JP4691937B2

JP4691937B2 - (E) -1,2-bis (cyclohexyl) ethylene derivative production method and production intermediate thereof

Info

Publication number: JP4691937B2
Application number: JP2004279238A
Authority: JP
Inventors: 佳孝斉藤
Original assignee: DIC Corp
Current assignee: DIC Corp
Priority date: 2004-09-27
Filing date: 2004-09-27
Publication date: 2011-06-01
Anticipated expiration: 2024-09-27
Also published as: JP2006089432A

Description

本発明は電気光学的液晶表示材料として有用な、(E)-1,2-ビス(シクロヘキシル)エチレン誘導体の製造方法及びその製造中間体に関する。 The present invention relates to a method for producing an (E) -1,2-bis (cyclohexyl) ethylene derivative useful as an electro-optical liquid crystal display material and an intermediate for the production.

液晶表示素子は、時計、電卓をはじめとしては、家庭用各種電気機器、測定機器、自動車用パネル、ワープロ、電子手帳、プリンター、コンピューター、テレビ等に用いられるようになっている。これに用いられる液晶材料として、正又は負の誘電率異方性を有する液晶材料が電場応答する為に必須であるが、併せて応答速度を向上させる等のため、組成物の粘性を下げる働きを有する液晶材料(減粘剤)を用いることが一般的である。減粘剤には同時に優れた液晶性を有することが求められているが、(E)-1,2-ビス(シクロヘキシル)エチレン誘導体はこの目的のために極めて有用である(非特許文献1参照)。その製造法については、幾つかが知られている(特許文献１、特許文献2及び非特許文献2参照)。しかしながら、これらの製造方法は必ずしも実用的なものではない。例えば特許文献１及び特許文献2では、(Z)-体を過酸化物で酸化し、次いでジブロモトリフェニルホスホランで臭素化した後、亜鉛で還元することによって(E)-体を得ているが、その収率は低い。また、非特許文献2では、1,2-ビス(トランス-4-アルキルシクロヘキシル)エタン-1,2-ジケトンをジヒドラゾンとし、これを1,2-ビス(トランス-4-アルキルシクロヘキシル)アセチレンに変換した後、これを還元することによって(E)-1,2-ビス(シクロヘキシル)エチレン誘導体を得ているが、毒性の高いヒドラジン及びヘキサメチルりん酸トリアミド(HMPT)を用いている他、発火性の金属リチウムを用いており、実用的なものではない。 Liquid crystal display elements are used in various electric appliances for home use, measuring instruments, automobile panels, word processors, electronic notebooks, printers, computers, televisions, as well as watches and calculators. As a liquid crystal material used for this, a liquid crystal material having positive or negative dielectric anisotropy is indispensable for an electric field response. However, in order to improve the response speed, etc., it works to lower the viscosity of the composition. It is common to use a liquid crystal material (thickening agent) having Although a thinning agent is required to have excellent liquid crystallinity at the same time, (E) -1,2-bis (cyclohexyl) ethylene derivatives are extremely useful for this purpose (see Non-Patent Document 1). ). There are several known manufacturing methods (see Patent Document 1, Patent Document 2, and Non-Patent Document 2). However, these manufacturing methods are not always practical. For example, in Patent Document 1 and Patent Document 2, the (Z) -isomer is oxidized with peroxide, then brominated with dibromotriphenylphosphorane, and then reduced with zinc to obtain the (E) -isomer. However, the yield is low. In Non-Patent Document 2, 1,2-bis (trans-4-alkylcyclohexyl) ethane-1,2-diketone is converted to dihydrazone and converted to 1,2-bis (trans-4-alkylcyclohexyl) acetylene. After that, (E) -1,2-bis (cyclohexyl) ethylene derivative was obtained by reducing this, but in addition to using highly toxic hydrazine and hexamethylphosphoric triamide (HMPT), it was ignitable. Metallic lithium is used and is not practical.

特開平６−９２９２４号公報（１９頁）JP-A-6-92924 (page 19) 特許第３４１８３９８号公報（５頁）Japanese Patent No. 3418398 (5 pages) 液晶第１巻第一号１９頁（１９９７年）Liquid Crystal Volume 1 Issue 1 Page 19 (1997) Ｃｈｅｍｉｋｅｒ−Ｚｅｉｔｕｎｇ，１０４，ｐ．２６９（１９８０年）Chemiker-Zeitung, 104, p. 269 (1980)

本発明が解決しようとする課題は、(E)-1,2-ビス(シクロヘキシル)エチレン誘導体の実用的な製造法、及び有用な製造中間体を提供することにある。 The problem to be solved by the present invention is to provide a practical process for producing (E) -1,2-bis (cyclohexyl) ethylene derivatives and useful production intermediates.

本願発明者は上記課題を解決するために鋭意検討した結果本願発明の完成に至った。 The inventor of the present application has intensively studied to solve the above problems, and as a result, the present invention has been completed.

本願発明は、一般式(2) The present invention provides a general formula (2)

（式中、R¹及びR²はそれぞれ独立に水素原子、炭素原子数1〜20のアルキル基、炭素原子数1〜20のアルコキシル基、炭素原子数2〜20のアルケニル基又は炭素原子数2〜20のアルケニルオキシ基を表しこれらは炭素原子数1〜7のアルコキシル基又は1〜7個のハロゲン原子によって置換されていてもよく、A及びBはそれぞれ独立にトランス-1,4-シクロへキシレン基、ビシクロ[2.2.2]オクタン-1,4-ジイル基、又は1個以上のハロゲン原子により置換されていてもよい、1,4-フェニレン基、ピリジン-2,5-ジイル基、ピリミジン-2,5-ジイル基、ピラジン-2,5-ジイル基、ピリダジン-3,6-ジイル基、トランス-1,3-ジオキサン-2,5-ジイル基、トランスデカヒドロナフタレン-2,6-ジイル基、テトラヒドロナフタレン-2,6-ジイル基、ナフタレン-2,6-ジイル基を表し、L及びMはそれぞれ独立に-CH₂-、-CH₂CH₂-、-CH₂CH₂CH₂CH₂-、-CH(CH₃)CH₂-、-CH₂CH(CH₃)-、-CF=CF-、-CH₂O-、-OCH₂-、-CF₂O-、-OCF₂-又は単結合を表し、m及びnはそれぞれ独立に0又は1を表す。）で表される(Z)-1,2-ビス(シクロヘキシル)エチレン誘導体を酸化することにより一般式(3) (In the formula, R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or 2 carbon atoms. Represents an alkenyloxy group having ˜20, which may be substituted by an alkoxyl group having 1 to 7 carbon atoms or a halogen atom having 1 to 7 carbon atoms, and A and B are each independently trans-1,4-cyclohexane 1,4-phenylene group, pyridine-2,5-diyl group, pyrimidine optionally substituted by xylene group, bicyclo [2.2.2] octane-1,4-diyl group, or one or more halogen atoms -2,5-diyl group, pyrazine-2,5-diyl group, pyridazine-3,6-diyl group, trans-1,3-dioxane-2,5-diyl group, transdecahydronaphthalene-2,6- Diyl group, tetrahydronaphthalene-2,6-diyl group, naphthalene-2,6-diyl group, L and M are each -CH ₂ on standing _{_{-, - CH 2 CH 2 -}} , - CH 2 CH 2 CH 2 CH 2 -, - CH (CH 3) CH 2 -, - CH 2 CH (CH 3) -, - CF = CF- , -CH ₂ O-, -OCH _2- , -CF ₂ O-, -OCF ₂ -or a single bond, and m and n each independently represent 0 or 1). By oxidizing 1,2-bis (cyclohexyl) ethylene derivative, the general formula (3)

（式中、R¹、R²、A、B、L、M、m及びnは一般式(2)と同義である。）で表される1,2-ジオール誘導体を得、次いで一般式(4)

(Wherein R ¹ , R ² , A, B, L, M, m and n are as defined in the general formula (2)), a 1,2-diol derivative represented by the general formula ( Four)

（式中、R¹、R²、A、B、L、M、m及びnは一般式(2)と同義であり、Pは水素原子が置換されているか又は非置換のメチレン基を表す。）で表されるジオキソラン誘導体とした後に開裂することによる一般式(1)

(In the formula, R ¹ , R ² , A, B, L, M, m and n have the same meanings as in the general formula (2), and P represents a hydrogen atom-substituted or unsubstituted methylene group. General formula (1) by cleaving the dioxolane derivative represented by

（式中、R¹、R²、A、B、L、M、m及びnは一般式(2)と同義である。）で表される(E)-1,2-ビス(シクロヘキシル)エチレン誘導体の製造方法を提供しする。

(Wherein R ¹ , R ² , A, B, L, M, m and n have the same meanings as those in formula (2)) (E) -1,2-bis (cyclohexyl) ethylene A method for producing a derivative is provided.

又、本願発明は次に記載する本願発明の製造方法に使用する製造中間体を提供する。 Moreover, this invention provides the manufacturing intermediate used for the manufacturing method of this invention described below.

一般式(3) General formula (3)

（式中、R¹及びR²はそれぞれ独立に水素原子、炭素原子数1〜20のアルキル基、炭素原子数1〜20のアルコキシル基、炭素原子数2〜20のアルケニル基又は炭素原子数2〜20のアルケニルオキシ基を表しこれらは炭素原子数1〜7のアルコキシル基又は1〜7個のハロゲン原子によって置換されていてもよく、A及びBはそれぞれ独立にトランス-1,4-シクロへキシレン基、ビシクロ[2.2.2]オクタン-1,4-ジイル基、又は1個以上のハロゲン原子により置換されていてもよい、1,4-フェニレン基、ピリジン-2,5-ジイル基、ピリミジン-2,5-ジイル基、ピラジン-2,5-ジイル基、ピリダジン-3,6-ジイル基、トランス-1,3-ジオキサン-2,5-ジイル基、トランスデカヒドロナフタレン-2,6-ジイル基、テトラヒドロナフタレン-2,6-ジイル基、ナフタレン-2,6-ジイル基を表し、L及びMはそれぞれ独立に-CH₂-、-CH₂CH₂-、-CH₂CH₂CH₂CH₂-、-CH(CH₃)CH₂-、-CH₂CH(CH₃)-、-CF=CF-、-CH₂O-、-OCH₂-、-CF₂O-、-OCF₂-又は単結合を表し、m及びnはそれぞれ独立に0又は1を表す。）で表される1,2-ジオール誘導体。
一般式(7)

(In the formula, R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or 2 carbon atoms. Represents an alkenyloxy group having ˜20, which may be substituted by an alkoxyl group having 1 to 7 carbon atoms or a halogen atom having 1 to 7 carbon atoms, and A and B are each independently trans-1,4-cyclohexane 1,4-phenylene group, pyridine-2,5-diyl group, pyrimidine optionally substituted by xylene group, bicyclo [2.2.2] octane-1,4-diyl group, or one or more halogen atoms -2,5-diyl group, pyrazine-2,5-diyl group, pyridazine-3,6-diyl group, trans-1,3-dioxane-2,5-diyl group, transdecahydronaphthalene-2,6- Diyl group, tetrahydronaphthalene-2,6-diyl group, naphthalene-2,6-diyl group, L and M are each -CH ₂ on standing _{_{-, - CH 2 CH 2 -}} , - CH 2 CH 2 CH 2 CH 2 -, - CH (CH 3) CH 2 -, - CH 2 CH (CH 3) -, - CF = CF- , -CH ₂ O-, -OCH _2- , -CF ₂ O-, -OCF ₂ -or a single bond, and m and n each independently represents 0 or 1. Diol derivative.
General formula (7)

(式中、R¹及びR²はそれぞれ独立に水素原子、炭素原子数1〜20のアルキル基、炭素原子数1〜20のアルコキシル基、炭素原子数2〜20のアルケニル基又は炭素原子数2〜20のアルケニルオキシ基を表しこれらは炭素原子数1〜7のアルコキシル基又は1〜7個のハロゲン原子によって置換されていてもよく、A及びBはそれぞれ独立にトランス-1,4-シクロへキシレン基、ビシクロ[2.2.2]オクタン-1,4-ジイル基、又は1個以上のハロゲン原子により置換されていてもよい、1,4-フェニレン基、ピリジン-2,5-ジイル基、ピリミジン-2,5-ジイル基、ピラジン-2,5-ジイル基、ピリダジン-3,6-ジイル基、トランス-1,3-ジオキサン-2,5-ジイル基、トランスデカヒドロナフタレン-2,6-ジイル基、テトラヒドロナフタレン-2,6-ジイル基、ナフタレン-2,6-ジイル基を表し、L及びMはそれぞれ独立に-CH₂-、-CH₂CH₂-、-CH₂CH₂CH₂CH₂-、-CH(CH₃)CH₂-、-CH₂CH(CH₃)-、-CF=CF-、-CH₂O-、-OCH₂-、-CF₂O-、-OCF₂-又は単結合を表し、m及びnはそれぞれ独立に0又は1を表し、R³及びR⁴はそれぞれ独立に水素原子、ホルミル基又は炭素数1〜10のアシル基を表す。)で表されるジオキソラン誘導体。
一般式(8) (In the formula, R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or 2 carbon atoms. Represents an alkenyloxy group having ˜20, which may be substituted by an alkoxyl group having 1 to 7 carbon atoms or a halogen atom having 1 to 7 carbon atoms, and A and B are each independently trans-1,4-cyclohexane 1,4-phenylene group, pyridine-2,5-diyl group, pyrimidine optionally substituted by xylene group, bicyclo [2.2.2] octane-1,4-diyl group, or one or more halogen atoms -2,5-diyl group, pyrazine-2,5-diyl group, pyridazine-3,6-diyl group, trans-1,3-dioxane-2,5-diyl group, transdecahydronaphthalene-2,6- Diyl group, tetrahydronaphthalene-2,6-diyl group, naphthalene-2,6-diyl group, L and M are each independently -CH ₂ on standing _{_{-, - CH 2 CH 2 -}} , - CH 2 CH 2 CH 2 CH 2 -, - CH (CH 3) CH 2 -, - CH 2 CH (CH 3) -, - CF = CF- , -CH ₂ O-, -OCH _2- , -CF ₂ O-, -OCF ₂ -or a single bond, m and n each independently represent 0 or 1, and R ³ and R ⁴ each independently A hydrogen atom, a formyl group, or an acyl group having 1 to 10 carbon atoms).
General formula (8)

（式中、R¹及びR²はそれぞれ独立に水素原子、炭素原子数1〜20のアルキル基、炭素原子数1〜20のアルコキシル基、炭素原子数2〜20のアルケニル基又は炭素原子数2〜20のアルケニルオキシ基を表しこれらは炭素原子数1〜7のアルコキシル基又は1〜7個のハロゲン原子によって置換されていてもよく、A及びBはそれぞれ独立にトランス-1,4-シクロへキシレン基、ビシクロ[2.2.2]オクタン-1,4-ジイル基、又は1個以上のハロゲン原子により置換されていてもよい、1,4-フェニレン基、ピリジン-2,5-ジイル基、ピリミジン-2,5-ジイル基、ピラジン-2,5-ジイル基、ピリダジン-3,6-ジイル基、トランス-1,3-ジオキサン-2,5-ジイル基、トランスデカヒドロナフタレン-2,6-ジイル基、テトラヒドロナフタレン-2,6-ジイル基、ナフタレン-2,6-ジイル基を表し、L及びMはそれぞれ独立に-CH₂-、-CH₂CH₂-、-CH₂CH₂CH₂CH₂-、-CH(CH₃)CH₂-、-CH₂CH(CH₃)-、-CF=CF-、-CH₂O-、-OCH₂-、-CF₂O-、-OCF₂-又は単結合を表し、m及びnはそれぞれ独立に0又は1を表す。）で表されるジオキソラン誘導体。 (In the formula, R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or 2 carbon atoms. Represents an alkenyloxy group having ˜20, which may be substituted by an alkoxyl group having 1 to 7 carbon atoms or a halogen atom having 1 to 7 carbon atoms, and A and B are each independently trans-1,4-cyclohexane 1,4-phenylene group, pyridine-2,5-diyl group, pyrimidine optionally substituted by xylene group, bicyclo [2.2.2] octane-1,4-diyl group, or one or more halogen atoms -2,5-diyl group, pyrazine-2,5-diyl group, pyridazine-3,6-diyl group, trans-1,3-dioxane-2,5-diyl group, transdecahydronaphthalene-2,6- Diyl group, tetrahydronaphthalene-2,6-diyl group, naphthalene-2,6-diyl group, L and M are each -CH ₂ on standing _{_{-, - CH 2 CH 2 -}} , - CH 2 CH 2 CH 2 CH 2 -, - CH (CH 3) CH 2 -, - CH 2 CH (CH 3) -, - CF = CF- , -CH ₂ O-, -OCH _2- , -CF ₂ O-, -OCF ₂ -or a single bond, and m and n each independently represents 0 or 1.

本発明の製造方法により、効率的な製造が困難であった(E)-1,2-ビス(シクロヘキシル)エチレン誘導体の実用的な製造が可能となった。当該化合物は液晶組成物を構成する成分として有用である。 The production method of the present invention enables practical production of (E) -1,2-bis (cyclohexyl) ethylene derivatives, which were difficult to produce efficiently. The compound is useful as a component constituting the liquid crystal composition.

本願発明において、一般式(2)で表される(Z)-1,2-ビス(シクロヘキシル)エチレン誘導体から一般式(3)で表される1,2-ジオール誘導体を得る方法は特に制限はない。しかし、反応の効率等を考慮すると次に記載する方法が好ましい。
一般式(2)で表される(Z)-1,2-ビス(シクロヘキシル)エチレン誘導体を酸化して一般式(5) In the present invention, the method for obtaining the 1,2-diol derivative represented by the general formula (3) from the (Z) -1,2-bis (cyclohexyl) ethylene derivative represented by the general formula (2) is not particularly limited. Absent. However, considering the reaction efficiency, the following method is preferred.
The (Z) -1,2-bis (cyclohexyl) ethylene derivative represented by the general formula (2) is oxidized to give the general formula (5)

(式中、R¹、R²、A、B、L、M、m及びnは一般式(2)と同義である。)で表されるオキシラン誘導体とした後に一般式(3)で表される1,2-ジオール誘導体を得る工程が好ましい。
一般式(2)で表される(Z)-1,2-ビス(シクロヘキシル)エチレン誘導体を酸化した後、カルボン酸と反応させて一般式(6)

(Wherein R ¹ , R ² , A, B, L, M, m and n have the same meaning as in general formula (2)), and then represented by general formula (3). The step of obtaining a 1,2-diol derivative is preferred.
The (Z) -1,2-bis (cyclohexyl) ethylene derivative represented by the general formula (2) is oxidized and then reacted with a carboxylic acid to give the general formula (6)

(式中、R¹、R²、A、B、L、M、m及びnは一般式(2)と同義であり、R³及びR⁴はそれぞれ独立に水素原子、ホルミル基又は炭素数1〜10のアシル基を表す。)で表される化合物とし、これを加水分解することによって一般式(3)で表される1,2-ジオール誘導体を得る工程が好ましく、一般式（5）で表されるオキシラン誘導体をカルボン酸と反応させて一般式（6）で表される化合物を得る工程を経由することがより好ましい。
本願発明において、一般式(4)で表されるジオキソラン誘導体は、次工程の開裂反応が円滑に進行する限りにおいて制限はないが、一般式(7)

(In the formula, R ¹ , R ² , A, B, L, M, m and n are as defined in the general formula (2), and R ³ and R ⁴ are each independently a hydrogen atom, a formyl group or a carbon number of 1 Is preferably a step of obtaining a 1,2-diol derivative represented by the general formula (3) by hydrolyzing the compound represented by the general formula (5). It is more preferable to pass through the step of obtaining the compound represented by the general formula (6) by reacting the represented oxirane derivative with a carboxylic acid.
In the present invention, the dioxolane derivative represented by the general formula (4) is not limited as long as the cleavage reaction in the next step proceeds smoothly, but the general formula (7)

（式中、R¹、R²、A、B、L、M、m及びnは一般式(2)と同義であり、R⁵及びR⁶はそれぞれ独立に水素原子、置換基を有していても良いフェニル基、1個又は2個の炭素数1〜5のアルキル基で置換されていても良いアミノ基、炭素数1〜５のアルコキシル基、炭素数1〜5のアシルオキシ基又は炭素数1〜3のアルキル基）で表される化合物、一般式(8)

(In the formula, R ¹ , R ² , A, B, L, M, m and n are as defined in the general formula (2), and R ⁵ and R ⁶ each independently have a hydrogen atom or a substituent. A phenyl group which may be substituted, an amino group which may be substituted with one or two alkyl groups having 1 to 5 carbon atoms, an alkoxyl group having 1 to 5 carbon atoms, an acyloxy group having 1 to 5 carbon atoms or a carbon number A compound represented by formula (8):

（式中、R¹、R²、A、B、L、M、m及びnは一般式(2)と同義である。）で表される化合物又は、一般式(9)

(Wherein R ¹ , R ² , A, B, L, M, m and n have the same meanings as in general formula (2)) or general formula (9)

（式中、R¹、R²、A、B、L、M、m及びnは一般式(2)と同義であり、R⁷は炭素数1〜3のアルキル基で置換されていても良いフェニル基を表す。）で表される化合物であることが好ましい。

(In the formula, R ¹ , R ² , A, B, L, M, m and n are as defined in the general formula (2), and R ⁷ may be substituted with an alkyl group having 1 to 3 carbon atoms. It is preferably a compound represented by the following formula:

一般式(2)で表される(Z)-1,2-ビス(シクロヘキシル)エチレン誘導体を酸化して一般式(3)で表されるジオール誘導体を得る方法としては、過オキシ酸を使用することが好ましく、過オキシ酸はカルボン酸を酸化剤を用いて酸化して反応系中で発生させることが好ましい。この際に、カルボン酸としては炭素数1〜10のカルボン酸、トリフルオロ酢酸、o-スルホ安息香酸、フタル酸、コハク酸等が好ましく、ギ酸又は酢酸がより好ましく、ギ酸が特に好ましい。酸化剤としては過酸化水素水が好ましい。酸化剤で処理した後に塩基で処理することにより効率的にジオール誘導体を得ることができる。 As a method of oxidizing the (Z) -1,2-bis (cyclohexyl) ethylene derivative represented by the general formula (2) to obtain the diol derivative represented by the general formula (3), a peroxy acid is used. The peroxyacid is preferably generated in the reaction system by oxidizing the carboxylic acid with an oxidizing agent. In this case, the carboxylic acid is preferably a carboxylic acid having 1 to 10 carbon atoms, trifluoroacetic acid, o-sulfobenzoic acid, phthalic acid, succinic acid or the like, more preferably formic acid or acetic acid, and particularly preferably formic acid. As the oxidizing agent, hydrogen peroxide is preferable. A diol derivative can be obtained efficiently by treating with a base after treating with an oxidizing agent.

一般式(2)で表される(Z)-1,2-ビス(シクロヘキシル)エチレン誘導体を酸化して一般式(5)で表されるオキシラン誘導体を単離する工程も好ましく、その際に使用する酸化剤としては、過酸化水素、過ギ酸、過酢酸、トリフルオロ過酢酸、o-スルホ過安息香酸、過フタル酸、m-クロロ過安息香酸(MCPBA)等が好ましい。 A step of oxidizing the (Z) -1,2-bis (cyclohexyl) ethylene derivative represented by the general formula (2) to isolate the oxirane derivative represented by the general formula (5) is also preferable, and is used at that time. As the oxidizing agent, hydrogen peroxide, performic acid, peracetic acid, trifluoroperacetic acid, o-sulfoperbenzoic acid, perphthalic acid, m-chloroperbenzoic acid (MCPBA) and the like are preferable.

一般式(7)で表されるジオキソラン誘導体を得る方法としては、加熱下でオルトエステルを用いることが好ましく、その様なオルトエステルとしてはギ酸トリメチル、ギ酸トリエチル、酢酸トリメチル、酢酸トリエチルが好ましい。また、置換基を有していても良いベンズアルデヒドを加熱下で用いることも好ましい。また、ジアルキルホルムアミドジアルキルアセタールを加熱下で用いることも好ましく、その様なジアルキルホルムアミドジアルキルアセタールとしてはジメチルホルムアミドジメチルアセタールが好ましい。 As a method for obtaining the dioxolane derivative represented by the general formula (7), it is preferable to use an ortho ester under heating, and as such an ortho ester, trimethyl formate, triethyl formate, trimethyl acetate, and triethyl acetate are preferable. Moreover, it is also preferable to use the benzaldehyde which may have a substituent under a heating. It is also preferable to use a dialkylformamide dialkyl acetal under heating, and as such a dialkylformamide dialkyl acetal, dimethylformamide dimethyl acetal is preferable.

一般式(7)においてR5及びR6はそれぞれ独立的に、水素原子、メチル基、メトキシ基又はアセチルオキシ基を表すことが好ましく、少なくとも一方は水素原子を表すことがより好ましい。 In the general formula (7), R5 and R6 each independently preferably represent a hydrogen atom, a methyl group, a methoxy group or an acetyloxy group, and more preferably at least one represents a hydrogen atom.

一般式(8)で表されるジオキソラン誘導体を得る方法としてはチオカルボニル化合物を用いることが好ましく、その様なチオカルボニル化合物としてチオカルボニルジイミダゾールが好ましい。 As a method for obtaining the dioxolane derivative represented by the general formula (8), a thiocarbonyl compound is preferably used, and thiocarbonyldiimidazole is preferable as such a thiocarbonyl compound.

一般式(9)で表されるジオキソラン誘導体を得る方法としてはホスゲンインモニウムクロリドを作用させた後、ベンゼンスルホニルヒドラジン誘導体を作用させることが好ましく、その様なベンゼンスルホニルヒドラジン誘導体としてトシルヒドラジンが好ましい。 As a method for obtaining the dioxolane derivative represented by the general formula (9), it is preferable to act on phosgene imonium chloride and then to act on a benzenesulfonylhydrazine derivative, and tosylhydrazine is preferred as such a benzenesulfonylhydrazine derivative.

ジオキソラン誘導体から一般式(1)で表される(E)-1,2-ビス(シクロヘキシル)エチレン誘導体を得る方法としては、ジオキソラン誘導体を熱分解する方法、塩基の作用により開裂する方法等を好ましく挙げることができるが、ジオキソラン誘導体の種類によって適時選択すれば良い。 As a method for obtaining the (E) -1,2-bis (cyclohexyl) ethylene derivative represented by the general formula (1) from the dioxolane derivative, a method of thermally decomposing the dioxolane derivative, a method of cleaving by the action of a base, or the like is preferable. Although it may be mentioned, it may be selected as appropriate depending on the type of dioxolane derivative.

一般式(7)で表されるジオキソラン誘導体から一般式(1)で表される(E)-1,2-ビス(シクロヘキシル)エチレン誘導体を得る方法としては、ジオキソラン誘導体を熱分解することにより一般式(1)で表される(E)-1,2-ビス(シクロヘキシル)エチレン誘導体を得ることが好ましい。その際に使用する溶媒としては無水酢酸を用いることが好ましい。また、一般式(7)で表されるジオキソラン誘導体から一般式(1)で表される(E)-1,2-ビス(シクロヘキシル)エチレン誘導体を得る他の方法としては、アルキルリチウムを作用させることも好ましく挙げることができ、その様なアルキルリチウムとしてはブチルリチウム、フェニルリチウムが好ましい。 As a method for obtaining the (E) -1,2-bis (cyclohexyl) ethylene derivative represented by the general formula (1) from the dioxolane derivative represented by the general formula (7), it is generally possible to thermally decompose the dioxolane derivative. It is preferable to obtain an (E) -1,2-bis (cyclohexyl) ethylene derivative represented by the formula (1). Acetic anhydride is preferably used as the solvent used in that case. As another method of obtaining the (E) -1,2-bis (cyclohexyl) ethylene derivative represented by the general formula (1) from the dioxolane derivative represented by the general formula (7), alkyllithium is allowed to act. The alkyl lithium is preferably butyl lithium or phenyl lithium.

一般式(8)で表されるジオキソラン誘導体から一般式(1)で表される(E)-1,2-ビス(シクロヘキシル)エチレン誘導体を得る方法としては、ジオキソラン誘導体を熱分解することにより一般式(1)で表される(E)-1,2-ビス(シクロヘキシル)エチレン誘導体を得ることが好ましい。その際に使用する溶媒としては亜りん酸エステルを用いることが好ましく、その様な亜りん酸エステルとして、亜りん酸トリメチル、亜りん酸トリエチル、亜りん酸トリイソオクチルが好ましい。 As a method for obtaining the (E) -1,2-bis (cyclohexyl) ethylene derivative represented by the general formula (1) from the dioxolane derivative represented by the general formula (8), it is generally possible to thermally decompose the dioxolane derivative. It is preferable to obtain an (E) -1,2-bis (cyclohexyl) ethylene derivative represented by the formula (1). A phosphite ester is preferably used as the solvent used at that time, and as such a phosphite ester, trimethyl phosphite, triethyl phosphite, and triisooctyl phosphite are preferable.

一般式(9)で表されるジオキソラン誘導体から一般式(1)で表される(E)-1,2-ビス(シクロヘキシル)エチレン誘導体を得る方法としては、ジオキソラン誘導体に塩基を作用させた後、熱分解することにより一般式(1)で表される(E)-1,2-ビス(シクロヘキシル)エチレン誘導体を得ることが好ましい。その際に使用する塩基としては水素化ナトリウムが好ましい。 As a method for obtaining the (E) -1,2-bis (cyclohexyl) ethylene derivative represented by the general formula (1) from the dioxolane derivative represented by the general formula (9), a base is allowed to act on the dioxolane derivative. It is preferable to obtain (E) -1,2-bis (cyclohexyl) ethylene derivative represented by the general formula (1) by thermal decomposition. As a base used in this case, sodium hydride is preferable.

本願発明の製造方法は、一般式（1）で表される化合物の製造を効率的に行うことができるが、その置換基の差により次に記載する置換基を有する場合により効率的に製造を実施することができる。 The production method of the present invention can efficiently produce the compound represented by the general formula (1). However, due to the difference in substituents, the production method is more efficient when it has the following substituents. Can be implemented.

一般式(1)において、L及びMは、それぞれ独立して単結合であることが好ましく、L及びMが共に単結合であることがより好ましい。A及びBは、それぞれ独立的にトランス-1,4-シクロへキシレン基、又は1個以上のハロゲン原子により置換されていてもよい1,4-フェニレン基であることが好ましい、ｍ及びnは少なくとも一方が0であることが好ましく、共に0であることがより好ましい。 In the general formula (1), L and M are preferably each independently a single bond, and more preferably L and M are both a single bond. A and B are each independently preferably a trans-1,4-cyclohexylene group or a 1,4-phenylene group optionally substituted by one or more halogen atoms, and m and n are At least one of them is preferably 0, more preferably 0.

以下、実施例を挙げて本発明を更に詳述するが、本発明はこれらの実施例に限定されるものではない。
（実施例1）
(E)-1,2-ビス(トランス-4-プロピルシクロヘキシル)エチレンの合成 EXAMPLES Hereinafter, although an Example is given and this invention is further explained in full detail, this invention is not limited to these Examples.
(Example 1)
Synthesis of (E) -1,2-bis (trans-4-propylcyclohexyl) ethylene

特許文献１と同様にしてトランス-4-プロピルシクロヘキサンカルバルデヒド(196.2g)とトランス-4-プロピルシクロヘキシルメチルトリフェニルホスホニウムブロミド(673.7g)とから1,2-ビス(トランス-4-プロピルシクロヘキシル)エチレン(313.4g)を得た。本品における(E)-1,2-ビス(トランス-4-プロピルシクロヘキシル)エチレン(以下(E)-体と呼ぶ)と(Z)-1,2-ビス(トランス-4-プロピルシクロヘキシル)エチレン(以下(Z)-体と呼ぶ)との比は5:95であり、以下本品を(Z)-体とみなして扱った。
ギ酸2000mLに30%過酸化水素水186.5gを加え38℃に加温し、(Z)-体の303.4gを系内が50℃以下を保つように滴下し、更に45〜50℃で9時間攪拌した。室温まで冷却し、水500mLを加え暫時攪拌後、トルエンで抽出を行った。分離した有機層を水、飽和亜硫酸水素ナトリウム水溶液、水、飽和重曹水、飽和食塩水の順に洗浄し、無水硫酸ナトリウムで乾燥後、減圧下に濃縮し、423.32gの固体状の反応混合物を得た。得られた反応混合物の全量を、室温下に激しく攪拌しながらエタノール500mLに分散させ、ここに30%水酸化ナトリウム水溶液600gを加え、2時間激しく攪拌した。次いで、氷浴上で濃塩酸400mLを反応液が40℃以下を保つように加え、系を酸性にした。白色の析出物を濾別し、これをテトラヒドロフラン(THF)1500mLとトルエン100mLの混合溶媒に溶解した。水層を分離し、有機層を飽和食塩水で中性になるまで洗浄し、無水硫酸ナトリウムで乾燥後、減圧下に濃縮し、337.6gの1,2-ビス(trans-4-プロピルシクロヘキシル)-1,2-エタンジオールを得た。 1,2-bis (trans-4-propylcyclohexyl) from trans-4-propylcyclohexanecarbaldehyde (196.2 g) and trans-4-propylcyclohexylmethyltriphenylphosphonium bromide (673.7 g) in the same manner as in Patent Document 1. Ethylene (313.4 g) was obtained. (E) -1,2-bis (trans-4-propylcyclohexyl) ethylene (hereinafter referred to as (E) -isomer) and (Z) -1,2-bis (trans-4-propylcyclohexyl) ethylene in this product (Hereinafter referred to as (Z) -body) was 5:95. Hereinafter, this product was treated as (Z) -body.
Add 186.5 g of 30% hydrogen peroxide solution to 2000 mL of formic acid and warm to 38 ° C. Add 303.4 g of (Z) -form dropwise so that the system is kept at 50 ° C or less, and further at 45-50 ° C for 9 hours Stir. After cooling to room temperature, 500 mL of water was added and stirred for a while, followed by extraction with toluene. The separated organic layer was washed with water, saturated aqueous sodium hydrogensulfite solution, water, saturated aqueous sodium bicarbonate, and saturated brine in that order, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain 423.32 g of a solid reaction mixture. It was. The total amount of the obtained reaction mixture was dispersed in 500 mL of ethanol while stirring vigorously at room temperature, and 600 g of a 30% aqueous sodium hydroxide solution was added thereto, followed by vigorous stirring for 2 hours. Next, 400 mL of concentrated hydrochloric acid was added on an ice bath so that the reaction solution kept at 40 ° C. or lower, and the system was acidified. The white precipitate was filtered off and dissolved in a mixed solvent of tetrahydrofuran (THF) 1500 mL and toluene 100 mL. The aqueous layer was separated, and the organic layer was washed with saturated brine until neutral, dried over anhydrous sodium sulfate, and concentrated under reduced pressure, 337.6 g of 1,2-bis (trans-4-propylcyclohexyl) -1,2-ethanediol was obtained.

得られた1,2-ビス(trans-4-プロピルシクロヘキシル)-1,2-エタンジオールの全量とオルトギ酸トリメチル1000mLと濃塩酸2mLを混合し、2時間還流した。冷却後、過剰のオルトギ酸トリメチルを減圧下に留去し、黄色油状の2-メトキシ-4,5-ジ(トランス-4-プロピルシクロヘキシル)-1,3-ジオキサン粗生成物400.4gを得た。
得られた粗生成物と無水酢酸1200mLを混合し、5時間還流した。室温まで冷却し、ヘキサンで抽出を行った。分離した有機層を水、飽和重曹水、飽和食塩水の順に洗浄し、無水硫酸ナトリウムで乾燥後、濃縮し、301.4gの反応混合物を得た。本反応混合物における(E)-体と(Z)-体の比は95:5であった。
次いでシリカゲルカラムクロマトグラフィー(溶媒：ヘキサン)を行った後、アセトンから再結晶させ、243.1gの(E)-1,2-ビス(トランス-4-プロピルシクロヘキシル)エチレンを得た。
結晶-スメクチック相転移温度は37℃、スメクチック-ネマチック相転移温度は53℃、ネマチック-等方相転移温度は69℃であった。 The total amount of 1,2-bis (trans-4-propylcyclohexyl) -1,2-ethanediol obtained, 1000 mL of trimethyl orthoformate and 2 mL of concentrated hydrochloric acid were mixed and refluxed for 2 hours. After cooling, excess trimethyl orthoformate was distilled off under reduced pressure to obtain 400.4 g of a crude oily 2-methoxy-4,5-di (trans-4-propylcyclohexyl) -1,3-dioxane as a yellow oil. .
The obtained crude product and 1200 mL of acetic anhydride were mixed and refluxed for 5 hours. The mixture was cooled to room temperature and extracted with hexane. The separated organic layer was washed with water, saturated aqueous sodium hydrogen carbonate and saturated brine in that order, dried over anhydrous sodium sulfate, and concentrated to obtain 301.4 g of a reaction mixture. The ratio of (E) -form to (Z) -form in this reaction mixture was 95: 5.
Subsequently, after silica gel column chromatography (solvent: hexane), recrystallization from acetone gave 243.1 g of (E) -1,2-bis (trans-4-propylcyclohexyl) ethylene.
The crystal-smectic phase transition temperature was 37 ° C, the smectic-nematic phase transition temperature was 53 ° C, and the nematic-isotropic phase transition temperature was 69 ° C.

(実施例2)
実施例１と同様にして(E)-1,2-ビス(トランス-4-エチルシクロヘキシル)エチレンを合成した。
結晶-等方相転移温度は35℃であった。
(実施例3)
実施例１と同様にして(E)-1,2-ビス(トランス-4-ブチルシクロヘキシル)エチレンを合成した。
結晶-スメクチック相転移温度は59℃、スメクチック-等方相転移温度は85℃であった。
(実施例4)
実施例１と同様にして(E)-1,2-ビス(トランス-4-ペンチルシクロヘキシル)エチレンを合成した。
結晶-スメクチック相転移温度は54℃、スメクチック-等方相転移温度は99℃であった。

(Example 2)
In the same manner as in Example 1, (E) -1,2-bis (trans-4-ethylcyclohexyl) ethylene was synthesized.
The crystal-isotropic phase transition temperature was 35 ° C.
(Example 3)
In the same manner as in Example 1, (E) -1,2-bis (trans-4-butylcyclohexyl) ethylene was synthesized.
The crystal-smectic phase transition temperature was 59 ° C, and the smectic-isotropic phase transition temperature was 85 ° C.
(Example 4)
In the same manner as in Example 1, (E) -1,2-bis (trans-4-pentylcyclohexyl) ethylene was synthesized.
The crystal-smectic phase transition temperature was 54 ° C, and the smectic-isotropic phase transition temperature was 99 ° C.

Claims

General formula (2)

(In the formula, R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or 2 carbon atoms. Represents an alkenyloxy group having ˜20, which may be substituted by an alkoxyl group having 1 to 7 carbon atoms or a halogen atom having 1 to 7 carbon atoms, and A and B are each independently trans-1,4-cyclohexane 1,4-phenylene group, pyridine-2,5-diyl group, pyrimidine optionally substituted by xylene group, bicyclo [2.2.2] octane-1,4-diyl group, or one or more halogen atoms -2,5-diyl group, pyrazine-2,5-diyl group, pyridazine-3,6-diyl group, trans-1,3-dioxane-2,5-diyl group, transdecahydronaphthalene-2,6- Diyl group, tetrahydronaphthalene-2,6-diyl group, naphthalene-2,6-diyl group, L and M are each -CH ₂ on standing _{_{-, - CH 2 CH 2 -}} , - CH 2 CH 2 CH 2 CH 2 -, - CH (CH 3) CH 2 -, - CH 2 CH (CH 3) -, - CF = CF- , -CH ₂ O-, -OCH _2- , -CF ₂ O-, -OCF ₂ -or a single bond, and m and n each independently represent 0 or 1). By oxidizing 1,2-bis (cyclohexyl) ethylene derivative, the general formula (3)

(Wherein R ¹ , R ² , A, B, L, M, m and n have the same meanings as those in formula (2)) (E) -1,2-bis (cyclohexyl) ethylene A method for producing a derivative.

In obtaining the 1,2-diol derivative represented by the general formula (3) from the (Z) -1,2-bis (cyclohexyl) ethylene derivative represented by the general formula (2), it is represented by the general formula (2). (Z) -1,2-bis (cyclohexyl) ethylene derivative produced by oxidation is represented by the general formula (5)

(Wherein R ¹ , R ² , A, B, L, M, m and n have the same meanings as in general formula (2)), and then represented by general formula (3) The process according to claim 1, wherein a 1,2-diol derivative is obtained.

In obtaining the 1,2-diol derivative represented by the general formula (3) from the (Z) -1,2-bis (cyclohexyl) ethylene derivative represented by the general formula (2), it is represented by the general formula (2). (Z) -1,2-bis (cyclohexyl) ethylene derivative is oxidized and then reacted with carboxylic acid to give a general formula (6)

(In the formula, R ¹ , R ² , A, B, L, M, m and n are as defined in the general formula (2), and R ³ and R ⁴ are each independently a hydrogen atom, a formyl group or a carbon number of 1 3. The production method according to claim 1, wherein the 1,2-diol derivative represented by the general formula (3) is obtained by hydrolyzing the compound represented by:

4. The production method according to claim 2, wherein the oxidation method is peroxy acid.

The dioxolane derivative has the general formula (7)

(In the formula, R ¹ , R ² , A, B, L, M, m and n are as defined in the general formula (2), and R ⁵ and R ⁶ each independently have a hydrogen atom or a substituent. A phenyl group which may be substituted, an amino group which may be substituted with one or two alkyl groups having 1 to 5 carbon atoms, an alkoxyl group having 1 to 5 carbon atoms, an acyloxy group having 1 to 5 carbon atoms or a carbon number The method according to any one of claims 1 to 4, which is a compound represented by 1 to 3 alkyl groups).

^6. The production method according to claim 5, wherein R ⁵ is a methoxy group and R ⁶ is a hydrogen atom in the general formula (7).

^6. The production method according to claim ^5, wherein R ⁵ is an acetyloxy group and R ⁶ is a hydrogen atom in the general formula (7).

The dioxolane derivative has the general formula (8)

5. The compound represented by any one of claims 1 to 4, wherein R ¹ , R ² , A, B, L, M, m, and n are the same as those in the general formula (2). Manufacturing method.

The dioxolane derivative has the general formula (9)

(In the formula, R ¹ , R ² , A, B, L, M, m and n are as defined in the general formula (2), and R ⁷ may be substituted with an alkyl group having 1 to 3 carbon atoms. The production method according to any one of claims 1 to 4, which is a compound represented by the formula:

In obtaining an (E) -1,2-bis (cyclohexyl) ethylene derivative represented by the general formula (1) from a dioxolane derivative, the dioxolane derivative is thermally decomposed to represent (E)- 10. The production method according to any one of claims 1 to 9, wherein a 1,2-bis (cyclohexyl) ethylene derivative is obtained.

10. The production method according to any one of claims 1 to 9, wherein in the general formula (1), L or M is a single bond.

In the general formula (1), A or B is a trans-1,4-cyclohexylene group or a 1,4-phenylene group optionally substituted by one or more halogen atoms. The manufacturing method in any one.

10. The production method according to claim 1, wherein m or n is 0 in the general formula (1).

General formula (7)

(In the formula, R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or 2 carbon atoms. Represents an alkenyloxy group having ˜20, which may be substituted by an alkoxyl group having 1 to 7 carbon atoms or a halogen atom having 1 to 7 carbon atoms, and A and B are each independently trans-1,4-cyclohexane 1,4-phenylene group, pyridine-2,5-diyl group, pyrimidine optionally substituted by xylene group, bicyclo [2.2.2] octane-1,4-diyl group, or one or more halogen atoms -2,5-diyl group, pyrazine-2,5-diyl group, pyridazine-3,6-diyl group, trans-1,3-dioxane-2,5-diyl group, transdecahydronaphthalene-2,6- Diyl group, tetrahydronaphthalene-2,6-diyl group, naphthalene-2,6-diyl group, L and M are each independently -CH ₂ on standing _{_{-, - CH 2 CH 2 -}} , - CH 2 CH 2 CH 2 CH 2 -, - CH (CH 3) CH 2 -, - CH 2 CH (CH 3) -, - CF = CF- , -CH ₂ O-, -OCH _2- , -CF ₂ O-, -OCF ₂ -or a single bond, m and n each independently represent 0 or 1, and R ⁵ and R ⁶ each independently A hydrogen atom, a phenyl group, an amino group optionally substituted with one or two alkyl groups having 1 to 5 carbon atoms, an alkoxyl group having 1 to 5 carbon atoms, an acyloxy group having 1 to 5 carbon atoms, or a carbon number A dioxolane derivative represented by 1 to 3 alkyl groups).

15. The dioxolane derivative according to claim 14 , wherein R ⁵ is a methoxy group and R ⁶ is a hydrogen atom in the general formula (7).

15. The dioxolane derivative according to claim 14 , wherein R ⁵ is an acetyloxy group and R ⁶ is a hydrogen atom in the general formula (7).

General formula (8)

(In the formula, R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or 2 carbon atoms. Represents an alkenyloxy group having ˜20, which may be substituted by an alkoxyl group having 1 to 7 carbon atoms or a halogen atom having 1 to 7 carbon atoms, and A and B are each independently trans-1,4-cyclohexane 1,4-phenylene group, pyridine-2,5-diyl group, pyrimidine optionally substituted by xylene group, bicyclo [2.2.2] octane-1,4-diyl group, or one or more halogen atoms -2,5-diyl group, pyrazine-2,5-diyl group, pyridazine-3,6-diyl group, trans-1,3-dioxane-2,5-diyl group, transdecahydronaphthalene-2,6- Diyl group, tetrahydronaphthalene-2,6-diyl group, naphthalene-2,6-diyl group, L and M are each -CH ₂ on standing _{_{-, - CH 2 CH 2 -}} , - CH 2 CH 2 CH 2 CH 2 -, - CH (CH 3) CH 2 -, - CH 2 CH (CH 3) -, - CF = CF- , -CH ₂ O-, -OCH _2- , -CF ₂ O-, -OCF ₂ -or a single bond, and m and n each independently represents 0 or 1.