)
-5- (4-hexylphenyl) pyridine, 2- (2-octylpyridin-5-yl) -5- (4-heptylphenyl) pyridine, 2- (2-
Octylpyridin-5-yl) -5- (4-octylphenyl) pyridine, 2- (2-octylpyridin-5-yl) -5- (4-nonylphenyl) pyridine, 2- (2-octylpyridine-5 -Il) -5
-(4-decylphenyl) pyridine, 2- (2-octylpyridine
-5-yl) -5- (4-undecylphenyl) pyridine, 2- (2-octylpyridin-5-yl) -5- (4-dodecylphenyl) pyridine

【００１５】および、上記の化合物の2-オクチルピリジ
ン-5-イル基が、2-メチルピリジン-5-イル基、2-エチル
ピリジン-5-イル基、2-プロピルピリジン-5-イル基、2-
ブチルピリジン-5-イル基、2-ペンチルピリジン-5-イル
基、2-ヘキシルピリジン-5-イル基、2-ヘプチルピリジ
ン-5-イル基、2-ノニルピリジン-5-イル基、2-デシルピ
リジン-5-イル基、2-ウンデシルピリジン-5-イル基また
は2-ドデシルピリジン-5-イル基に代わった化合物であ
る。And the 2-octylpyridin-5-yl group of the above compound is a 2-methylpyridin-5-yl group, a 2-ethylpyridin-5-yl group, a 2-propylpyridin-5-yl group, 2-
Butylpyridin-5-yl group, 2-pentylpyridin-5-yl group, 2-hexylpyridin-5-yl group, 2-heptylpyridin-5-yl group, 2-nonylpyridin-5-yl group, 2- It is a compound replacing decylpyridin-5-yl, 2-undecylpyridin-5-yl or 2-dodecylpyridin-5-yl.

【００１６】表1に代表的な化合物と相転移温度を示
す。Table 1 shows typical compounds and phase transition temperatures.

【００１７】[0017]

【表１】 [Table 1]

【００１８】上記一般式（Ｉ）の化合物はたとえば次の
ようにして得られる。The compound of the above general formula (I) can be obtained, for example, as follows.

【００１９】一般式（Ｉ）において環Aおよび環Bが1,4-
フェニレン基の場合、たとえば化3に示したように、一
般式（II）で表されるアルキルブロモベンゼンをブチル
リチウム等でリチオ化した後、ホウ酸トリメチルと反応
させ、一般式（III）で表されるボロン酸誘導体とし、
これをテトラキストリフェニルホスフィンパラジウム
（0）〔Pd(PPh₃)₄〕などのパラジウム触媒存在下、2,5-
ジブロモピリジンと反応させて、一般式（IV）で表され
るブロモフェニルピリジン誘導体を得る。これをジクロ
ロジフェニルホスフィノエタンニッケル錯体〔NiCl₂(dp
pe)〕等のニッケル触媒存在下、一般式（V）で示される
グリニャール反応剤とを反応させることによって合成で
きる。In the general formula (I), ring A and ring B are 1,4-
In the case of a phenylene group, for example, as shown in the chemical formula 3, the alkyl bromobenzene represented by the general formula (II) is lithiated with butyllithium or the like, and then reacted with trimethyl borate to obtain a compound represented by the general formula (III). Boronic acid derivative to be
In the presence of a palladium catalyst such as tetrakistriphenylphosphine palladium (0) [Pd (PPh ₃ ) ₄ ],
By reacting with dibromopyridine, a bromophenylpyridine derivative represented by the general formula (IV) is obtained. This was converted to a dichlorodiphenylphosphinoethane nickel complex [NiCl ₂ (dp
pe)] in the presence of a nickel catalyst such as the one represented by the general formula (V).

【００２０】[0020]

【化３】 Embedded image

【００２１】（式中、R¹は炭素数１〜１２のアルキル基
を示し、R²は炭素数１〜１２のアルキル基または水素を
示す。）(In the formula, R ¹ represents an alkyl group having 1 to 12 carbon atoms, and R ² represents an alkyl group having 1 to 12 carbon atoms or hydrogen.)

【００２２】一般式（I）において環Ａが1,4-フェニレ
ン基、環Bがピリジン-2,5-ジイル基（５位にR²）の場
合、例えば、化4に示すように、一般式（IV）で表され
るブロモフェニルピリジン誘導体を、一般式（VI）で表
されるボロン酸誘導体に変換した後、Pd(PPh₃)₄などの
パラジウム触媒存在下、一般式（VII）で表される2-ブ
ロモピリジン誘導体と反応させることによって合成でき
る。In the general formula (I), when ring A is a 1,4-phenylene group and ring B is a pyridine-2,5-diyl group (R ^{2 at the} 5-position), for example, After converting the bromophenylpyridine derivative represented by the formula (IV) into the boronic acid derivative represented by the general formula (VI), the compound is converted into a compound represented by the general formula (VII) in the presence of a palladium catalyst such as Pd (PPh ₃ ) _4. It can be synthesized by reacting with the indicated 2-bromopyridine derivative.

【００２３】[0023]

【化４】 Embedded image

【００２４】（式中、R¹は炭素数１〜１２のアルキル基
を示し、R²は炭素数１〜１２のアルキル基または水素を
示す。）(In the formula, R ¹ represents an alkyl group having 1 to 12 carbon atoms, and R ² represents an alkyl group having 1 to 12 carbon atoms or hydrogen.)

【００２５】また、R²が炭素数２〜１２のアルキル基の
場合、例えば、化5に示すように、一般式（VI）で表さ
れるボロン酸誘導体をPd(PPh₃)₄などのパラジウム触媒
存在下、2,5-ジブロモピリジン誘導体と反応させ、一般
式（VIII）で表されるブロモピリジン誘導体を得た後、
一般式（IX）で表されるアセチレン化合物と反応させ、
一般式（X）で表されるエチニルピリジン化合物を合成
する。このアセチレン部位を水素添加することによって
合成することもできる。When R ² is an alkyl group having 2 to 12 carbon atoms, for example, as shown in Chemical formula 5, a boronic acid derivative represented by the general formula (VI) is converted to a palladium such as Pd (PPh ₃ ) _4. After reacting with a 2,5-dibromopyridine derivative in the presence of a catalyst to obtain a bromopyridine derivative represented by the general formula (VIII),
Reacting with an acetylene compound represented by the general formula (IX),
An ethynylpyridine compound represented by the general formula (X) is synthesized. It can also be synthesized by hydrogenating this acetylene moiety.

【００２６】[0026]

【化５】 Embedded image

【００２７】（式中、R¹は炭素数１〜１２のアルキル基
を示し、R³は炭素数２〜１２のアルキル基または水素を
示す。）(In the formula, R ¹ represents an alkyl group having 1 to 12 carbon atoms, and R ³ represents an alkyl group having 2 to 12 carbon atoms or hydrogen.)

【００２８】一般式（Ｉ）において環Aが1,4-フェニレ
ン基、環Bがピリジン-2,5-ジイル基（２位にR²）の場
合、例えば、化6に示すように、一般式（VI）で表され
るボロン酸誘導体をPd(PPh₃)₄などのパラジウム触媒存
在下、一般式（XI）で表される5-ブロモピリジン誘導体
と反応させることによって合成できる。In the general formula (I), when ring A is a 1,4-phenylene group and ring B is a pyridine-2,5-diyl group (R ^{2 at the} 2-position), for example, It can be synthesized by reacting a boronic acid derivative represented by the formula (VI) with a 5-bromopyridine derivative represented by the general formula (XI) in the presence of a palladium catalyst such as Pd (PPh ₃ ) ₄ .

【００２９】[0029]

【化６】 Embedded image

【００３０】（式中、R¹は炭素数１〜１２のアルキル基
を示し、R²は炭素数１〜１２のアルキル基または水素を
示す。）(In the formula, R ¹ represents an alkyl group having 1 to 12 carbon atoms, and R ² represents an alkyl group having 1 to 12 carbon atoms or hydrogen.)

【００３１】一般式（I）において環Aがピリジン-2,5-
ジイル基（２位にR¹）、環Bが1,4-フェニレン基の場
合、例えば、化7に示すように、一般式（XII）で表され
る5-ブロモピリジン誘導体を、一般式（XIII）で表され
るボロン酸誘導体に変換し、Pd(PPh₃)₄などのパラジウ
ム触媒存在下、2,5-ジブロモピリジンと反応させ、一般
式（XIV）で表される5-ブロモピリジン誘導体を得る。
これをNiCl₂(dppe) 等のニッケル触媒存在下、一般式
（V）で示されるグリニャール反応剤とを反応させるこ
とによって合成できる。In the general formula (I), ring A is pyridine-2,5-
When a diyl group (R ^{1 at the} 2-position) and ring B are 1,4-phenylene groups, for example, as shown in Chemical formula 7, a 5-bromopyridine derivative represented by the general formula (XII) is converted to a compound represented by the general formula (XII) XIII) is converted to a boronic acid derivative represented by the formula (XIV), and is reacted with 2,5-dibromopyridine in the presence of a palladium catalyst such as Pd (PPh ₃ ) ₄ to give a 5-bromopyridine derivative represented by the general formula (XIV) Get.
This can be synthesized by reacting with a Grignard reagent represented by the general formula (V) in the presence of a nickel catalyst such as NiCl ₂ (dppe).

【００３２】[0032]

【化７】 Embedded image

【００３３】（式中、R¹は炭素数１〜１２のアルキル基
を示し、R²は炭素数１〜１２のアルキル基または水素を
示す。）(In the formula, R ¹ represents an alkyl group having 1 to 12 carbon atoms, and R ² represents an alkyl group having 1 to 12 carbon atoms or hydrogen.)

【００３４】本発明の液晶組成物においては、上記一般
式（I）で示される三環系フェニルピリジン誘導体を、
フェニルピリジン化合物、フェニルピリミジン化合物、
ビフェニルピリジン化合物、フェニル=安息香酸エステ
ル化合物、フェニルシクロヘキサン化合物、フェニル=
ビフェニルカルボン酸エステル化合物、ビフェニル=安
息香酸エステル化合物、テルフェニル化合物、2,5-ジフ
ェニルピリミジン化合物、強誘電性キラル化合物等を混
合してなる強誘電性液晶組成物に添加して、室温付近の
広い温度範囲でキラルスメクチックＣ相を示す液晶表示
材料とすることができる。あるいは、シアノビフェニル
化合物、シアノフェニルシクロヘキサン化合物、シアノ
テルフェニル化合物、フッ素化ビフェニル化合物、フッ
素化ビフェニルシクロヘキサン化合物、フッ素化ビシク
ロヘキサンフェニル化合物、ビシクロヘキサン=安息香
酸エステル化合物等を混合してなるネマチック液晶組成
物に添加して、室温付近の広い温度範囲でネマチック相
を示す液晶表示材料とする事ができる。この際、本発明
の一般式（I）で表される三環系フェニルピリジン誘導
体は、上記液晶組成物に配合される他の構成成分の種
類、比率にもよるが、0.5〜50重量％の範囲内で適宜選
択して配合することができる。また、本発明の三環系フ
ェニルピリジン誘導体の配合にあたっては、いずれか１
種の化合物を単独で用いても、複数種の化合物をその総
量が上記の組成範囲になるように混合して用いても良
い。In the liquid crystal composition of the present invention, the tricyclic phenylpyridine derivative represented by the above general formula (I) is
Phenylpyridine compounds, phenylpyrimidine compounds,
Biphenylpyridine compound, phenyl = benzoic acid ester compound, phenylcyclohexane compound, phenyl =
Biphenyl carboxylic acid ester compound, biphenyl = benzoic acid ester compound, terphenyl compound, 2,5-diphenylpyrimidine compound, ferroelectric chiral compound, etc. A liquid crystal display material showing a chiral smectic C phase in a wide temperature range can be obtained. Alternatively, a nematic liquid crystal composition obtained by mixing a cyanobiphenyl compound, a cyanophenylcyclohexane compound, a cyanotelphenyl compound, a fluorinated biphenyl compound, a fluorinated biphenylcyclohexane compound, a fluorinated bicyclohexanephenyl compound, a bicyclohexane = benzoic acid ester compound, or the like. Liquid crystal display material exhibiting a nematic phase in a wide temperature range around room temperature by adding to a liquid crystal display material. At this time, the tricyclic phenylpyridine derivative represented by the general formula (I) of the present invention has a content of 0.5 to 50% by weight, depending on the types and ratios of other components to be mixed in the liquid crystal composition. It can be appropriately selected and blended within the range. In addition, when blending the tricyclic phenylpyridine derivative of the present invention, any one of
One kind of compound may be used alone, or a plurality of kinds of compounds may be mixed and used so that the total amount falls within the above composition range.

【００３５】[0035]

【実施例】以下に具体例を挙げて、本発明の三環系フェ
ニルピリジン誘導体とその製造方法、並びに本発明の三
環系フェニルピリジン誘導体を構成成分として得られる
液晶組成物における利点に関してより詳しく説明する
が、勿論本発明の主旨、及び適用範囲は、これら実施例
により制限されるものではない。The present invention will be described in more detail with reference to the following specific examples. Although described, the gist and scope of the present invention are, of course, not limited by these examples.

【００３６】（実施例１） 2-(4-デシルフェニル)-5-
(4-オクチルフェニル)ピリジンの合成Example 1 2- (4-decylphenyl) -5-
Synthesis of (4-octylphenyl) pyridine

【００３７】[0037]

【化８】 Embedded image

【００３８】（1-1） 5-ブロモ-2-(4-デシルフェニル)
ピリジンの合成 4-デシルブロモベンゼン（1.0g, 3.36mmol）のテトラヒ
ドロフラン（THF）（18ml）溶液に、−78℃でブチルリ
チウム（1.52Mヘキサン溶液, 2.20ml, 3.36mmol）を加
え、３時間攪拌した。次いで、この溶液にホウ酸トリメ
チル（0.49ml）を加え、室温まで昇温した。反応液に1M
塩酸を加え、エーテルで抽出し、飽和食塩水で洗浄し、
無水硫酸マグネシウムで乾燥した後、溶媒を減圧留去し
た。残渣にエタノール（4ml）、2,5-ジブロモピリジン
（724mg, 3.05mmol）のトルエン（9ml）溶液、テトラキ
ストリフェニルホスフィンパラジウム(0)（28.7mg）お
よび2M炭酸水素ナトリウム水溶液（4.3ml）を加え、５
時間加熱還流した。室温まで冷却した後、２相を分液
し、水相をエーテルで抽出した。有機層を合わせ、水、
及び飽和食塩水で順次洗浄後、無水硫酸マグネシウムで
乾燥した。溶媒を減圧下に留去した後、残渣をシリカゲ
ルカラムクロマトグラフィー及びシリカゲル薄層クロマ
トグラフィー（展開溶媒：酢酸エチル／ヘキサン = 19
／1）で分離精製し、次に示す物性値を有する白色固体
（934mg）を得、5-ブロモ-2-(4-デシルフェニル)ピリジ
ンであることが確認された。(1-1) 5-bromo-2- (4-decylphenyl)
Synthesis of pyridine To a solution of 4-decylbromobenzene (1.0 g, 3.36 mmol) in tetrahydrofuran (THF) (18 ml) was added butyllithium (1.52 M hexane solution, 2.20 ml, 3.36 mmol) at -78 ° C and stirred for 3 hours. did. Next, trimethyl borate (0.49 ml) was added to the solution, and the temperature was raised to room temperature. 1M in reaction solution
Add hydrochloric acid, extract with ether, wash with saturated saline,
After drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure. To the residue were added ethanol (4 ml), a solution of 2,5-dibromopyridine (724 mg, 3.05 mmol) in toluene (9 ml), tetrakistriphenylphosphine palladium (0) (28.7 mg) and a 2M aqueous solution of sodium hydrogen carbonate (4.3 ml). , 5
Heated to reflux for an hour. After cooling to room temperature, the two phases were separated and the aqueous phase was extracted with ether. Combine the organic layers, water,
And saturated saline, and then dried over anhydrous magnesium sulfate. After the solvent was distilled off under reduced pressure, the residue was subjected to silica gel column chromatography and silica gel thin layer chromatography (developing solvent: ethyl acetate / hexane = 19).
/ 1) to give a white solid (934 mg) having the following physical data, which was confirmed to be 5-bromo-2- (4-decylphenyl) pyridine.

【００３９】MS (EI): m/z 375 (M⁺+2, 61%), 373 (M⁺,
61), 246 (100). IR (KBr): 2948, 2919, 2851, 1460, 814 cm^-1.¹ H-NMR(CDCl₃, 200MHz):δ0.88 (t, J = 6.4Hz, 3H),
1.24-1.38 (m, 14H), 1.53-1.73(m, 2H), 2.65 (t, J =
7.6Hz, 2H), 7.28 (d, J = 8.1Hz, 2H), 7.60 (d, J =
8.4Hz, 1H), 7.84 (dd, J = 2.0 and 8.4Hz, 1H), 7.8
7 (d, J = 8.1Hz,2H), 8.71 (d, J = 2.0Hz, 1H).MS (EI): m / z 375 (M ⁺ +2, 61%), 373 (M ⁺ ,
. 61), 246 (100) IR (KBr):. 2948, 2919, 2851, 1460, 814 cm -1 1 H-NMR (CDCl 3, 200MHz): δ0.88 (t, J = 6.4Hz, 3H) ,
1.24-1.38 (m, 14H), 1.53-1.73 (m, 2H), 2.65 (t, J =
7.6Hz, 2H), 7.28 (d, J = 8.1Hz, 2H), 7.60 (d, J =
8.4Hz, 1H), 7.84 (dd, J = 2.0 and 8.4Hz, 1H), 7.8
7 (d, J = 8.1Hz, 2H), 8.71 (d, J = 2.0Hz, 1H).

【００４０】（1-2） 2-(4-デシルフェニル)-5-(4-オ
クチルフェニル)ピリジンの合成 5-ブロモ-2-(4-デシルフェニル)ピリジン（282mg, 0.75
mmol）とジクロロジフェニルホスフィノエタンニッケル
錯体（NiCl₂(dppe)）（19.8mg, 0.038mmol）のTHF（4m
l）溶液に、4-オクチルブロモベンゼン（404mg, 1.5mmo
l）、マグネシウム（50mg, 2.0mmol）およびTHF（4ml）
より調製したグリニャール反応剤を０℃で１時間かけて
滴下し、更に０℃で１時間撹拌した後、室温で１５時間
撹拌した。反応液に1 M塩酸を加え、ジクロロメタンで
抽出し、水及び飽和食塩水で順次洗浄後、無水硫酸マグ
ネシウムで乾燥した。溶媒を減圧下に留去した後、残渣
をシリカゲル薄層クロマトグラフィー(展開溶媒：酢酸
エチル／ヘキサン = 1/19)で分離精製し、これをエタノ
ールで再結晶することにより,次の物性値を有する無色
微細板状結晶（204mg）を得、2-(4-デシルフェニル)-5-
(4-オクチルフェニル)ピリジンであることが確認され
た。(1-2) Synthesis of 2- (4-decylphenyl) -5- (4-octylphenyl) pyridine 5-bromo-2- (4-decylphenyl) pyridine (282 mg, 0.75
mmol) and dichlorodiphenylphosphinoethane nickel complex (NiCl ₂ (dppe)) (19.8 mg, 0.038 mmol) in THF (4 m
l) Add 4-octylbromobenzene (404mg, 1.5mmo
l), magnesium (50mg, 2.0mmol) and THF (4ml)
The Grignard reagent prepared above was added dropwise at 0 ° C over 1 hour, further stirred at 0 ° C for 1 hour, and then stirred at room temperature for 15 hours. The reaction solution was added with 1 M hydrochloric acid, extracted with dichloromethane, washed with water and saturated saline in that order, and dried over anhydrous magnesium sulfate. After evaporating the solvent under reduced pressure, the residue was separated and purified by silica gel thin-layer chromatography (developing solvent: ethyl acetate / hexane = 1/19), and recrystallized from ethanol to obtain the following physical data. To give 2- (4-decylphenyl) -5-
It was confirmed to be (4-octylphenyl) pyridine.

【００４１】融点46℃、相転移温度 Cr 46 Sx2 51 Sx1
156 Sc 167 S_A 178 Iso R_f = 0.40 (Hexane / AcOEt = 19 / 1) IR (KBr) 2920, 2851, 1474, 812 cm^-1. MS (EI): m/z 484 (M⁺+1, 100%).¹ H-NMR (CDCl₃, 200MHz):δ0.88 (t, J = 7.3Hz, 6H),
1.10-1.43 (m, 24H), 1.52-1.75 (m, 4H), 2.67 (t, J
= 7.3Hz, 4H), 7.30 (d, J = 8.2Hz, 4H), 7.55(d, J =
8.2Hz, 2H), 7.77 (d, J = 8.3Hz, 1H), 7.92 (dd, J
= 8.3 and 2.5Hz, 1 H), 7.95 (d, J = 8.2Hz, 2H), 8.
90 (d, J = 2.5Hz, 1H). 元素分析： C, 87.07; H, 9.97; N, 2.83.（Calcd for
C₃₅H₄₉N :C, 86.90; H,10.21; N, 2.90.）Melting point 46 ° C., phase transition temperature Cr 46 Sx2 51 Sx1
156 Sc 167 S _A 178 Iso R _f = 0.40 (Hexane / AcOEt = 19/1) IR (KBr) 2920, 2851, 1474, 812 cm ^-1 .MS (EI): m / z 484 (M ⁺ +1, ^{. 100%) 1 H-NMR} (CDCl 3, 200MHz): δ0.88 (t, J = 7.3Hz, 6H),
1.10-1.43 (m, 24H), 1.52-1.75 (m, 4H), 2.67 (t, J
= 7.3Hz, 4H), 7.30 (d, J = 8.2Hz, 4H), 7.55 (d, J =
8.2Hz, 2H), 7.77 (d, J = 8.3Hz, 1H), 7.92 (dd, J
= 8.3 and 2.5Hz, 1H), 7.95 (d, J = 8.2Hz, 2H), 8.
90 (d, J = 2.5Hz, 1H). Elemental analysis: C, 87.07; H, 9.97; N, 2.83. (Calcd for
C ₃₅ H ₄₉ N: C, 86.90; H, 10.21; N, 2.90.)

【００４２】（実施例２） 5-(5-ヘキシルピリジン-2-
イル)-2-(4-オクチルフェニル)ピリジンの合成Example 2 5- (5-hexylpyridine-2-)
Synthesis of (yl) -2- (4-octylphenyl) pyridine

【００４３】[0043]

【化９】 Embedded image

【００４４】（2-1） 5-ブロモ-2-(4-オクチルフェニ
ル)ピリジンの合成 4-オクチルブロモベンゼン（1.62g, 6.03mmol）のテト
ラヒドロフラン（THF）（30ml）溶液に、−78℃でブチ
ルリチウム（1.54Mヘキサン溶液, 3.9ml, 6.01mmol）を
加え、３時間攪拌した。次いで、この溶液にホウ酸トリ
メチル（0.88ml）を加え、室温まで昇温した。反応液に
1M塩酸を加え、エーテルで抽出し、飽和食塩水で洗浄
し、無水硫酸マグネシウムで乾燥した後、溶媒を減圧留
去した。残渣にエタノール（7.2ml）、2,5-ジブロモピ
リジン（1.3g, 5.49mmol）のトルエン（16ml）溶液、テ
トラキストリフェニルホスフィンパラジウム(0)（52m
g）および2M炭酸水素ナトリウム水溶液（7.7ml）を加
え、５時間加熱還流した。室温まで冷却した後、２相を
分液し、水相をエーテルで抽出した。有機層を合わせ、
水、及び飽和食塩水で順次洗浄後、無水硫酸マグネシウ
ムで乾燥した。溶媒を減圧下に留去した後、残渣をシリ
カゲルカラムクロマトグラフィー及びシリカゲル薄層ク
ロマトグラフィー（展開溶媒：酢酸エチル／ヘキサン =
19／1）で分離精製し、次の物性値を有する白色固体
（1.41g）を得、5-ブロモ-2-(4-オクチルフェニル)ピリ
ジンであることが確認された。(2-1) Synthesis of 5-bromo-2- (4-octylphenyl) pyridine A solution of 4-octylbromobenzene (1.62 g, 6.03 mmol) in tetrahydrofuran (THF) (30 ml) was added at -78 ° C. Butyllithium (1.54 M hexane solution, 3.9 ml, 6.01 mmol) was added and stirred for 3 hours. Next, trimethyl borate (0.88 ml) was added to the solution, and the temperature was raised to room temperature. To the reaction solution
1M Hydrochloric acid was added, extracted with ether, washed with saturated saline, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. Ethanol (7.2 ml), a solution of 2,5-dibromopyridine (1.3 g, 5.49 mmol) in toluene (16 ml), tetrakistriphenylphosphine palladium (0) (52 m
g) and a 2M aqueous sodium hydrogen carbonate solution (7.7 ml) were added, and the mixture was heated under reflux for 5 hours. After cooling to room temperature, the two phases were separated and the aqueous phase was extracted with ether. Combine the organic layers,
After washing with water and saturated saline solution in that order, it was dried over anhydrous magnesium sulfate. After the solvent was distilled off under reduced pressure, the residue was subjected to silica gel column chromatography and silica gel thin layer chromatography (developing solvent: ethyl acetate / hexane =
Separation and purification on 19/1) gave a white solid (1.41 g) having the following physical data, which was confirmed to be 5-bromo-2- (4-octylphenyl) pyridine.

【００４５】R_f = 0.40 (Hexane / AcOEt = 19 / 1) IR (KBr): 3447, 2926, 2853, 2361, 1460, 1362, 109
2, 820 cm^-1. MS (EI): m/z 347 (M⁺+2, 56%), 345 (M⁺, 58), 246 (1
00).¹ H-NMR (CDCl₃, 200MHz):δ0.88 (t, J = 6.4Hz, 3H),
1.22-1.42 (m, 10H), 1.55-1.72 (m, 2H), 2.65 (t, J
= 7.6Hz, 2H), 7.28 (d, J = 8.2Hz, 2H), 7.60(d, J =
8.2Hz, 1H), 7.84 (dd, J = 8.2 and 2.3Hz, 1H), 7.8
7 (d, J = 8.2Hz, 2H), 8.71 (d, J = 2.3Hz, 1H). HRMS: m/z ; 345.1087 (Calcd for C₁₉H₂₄NBr 345.109
0.)R _f = 0.40 (Hexane / AcOEt = 19/1) IR (KBr): 3447, 2926, 2853, 2361, 1460, 1362, 109
2, 820 cm ^-1 .MS (EI): m / z 347 (M ⁺ +2, 56%), 345 (M ⁺ , 58), 246 (1
^{. 00) 1 H-NMR (} CDCl 3, 200MHz): δ0.88 (t, J = 6.4Hz, 3H),
1.22-1.42 (m, 10H), 1.55-1.72 (m, 2H), 2.65 (t, J
= 7.6Hz, 2H), 7.28 (d, J = 8.2Hz, 2H), 7.60 (d, J =
8.2Hz, 1H), 7.84 (dd, J = 8.2 and 2.3Hz, 1H), 7.8
7 (d, J = 8.2Hz, 2H), 8.71 (d, J = 2.3Hz, 1H) .HRMS: m / z; 345.1087 (Calcd for C ₁₉ H ₂₄ NBr 345.109
0.)

【００４６】（2-2） 5-(5-ブロモピリジン-2-イル)-2
-(4-オクチルフェニル)ピリジンの合成 5-ブロモ-2-(4-オクチルフェニル)ピリジン（277mg, 0.
8mmol）のTHF（4ml）溶液に、−78℃でブチルリチウム
（1.54Mヘキサン溶液, 0.52ml, 0.8mmol）を加え、３時
間攪拌した。次いで、この溶液にホウ酸トリメチル（0.
12ml）を加え、室温まで昇温した。反応液に1 M塩酸を
加え、エーテルで抽出し、飽和食塩水で洗浄し、無水硫
酸マグネシウムで乾燥した後、溶媒を減圧留去した。残
渣にエタノール（2ml）、2,5-ジブロモピリジン（175m
g, 0.74mmol）のトルエン（4ml）溶液、テトラキストリ
フェニルホスフィンパラジウム(0)（7mg）および2M炭酸
水素ナトリウム水溶液（1ml）を加え、５時間加熱還流
した。室温まで冷却した後、２相を分液し、水相をエー
テルで抽出した。有機層を合わせ、水、及び飽和食塩水
で順次洗浄後、無水硫酸マグネシウムで乾燥した。溶媒
を減圧下に留去した後、残渣をシリカゲル薄層クロマト
グラフィー（展開溶媒：クロロホルム／ヘキサン = １
／１）で分離精製し、白色固体（200mg）を得、これを
クロロホルム−ヘキサンで再結晶することにより、次に
示した物性値を有する無色微細針状結晶（190mg）を得
た。この結晶物は5-(5-ブロモピリジン-2-イル)-2-(4-
オクチルフェニル)ピリジンであることが確認された。(2-2) 5- (5-bromopyridin-2-yl) -2
Synthesis of-(4-octylphenyl) pyridine 5-bromo-2- (4-octylphenyl) pyridine (277 mg, 0.
Butyllithium (1.54M hexane solution, 0.52 ml, 0.8 mmol) was added to a solution of 8 mmol) in THF (4 ml) at −78 ° C., and the mixture was stirred for 3 hours. Then, trimethyl borate (0.
12 ml), and the mixture was heated to room temperature. 1 M hydrochloric acid was added to the reaction solution, extracted with ether, washed with saturated saline, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. Ethanol (2 ml) and 2,5-dibromopyridine (175 m
g, 0.74 mmol) in toluene (4 ml), tetrakistriphenylphosphine palladium (0) (7 mg) and a 2M aqueous sodium hydrogen carbonate solution (1 ml), and the mixture was heated under reflux for 5 hours. After cooling to room temperature, the two phases were separated and the aqueous phase was extracted with ether. The organic layers were combined, washed sequentially with water and saturated saline, and then dried over anhydrous magnesium sulfate. After the solvent was distilled off under reduced pressure, the residue was subjected to silica gel thin layer chromatography (developing solvent: chloroform / hexane = 1).
/ 1) to give a white solid (200 mg), which was recrystallized from chloroform-hexane to give colorless fine needle crystals (190 mg) having the following physical data. This crystalline material is 5- (5-bromopyridin-2-yl) -2- (4-
(Octylphenyl) pyridine.

【００４７】R_f = 0.20 (Hexane / CHCl₃ = 1 / 1) MS (EI): m/z 424 (M⁺+2, 70%), 422 (M⁺, 70), 337 (3
1), 323 (100). IR (KBr): 3450, 2924, 2851, 1589, 1456, 1094, 100
1, 818 cm^-1.¹ H-NMR (CDCl₃, 200MHz):δ0.88 (t, J = 6.7Hz, 3H),
1.19-1.43 (m, 10H), 1.57-1.75 (m, 2H), 2.67 (t, J
= 7.6Hz, 2H), 7.30 (d, J = 8.2Hz, 2H), 7.67(d, J =
8.4Hz, 1H), 7.81 (d, J = 8.4Hz, 1H), 7.90 (dd, J
= 8.4 and 2.3 Hz, 1H), 7.97 (d, J = 8.2Hz, 2H), 8.
34 (dd, J = 8.4 and 2.3Hz, 1H), 8.77(d, J = 2.3Hz,
1H), 9.21 (d, J = 2.3Hz, 1H). HRMS: m/z ; 422.1376. (Calcd for C₂₄H₂₇N₂Br 422.13
57.) 元素分析：C, 68.18; H, 6.49; N, 6.61; Br, 18.72.
(Calcd for C₂₄H₂₇N₂Br :C, 68.08; H, 6.43; N, 6.62;
Br, 18.87.)R _f = 0.20 (Hexane / CHCl ₃ = 1/1) MS (EI): m / z 424 (M ⁺ +2, 70%), 422 (M ⁺ , 70), 337 (3
1), 323 (100) .IR (KBr): 3450, 2924, 2851, 1589, 1456, 1094, 100
^{. 1, 818 cm -1 1 H} -NMR (CDCl 3, 200MHz): δ0.88 (t, J = 6.7Hz, 3H),
1.19-1.43 (m, 10H), 1.57-1.75 (m, 2H), 2.67 (t, J
= 7.6Hz, 2H), 7.30 (d, J = 8.2Hz, 2H), 7.67 (d, J =
8.4Hz, 1H), 7.81 (d, J = 8.4Hz, 1H), 7.90 (dd, J
= 8.4 and 2.3 Hz, 1H), 7.97 (d, J = 8.2Hz, 2H), 8.
34 (dd, J = 8.4 and 2.3Hz, 1H), 8.77 (d, J = 2.3Hz,
1H), 9.21 (d, J = 2.3Hz, 1H) .HRMS: m / z; 422.1376. (Calcd for C ₂₄ H ₂₇ N ₂ Br 422.13
57.) Elemental analysis: C, 68.18; H, 6.49; N, 6.61; Br, 18.72.
(Calcd for C ₂₄ H ₂₇ N ₂ Br: C, 68.08; H, 6.43; N, 6.62;
Br, 18.87.)

【００４８】（2-3） 5-[5-(1-ヘキシニル)ピリジン-2
-イル]-2-(4-オクチルフェニル)ピリジンの合成 ネジ付き試験管に5-(5-ブロモピリジン-2-イル)-2-(4-
オクチルフェニル)ピリジン（100mg, 0.24mmol）、塩化
パラジウムビストリフェニルホスフィン（6.0mg,0.008m
mol）、ヨウ化第一銅（3.0mg, 0.016mmol）、1-ヘキシ
ン（0.1ml, 0.87mmol）及びトリエチルアミン（2ml）を
入れ、80℃で12時間加熱撹拌した。反応液に水を加え、
クロロホルムで抽出し、水、及び飽和食塩水で順次洗浄
後、無水硫酸マグネシウムで乾燥した。溶媒を減圧留去
し、残渣をシリカゲルカラムクロマトグラフィー（展開
溶媒：クロロホルム）で分離精製し、次の物性値を有す
る白色固体（99mg）を得、5-[5-(1-ヘキシニル)ピリジ
ン-2-イル]-2-(4-オクチルフェニル)ピリジンであるこ
とが確認された。(2-3) 5- [5- (1-hexynyl) pyridine-2
Synthesis of-(yl) -2- (4-octylphenyl) pyridine 5- (5-bromopyridin-2-yl) -2- (4-
(Octylphenyl) pyridine (100mg, 0.24mmol), palladium bistriphenylphosphine chloride (6.0mg, 0.008m
mol), cuprous iodide (3.0 mg, 0.016 mmol), 1-hexyne (0.1 ml, 0.87 mmol) and triethylamine (2 ml), and the mixture was heated with stirring at 80 ° C. for 12 hours. Add water to the reaction solution,
The mixture was extracted with chloroform, washed sequentially with water and saturated saline, and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was separated and purified by silica gel column chromatography (developing solvent: chloroform) to obtain a white solid (99 mg) having the following physical property values. 5- [5- (1-hexynyl) pyridine- 2-yl] -2- (4-octylphenyl) pyridine was confirmed.

【００４９】R_f = 0.20 (Hexane / CHCl₃ = 1 / 1) MS (EI): m/z 424 (M⁺, 100%), 339 (27), 325 (80). IR (KBr): 3449, 2957, 2924, 2853, 1468, 1364, 826
cm^-1.¹ H-NMR (CDCl₃, 500MHz):δ0.88 (t, J = 6.8Hz, 3H),
0.97 (t, J = 7.3Hz, 3H), 1.22-1.38 (m, 12H), 1.47-
1.67 (m, 4H), 2.47 (t, J = 7.1Hz, 2H), 2.67(t, J =
7.7Hz, 2H), 7.31 (d, J = 8.1Hz, 2H), 7.72 (d, J =
8.2Hz, 1H), 7.77 (dd, J = 8.2 and 2.0 Hz, 1H), 7.
82 (d, J = 8.3 Hz, 1H), 7.98 (d, J =8.1Hz, 2H), 8.
39 (dd, J = 8.3 and 2.0Hz, 1H), 8.72 (br s, 1H),
9.23 (d,J = 2.0Hz, 1H).R _f = 0.20 (Hexane / CHCl ₃ = 1/1) MS (EI): m / z 424 (M ⁺ , 100%), 339 (27), 325 (80) .IR (KBr): 3449 , 2957, 2924, 2853, 1468, 1364, 826
^{. cm -1 1 H-NMR (} CDCl 3, 500MHz): δ0.88 (t, J = 6.8Hz, 3H),
0.97 (t, J = 7.3Hz, 3H), 1.22-1.38 (m, 12H), 1.47-
1.67 (m, 4H), 2.47 (t, J = 7.1Hz, 2H), 2.67 (t, J =
7.7Hz, 2H), 7.31 (d, J = 8.1Hz, 2H), 7.72 (d, J =
8.2Hz, 1H), 7.77 (dd, J = 8.2 and 2.0 Hz, 1H), 7.
82 (d, J = 8.3 Hz, 1H), 7.98 (d, J = 8.1 Hz, 2H), 8.
39 (dd, J = 8.3 and 2.0Hz, 1H), 8.72 (br s, 1H),
9.23 (d, J = 2.0Hz, 1H).

【００５０】(2-4) 5-(5-ヘキシルピリジン-2-イル)-2
-(4-オクチルフェニル)ピリジンの合成 5-[5-(1-ヘキシニル)ピリジン-2-イル]-2-(4-オクチル
フェニル)ピリジン（99mg, 0.23mmol）のエタノール（1
0ml）−ジクロロメタン（4ml）混合溶媒に10% Pd-C（3.
0mg）を入れ、水素置換し室温で17.5時間撹拌した。反
応終了後、セライト濾過により触媒を除去し、クロロホ
ルムで洗浄し、溶媒を減圧留去し、残渣をシリカゲル薄
層クロマトグラフィー（展開溶媒：クロロホルム）で分
離精製し、白色固体を得、これをエタノールで再結晶す
ることにより、次の物性値を有する無色微細針状結晶
（97mg）を得た。この結晶物は5-(5-ヘキシルピリジン-
2-イル)-2-(4-オクチルフェニル)ピリジンであることが
確認された。(2-4) 5- (5-hexylpyridin-2-yl) -2
Synthesis of 5- (5-octylphenyl) pyridine 5- [5- (1-hexynyl) pyridin-2-yl] -2- (4-octylphenyl) pyridine (99 mg, 0.23 mmol) in ethanol (1
0 ml) -dichloromethane (4 ml) mixed solvent in 10% Pd-C (3.
0 mg), and the mixture was replaced with hydrogen and stirred at room temperature for 17.5 hours. After completion of the reaction, the catalyst was removed by filtration through Celite, washed with chloroform, the solvent was distilled off under reduced pressure, and the residue was separated and purified by silica gel thin-layer chromatography (developing solvent: chloroform) to obtain a white solid, which was then ethanol To give colorless fine needle crystals (97 mg) having the following physical data. This crystal is 5- (5-hexylpyridine-
2-yl) -2- (4-octylphenyl) pyridine was confirmed.

【００５１】融点；68℃ 相転移温度；Cr 68 Sx 139 Sc 182 S_A 187 Iso R_f = 0.20 (CHCl₃) MS (EI): m/z 428 (M⁺, 100%), 385 (6), 357 (17), 34
3 (28), 329 (68), 258(29). IR (KBr): 3453, 2957, 2924, 2853, 1593, 1468, 822
cm^-1.¹ H-NMR (CDCl₃, 200MHz):δ0.86 (t, J = 6.5Hz, 3H),
0.88 (t, J = 6.5Hz, 3H), 1.20-1.45 (m, 16H), 1.58-
1.75 (m, 4H), 2.66 (t, J = 7.2Hz, 4H), 7.30(d, J =
8.2Hz, 2H), 7.58 (dd, J = 8.2 and 2.2Hz, 1H), 7.7
0 (d, J = 8.2Hz, 1 H), 7.81 (d, J = 8.2Hz, 1H), 7.
98 (d, J = 8.2Hz, 2H), 8.36 (dd, J =8.2 and 2.2Hz,
1H), 8.55 (d, J = 2.2Hz, 1H), 9.22 (d, J = 2.2Hz,
1H). 元素分析：C, 83.90; H, 9.34; N, 6.38.（Calcd for C
₃₀H₄₀N₂ :C, 84.06; H,9.41; N, 6.54.）Melting point: 68 ° C. Phase transition temperature: Cr 68 Sx 139 Sc 182 S _A 187 IsoR _f = 0.20 (CHCl ₃ ) MS (EI): m / z 428 (M ⁺ , 100%), 385 (6) , 357 (17), 34
3 (28), 329 (68), 258 (29) .IR (KBr): 3453, 2957, 2924, 2853, 1593, 1468, 822
^{. cm -1 1 H-NMR (} CDCl 3, 200MHz): δ0.86 (t, J = 6.5Hz, 3H),
0.88 (t, J = 6.5Hz, 3H), 1.20-1.45 (m, 16H), 1.58-
1.75 (m, 4H), 2.66 (t, J = 7.2Hz, 4H), 7.30 (d, J =
8.2Hz, 2H), 7.58 (dd, J = 8.2 and 2.2Hz, 1H), 7.7
0 (d, J = 8.2Hz, 1H), 7.81 (d, J = 8.2Hz, 1H), 7.
98 (d, J = 8.2Hz, 2H), 8.36 (dd, J = 8.2 and 2.2Hz,
1H), 8.55 (d, J = 2.2Hz, 1H), 9.22 (d, J = 2.2Hz,
1H). Elemental analysis: C, 83.90; H, 9.34; N, 6.38. (Calcd for C
₃₀ H ₄₀ N ₂ : C, 84.06; H, 9.41; N, 6.54.)

【００５２】（実施例３） 5-(5-ブチルピリジン-2-イ
ル)-2-(4-オクチルフェニル)ピリジンの合成Example 3 Synthesis of 5- (5-butylpyridin-2-yl) -2- (4-octylphenyl) pyridine

【００５３】[0053]

【化１０】 Embedded image

【００５４】（3-1） 5-[5-(1-ブチニル)ピリジン-2-
イル]-2-(4-オクチルフェニル)ピリジンの合成 実施例（2-2）で合成した5-(5-ブロモピリジン-2-イル)
-2-(4-オクチルフェニル)ピリジン（150mg, 0.35mmo
l）、塩化パラジウムビストリフェニルホスフィン（24m
g, 0.034mmol）、ヨウ化第一銅（10mg, 0.053mmol）及
びトリエチルアミン（4ml）をネジ付き試験管に入れ、
−78℃に冷却した。1-ブチンを過剰量吹き込み、封をし
て、80℃で24時間加熱撹拌した。反応液に水を加えた、
クロロホルム−エタノール（５％）混合溶液で抽出し、
水、及び飽和食塩水で順次洗浄後、無水硫酸マグネシウ
ムで乾燥した。溶媒を減圧留去し、残渣をシリカゲル薄
層クロマトグラフィー（展開溶媒：クロロホルム）で分
離精製し、次の物性値を有する淡黄色粘性体（140mg）
を得、5-[5-(1-ブチニル)ピリジン-2-イル]-2-(4-オク
チルフェニル)ピリジンであることが確認された。(3-1) 5- [5- (1-butynyl) pyridine-2-
Synthesis of yl] -2- (4-octylphenyl) pyridine 5- (5-bromopyridin-2-yl) synthesized in Example (2-2)
-2- (4-octylphenyl) pyridine (150mg, 0.35mmo
l), palladium chloride bistriphenylphosphine (24m
g, 0.034 mmol), cuprous iodide (10 mg, 0.053 mmol) and triethylamine (4 ml) in a test tube with a screw,
Cooled to -78 ° C. An excessive amount of 1-butyne was blown, sealed, and heated and stirred at 80 ° C. for 24 hours. Water was added to the reaction solution,
Extract with chloroform-ethanol (5%) mixed solution,
After washing with water and saturated saline solution in that order, it was dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was separated and purified by silica gel thin-layer chromatography (developing solvent: chloroform) to give a pale yellow viscous substance (140 mg) having the following physical properties.
Was obtained, and it was confirmed to be 5- [5- (1-butynyl) pyridin-2-yl] -2- (4-octylphenyl) pyridine.

【００５５】R_f = 0.29 (CHCl₃) MS (EI): m/z 396 (M⁺, 100%), 297 (72). IR (KBr): 3450, 2960, 2940, 2860, 2375, 1595, 147
0, 830, 770 cm^-1.¹ H-NMR (CDCl₃, 500MHz):δ0.88 (t, J = 6.9Hz, 3H),
1.23-1.39 (m, 8H), 1.28 (t, J = 7.5Hz, 3H), 1.61-
1.72 (m, 4H), 2.48 (q, J = 7.5Hz, 2H), 2.67 (t, J
= 7.7Hz, 2H), 7.31 (d, J = 8.1Hz, 2H), 7.72 (d, J
= 8.2Hz, 1H), 7.77 (dd, J = 8.2 and 1.9Hz, 1H), 7.
82 (d, J = 8.3Hz, 1H), 7.98 (d, J = 8.1Hz, 2H), 8.
39 (dd, J = 8.3 and 1.9Hz, 1H), 8.72 (d, J = 1.9H
z, 1H), 9.23(d, J = 1.9Hz, 1H). HRMS: m/z ; 396.2570.(Calcd for C₂₈H₃₂N₂ 396.256
4.)R _f = 0.29 (CHCl ₃ ) MS (EI): m / z 396 (M ⁺ , 100%), 297 (72) .IR (KBr): 3450, 2960, 2940, 2860, 2375, 1595, 147
^{. 0, 830, 770 cm -1} 1 H-NMR (CDCl 3, 500MHz): δ0.88 (t, J = 6.9Hz, 3H),
1.23-1.39 (m, 8H), 1.28 (t, J = 7.5Hz, 3H), 1.61-
1.72 (m, 4H), 2.48 (q, J = 7.5Hz, 2H), 2.67 (t, J
= 7.7Hz, 2H), 7.31 (d, J = 8.1Hz, 2H), 7.72 (d, J
= 8.2Hz, 1H), 7.77 (dd, J = 8.2 and 1.9Hz, 1H), 7.
82 (d, J = 8.3Hz, 1H), 7.98 (d, J = 8.1Hz, 2H), 8.
39 (dd, J = 8.3 and 1.9Hz, 1H), 8.72 (d, J = 1.9H
z, 1H), 9.23 (d, J = 1.9Hz, 1H) .HRMS: m / z; 396.2570. (Calcd for C ₂₈ H ₃₂ N ₂ 396.256
Four.)

【００５６】(3-2) 5-(5-ブチルピリジン-2-イル)-2-
(4-オクチルフェニル)ピリジンの合成 5-[5-(1-ブチニル)ピリジン-2-イル]-2-(4-オクチルフ
ェニル)ピリジン（81mg, 0.16mmol）のエタノール（10m
l）−ジクロロメタン（10ml）混合溶媒に10%Pd-C（15m
g）を入れ、水素置換し室温で14.5時間撹拌した。反応
終了後、セライト濾過により触媒を除去し、クロロホル
ムで洗浄し、溶媒を減圧留去し、残渣をシリカゲル薄層
クロマトグラフィー（展開溶媒：クロロホルム）で分離
精製し、淡黄色固体（54mg）を得、エタノールで再結晶
することにより、次の物性値を有する淡黄色微細針状結
晶を得た。この結晶物は5-(5-ブチルピリジン-2-イル)-
2-(4-オクチルフェニル)ピリジンであることが確認され
た。(3-2) 5- (5-butylpyridin-2-yl) -2-
Synthesis of (4-octylphenyl) pyridine 5- [5- (1-butynyl) pyridin-2-yl] -2- (4-octylphenyl) pyridine (81 mg, 0.16 mmol) in ethanol (10 m
l)-10% Pd-C (15m
g) was added, the atmosphere was replaced with hydrogen, and the mixture was stirred at room temperature for 14.5 hours. After completion of the reaction, the catalyst was removed by filtration through Celite, washed with chloroform, the solvent was distilled off under reduced pressure, and the residue was separated and purified by silica gel thin-layer chromatography (developing solvent: chloroform) to obtain a pale yellow solid (54 mg). By recrystallizing with ethanol, pale yellow fine needle crystals having the following physical properties were obtained. This crystal is 5- (5-butylpyridin-2-yl)-
It was confirmed to be 2- (4-octylphenyl) pyridine.

【００５７】融点：48℃ 相転移温度： Cr 48 Sx3 59 Sx2 90 Sx1 121 Sc 166 S_A
176 N 185 Iso R_f = 0.19 (CHCl₃) MS (EI): m/z 400 (M⁺, 100%). IR (KBr): 3457, 2955, 2922, 2855, 1588, 1468, 820
cm^-1.¹ H-NMR (CDCl₃, 200MHz):δ0.88 (t, J = 6.5Hz, 3H),
0.95 (t, J = 7.2Hz, 3H), 1.20-1.45 (m, 12H), 1.55-
1.73 (m, 4H), 2.60 (t, J = 7.5 Hz, 4H), 7.30(d, J
= 8.2Hz, 2H), 7.57 (dd, J = 8.1 and 2.1Hz, 1H), 7.
69 (d, J = 8.1Hz, 1H), 7.80 (d, J = 8.3Hz, 1H), 7.
98 (d, J = 8.2Hz, 2H), 8.36 (dd, J =8.3 and 2.1Hz,
1H), 8.54 (d, J = 2.1Hz, 1H), 9.22 (d, J = 2.1Hz,
1H). HRMS: m/z; 400.2880. (Calcd for C₂₈H₃₆N₂; 400.287
7.) 元素分析： C, 83.73; H, 9.23; N, 6.77. (Calcd for
C₂₈H₃₆N₂ :C, 83.95; H,9.06; N, 6.99.)Melting point: 48 ° C. Phase transition temperature: Cr 48 Sx3 59 Sx2 90 Sx1 121 Sc 166 S _A
176 N 185 Iso R _f = 0.19 (CHCl ₃ ) MS (EI): m / z 400 (M ⁺ , 100%). IR (KBr): 3457, 2955, 2922, 2855, 1588, 1468, 820
^{. cm -1 1 H-NMR (} CDCl 3, 200MHz): δ0.88 (t, J = 6.5Hz, 3H),
0.95 (t, J = 7.2Hz, 3H), 1.20-1.45 (m, 12H), 1.55-
1.73 (m, 4H), 2.60 (t, J = 7.5 Hz, 4H), 7.30 (d, J
= 8.2Hz, 2H), 7.57 (dd, J = 8.1 and 2.1Hz, 1H), 7.
69 (d, J = 8.1Hz, 1H), 7.80 (d, J = 8.3Hz, 1H), 7.
98 (d, J = 8.2Hz, 2H), 8.36 (dd, J = 8.3 and 2.1Hz,
1H), 8.54 (d, J = 2.1Hz, 1H), 9.22 (d, J = 2.1Hz,
1H) .HRMS: m / z; 400.2880. (Calcd for C ₂₈ H ₃₆ N ₂ ; 400.287
7.) Elemental analysis: C, 83.73; H, 9.23; N, 6.77. (Calcd for
(C ₂₈ H ₃₆ N ₂ : C, 83.95; H, 9.06; N, 6.99.)

【００５８】（実施例４） 2-(4-ヘキシルフェニル)-5
-(5-ペンチルピリジン-2-イル)ピリジンの合成Example 4 2- (4-hexylphenyl) -5
Synthesis of-(5-pentylpyridin-2-yl) pyridine

【００５９】[0059]

【化１１】 Embedded image

【００６０】（4-1）5-ブロモ-2-(4-ヘキシルフェニル)
ピリジンの合成 4-ヘキシルブロモベンゼン（1.01g, 4.15mmol）のTHF
（23ml）溶液に、−78℃でブチルリチウム（1.54Mヘキ
サン溶液, 2.7ml, 4.15mmol）を加え、３時間攪拌し
た。次いで、この溶液にホウ酸トリメチル（0.6ml）を
加え、室温まで昇温した。反応液に1 M塩酸を加え、ク
ロロホルム−エタノール（５％）混合溶液で抽出した。
これを飽和食塩水で洗浄し、無水硫酸マグネシウムで乾
燥した後、溶媒を減圧留去した。残渣にエタノール（5m
l）、2,5-ジブロモピリジン（904mg, 3.81mmol）のトル
エン（10ml）溶液、テトラキストリフェニルホスフィン
パラジウム(0)（36mg）および2 M炭酸水素ナトリウム水
溶液（5.5ml）を加え、５時間加熱還流した。室温まで
冷却した後、２相を分液し、水相をエーテルで抽出し
た。有機層を合わせ、水、及び飽和食塩水で順次洗浄
後、無水硫酸マグネシウムで乾燥した。溶媒を減圧下に
留去した後、残渣をシリカゲルカラムクロマトグラフィ
ー（展開溶媒：酢酸エチル／ヘキサン = 19／1）で分離
精製し、次の物性値を有する白色固体（692mg）を得、5
-ブロモ-2-(4-ヘキシルフェニル)ピリジンであることが
確認された。(4-1) 5-bromo-2- (4-hexylphenyl)
Synthesis of pyridine THF of 4-hexylbromobenzene (1.01g, 4.15mmol)
Butyllithium (1.54 M hexane solution, 2.7 ml, 4.15 mmol) was added to the (23 ml) solution at −78 ° C., and the mixture was stirred for 3 hours. Next, trimethyl borate (0.6 ml) was added to the solution, and the temperature was raised to room temperature. 1 M hydrochloric acid was added to the reaction solution, and the mixture was extracted with a mixed solution of chloroform-ethanol (5%).
This was washed with saturated saline, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. Ethanol (5m
l), a solution of 2,5-dibromopyridine (904 mg, 3.81 mmol) in toluene (10 ml), tetrakistriphenylphosphine palladium (0) (36 mg) and a 2 M aqueous sodium hydrogen carbonate solution (5.5 ml) were added, and the mixture was heated for 5 hours. Refluxed. After cooling to room temperature, the two phases were separated and the aqueous phase was extracted with ether. The organic layers were combined, washed sequentially with water and saturated saline, and then dried over anhydrous magnesium sulfate. After evaporating the solvent under reduced pressure, the residue was separated and purified by silica gel column chromatography (eluent: ethyl acetate / hexane = 19/1) to obtain a white solid (692 mg) having the following physical data.
-Bromo-2- (4-hexylphenyl) pyridine was confirmed.

【００６１】R_f = 0.55 (Hexane / AcOEt = 19 / 1) IR (KBr): 3455, 2957, 2926, 2855, 1574, 1460, 100
3, 820 cm^-1. MS (EI): m/z 319 (M⁺+2, 67%), 317 (M⁺, 69), 248 (1
00).¹ H-NMR (CDCl₃, 200MHz):δ0.88 (t, J = 6.5Hz, 3H),
1.23-1.42 (m, 6H), 1.56-1.61 (m, 2H), 2.65 (t, J =
7.6Hz, 2H), 7.28 (d, J = 8.2Hz, 2H), 7.60 (d, J =
8.4Hz, 1H), 7.84 (dd, J = 8.4 and 2.2Hz, 1H), 7.8
7 (d, J = 8.2Hz,2H), 8.71 (d, J = 2.2Hz, 1H). 元素分析： C, 64.42; H, 6.43; N, 4.25; Br, 24.89.
（Calcd for C₁₇H₂₀NBr :C, 64.16; H, 6.33; N, 4.40;
Br, 25.11.）R _f = 0.55 (Hexane / AcOEt = 19/1) IR (KBr): 3455, 2957, 2926, 2855, 1574, 1460, 100
3, 820 cm ^-1 .MS (EI): m / z 319 (M ⁺ +2, 67%), 317 (M ⁺ , 69), 248 (1
^{. 00) 1 H-NMR (} CDCl 3, 200MHz): δ0.88 (t, J = 6.5Hz, 3H),
1.23-1.42 (m, 6H), 1.56-1.61 (m, 2H), 2.65 (t, J =
7.6Hz, 2H), 7.28 (d, J = 8.2Hz, 2H), 7.60 (d, J =
8.4Hz, 1H), 7.84 (dd, J = 8.4 and 2.2Hz, 1H), 7.8
7 (d, J = 8.2Hz, 2H), 8.71 (d, J = 2.2Hz, 1H). Elemental analysis: C, 64.42; H, 6.43; N, 4.25; Br, 24.89.
(Calcd for C ₁₇ H ₂₀ NBr: C, 64.16; H, 6.33; N, 4.40;
Br, 25.11.)

【００６２】（4-2） 5-(5-ブロモピリジン-2-イル)-2
-(4-ヘキシルフェニル)ピリジンの合成 5-ブロモ-2-(4-ヘキシルフェニル)ピリジン（440mg, 1.
38mmol）のTHF（15ml）溶液に、−78℃でブチルリチウ
ム（1.54Mヘキサン溶液, 0.9ml, 1.38mmol）を加え、３
時間攪拌した。次いで、この溶液にホウ酸トリメチル
（0.30ml）を加え、室温まで昇温した。反応液に1 M塩
酸を加え、クロロホルム−エタノール（５％）で抽出
し、飽和食塩水で洗浄し、無水硫酸マグネシウムで乾燥
した後、溶媒を減圧留去した。残渣にエタノール（3m
l）、2,5-ジブロモピリジン（0.5g, 2.11mmol）のトル
エン（5ml）溶液、テトラキストリフェニルホスフィン
パラジウム(0)（20mg）および2 M炭酸水素ナトリウム水
溶液（3ml）を加え、６時間加熱還流した。室温まで冷
却した後、２相を分液し、水相をクロロホルム−エタノ
ール（５％）で抽出した。有機層を合わせ、水、及び飽
和食塩水で順次洗浄後、無水硫酸マグネシウムで乾燥し
た。溶媒を減圧下に留去した後、残渣をシリカゲルカラ
ムクロマトグラフィー（展開溶媒：クロロホルム）で分
離精製し、次の物性値を有する白色固体（337mg）を
得、5-(5-ブロモピリジン-2-イル)-2-(4-ヘキシルフェ
ニル)ピリジンであることが確認された。(4-2) 5- (5-bromopyridin-2-yl) -2
Synthesis of-(4-hexylphenyl) pyridine 5-bromo-2- (4-hexylphenyl) pyridine (440 mg, 1.
Butyllithium (1.54 M hexane solution, 0.9 ml, 1.38 mmol) was added to a solution of 38 mmol) in THF (15 ml) at −78 ° C.
Stirred for hours. Next, trimethyl borate (0.30 ml) was added to the solution, and the temperature was raised to room temperature. 1 M hydrochloric acid was added to the reaction solution, extracted with chloroform-ethanol (5%), washed with saturated saline, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. Ethanol (3m
l), a solution of 2,5-dibromopyridine (0.5 g, 2.11 mmol) in toluene (5 ml), tetrakistriphenylphosphine palladium (0) (20 mg) and a 2 M aqueous sodium hydrogen carbonate solution (3 ml) were added, and the mixture was heated for 6 hours. Refluxed. After cooling to room temperature, the two phases were separated and the aqueous phase was extracted with chloroform-ethanol (5%). The organic layers were combined, washed sequentially with water and saturated saline, and then dried over anhydrous magnesium sulfate. After evaporating the solvent under reduced pressure, the residue was separated and purified by silica gel column chromatography (developing solvent: chloroform) to obtain a white solid (337 mg) having the following physical data. 5- (5-Bromopyridine-2) -Yl) -2- (4-hexylphenyl) pyridine.

【００６３】R_f = 0.50 (CHCl₃) IR (KBr): 3437, 2955, 2928, 2855, 1591, 1578, 146
0, 1005, 820 cm^-1. MS (EI): m/z 396 (M⁺+2, 100%), 394 (M⁺, 99).¹ H-NMR (CDCl₃, 200MHz):δ0.89 (t, J = 6.5Hz, 3H),
1.24-1.41 (m, 6H), 1.55-1.73 (m, 2H), 2.67 (t, J =
7.6Hz, 2H), 7.31 (d, J = 8.2Hz, 2H), 7.69 (d, J =
8.5Hz, 1H), 7.83 (d, J = 8.4Hz, 1H), 7.92 (dd, J
= 8.5 and 2.3Hz,1H), 7.98 (d, J = 8.2Hz, 2H), 8.36
(dd, J = 8.4 and 2.3Hz, 1H), 8.78 (d, J = 2.3Hz,
1H), 9.22 (d, J = 2.3Hz, 1H). HRMS: m/z; 394.1040. (Calcd for C₂₂H₂₃N₂Br 394.104
3.) 元素分析： C, 66.83; H, 5.82; N, 7.01; Br, 20.33.
(Calcd for C₂₂H₂₃N₂Br:C, 66.84; H, 5.86; N, 7.09;
Br, 20.21.)R _f = 0.50 (CHCl ₃ ) IR (KBr): 3437, 2955, 2928, 2855, 1591, 1578, 146
^{. 0, 1005, 820 cm -1} MS (EI):. M / z 396 (M + +2, 100%), 394 (M +, 99) 1 H-NMR (CDCl 3, 200MHz): δ0.89 (t, J = 6.5Hz, 3H),
1.24-1.41 (m, 6H), 1.55-1.73 (m, 2H), 2.67 (t, J =
7.6Hz, 2H), 7.31 (d, J = 8.2Hz, 2H), 7.69 (d, J =
8.5Hz, 1H), 7.83 (d, J = 8.4Hz, 1H), 7.92 (dd, J
= 8.5 and 2.3Hz, 1H), 7.98 (d, J = 8.2Hz, 2H), 8.36
(dd, J = 8.4 and 2.3Hz, 1H), 8.78 (d, J = 2.3Hz,
1H), 9.22 (d, J = 2.3Hz, 1H) .HRMS: m / z; 394.1040. (Calcd for C ₂₂ H ₂₃ N ₂ Br 394.104
3.) Elemental analysis: C, 66.83; H, 5.82; N, 7.01; Br, 20.33.
(Calcd for C ₂₂ H ₂₃ N ₂ Br: C, 66.84; H, 5.86; N, 7.09;
Br, 20.21.)

【００６４】（4-3） 2-(4-ヘキシルフェニル)-5-[5-
(1-ペンチニル)ピリジン-2-イル]ピリジンの合成 ネジ付き試験管に5-(5-ブロモピリジン-2-イル)-2-(4-
ヘキシルフェニル)ピリジン（146mg, 0.37mmol）、塩化
パラジウムビストリフェニルホスフィン（11mg, 0.016m
mol）、ヨウ化第一銅（6.0mg, 0.032mmol）、1-ペンチ
ン（0.2 ml, 2.0mmol）及びトリエチルアミン（4ml）を
入れ、80℃で5.5時間加熱撹拌した。反応液に水を加
え、クロロホルム−エタノール（５％）で抽出し、水、
及び飽和食塩水で順次洗浄後、無水硫酸マグネシウムで
乾燥した。溶媒を減圧留去し、残渣をシリカゲル薄層ク
ロマトグラフィー（展開溶媒：クロロホルム）で分離精
製し、次の物性値を有する白色固体（132mg）を得、2-
(4-ヘキシルフェニル)-5-[5-(1-ペンチニル)ピリジン-2
-イル]ピリジンであることが確認された。(4-3) 2- (4-hexylphenyl) -5- [5-
Synthesis of (1-pentynyl) pyridin-2-yl] pyridine 5- (5-bromopyridin-2-yl) -2- (4-
Hexylphenyl) pyridine (146mg, 0.37mmol), palladium bistriphenylphosphine (11mg, 0.016m
mol), cuprous iodide (6.0 mg, 0.032 mmol), 1-pentyne (0.2 ml, 2.0 mmol) and triethylamine (4 ml), and the mixture was heated with stirring at 80 ° C. for 5.5 hours. Water was added to the reaction solution, and extracted with chloroform-ethanol (5%).
And saturated saline, and then dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was separated and purified by silica gel thin layer chromatography (developing solvent: chloroform) to obtain a white solid (132 mg) having the following physical properties.
(4-hexylphenyl) -5- [5- (1-pentynyl) pyridine-2
-Yl] pyridine.

【００６５】R_f = 0.50 (CHCl₃) MS (EI): m/z 382 (M⁺, 100%), 311 (56). IR (KBr): 3437, 2961, 2928, 2855, 2220, 1586, 146
6, 1362, 823, 772 cm^-1.¹ H-NMR (CDCl₃, 500MHz):δ0.89 (t, J = 6.9Hz, 3H),
1.08 (t, J = 7.4Hz, 3H), 1.28-1.39 (m, 6H), 1.62-
1.70 (m, 4H), 2.44 (t, J = 7.0Hz, 2H), 2.67 (t, J
= 7.7Hz, 2H), 7.31 (d, J = 8.1Hz, 2H), 7.72 (d, J
= 8.2Hz, 1H), 7.77 (dd, J = 8.2 and 2.0Hz, 1H), 7.
82 (d, J = 8.3Hz, 1H), 7.98 (d, J = 8.1Hz, 2H), 8.
38 (dd, J = 8.3 and 2.0Hz, 1H), 8.72 (d, J = 2.0H
z, 1H), 9.23(d, J = 2.0Hz, 1H). 元素分析：C, 84.66; H, 7.92; N, 7.21.(Calcd for C
₂₇H₃₀N₂ :C, 84.77; H, 7.90; N, 7.32.)R _f = 0.50 (CHCl ₃ ) MS (EI): m / z 382 (M ⁺ , 100%), 311 (56) .IR (KBr): 3437, 2961, 2928, 2855, 2220, 1586, 146
. 6, 1362, 823, 772 cm -1 1 H-NMR (CDCl 3, 500MHz): δ0.89 (t, J = 6.9Hz, 3H),
1.08 (t, J = 7.4Hz, 3H), 1.28-1.39 (m, 6H), 1.62-
1.70 (m, 4H), 2.44 (t, J = 7.0Hz, 2H), 2.67 (t, J
= 7.7Hz, 2H), 7.31 (d, J = 8.1Hz, 2H), 7.72 (d, J
= 8.2Hz, 1H), 7.77 (dd, J = 8.2 and 2.0Hz, 1H), 7.
82 (d, J = 8.3Hz, 1H), 7.98 (d, J = 8.1Hz, 2H), 8.
38 (dd, J = 8.3 and 2.0Hz, 1H), 8.72 (d, J = 2.0H
z, 1H), 9.23 (d, J = 2.0Hz, 1H). Elemental analysis: C, 84.66; H, 7.92; N, 7.21. (Calcd for C
_{27 H 30 N 2: C,} 84.77; H, 7.90; N, 7.32).

【００６６】(4-4) 2-(4-ヘキシルフェニル)-5-(5-ペ
ンチルピリジン-2-イル)ピリジンの合成 2-(4-ヘキシルフェニル)-5-[5-(1-ペンチニル)ピリジン
-2-イル]ピリジン（61mg, 0.16mmol）のエタノール（3m
l）−ジクロロメタン（3ml）混合溶媒に10%Pd-C（3.0m
g）を入れ、水素置換し室温で17.5時間撹拌した。反応
終了後、セライト濾過により触媒を除去し、クロロホル
ムで洗浄し、溶媒を減圧留去し、残渣をシリカゲル薄層
クロマトグラフィー（展開溶媒：クロロホルム）で分離
精製し、白色固体（56mg）を得、これをエタノールで再
結晶することにより、次の物性値を有する無色微細針状
結晶を得た。この結晶物は、2-(4-ヘキシルフェニル)-5
-(5-ペンチルピリジン-2-イル)ピリジンであることが確
認された。(4-4) Synthesis of 2- (4-hexylphenyl) -5- (5-pentylpyridin-2-yl) pyridine 2- (4-hexylphenyl) -5- [5- (1-pentynyl) ) Pyridine
2-yl] pyridine (61mg, 0.16mmol) in ethanol (3m
l)-10% Pd-C (3.0m) in a mixed solvent of dichloromethane (3ml)
g) was added, the atmosphere was replaced with hydrogen, and the mixture was stirred at room temperature for 17.5 hours. After completion of the reaction, the catalyst was removed by filtration through Celite, washed with chloroform, the solvent was distilled off under reduced pressure, and the residue was separated and purified by silica gel thin-layer chromatography (developing solvent: chloroform) to obtain a white solid (56 mg). This was recrystallized from ethanol to obtain colorless fine needle crystals having the following physical properties. This crystal is 2- (4-hexylphenyl) -5
It was confirmed that the compound was-(5-pentylpyridin-2-yl) pyridine.

【００６７】融点：71℃ 相転移温度： Cr 71 Sx2 107 Sx1 132 Sc 179 S_A 189 N
194 Iso R_f = 0.31 (CHCl₃) MS (EI): m/z 386(M⁺, 100%), 329(15), 315(49), 258
(16). IR (KBr): 3455, 2955, 2928, 2855, 1593, 1468, 101
1, 820 cm^-1.¹ H-NMR (CDCl₃, 500MHz):δ0.89 (t, J = 7.0Hz, 3H),
0.91 (t, J = 6.9Hz, 3H), 1.28-1.39 (m, 10H), 1.62-
1.69 (m, 4H), 2.66 (t, J = 7.5Hz, 2H), 2.67(t, J =
7.5Hz, 2H), 7.30 (d, J = 8.2Hz, 2H), 7.60 (dd, J
= 8.1 and 2.2Hz, 1H), 7.70 (d, J = 8.1Hz, 1H), 7.8
1 (d, J = 8.3Hz, 1H), 7.98 (d, J = 8.2Hz, 2H), 8.3
7 (dd, J = 8.3 and 2.2Hz, 1H), 8.55 (d, J = 2.2Hz,
1H), 9.22 (d, J = 2.2Hz, 1H). 元素分析：C, 84.11; H, 9.01; N, 7.21.（Calcd for C
₂₇H₃₄N₂ :C, 83.89; H,8.87; N, 7.25.）Melting point: 71 ° C. Phase transition temperature: Cr 71 Sx2 107 Sx1 132 Sc 179 S _A 189 N
194 Iso R _f = 0.31 (CHCl ₃ ) MS (EI): m / z 386 (M ⁺ , 100%), 329 (15), 315 (49), 258
(16) .IR (KBr): 3455, 2955, 2928, 2855, 1593, 1468, 101
^{. 1, 820 cm -1 1 H} -NMR (CDCl 3, 500MHz): δ0.89 (t, J = 7.0Hz, 3H),
0.91 (t, J = 6.9Hz, 3H), 1.28-1.39 (m, 10H), 1.62-
1.69 (m, 4H), 2.66 (t, J = 7.5Hz, 2H), 2.67 (t, J =
7.5Hz, 2H), 7.30 (d, J = 8.2Hz, 2H), 7.60 (dd, J
= 8.1 and 2.2Hz, 1H), 7.70 (d, J = 8.1Hz, 1H), 7.8
1 (d, J = 8.3Hz, 1H), 7.98 (d, J = 8.2Hz, 2H), 8.3
7 (dd, J = 8.3 and 2.2Hz, 1H), 8.55 (d, J = 2.2Hz,
1H), 9.22 (d, J = 2.2Hz, 1H). Elemental analysis: C, 84.11; H, 9.01; N, 7.21. (Calcd for C
₂₇ H ₃₄ N ₂ : C, 83.89; H, 8.87; N, 7.25.)

【００６８】（実施例５） 5-(5-メチルピリジン-2-イ
ル)-2-(4-オクチルフェニル)ピリジンの合成Example 5 Synthesis of 5- (5-methylpyridin-2-yl) -2- (4-octylphenyl) pyridine

【００６９】[0069]

【化１２】 Embedded image

【００７０】実施例（2-1）で得た5-ブロモ-2-(4-オク
チルフェニル)ピリジン（201mg, 0.58mmol）のTHF（5m
l）溶液に、−78℃でブチルリチウム（1.54Mヘキサン溶
液, 0.40ml, 0.62mmol）を加え、３時間攪拌した。次い
で、この溶液にホウ酸トリメチル（0.085ml）を加え、
室温まで昇温した。反応液に1 M塩酸を加え、クロロホ
ルムで抽出し、水および飽和食塩水で洗浄し、無水硫酸
マグネシウムで乾燥した後、溶媒を減圧留去した。残渣
にエタノール（2ml）、2-ブロモ-5-メチルピリジン（95
mg, 0.55mmol）のトルエン（3ml）溶液、テトラキスト
リフェニルホスフィンパラジウム(0)（5mg）および2 M
炭酸水素ナトリウム水溶液（0.8ml）を加え、５時間加
熱還流した。室温まで冷却した後、２相を分液し、水相
をクロロホルムで抽出した。有機層を合わせ、水、及び
飽和食塩水で順次洗浄後、無水硫酸マグネシウムで乾燥
した。溶媒を減圧下に留去した後、残渣をシリカゲル薄
層クロマトグラフィー（展開溶媒：クロロホルム）で分
離精製し、白色固体（152mg）を得、これをエタノール
で再結晶することにより、次に示す物性値を有する無色
微細針状結晶（90mg）を得た。この結晶物は5-(5-メチ
ルピリジン-2-イル)-2-(4-オクチルフェニル)ピリジン
であることが確認された。The 5-bromo-2- (4-octylphenyl) pyridine (201 mg, 0.58 mmol) obtained in Example (2-1) in THF (5 m
l) Butyl lithium (1.54M hexane solution, 0.40 ml, 0.62 mmol) was added to the solution at -78 ° C, and the mixture was stirred for 3 hours. Then, to this solution was added trimethyl borate (0.085 ml),
The temperature was raised to room temperature. 1 M hydrochloric acid was added to the reaction solution, extracted with chloroform, washed with water and saturated saline, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. Ethanol (2 ml) and 2-bromo-5-methylpyridine (95
mg, 0.55 mmol) in toluene (3 ml), tetrakistriphenylphosphinepalladium (0) (5 mg) and 2 M
An aqueous sodium hydrogen carbonate solution (0.8 ml) was added, and the mixture was heated under reflux for 5 hours. After cooling to room temperature, the two phases were separated and the aqueous phase was extracted with chloroform. The organic layers were combined, washed sequentially with water and saturated saline, and then dried over anhydrous magnesium sulfate. After evaporating the solvent under reduced pressure, the residue was separated and purified by silica gel thin-layer chromatography (developing solvent: chloroform) to obtain a white solid (152 mg), which was recrystallized from ethanol to give the following physical properties. Colorless fine needle crystals having a value (90 mg) were obtained. This crystal was confirmed to be 5- (5-methylpyridin-2-yl) -2- (4-octylphenyl) pyridine.

【００７１】融点： 80℃ 相転移温度： Cr 80 Sc 84 N 180 Iso R_f = 0.15 (CHCl₃) MS (EI): m/z 358 (M⁺, 76%), 315 (5), 287 (5), 273
(33), 259 (100). IR (KBr): 3447, 2922, 2849, 1591, 1470, 816 cm^-1.¹ H-NMR (CDCl₃, 200MHz):δ0.88 (t, J = 6.4Hz, 3H),
1.20-1.40 (m, 10H), 1.56-1.72 (m, 2H), 2.40 (s, 3
H), 2.67 (t, J = 7.6Hz, 2H), 7.30 (d, J = 8.2Hz, 2
H), 7.59 (dd, J = 7.9 and 2.1Hz, 1H), 7.70 (d, J =
7.9Hz, 1H), 7.81(d, J = 8.3Hz, 1H), 7.97 (d, J =
8.2Hz, 2H), 8.37 (dd, J = 8.3 and 2.2Hz, 1H), 8.56
(br d, J = 2.1Hz, 1H), 9.21 (d, J = 2.2Hz, 1H). 元素分析：C, 83.41; H, 8.48; N, 7.66.（Calcd for C
₂₅H₃₀N₂ :C, 83.75; H,8.43; N, 7.81.）Melting point: 80 ° C. Phase transition temperature: Cr 80 Sc 84 N 180 IsoR _f = 0.15 (CHCl ₃ ) MS (EI): m / z 358 (M ⁺ , 76%), 315 (5), 287 ( 5), 273
. (33), 259 (100 ) IR (KBr):. 3447, 2922, 2849, 1591, 1470, 816 cm -1 1 H-NMR (CDCl 3, 200MHz): δ0.88 (t, J = 6.4Hz , 3H),
1.20-1.40 (m, 10H), 1.56-1.72 (m, 2H), 2.40 (s, 3
H), 2.67 (t, J = 7.6Hz, 2H), 7.30 (d, J = 8.2Hz, 2
H), 7.59 (dd, J = 7.9 and 2.1Hz, 1H), 7.70 (d, J =
7.9Hz, 1H), 7.81 (d, J = 8.3Hz, 1H), 7.97 (d, J =
8.2Hz, 2H), 8.37 (dd, J = 8.3 and 2.2Hz, 1H), 8.56
(br d, J = 2.1Hz, 1H), 9.21 (d, J = 2.2Hz, 1H). Elemental analysis: C, 83.41; H, 8.48; N, 7.66. (Calcd for C
₂₅ H ₃₀ N ₂ : C, 83.75; H, 8.43; N, 7.81.)

【００７２】（実施例６）5-(ピリジン-2-イル)-2-(4-
オクチルフェニル)ピリジンの合成Example 6 5- (pyridin-2-yl) -2- (4-
Synthesis of (octylphenyl) pyridine

【００７３】[0073]

【化１３】 Embedded image

【００７４】実施例（2-1）で得た5-ブロモ-2-(4-オク
チルフェニル)ピリジン（100mg, 0.29mmol）のTHF（3 m
l）溶液に、−78℃でブチルリチウム（1.6 Mヘキサン溶
液, 0.18ml, 0.31mmol）を加え、３時間攪拌した。次い
で、この溶液にホウ酸トリメチル（0.05ml）を加え、室
温まで昇温した。反応液に1 M塩酸を加え、クロロホル
ム−エタノール（5%）混合溶媒で抽出し、水および飽和
食塩水で洗浄し、無水硫酸マグネシウムで乾燥した後、
溶媒を減圧留去した。残渣にエタノール（2ml）、2-ブ
ロモピリジン（44mg, 0.28mmol）のトルエン（3ml）溶
液、テトラキストリフェニルホスフィンパラジウム(0)
（5mg）および2 M炭酸水素ナトリウム水溶液（0.4ml）
を加え、12時間加熱還流した。室温まで冷却した後、２
相を分液し、水相を酢酸エチルで抽出した。有機層を合
わせ、水、及び飽和食塩水で順次洗浄後、無水硫酸マグ
ネシウムで乾燥した。溶媒を減圧下に留去した後、残渣
をシリカゲル薄層クロマトグラフィー（展開溶媒：クロ
ロホルム）で分離精製し、次に示した物性値を有する白
色固体（60mg）を得、5-(ピリジン-2-イル)-2-(4-オク
チルフェニル)ピリジンであることが確認された。The 5-bromo-2- (4-octylphenyl) pyridine (100 mg, 0.29 mmol) obtained in Example (2-1) in THF (3 m
l) Butyl lithium (1.6 M hexane solution, 0.18 ml, 0.31 mmol) was added to the solution at −78 ° C., and the mixture was stirred for 3 hours. Next, trimethyl borate (0.05 ml) was added to the solution, and the temperature was raised to room temperature. 1 M hydrochloric acid was added to the reaction solution, and the mixture was extracted with a mixed solvent of chloroform-ethanol (5%), washed with water and saturated saline, and dried over anhydrous magnesium sulfate.
The solvent was distilled off under reduced pressure. To the residue, ethanol (2 ml), a solution of 2-bromopyridine (44 mg, 0.28 mmol) in toluene (3 ml), tetrakistriphenylphosphine palladium (0)
(5 mg) and 2 M aqueous sodium bicarbonate solution (0.4 ml)
Was added and the mixture was heated under reflux for 12 hours. After cooling to room temperature, 2
The phases were separated and the aqueous phase was extracted with ethyl acetate. The organic layers were combined, washed sequentially with water and saturated saline, and then dried over anhydrous magnesium sulfate. After evaporating the solvent under reduced pressure, the residue was separated and purified by silica gel thin-layer chromatography (developing solvent: chloroform) to obtain a white solid (60 mg) having the following physical data. -Yl) -2- (4-octylphenyl) pyridine.

【００７５】融点： 82℃ 相転移温度： Cr 82 (N 76) Iso Rf = 0.15 (CHCl₃) MS (EI): m/z 344 (M⁺, 59), 301 (5), 273 (4), 259
(32), 245 (100). IR (KBr): 3447, 2924, 2851, 1586, 1460, 1431, 833,
783 cm^-1.¹ H-NMR (CDCl₃, 200MHz):δ0.88 (t, J = 6.4Hz, 3H),
1.20-1.41 (m, 10H), 1.55-1.74 (m, 2H), 2.67 (t, J
= 7.6Hz, 2H), 7.24-7.33 (m, 1H), 7.30 (d, J= 8.2H
z, 2H), 7.75-7.80 (m, 2H), 7.82 (d, J = 8.3Hz, 1
H), 7.98 (d, J = 8.2Hz, 2H), 8.39 (dd, J = 8.2 and
2.4Hz, 1H), 8.73 (d, J = 4.7Hz, 1H), 9.24 (d, J =
2.4Hz, 1H).Melting point: 82 ° C. Phase transition temperature: Cr 82 (N 76) Iso Rf = 0.15 (CHCl ₃ ) MS (EI): m / z 344 (M ⁺ , 59), 301 (5), 273 (4) , 259
(32), 245 (100) .IR (KBr): 3447, 2924, 2851, 1586, 1460, 1431, 833,
^{. 783 cm -1 1 H-NMR} (CDCl 3, 200MHz): δ0.88 (t, J = 6.4Hz, 3H),
1.20-1.41 (m, 10H), 1.55-1.74 (m, 2H), 2.67 (t, J
= 7.6Hz, 2H), 7.24-7.33 (m, 1H), 7.30 (d, J = 8.2H
z, 2H), 7.75-7.80 (m, 2H), 7.82 (d, J = 8.3Hz, 1
H), 7.98 (d, J = 8.2Hz, 2H), 8.39 (dd, J = 8.2 and
2.4Hz, 1H), 8.73 (d, J = 4.7Hz, 1H), 9.24 (d, J =
2.4Hz, 1H).

【００７６】（実施例７）5-(2-ヘキシルピリジン-5-イ
ル)-2-(4-オクチルフェニル)ピリジンの合成Example 7 Synthesis of 5- (2-hexylpyridin-5-yl) -2- (4-octylphenyl) pyridine

【００７７】[0077]

【化１４】 Embedded image

【００７８】実施例（2-1）で得た5-ブロモ-2-(4-オク
チルフェニル)ピリジン（88mg, 0.25mmol）のTHF（3m
l）溶液に、−78℃でブチルリチウム（1.54Mヘキサン溶
液, 0.16ml, 0.25mmol）を加え、３時間攪拌した。次い
で、この溶液にホウ酸トリメチル（0.06ml）を加え、室
温まで昇温した。反応液に1 M塩酸を加え、クロロホル
ムで抽出し、水および飽和食塩水で洗浄し、無水硫酸マ
グネシウムで乾燥した後、溶媒を減圧留去した。残渣に
エタノール（2ml）、5-ブロモ-2-ヘキシルピリジン（57
mg, 0.23mmol）のトルエン（3ml）溶液、テトラキスト
リフェニルホスフィンパラジウム(0)（4mg）および2 M
炭酸水素ナトリウム水溶液（0.6ml）を加え、５時間加
熱還流した。室温まで冷却した後、２相を分液し、水相
をクロロホルムで抽出した。有機層を合わせ、水、及び
飽和食塩水で順次洗浄後、無水硫酸マグネシウムで乾燥
した。溶媒を減圧下に留去した後、残渣をシリカゲル薄
層クロマトグラフィー（展開溶媒：クロロホルム）で分
離精製し、白色固体（79mg）を得、これをエタノールで
再結晶することにより、つぎの物性値を有する無色微細
針状結晶（90mg）を得た。この結晶は5-(2-ヘキシルピ
リジン-5-イル)-2-(4-オクチルフェニル)ピリジンであ
ることが確認された。The 5-bromo-2- (4-octylphenyl) pyridine (88 mg, 0.25 mmol) obtained in Example (2-1) in THF (3 m
l) To the solution was added butyllithium (1.54 M hexane solution, 0.16 ml, 0.25 mmol) at -78 ° C, and the mixture was stirred for 3 hours. Next, trimethyl borate (0.06 ml) was added to the solution, and the temperature was raised to room temperature. 1 M hydrochloric acid was added to the reaction solution, extracted with chloroform, washed with water and saturated saline, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. Ethanol (2 ml) and 5-bromo-2-hexylpyridine (57
mg, 0.23 mmol) in toluene (3 ml), tetrakistriphenylphosphine palladium (0) (4 mg) and 2 M
An aqueous sodium hydrogen carbonate solution (0.6 ml) was added, and the mixture was heated under reflux for 5 hours. After cooling to room temperature, the two phases were separated and the aqueous phase was extracted with chloroform. The organic layers were combined, washed sequentially with water and saturated saline, and then dried over anhydrous magnesium sulfate. After evaporating the solvent under reduced pressure, the residue was separated and purified by silica gel thin-layer chromatography (developing solvent: chloroform) to obtain a white solid (79 mg). To obtain colorless fine needle crystals (90 mg). This crystal was confirmed to be 5- (2-hexylpyridin-5-yl) -2- (4-octylphenyl) pyridine.

【００７９】融点： 25℃ 相転移温度： Cr 25 Sx 164 Sc 177 S_A 196 Iso R_f = 0.10 (CHCl₃) MS (EI): m/z 428 (M⁺, 9), 358 (100). IR (KBr): 3436, 2957, 2922, 2853, 1593, 1470, 820
cm^-1.¹ H-NMR (CDCl₃, 500 MHz):δ0.88 (t, J = 7.0Hz, 3H),
0.89 (t, J = 7.0Hz, 3H), 1.22-1.44 (m, 16H), 1.62
-1.69 (m, 2H), 1.74-1.81 (m, 2H), 2.67 (t, J= 7.7H
z, 2H), 2.85 (t, J = 7.8Hz, 2H), 7.26 (d, J = 8.0H
z, 1H), 7.31 (d, J = 8.1Hz, 2H), 7.80 (d, J = 8.2H
z, 1H), 7.83 (dd, J = 8.0 and 2.3Hz,1H), 7.91 (dd,
J = 8.2 and 2.3Hz, 1H), 7.95 (d, J = 8.1Hz, 2H),
8.80 (d,J = 2.3Hz, 1H), 8.89 (d, J = 2.3Hz, 1H). HRMS: m/z 428.3194.（Calcd for C₃₀H₄₀N₂ 428.319
0.） 元素分析：C, 84.31; H, 9.70; N, 6.42.（Calcd for C
₃₀H₄₀N₂ :C, 84.06; H,9.41; N, 6.54.）Melting point: 25 ° C. Phase transition temperature: Cr 25 Sx 164 Sc 177 S _A 196 IsoR _f = 0.10 (CHCl ₃ ) MS (EI): m / z 428 (M ⁺ , 9), 358 (100). IR (KBr): 3436, 2957, 2922, 2853, 1593, 1470, 820
^{. cm -1 1 H-NMR (} CDCl 3, 500 MHz): δ0.88 (t, J = 7.0Hz, 3H),
0.89 (t, J = 7.0Hz, 3H), 1.22-1.44 (m, 16H), 1.62
-1.69 (m, 2H), 1.74-1.81 (m, 2H), 2.67 (t, J = 7.7H
z, 2H), 2.85 (t, J = 7.8Hz, 2H), 7.26 (d, J = 8.0H
z, 1H), 7.31 (d, J = 8.1Hz, 2H), 7.80 (d, J = 8.2H
z, 1H), 7.83 (dd, J = 8.0 and 2.3Hz, 1H), 7.91 (dd,
J = 8.2 and 2.3Hz, 1H), 7.95 (d, J = 8.1Hz, 2H),
8.80 (d, J = 2.3Hz, 1H), 8.89 (d, J = 2.3Hz, 1H). HRMS: m / z 428.3194. (Calcd for C ₃₀ H ₄₀ N ₂ 428.319
0.) Elemental analysis: C, 84.31; H, 9.70; N, 6.42. (Calcd for C
₃₀ H ₄₀ N ₂ : C, 84.06; H, 9.41; N, 6.54.)

【００８０】（実施例８） 2-(2-ヘキシルピリジン-5-
イル)-5-(4-オクチルフェニル)ピリジンの合成Example 8 2- (2-hexylpyridine-5-
Synthesis of (yl) -5- (4-octylphenyl) pyridine

【００８１】[0081]

【化１５】 Embedded image

【００８２】（8-1） 5-ブロモ-2-(2-ヘキシルピリジ
ン-5-イル)ピリジンの合成 5-ブロモ-2-ヘキシルピリジン（308mg, 1.27mmol）のTH
F（10ml）溶液に、−78℃でブチルリチウム（1.58Mヘキ
サン溶液, 0.8ml, 1.26mmol）を加え、3.5時間攪拌し
た。次いで、この溶液にホウ酸トリメチル（0.18ml）を
加え、室温まで昇温した。反応液に1M塩酸を加え、クロ
ロホルム−エタノール（５％）混合溶液で抽出し、水お
よび飽和食塩水で洗浄し、無水硫酸マグネシウムで乾燥
した後、溶媒を減圧留去した。残渣にエタノール（5m
l）、2,5-ジブロモピリジン（273mg,1.15mmol）のトル
エン（9ml）溶液、テトラキストリフェニルホスフィン
パラジウム(0)（12mg）および2 M炭酸水素ナトリウム水
溶液（1.7ml）を加え、19時間加熱還流した。室温まで
冷却した後、２相を分液し、水相をクロロホルム−エタ
ノール（５％）混合溶液で抽出した。有機層を合わせ、
水、及び飽和食塩水で順次洗浄後、無水硫酸マグネシウ
ムで乾燥した。溶媒を減圧下に留去した後、シリカゲル
カラムクロマトグラフィー及びシリカゲル薄層クロマト
グラフィー(展開溶媒：酢酸エチル／ヘキサン = 1／4)
で分離精製し、白色固体（178mg）を得、これをエタノ
ールで再結晶することにより、次に示す物性値を有する
無色微細針状結晶を得た。この結晶は5-ブロモ-2-(2-ヘ
キシルピリジン-5-イル)ピリジンであることが確認され
た。(8-1) Synthesis of 5-bromo-2- (2-hexylpyridin-5-yl) pyridine TH of 5-bromo-2-hexylpyridine (308 mg, 1.27 mmol)
Butyllithium (1.58 M hexane solution, 0.8 ml, 1.26 mmol) was added to the F (10 ml) solution at −78 ° C., and the mixture was stirred for 3.5 hours. Next, trimethyl borate (0.18 ml) was added to the solution, and the temperature was raised to room temperature. 1M Hydrochloric acid was added to the reaction solution, extracted with a mixed solution of chloroform-ethanol (5%), washed with water and saturated saline, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. Ethanol (5m
l), a solution of 2,5-dibromopyridine (273 mg, 1.15 mmol) in toluene (9 ml), tetrakistriphenylphosphine palladium (0) (12 mg) and a 2 M aqueous sodium hydrogen carbonate solution (1.7 ml) were added, and the mixture was heated for 19 hours. Refluxed. After cooling to room temperature, the two phases were separated, and the aqueous phase was extracted with a mixed solution of chloroform-ethanol (5%). Combine the organic layers,
After washing with water and saturated saline solution in that order, it was dried over anhydrous magnesium sulfate. After evaporating the solvent under reduced pressure, silica gel column chromatography and silica gel thin layer chromatography (developing solvent: ethyl acetate / hexane = 1/4)
A white solid (178 mg) was obtained and recrystallized from ethanol to give colorless fine needle crystals having the following physical data. This crystal was confirmed to be 5-bromo-2- (2-hexylpyridin-5-yl) pyridine.

【００８３】R_f = 0.45 (Hexane / AcOEt = 4 / 1) MS (EI): m/z 320 (M⁺+2, 2%), 318 (M⁺, 2), 248 (10
0). IR (KBr): 3457, 2955, 2922, 2855, 1597, 1578, 146
6, 1098, 822 cm^-1.¹ H-NMR (CDCl₃, 200 MHz):δ0.88 (t, J = 6.6Hz, 3H),
1.22-1.45 (m, 6H), 1.66-1.83 (m, 2H), 2.84 (t, J
= 7.7Hz, 2H), 7.25 (d, J = 8.1Hz, 1H), 7.62(d, J =
8.6Hz, 1H), 7.88 (dd, J = 8.6 and 2.3Hz, 1H), 8.2
0 (dd, J = 8.1and 2.3Hz, 1H), 8.74 (d, J = 2.3Hz,
1H), 9.06 (d, J = 2.3Hz, 1H). HRMS: m/z 318.0705.（Calcd for C₁₆H₁₉N₂ Br 318.073
0.） 元素分析： C, 60.47; H, 5.98; N, 8.52; Br, 25.02.
(Calcd for C₁₆H₁₉N₂Br:C, 60.20; H, 6.00; N, 8.78;
Br, 25.03.)R _f = 0.45 (Hexane / AcOEt = 4/1) MS (EI): m / z 320 (M ⁺⁺ 2, 2%), 318 (M ⁺ , 2), 248 (10
0) .IR (KBr): 3457, 2955, 2922, 2855, 1597, 1578, 146
^{. 6, 1098, 822 cm -1} 1 H-NMR (CDCl 3, 200 MHz): δ0.88 (t, J = 6.6Hz, 3H),
1.22-1.45 (m, 6H), 1.66-1.83 (m, 2H), 2.84 (t, J
= 7.7Hz, 2H), 7.25 (d, J = 8.1Hz, 1H), 7.62 (d, J =
8.6Hz, 1H), 7.88 (dd, J = 8.6 and 2.3Hz, 1H), 8.2
0 (dd, J = 8.1and 2.3Hz, 1H), 8.74 (d, J = 2.3Hz,
1H), 9.06 (d, J = 2.3Hz, 1H). HRMS: m / z 318.0705. (Calcd for C ₁₆ H ₁₉ N ₂ Br 318.073
0.) Elemental analysis: C, 60.47; H, 5.98; N, 8.52; Br, 25.02.
(Calcd for C ₁₆ H ₁₉ N ₂ Br: C, 60.20; H, 6.00; N, 8.78;
(Br, 25.03.)

【００８４】（8-2） 2-(2-ヘキシルピリジン-5-イル)
-5-(4-オクチルフェニル)ピリジンの合成 5-ブロモ-2-(2-ヘキシルピリジン-5-イル)ピリジン（17
8mg, 0.56mmol）とNiCl₂(dppe)（25mg, 0.047mmol）のT
HF（4ml）溶液に、4-オクチルブロモベンゼン（354mg,
1.3mmol）、マグネシウム（48mg, 2.0mol）およびTHF
（4ml）より調製したグリニャール反応剤を０℃で１時
間かけて滴下し、更に０℃で１時間撹拌した後、室温で
17時間撹拌した。反応液に1 M塩酸を加え、クロロホル
ム−エタノール（５％）混合溶液で抽出し、水及び飽和
食塩水で順次洗浄後、無水硫酸マグネシウムで乾燥し
た。溶媒を減圧下に留去した後、残渣をシリカゲル薄層
クロマトグラフィー(展開溶媒：クロロホルム／エタノ
ール = 99/1)で分離精製し、白色固体（165mg）を得
た。これをエタノールで再結晶することにより、次に示
す物性値を有する無色微細板状結晶を得た。この結晶は
2-(2-ヘキシルピリジン-5-イル)-5-(4-オクチルフェニ
ル)ピリジンであることが確認された。(8-2) 2- (2-hexylpyridin-5-yl)
Synthesis of 5-5- (4-octylphenyl) pyridine 5-bromo-2- (2-hexylpyridin-5-yl) pyridine (17
8mg, 0.56mmol) and NiCl ₂ (dppe) (25mg, 0.047mmol) T
To a solution of HF (4 ml) was added 4-octylbromobenzene (354 mg,
1.3mmol), magnesium (48mg, 2.0mol) and THF
(4 ml) was added dropwise at 0 ° C. over 1 hour, and the mixture was further stirred at 0 ° C. for 1 hour.
Stir for 17 hours. 1 M hydrochloric acid was added to the reaction solution, extracted with a mixed solution of chloroform-ethanol (5%), washed sequentially with water and saturated saline, and then dried over anhydrous magnesium sulfate. After evaporating the solvent under reduced pressure, the residue was separated and purified by silica gel thin-layer chromatography (developing solvent: chloroform / ethanol = 99/1) to obtain a white solid (165 mg). This was recrystallized from ethanol to obtain colorless fine plate-like crystals having the following physical properties. This crystal
It was confirmed to be 2- (2-hexylpyridin-5-yl) -5- (4-octylphenyl) pyridine.

【００８５】融点： 34℃ 相転移温度： Cr 34 Sx 164 Sc 170 S_A 195 Iso R_f = 0.50 (CHCl₃ / EtOH = 99 / 1) IR (KBr): 3443, 2961, 2922, 2849, 1468, 816 cm^-1. MS (EI): m/z 428 (M⁺, 6%), 358 (100).¹ H-NMR (CDCl₃, 500MHz):δ0.89 (t, J = 6.7Hz, 6H),
1.22-1.43 (m, 16H), 1.66 (quint, J = 7.6Hz, 2H),
1.77 (quint, J = 7.6Hz, 2H), 2.67 (t, J = 7.6Hz, 2
H), 2.86 (t, J = 7.6Hz, 2H), 7.26 (d, J = 8.1Hz, 1
H), 7.31 (d, J =8.0Hz, 2H), 7.55 (d, J = 8.0Hz, 2
H), 7.79 (d, J = 8.2Hz, 1H), 7.96 (dd,J = 8.2 and
2.2Hz, 1H), 8.28 (dd, J = 8.1 and 2.2Hz, 1H), 8.93
(d, J = 2.2Hz, 1H), 9.13 (d, J = 2.2Hz, 1H). HRMS: m/z 428.3205.（Calcd for C₃₀H₄₀N₂ 428.318
9.） 元素分析：C, 84.14; H, 9.70; N, 6.45.（Calcd for C
₃₀H₄₀N₂ :C, 84.06; H,9.41; N, 6.54.）Melting point: 34 ° C. Phase transition temperature: Cr 34 Sx 164 Sc 170 S _A 195 Iso R _f = 0.50 (CHCl ₃ / EtOH = 99/1) IR (KBr): 3443, 2961, 2922, 2849, 1468, ^{. 816 cm -1 MS (EI)} :. m / z 428 (M +, 6%), 358 (100) 1 H-NMR (CDCl 3, 500MHz): δ0.89 (t, J = 6.7Hz, 6H ),
1.22-1.43 (m, 16H), 1.66 (quint, J = 7.6Hz, 2H),
1.77 (quint, J = 7.6Hz, 2H), 2.67 (t, J = 7.6Hz, 2
H), 2.86 (t, J = 7.6Hz, 2H), 7.26 (d, J = 8.1Hz, 1
H), 7.31 (d, J = 8.0Hz, 2H), 7.55 (d, J = 8.0Hz, 2
H), 7.79 (d, J = 8.2Hz, 1H), 7.96 (dd, J = 8.2 and
2.2Hz, 1H), 8.28 (dd, J = 8.1 and 2.2Hz, 1H), 8.93
(d, J = 2.2Hz, 1H), 9.13 (d, J = 2.2Hz, 1H) .HRMS: m / z 428.3205. (Calcd for C ₃₀ H ₄₀ N ₂ 428.318
9.) Elemental analysis: C, 84.14; H, 9.70; N, 6.45. (Calcd for C
₃₀ H ₄₀ N ₂ : C, 84.06; H, 9.41; N, 6.54.)

【００８６】（実施例9）表２に示す強誘電性液晶組成
物Aに対し、実施例１、２、３、４記載の各化合物を表
２記載の重量比で添加し、液晶組成物B〜Eを作製した。(Example 9) To the ferroelectric liquid crystal composition A shown in Table 2, the compounds described in Examples 1, 2, 3, and 4 were added in the weight ratios shown in Table 2, and the liquid crystal composition B was added. ~ E were prepared.

【００８７】これらの液晶組成物について、相転移温
度、およびポリイミドを塗布したラビング処理済みの透
明電極付きガラスからなる厚さ２μｍのセルに注入し、
２５℃で１０V/μｍの矩形派を印加したときの自発分
極、傾き角、応答速度を求めた。表３に示したとおり、
実施例１、２、３、４記載の化合物を強誘電性液晶組成
物に添加することにより、応答速度を遅くすることなく
Sc*相の上限温度を上げることができた。These liquid crystal compositions were injected into a 2 μm-thick cell made of rubbed glass with a transparent electrode coated with polyimide and having a phase transition temperature.
The spontaneous polarization, the inclination angle, and the response speed when a rectangular group of 10 V / μm was applied at 25 ° C. were obtained. As shown in Table 3,
By adding the compounds described in Examples 1, 2, 3, and 4 to the ferroelectric liquid crystal composition, the response speed was not reduced.
The maximum temperature of the Sc * phase could be increased.

【００８８】[0088]

【表２】 [Table 2]

【００８９】[0089]

【表３】 [Table 3]

【００９０】（実施例１０）実施例５及び６に記載の化
合物をメルク社製ネマチック液晶組成物ZLI 1132に表４
記載の重量比で添加し、液晶組成物F、Gを作製した。表
５にこれらの液晶組成物の相転移温度を示した。このよ
うに実施例５、６記載の化合物を添加することにより、
N相の上限温度を上げることができた。Example 10 The compounds described in Examples 5 and 6 were added to a nematic liquid crystal composition ZLI 1132 manufactured by Merck & Co., Ltd., as shown in Table 4.
Liquid crystal compositions F and G were prepared by adding at the stated weight ratios. Table 5 shows the phase transition temperatures of these liquid crystal compositions. Thus, by adding the compounds described in Examples 5 and 6,
The maximum temperature of N phase could be raised.

【００９１】[0091]

【表４】 [Table 4]

【００９２】[0092]

【表５】 [Table 5]

【００９３】[0093]

【発明の効果】以上のように、本発明のピリジン化合物
は、強誘電性液晶組成物に添加することによって、キラ
ルスメクチックＣ相を示す温度範囲を拡大でき、あるい
は、ネマチック液晶組成物に添加して、ネマチック相を
示す温度範囲を拡大でき、応答速度の速い液晶表示材料
を得ることができる点で優れた効果を奏する。As described above, by adding the pyridine compound of the present invention to the ferroelectric liquid crystal composition, the temperature range showing the chiral smectic C phase can be expanded, or the pyridine compound can be added to the nematic liquid crystal composition. Therefore, the temperature range showing the nematic phase can be expanded, and a liquid crystal display material having a high response speed can be obtained, which is an excellent effect.

───────────────────────────────────────────────────── フロントページの続き (72)発明者 萩原 恵美子 神奈川県相模原市東大沼４−17−６ (72)発明者 檜山 爲次郎 神奈川県相模原市上鶴間４−29−３−101 Ｆターム(参考） 4C055 AA01 BA02 BA05 BA06 BA08 BA25 CA01 CA02 CA05 CA06 CA08 CA25 DA01 EA01 4H027 BA01 BA06 BD02 BD08 DC01 DE01 DE03 DN03  ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Emiko Hagiwara 4-17-6 Higashi-Onuma, Sagamihara City, Kanagawa Prefecture (72) Inventor Tajiro Hiyama 4-29-3-101 Kamizuruma, Sagamihara City, Kanagawa Prefecture F-term (reference) 4C055 AA01 BA02 BA05 BA06 BA08 BA25 CA01 CA02 CA05 CA06 CA08 CA25 DA01 EA01 4H027 BA01 BA06 BD02 BD08 DC01 DE01 DE03 DN03

Claims (2)

【特許請求の範囲】[Claims] 【請求項１】 一般式（I） 【化１】 〔式中、R¹は炭素数１〜１２のアルキル基を、R²は炭素
数１〜１２のアルキル基または水素を、環Aは1,4-フェ
ニレン基またはピリジン-2,5-ジイル基（２位にR¹）を
示し、環Bは環Aが1,4-フェニレン基の場合、1,4-フェニ
レン基、ピリジン-2,5-ジイル基（２位または5位にR²）
を、環Aがピリジン-2,5-ジイル基（２位にR¹）の場合、
1,4-フェニレン基を示す。〕で表される三環系フェニル
ピリジン誘導体。1. A compound of the general formula (I) Wherein R ¹ is an alkyl group having 1 to 12 carbon atoms, R ² is an alkyl group having 1 to 12 carbon atoms or hydrogen, and ring A is a 1,4-phenylene group or a pyridine-2,5-diyl group. (R ^{1 at the} 2-position), and Ring B is a 1,4-phenylene group or a pyridine-2,5-diyl group (R ^{2 at the 2-} or 5-position) when Ring A is a 1,4-phenylene group
When ring A is a pyridine-2,5-diyl group (R ^{1 at the} 2-position),
Shows a 1,4-phenylene group. A phenylpyridine derivative represented by the formula: 【請求項２】 請求項１に記載の三環系フェニルピリジ
ン誘導体を少なくとも１種含有することを特徴とする液
晶組成物。2. A liquid crystal composition comprising at least one tricyclic phenylpyridine derivative according to claim 1.