KR101308544B1 - Polymerizable mesogens or liquid crystal compounds and preparation methods thereof - Google Patents
Polymerizable mesogens or liquid crystal compounds and preparation methods thereofDownload PDFInfo
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Abstract
Translated fromKorean
Description
Translated fromKorean본 발명은 중합성 메조겐 또는 액정 화합물 및 이의 제조 방법에 관한 것이다.
The present invention relates to a polymerizable mesogen or a liquid crystal compound and a method for producing the same.
워드프로세서나 노트북, PC 용 모니터 등의 OA 기기, 휴대 단말, 텔레비전 등에 사용되는 표시 장치로서는, CRT(Cathode Ray Tube)가 지금까지 주로 사용되어 왔다. 그러나, 최근에 액정 표시 장치(LCD)가 CRT에 비하여 저소비 전력으로 인해 배터리로 수 시간 구동할 수 있고, 부피가 적어 차지하는 공간이 좁으며, 무게가 가벼워 휴대가 용이한 점 등의 이유로 빠른 속도로 보급이 확산되고 있다. 상기 액정 표시 장치(LCD)는 액정 셀 및 편광판을 가진다. 편광판은 보호 필름 및 편광막으로 이루어져있고, 이는 폴리비닐알코올 필름으로 이루어지는 편광막을 요오드로 염색하고, 연신을 실시하여 양면을 보호 필름으로 적층하여 제조할 수 있다. 예를 들어, 투과형 LCD에서는, 상기 편광판을 액정 셀의 양측에 장착하고, 나아가서는 1 장 이상의 광학 이방성층을 갖는 광학 보상 시트를 배치하는 경우도 있다. 한편, 반사형 LCD에서는 반사판, 액정 셀, 1 장 이상의 광학 보상 시트, 및 편광판의 순서대로 배치한다. 액정 셀은 액정 분자, 그것을 봉입하기 위한 2 장의 기판 및 액정 분자에 전압을 가하기 위한 전극층으로 이루어진다. 액정 셀은 액정 분자의 배향 상태의 차이로 ON, OFF 표시를 실시하고, 투과형 및 반사형 중 어느 것에도 적용할 수 있어, TN(Twisted Nematic), IPS(In-Plane Switching), OCB(Optically Compensatory Bend), VA(Vertically Aligned), ECB(Electrically Controlled Birefringence), STN(Super Twisted Nematic)과 같은 다양한 액정 모드의 디스플레이가 개발되고 있다. 이들 각각의 모드는 고유한 액정 배열을 하고 있으며, 고유한 광학 이방성을 갖고 있다. 따라서, 이들 액정 모드의 광학 이방성으로 인해 선형 편광된 빛의 광축의 변화를 보상하기 위해서는 다양한 광학 이방성의 보상 필름이 요구되고 있는 실정이다.
CRT (Cathode Ray Tube) has been mainly used as a display device used for OA devices such as word processors, notebook computers, PC monitors, portable terminals, televisions, and the like. Recently, however, liquid crystal displays (LCDs) can be driven by batteries for hours due to lower power consumption than CRTs, and have a small volume, a small space, and a low weight, making them portable. The spread is spreading. The liquid crystal display (LCD) has a liquid crystal cell and a polarizing plate. The polarizing plate consists of a protective film and a polarizing film, which can be produced by dyeing a polarizing film made of a polyvinyl alcohol film with iodine, stretching, and laminating both sides with a protective film. For example, in a transmissive LCD, the polarizing plate may be mounted on both sides of the liquid crystal cell, and further, an optical compensation sheet having one or more optically anisotropic layers may be disposed. On the other hand, in a reflective LCD, a reflective plate, a liquid crystal cell, at least one optical compensation sheet, and a polarizing plate are arranged in this order. A liquid crystal cell is composed of a liquid crystal molecule, two substrates for sealing it, and an electrode layer for applying a voltage to the liquid crystal molecules. The liquid crystal cell performs ON and OFF display due to the difference in the alignment state of the liquid crystal molecules, and can be applied to any of the transmission type and the reflection type, so that TN (Twisted Nematic), IPS (In-Plane Switching) and OCB (Optically Compensatory) Displays of various liquid crystal modes such as Bend), Vertically Aligned (VA), Electrically Controlled Birefringence (ECB), and Super Twisted Nematic (STN) are being developed. Each of these modes has a unique liquid crystal array and has inherent optical anisotropy. Therefore, in order to compensate for the change in the optical axis of linearly polarized light due to the optical anisotropy of these liquid crystal modes, various optical anisotropy compensation films are required.
액정 모드의 광학 이방성을 보상하기 위하여 중합성기를 가지는 액정을 편광판이나 위상차판 등의 광학 소자에 응용할 수 있다. 이러한 광학 소자는 광학 이방성을 가지는 중합성 액정을 액정상태에서 중합하고 그 상태를 고정화함으로써 얻을 수 있고 상기 중합성 액정은 액정상태에서 적절한 배향 제어를 행한 뒤 배향상태를 유지하며 중합시킬 수 있다. 따라서, 액정 골격의 배향 상태를 호모지니어스 배향, 하이브리드 배향, 경사배향, 호메오트로픽 배향 또는 트위스트 배향 등의 상태로 고정화하는 것에 의해 여러 가지의 광학 이방성을 가지는 중합체를 얻을 수 있다.In order to compensate the optical anisotropy of the liquid crystal mode, a liquid crystal having a polymerizable group can be applied to optical elements such as polarizing plates and retardation plates. Such an optical element can be obtained by polymerizing a polymerizable liquid crystal having optical anisotropy in a liquid crystal state and fixing the state, and the polymerizable liquid crystal can be polymerized while maintaining an alignment state after performing proper alignment control in the liquid crystal state. Therefore, the polymer which has various optical anisotropy can be obtained by fixing the orientation state of a liquid crystal frame to states, such as homogeneous orientation, hybrid orientation, diagonal orientation, homeotropic orientation, or twist orientation.
상기 호모지니어스 배향을 가지는 중합체는 예를 들면 1/2 파장판, 1/4 파장판, 또는 다른 광학기능을 가지는 필름과 조합하여 사용할 수 있고, 하이브리드 배향을 가지는 중합체는 TN 모드용 시야각 보상판으로 응용할 수 있다. 또한, 호메오트로픽 배향을 가지는 중합체는 다른 광학기능을 가지는 필름과 조합하여 편광판의 시야각 특성을 개선할 수 있고, 광축의 방향이 nz 방향에 있고 광축 방향의 굴절율이 직교하는 방향의 굴절율보다 크면 굴절율 타원체에서는 포지티브 c-플레이트로 분류된다. 상기 포지티브 c-플레이트는 다른 광학기능을 가지는 필름과의 조합으로 수평 배향한 액정 디스플레이 모드인 IPS 모드(In-plane Switching mode)등의 광학 보상, 특히 편광판의 시야각 특성의 개선용에 응용할 수 있다. 또한 호스트 액정, 중합성 액정, 또는 중합성 메조겐 또는 액정 화합물을 혼합한 후 액정 셀을 제작하고 전기장을 인가한 상태에서 자외선 중합하여 기존의 PVA 모드(Patterned Vertically Aligned mode) 또는 MVA 모드(Multi Domain Vertically Aligned Mode)의 빛샘 현상 및 응답속도 저하를 극복할 수 있는 신규 모드용 중합체로 PS-VA 모드(Polymer Sustainable Vertically Aligned mode)에 응용할 수 있다.
The homogenous alignment polymer may be used in combination with, for example, a half wave plate, a quarter wave plate, or a film having another optical function, and the polymer having a hybrid alignment may be used as a viewing angle compensation plate for TN mode. It can be applied. In addition, the polymer having a homeotropic orientation can improve the viewing angle characteristic of the polarizing plate in combination with a film having other optical functions, and the refractive index is higher when the direction of the optical axis is in the nz direction and the refractive index in the optical axis direction is larger than the refractive index in the orthogonal direction. Ellipsoids are classified as positive c-plates. The positive c-plate may be applied to optical compensation such as IPS mode (In-plane Switching mode), which is a liquid crystal display mode that is horizontally aligned in combination with a film having other optical functions, and particularly for improving viewing angle characteristics of a polarizing plate. In addition, a host liquid crystal, a polymerizable liquid crystal, or a polymerizable mesogen or a liquid crystal compound is mixed, and then a liquid crystal cell is manufactured and UV-polymerized while applying an electric field, thereby making it known as a conventional vertically aligned (PVA) mode or a multi-domain (MVA) mode. It is a new mode polymer that can overcome the light leakage phenomenon and the degradation of response of Vertically Aligned Mode. It can be applied to PS-VA mode (Polymer Sustainable Vertically Aligned mode).
상기와 같은 액정표시장치를 구성하는 액정 디스플레이 모드 및/또는 이에 필요한 광학 이방성을 갖는 중합성 필름은 요구 성능에 따라 원반형 구조 또는 막대형 구조의 중합성 액정 또는 중합성 메조겐 화합물로부터 선택이 가능하다.The polymerizable film having the liquid crystal display mode and / or optical anisotropy necessary for constituting the liquid crystal display device as described above may be selected from a polymerizable liquid crystal or a polymerizable mesogenic compound having a disc structure or a rod structure according to the required performance. .
상기 중합성 액정 조성물은 네마틱 상을 가지고 배향성이 균일해야 하며 용도에 따른 배향 형태를 달리할 수 있어야 한다. 또한, 중합 후에는 기판과의 밀착성, 광학 이방성, 투명성 및 좋은 내후성을 가져야 광학 이방성을 가지는 필름을 제조할 수 있다.
The polymerizable liquid crystal composition should have a nematic phase and have a uniform orientation and be able to vary an orientation form according to a use. In addition, after polymerization, a film having optical anisotropy can be produced only by adhesion to the substrate, optical anisotropy, transparency and good weather resistance.
이에, 본 발명자는 복굴절 0.1 내지 0.15의 값을 가지고 투명하며 유기 용매에 대한 용해도가 우수하고 다른 중합성 물질과의 상용성 또한 우수한 화합물을 개발하고 이로부터 제조된 중합성 액정 조성물 및 고분자 필름은 광학 이방 특성 및 좋은 내후성을 가져 액정 디스플레이용 광학 필름 부재로 사용될 수 있음을 발견하여 본 발명을 완성하였다.
Accordingly, the present inventors have developed a compound having a value of 0.1 to 0.15 of birefringence, a compound having excellent solubility in organic solvents and excellent compatibility with other polymerizable materials, and the polymerizable liquid crystal composition and polymer film prepared therefrom are optical The present invention has been completed by discovering that it can be used as an optical film member for a liquid crystal display having anisotropic properties and good weather resistance.
본 발명의 목적은 중합성 메조겐 또는 액정 화합물을 제공하는 데 있다.An object of the present invention is to provide a polymerizable mesogen or a liquid crystal compound.
본 발명의 다른 목적은 상기 화합물의 제조방법을 제공하는 데 있다.Another object of the present invention is to provide a method for preparing the compound.
본 발명의 또 다른 목적은 상기 화합물을 포함하는 중합성 액정 조성물을 제공하는 데 있다.Another object of the present invention to provide a polymerizable liquid crystal composition comprising the compound.
본 발명의 다른 목적은 상기 화합물의 중합체를 포함하는 고분자 필름을 제공하는 데 있다.
Another object of the present invention is to provide a polymer film comprising a polymer of the compound.
상기 목적을 달성하기 위하여, 본 발명은 하기 화학식 1로 표시되는 화합물을 제공한다:In order to achieve the above object, the present invention provides a compound represented by the following formula (1)
[화학식 1][Formula 1]
(상기 Ar, A, R, X, Y 및 n은 본 명세서에서 기재한 바와 같다.).(Ar, A, R, X, Y and n are as described herein.)
또한, 본 발명은 상기 화합물의 제조방법을 제공한다.The present invention also provides a method for preparing the compound.
나아가, 본 발명은 상기 화합물을 포함하는 중합성 액정 조성물을 제공한다.Furthermore, this invention provides the polymeric liquid crystal composition containing the said compound.
또한, 본 발명은 상기 화합물의 중합체를 포함하는 고분자 필름을 제공한다.
The present invention also provides a polymer film comprising the polymer of the compound.
본 발명에 따른 화학식 1의 아세틸렌기가 도입된 화합물은 복굴절 0.1 내지 0.15의 값을 가지고 투명하며 유기 용매에 대한 용해도가 우수하고 다른 중합성 물질과의 상용성 또한 우수하므로 중합성 액정 조성물 성분으로 유용하게 사용될 수 있고, 상기 액정 조성물을 사용하여 제조한 고분자 필름은 광학 이방 특성 및 좋은 내후성을 가지므로 액정 디스플레이용 광학 필름 부재로 유용하게 사용될 수 있다.
The compound in which the acetylene group of Formula 1 is introduced according to the present invention has a value of 0.1 to 0.15 of birefringence, is transparent, has excellent solubility in organic solvents, and is excellent in compatibility with other polymerizable materials, and thus is useful as a polymerizable liquid crystal composition component. The polymer film prepared using the liquid crystal composition may be used as an optical film member for a liquid crystal display because it has optical anisotropy and good weather resistance.
도 1은 본 발명의 일실시예에 따른 중합성 액정 화합물의 UV-vis 스펙트럼 결과이다.
도 2는 본 발명의 일실시예에 따른 중합성 액정 화합물의 네마틱 액상을 편광 현미경 사진(POM)이다.
도 3은 본 발명의 일실시예에 따른 중합성 액정 화합물을 배향하고 필름화 한 후 편광 광학 현미경으로 관찰한 사진이다.
도 4는 본 발명의 일실시예에 따른 중합성 액정 화합물을 필름화 한 후 광탄성 변조기(PEM)로 빛의 투과도를 측정한 결과이다.1 is a UV-vis spectrum result of a polymerizable liquid crystal compound according to an embodiment of the present invention.
2 is a polarization micrograph (POM) of the nematic liquid phase of the polymerizable liquid crystal compound according to the exemplary embodiment of the present invention.
3 is a photograph observed by polarizing optical microscope after the alignment and film formation of the polymerizable liquid crystal compound according to an embodiment of the present invention.
4 is a result of measuring the light transmittance with a photoelastic modulator (PEM) after filming the polymerizable liquid crystal compound according to an embodiment of the present invention.
이하, 본 발명을 상세히 설명한다.
Hereinafter, the present invention will be described in detail.
본 발명은 하기 화학식 1로 표시되는 화합물을 제공한다.The present invention provides a compound represented by the following formula (1).
상기 화학식 1에서,In Formula 1,
Ar은 C6~C30의 방향족 또는 비방향족의 고리화합물이고, 이때 상기 방향족 또는 비방향족의 고리화합물은 비치환되거나 1 내지 5개의 할로겐 또는 C1~C8의 직쇄, 측쇄 또는 고리형 알킬로 치환되며;Ar is a C6 to C30 aromatic or non-aromatic cyclic compound, wherein the aromatic or non-aromatic cyclic compound is unsubstituted or substituted with 1 to 5 halogens or C1 to C8 straight, branched or cyclic alkyl. Substituted;
A는
R은 C1~C20의 알킬렌이고, 상기 알킬렌기 중 1 이상의 메틸렌기는 O, S 또는 CF2로 치환될 수 있고, 이때 하나 이상의 O 또는 S는 서로 인접하지 않고;R is C1 to C20 alkylene, wherein at least one methylene group in the alkylene group may be substituted with O, S or CF2 , wherein at least one O or S is not adjacent to each other;
X는 -CH2-, -O-, -S-, -NH- 또는 -CO2-이고;X is -CH2- , -O-, -S-, -NH- or -CO2- ;
Y는
n은 2 내지 6의 정수이다.
n is an integer of 2-6.
바람직하게, 상기 Ar은 C6~C30의 방향족 또는 비방향족의 고리화합물로서, 예를 들면 페닐렌, 플루오렌, 트리페닐렌, 코로넨 등이 될 수 있고, 이때 상기 방향족 또는 비방향족의 고리화합물은 비치환되거나 1 이상의 F, Cl, Br 또는 메틸, 에틸, 프로필, 이소프로필, 부틸로 치환될 수 있다.
Preferably, Ar is a C6 ~ C30 aromatic or non-aromatic cyclic compound, for example, may be phenylene, fluorene, triphenylene, coronene, etc., wherein the aromatic or non-aromatic ring The compound may be unsubstituted or substituted with one or more F, Cl, Br or methyl, ethyl, propyl, isopropyl, butyl.
더욱 바람직하게는,More preferably,
상기 Ar은
A는
R은 C1~C12의 알킬렌이고, 상기 알킬렌기 중 1 이상의 메틸렌기는 O 또는 S로 치환될 수 있고, 이때 1 이상의 O 또는 S는 서로 인접하지 않아야 하고;R is C1 to C12 alkylene, wherein at least one methylene group in the alkylene group may be substituted with O or S, wherein at least one O or S should not be adjacent to each other;
X는 -O- 이고;X is -O-;
Y는
n은 2 내지 6이다.
n is 2 to 6;
또한, 본 발명은 하기 반응식 1에 나타난 바와 같이,The present invention also relates to a process for producing a compound represented by the formula (1)
출발물질인 화학식 2의 화합물을 유기용매 및 염기하에서 화학식 3의 화합물과 반응시켜 화학식 4의 화합물을 제조하는 단계(단계 1);Preparing a compound of formula 4 by reacting a compound of formula 2, which is a starting material, with a compound of formula 3 in an organic solvent and a base (step 1);
상기 단계 1에서 제조된 화학식 4의 화합물을 유기 용매 및 산 존재하에 반응시켜 화학식 5의 화합물을 제조하는 단계(단계 2);Preparing a compound of Chemical Formula 5 by reacting the compound of Chemical Formula 4 prepared in Step 1 in the presence of an organic solvent and an acid (Step 2);
상기 단계 2에서 제조된 화학식 5의 화합물을 유기 용매 및 염기 존재하에 화학식 6의 화합물과 반응시켜 화학식 1의 화합물을 제조하는 단계(단계 3)를 포함하는 본 발명의 화합물의 제조방법을 제공한다.It provides a method of preparing a compound of the present invention comprising the step (step 3) of preparing a compound of formula 1 by reacting the compound of formula 5 prepared in step 2 with a compound of formula 6 in the presence of an organic solvent and a base.
[반응식 1][Reaction Scheme 1]
(상기 반응식 1에서,(In the above Reaction Scheme 1,
Ar, A, R, X, Y 및 n은 상기 화학식 1에서 정의한 바와 같고,Ar, A, R, X, Y and n are as defined in Formula 1,
THP는 테트라하이드로파이란이다.)
THP is tetrahydroparan.)
나아가, 상기 반응식 1에서 화학식 3으로 표시되는 화합물은 하기 반응식 2에 나타난 바와 같이,Furthermore, the compound represented by Formula 3 in Scheme 1 is, as shown in Scheme 2 below,
화학식 7의 화합물을 유기 용매 하에서 화학식 8의 화합물과 반응시켜 화학식 9의 화합물을 제조하는 단계(단계 i);Reacting a compound of formula 7 with a compound of formula 8 in an organic solvent to prepare a compound of formula 9 (step i);
상기 단계 i에서 제조된 화학식 9의 화합물을 유기 용매 및 염기하에서 화학식 10의 DHP와 반응시켜 화학식 11의 화합물을 제조하는 단계(단계 ii);Preparing a compound of formula 11 by reacting the compound of formula 9 prepared in step i with DHP of formula 10 in an organic solvent and a base (step ii);
상기 단계 ii에서 제조된 화학식 11의 화합물을 화학식 12의 화합물과 반응시켜 화학식 13의 화합물을 제조하는 단계(단계 iii);Preparing a compound of formula 13 by reacting the compound of formula 11 prepared in step ii with a compound of formula 12 (step iii);
상기 단계 iii에서 제조된 화학식 13의 화합물을 NaH와 반응시켜 화학식 14의 화합물을 제조하는 단계(단계 iv);Preparing a compound of formula 14 by reacting the compound of formula 13 prepared in step iii with NaH (step iv);
상기 단계 iv에서 제조된 화학식 14의 화합물을 유기 용매 하에서 반응시켜 화학식 15의 화합물을 제조하는 단계(단계 v); 및Preparing a compound of Formula 15 by reacting the compound of Formula 14 prepared in step iv under an organic solvent (step v); And
상기 단계 v에서 제조된 화학식 15의 화합물을 KOH와 반응시켜 화학식 3의 화합물을 제조하는 단계(단계 vi)를 포함하는 제조방법에 의해 제조될 수 있다.The compound of Formula 15 prepared in step v may be reacted with KOH to prepare a compound of Formula 3 (step vi).
[반응식 2][Reaction Scheme 2]
(상기 반응식 2에서,(In the above Reaction Scheme 2,
A, R 및 X는 상기 화학식 1에서 정의한 바와 같고,A, R and X are as defined in Formula 1,
상기 DHP는 디하이드로파이란이고, THP는 테트라하이드로파이란이다.).
The DHP is dihydroparan and THP is tetrahydroparan).
또한, 본 발명은 상기 화학식 1의 화합물을 포함하는 중합성 액정 조성물을 제공한다.In addition, the present invention provides a polymerizable liquid crystal composition comprising the compound of Formula 1.
본 발명에 따른 화합물은 복굴절 0.1 내지 0.15의 값을 가지고 투명하며 유기 용매에 대한 용해도가 우수하고 다른 중합성 물질과의 상용성 또한 우수하므로 중합성 액정 조성물 성분으로 유용하게 사용될 수 있다.
The compound according to the present invention has a value of 0.1 to 0.15 of birefringence, is transparent and has excellent solubility in organic solvents and excellent compatibility with other polymerizable materials, and thus may be usefully used as a polymerizable liquid crystal composition component.
또한, 본 발명은 화학식 1의 화합물을 포함하는 고분자 필름 및 상기 고분자 필름을 이용한 광학 이방성 필름을 제공한다.The present invention also provides a polymer film comprising the compound of Formula 1 and an optically anisotropic film using the polymer film.
본 발명에 따른 상기 액정 조성물을 사용하여 제조한 고분자 필름은 광학 이방 특성 및 좋은 내후성을 가지므로 액정 디스플레이용 광학 필름 부재로 유용하게 사용할 수 있다.
Since the polymer film produced using the liquid crystal composition according to the present invention has optical anisotropy and good weather resistance, it can be usefully used as an optical film member for liquid crystal display.
이하, 본 발명을 실시예에 의해 더욱 상세하게 설명한다. 단, 하기의 실시예는 본 발명을 예시하는 것일 뿐, 본 발명의 내용이 하기 실시예에 한정되는 것은 아니다.
Hereinafter, the present invention will be described in more detail with reference to examples. However, the following examples are merely to illustrate the present invention, but the content of the present invention is not limited to the following examples.
<<제조예Manufacturing example 1> 3-(4-(6-( 1> 3- (4- (6- (테트라하이드로Tetrahydro-2H-파이란-2--2H-pyran-2-일옥시Sake))헥실옥시Hexyloxy))페닐Phenyl))프The로피올린산의 제조Preparation of Ropiolinic Acid
단계 1: 6-(4-Step 1: 6- (4-아이오도페녹시Iodophenoxy))헥산Hexane-1-올의 제조Preparation of -1-ol
N,N-디메틸포름아미드 500 ml에 4-아이오도페놀 15 g(68 mmol)과 6-클로로-1-헥사놀 11.6 ml(102 mmol), K2CO3 18.8 g(136 mmol), KI 1.13 g(7 mmol)을 넣고 120 ℃를 유지하면서 환류시켰다. 반응 종료 후 상온으로 냉각시키고 과량의 증류수에 퀀칭(quenching) 후 디클로로메탄으로 추출하여 MgSO4로 건조시킨 다음 농축하였다. 헥산:에틸아세테이트(5:1)의 용매로 컬럼 분리하여 목적 화합물을 수득하였다(수율=92%).15 g (68 mmol) of 4-iodophenol and 11.6 ml (102 mmol) of 6-chloro-1-hexanol, 18.8 g (136 mmol) of K2 CO3 , KI 1.13 in 500 ml of N, N-dimethylformamide g (7 mmol) was added thereto and refluxed at 120 ° C. After completion of the reaction, the mixture was cooled to room temperature, quenched with excess distilled water, extracted with dichloromethane, dried over MgSO4, and concentrated. Column separation with a solvent of hexane: ethyl acetate (5: 1) afforded the desired compound (yield = 92%).
1H NMR(300 MHz, DMSO-d6) δ 1.44(6H, m), δ 1.65(2H, quint), δ 3.37(2H, t), δ 3.91(2H, t), δ 4.37(1H, t), δ 6.78(2H, d), δ 7.55(2H, d).
1 H NMR (300 MHz, DMSO-d6 ) δ 1.44 (6H, m), δ 1.65 (2H, quint), δ 3.37 (2H, t), δ 3.91 (2H, t), δ 4.37 (1H, t ), δ 6.78 (2H, d), δ 7.55 (2H, d).
단계 2: 2-(6-(4-Step 2: 2- (6- (4-아이오도페녹시Iodophenoxy))헥실옥시Hexyloxy)-) -테트라하이드로Tetrahydro-2H--2H-파이란의Pyran 제조 Produce
디클로로메탄 500 ml에 상기 단계 1에서 제조한 6-(4-아이오도페녹시)헥산-1-올 20 g(63 mmol)과 피리디늄 p-톨루엔설포네이트(PPTS) 1.57 g(6 mmol)을 넣고 얼음배스하에서 1,2-디하이드로파이란 8.5 ml(94 mmol)을 넣은 후 상온으로 온도를 올렸다. 반응 종료 후 증류수에 퀀칭하여 상기 MC층을 분리한 다음 MgSO4로 건조시켜 농축하였다. 헥산:에틸아세테이트(3:1)의 용매로 컬럼 분리하여 목적 화합물을 수득하였다(수율=87.5%).In 500 ml of dichloromethane, 20 g (63 mmol) of 6- (4-iodophenoxy) hexane-1-ol prepared in Step 1 and 1.57 g (6 mmol) of pyridinium p-toluenesulfonate (PPTS) were added. The mixture was added 8.5 ml (94 mmol) of 1,2-dihydroparan under an ice bath, and the temperature was raised to room temperature. After completion of the reaction, the MC layer was separated by quenching in distilled water, dried over MgSO4 and concentrated. Column separation with a solvent of hexane: ethyl acetate (3: 1) afforded the desired compound (yield = 87.5%).
1H NMR(300 MHz, CDCl3) δ 1.5~1.8(14H, m), δ 3.37(2H, m), δ 3.91(4H, m), δ 4.57(1H, m), δ 6.67(2H, d), δ 7.54(2H, d).
1 H NMR (300 MHz, CDCl3 ) δ 1.5 to 1.8 (14H, m), δ 3.37 (2H, m), δ 3.91 (4H, m), δ 4.57 (1H, m), δ 6.67 (2H, d ), δ 7.54 (2H, d).
단계 3: 2-Step 3: 2-메틸methyl-4-(4-(6-(-4- (4- (6- (테트라하이드로Tetrahydro-2H-파이란-2--2H-pyran-2-일옥시Sake))헥실옥시Hexyloxy))페Pe닐)Neil)부트Boot-3-인-2-올의 제조Preparation of 3-yn-2-ol
TEA:THF=1:1 용매 400 ml에 상기 단계 2에서 수득한 2-(6-(4-아이오도페녹시)헥실옥시)-테트라하이드로-2H-파이란 16.5 g(41 mmol) 및 Pd(PPh3)2Cl2 1.4 g(2 mmol), PPh3 1.1 g(4 mmol)을 넣은 후 15분 동안 가스를 제거하였다. 반응물에 2-메틸부트-3-인-2-올 5.9 ml(61 mmol) 및 CuI 0.78 g(4 mmol)을 넣고 15분 동안 가스를 제거하는 작업을 진행한 후 85 ℃를 유지하며 환류시켰다. 반응 종료 후 과량의 증류수에 퀀칭하고 디클로로메탄으로 추출하여 MgSO4로 건조시킨 다음 농축하였다. 헥산:에틸아세테이트(3:1)의 용매로 컬럼 분리하였다(수율=89%).16.5 g (41 mmol) and Pd (2- (6- (4-iodophenoxy) hexyloxy) -tetrahydro-2H-pyrane obtained in step 2 above were added to 400 ml of TEA: THF = 1: 1 solvent. 1.4 g (2 mmol) of PPh3 )2 Cl2 and 1.1 g (4 mmol) of PPh3 were added thereto, and the gas was removed for 15 minutes. 5.9 ml (61 mmol) of 2-methylbut-3-yn-2-ol and 0.78 g (4 mmol) of CuI were added to the reaction, and the mixture was refluxed for 15 minutes. After the reaction was quenched in excess distilled water, extracted with dichloromethane, dried over MgSO4 and concentrated. Column separation was carried out with a solvent of hexane: ethyl acetate (3: 1) (yield = 89%).
1H NMR(300 MHz, CDCl3) δ 1.5~1.8(20H, m), δ 3.37(2H, m), δ 3.91(4H, m), δ 4.57(1H, m), δ 6.81(2H, d), δ 7.33(2H, d).
1 H NMR (300 MHz, CDCl3 ) δ 1.5 to 1.8 (20H, m), δ 3.37 (2H, m), δ 3.91 (4H, m), δ 4.57 (1H, m), δ 6.81 (2H, d ), δ 7.33 (2H, d).
단계 4: 2-(6-(4-Step 4: 2- (6- (4-에티닐페녹시Ethynylphenoxy))헥실옥시Hexyloxy)-) -테트라하이드로Tetrahydro-2H--2H-파이란의Pyran 제조 Produce
톨루엔 400 ml에 상기 단계 3에서 수득한 2-메틸-4-(4-(6-(테트라하이드로-2H-파이란-2-일옥시)헥실옥시)페닐)부트-3-인-2-올 17.2 g(48 mmol)을 넣은 후 얼음배스하에서 NaH 11.5 g(477mmol)을 천천히 추가하였다. 온도를 70 ℃로 유지하면서 환류시켰다. 반응 종료 후 메탄올로 퀀칭하고 증류수로 씻어내었다. 디클로로메탄으로 추출하여 MgSO4로 건조시킨 다음 농축하였다. 헥산:에틸아세테이트(8:1)의 용매로 컬럼 분리하여 목적 화합물을 수득하였다(수율=91%).In 400 ml of toluene, 2-methyl-4- (4- (6- (tetrahydro-2H-pyran-2-yloxy) hexyloxy) phenyl) but-3-yn-2-ol obtained in step 3 above. 17.2 g (48 mmol) was added thereto, and 11.5 g (477 mmol) of NaH was slowly added under an ice bath. It was refluxed maintaining the temperature at 70 ° C. After the reaction was quenched with methanol and washed with distilled water. Extracted with dichloromethane, dried over MgSO4 and concentrated. Column separation with a solvent of hexane: ethyl acetate (8: 1) afforded the desired compound (yield = 91%).
1H NMR(300 MHz, CDCl3) δ 1.4~1.8(14H, m), δ 2.98(1H, s), δ 3.37(2H, m), δ 3.91(4H, m), δ 4.57(1H, m), δ 6.84(2H, d), δ 7.41(2H, d).
1 H NMR (300 MHz, CDCl3 ) δ 1.4 to 1.8 (14H, m), δ 2.98 (1H, s), δ 3.37 (2H, m), δ 3.91 (4H, m), δ 4.57 (1H, m ), δ 6.84 (2H, d), δ 7.41 (2H, d).
단계 5:Step 5:메틸methyl 3-(4-(6-( 3- (4- (6- (테트라하이드로Tetrahydro-2H-파이란-2--2H-pyran-2-일옥시Sake))헥실옥시Hexyloxy))페닐Phenyl)프로피올레이트의 제조Preparation of Propiolate
THF 150 ml에 상기 단계 4에서 수득한 2-(6-(4-에티닐페녹시)헥실옥시)-테트라하이드로-2H-파이란 5 g(17 mmol)을 넣고 약 15분 동안 가스를 제거한 후 -78 ℃로 온도를 내린 다음 n-BuLi(2.5M in HX) 9.9 ml을 천천히 가하였다. 첨가가 끝나면 0 ℃에서 약 1시간 동안 반응을 시키고 다시 -78 ℃로 온도를 내린 후 메틸 클로로카르보네이트 2.57 ml(33 mmol)을 천천히 추가하고 상온으로 온도를 상승시켰다. 반응 종료 후 얼음배스하에서 NaHCO3:NH4Cl(1:1) 용액에 반응물을 천천히 첨가하여 퀀칭한 다음 디클로로메탄으로 추출하여 MgSO4로 건조시킨 후 농축하였다. 헥산:에틸아세테이트(6:1)의 용매로 컬럼 분리하여 목적 화합물을 수득하였다(수율=99%).5 g (17 mmol) of 2- (6- (4-ethynylphenoxy) hexyloxy) -tetrahydro-2H-pyran obtained in step 4 was added to 150 ml of THF, and the gas was removed for about 15 minutes. The temperature was lowered to -78 ° C and then slowly added 9.9 ml of n-BuLi (2.5M in HX). After the addition, the reaction was conducted at 0 ° C. for about 1 hour, and the temperature was lowered to −78 ° C., and then slowly added 2.57 ml (33 mmol) of methyl chlorocarbonate, and the temperature was raised to room temperature. After completion of the reaction, the reaction mixture was slowly quenched by adding NaHCO3 : NH4 Cl (1: 1) solution in an ice bath, extracted with dichloromethane, dried over MgSO4 , and concentrated. Column separation with a solvent of hexane: ethyl acetate (6: 1) gave the desired compound (yield = 99%).
1H NMR(300 MHz, CDCl3) δ 1.4~1.8(14H, m), δ 3.37(2H, m), δ 3.85(5H, m), δ 3.97(2H, t), δ 4.57(1H, m), δ 6.87(2H, d), δ 7.52(2H, d).
1 H NMR (300 MHz, CDCl3 ) δ 1.4 to 1.8 (14H, m), δ 3.37 (2H, m), δ 3.85 (5H, m), δ 3.97 (2H, t), δ 4.57 (1H, m ), δ 6.87 (2H, d), δ 7.52 (2H, d).
단계 6: 3-(4-(6-(Step 6: 3- (4- (6- (테트라하이드로Tetrahydro-2H-파이란-2--2H-pyran-2-일옥시Sake))헥실옥시Hexyloxy))페닐Phenyl))프로피PROFI올린산의 제조Preparation of Olinic Acid
메탄올 150 ml에 상기 단계 5에서 수득한 메틸 3-(4-(6-(테트라하이드로-2H-파이란-2-일옥시)헥실옥시)페닐)프로피올레이트 5.8 g(16 mmol) 및 포타슘 하이드록사이드(potassium hydroxide) 1.8 g(32 mmol), 5 ml의 증류수를 넣고 상온에서 반응시켰다. 반응 종료 후 메탄올을 증발시키고 농축한 다음 증류수를 추가하여 녹인 후 3N HCl 수용액을 가해 pH 2로 적정하였다. 디클로로메탄으로 추출하여 MgSO4로 건조시킨 후 농축하였다. 디클로로메탄:메탄올(50:1)의 용매로 컬럼 분리하여 목적 화합물을 수득하였다(수율=95%).5.8 g (16 mmol) of methyl 3- (4- (6- (tetrahydro-2H-pyran-2-yloxy) hexyloxy) phenyl) propiolate obtained in 150 ml of methanol and potassium hydroxide 1.8 g (32 mmol) of hydroxide (potassium hydroxide) and 5 ml of distilled water were added and reacted at room temperature. After completion of the reaction, methanol was evaporated and concentrated, and then distilled water was added to dissolve it, followed by titration to pH 2 by adding an aqueous 3N HCl solution. Extracted with dichloromethane, dried over MgSO4 and concentrated. Column separation with a solvent of dichloromethane: methanol (50: 1) gave the desired compound (yield = 95%).
1H NMR(300 MHz, CDCl3) δ 1.4~1.8(14H, m), δ 3.37(2H, m), δ 3.85(2H, m), δ 3.98(2H, t), δ 4.57(1H, m), δ 6.88(2H, d), δ 7.55(2H, d).
1 H NMR (300 MHz, CDCl3 ) δ 1.4 to 1.8 (14H, m), δ 3.37 (2H, m), δ 3.85 (2H, m), δ 3.98 (2H, t), δ 4.57 (1H, m ), δ 6.88 (2H, d), δ 7.55 (2H, d).
<<제조예Manufacturing example 2> 9,9- 2> 9,9-디에틸Diethyl-9H--9H-플루오렌Fluorene-2,7--2,7-디올의Diol 제조 Produce
단계 1: 2,7-Step 1: 2,7-디브로모Dibromo-9,9--9,9-디에틸Diethyl-9H--9H-플루오렌의Fluorene 제조 Produce
DMSO 200 ml에 2,7-디브로모-9H-플루오렌 15 g(46 mmol), 포타슘 t-부톡사이드(potassium t-butoxide) 13 g(115 mmol) 및 아이오도에탄(iodoethane) 11.2 ml (139 mmol)을 넣고 상온에서 반응시켰다. 반응 종료 후 과량의 증류수에 퀀칭하여 생성된 고체를 여과하고 헥산으로 컬럼 분리하여 목적 화합물을 수득하였다(수율=69.3%).In 200 ml of DMSO 15 g (46 mmol) of 2,7-dibromo-9H-fluorene, 13 g (115 mmol) of potassium t-butoxide and 11.2 ml of iodoethane ( 139 mmol) was added and reacted at room temperature. After completion of the reaction, the resulting solid was quenched in excess distilled water and the resulting solid was filtered and column separated with hexane to give the target compound (yield = 69.3%).
1H NMR(300 MHz, DMSO-d6) δ 0.20(6H, t), δ 2.05(4H, quart), δ 7.52(2H, dd), δ 7.55(2H, d), δ 7.81(2H, d).
1 H NMR (300 MHz, DMSO-d6 ) δ 0.20 (6H, t), δ 2.05 (4H, quart), δ 7.52 (2H, dd), δ 7.55 (2H, d), δ 7.81 (2H, d ).
단계 2: 9,9-Step 2: 9,9-디에틸Diethyl-9H--9H-플루오렌Fluorene-2,7--2,7-디올의Diol 제조 Produce
THF 200 ml에 상기 단계 1에서 수득한 화합물 2,7-디브로모-9,9-디에틸-9H-플루오렌 10 g(26.3 mmol)을 넣고 약 15분 동안 가스를 제거한 후 -78 ℃로 온도를 내리고 n-BuLi(헥산에 담긴 2.5M) 26 ml을 천천히 가하였다. 첨가가 끝나면 0 ℃에서 약 1시간 동안 반응을 시키고 다시 -78 ℃로 온도를 내린 후 트리메톡시 보레이트(trimethoxy boratre) 7.5 ml(65.8 mmol)을 천천히 가한 다음 상온으로 온도를 올렸다. 반응 종료 후 용매인 THF를 제거하고 증류수에 넣은 후 적정하였다. 이를 디클로로메탄으로 추출하여 용매를 날리고 다시 THF 60 ml 및 1N NaOH 160 ml에 녹인 후 30% 과산화수소 60 ml를 천천히 가하였다. 30분 후 적정하고 디클로로메탄으로 추출하여 MgSO4로 건조시키고 농축하였다. 헥산:에틸아세테이트(5:1)의 용매로 컬럼 분리하여 목적 화합물을 수득하였다(수율=34.2%).10 g (26.3 mmol) of the compound 2,7-dibromo-9,9-diethyl-9H-fluorene obtained in step 1 was added to 200 ml of THF, and the gas was removed for about 15 minutes, followed by −78 ° C. The temperature was lowered and slowly added 26 ml of n-BuLi (2.5M in hexane). After the addition, the reaction was conducted at 0 ° C. for about 1 hour, and after the temperature was lowered to −78 ° C., 7.5 ml (65.8 mmol) of trimethoxy boratre was slowly added thereto, and the temperature was raised to room temperature. After completion of the reaction, THF as a solvent was removed, placed in distilled water, and titrated. The solvent was extracted with dichloromethane, the solvent was removed, dissolved in 60 ml of THF and 160 ml of 1N NaOH, and then slowly added 60 ml of 30% hydrogen peroxide. After 30 minutes, titrated, extracted with dichloromethane, dried over MgSO4 and concentrated. Column separation with a solvent of hexane: ethyl acetate (5: 1) afforded the desired compound (yield = 34.2%).
1H NMR(300 MHz, DMSO-d6) δ 0.23(6H, t), δ 1.84(4H, quart), δ 6.65(2H, dd), δ 6.70(2H, d), δ 7.40(2H, d), δ 9.21(2H, s).
1 H NMR (300 MHz, DMSO-d6 ) δ 0.23 (6H, t), δ 1.84 (4H, quart), δ 6.65 (2H, dd), δ 6.70 (2H, d), δ 7.40 (2H, d ), δ 9.21 (2H, s).
<<실시예Example 1> (((((2- 1> (((((2-메틸methyl-1,4--1,4-페닐렌Phenylene))비스Vis((옥시Oxy))))비스Vis(3-(3-옥소프로Oxopro-1-핀-3,1-디일))-1-pin-3,1-diyl))비스Vis(4,1-(4,1-페닐렌Phenylene))))비스Vis((옥시Oxy))))비스Vis((헥산Hexane-6,1--6,1-디일Dill))디아크릴레이트(1a)의Of diacrylate (1a) 제조 Produce
단계 1: 2-Step 1: 2-메틸methyl-1,4--1,4-페닐렌Phenylene 비스(3-(4-((6-(( Bis (3- (4-((6-((테트라하이드로Tetrahydro-2H-파이란-2-일)-2H-pyran-2-yl)옥시Oxy))헥실Hexyl))옥시Oxy))페닐Phenyl))프로피올레이트Propiolate)의 제조Manufacturing
디클로로메탄 100 ml에 상기 제조예 1에서 제조한 화합물인 3-(4-(6-(테트라하이드로-2H-파이란-2-일옥시)헥실옥시)페닐)프로피올린산 22.3 g(64.4 mmol), DPTS 19.0 g(64.4 mmol) 및 DCC 13.3 g(64.4 mmol)을 넣고 약 10분 동안 반응시킨 후 디클로로메탄 10 ml에 녹인 메틸하이드로퀴논 1.0 g(8.1 mmol)을 적가하였다. 반응 종료 후 과량의 증류수에 퀀칭하고 추출하여 건조시켰다. 헥산:에틸아세테이트(8:1)의 용매로 컬럼 분리하여 목적 화합물을 수득하였다(수율=41%).22.3 g (64.4 mmol) of 3- (4- (6- (tetrahydro-2H-pyran-2-yloxy) hexyloxy) phenyl) propolinic acid as a compound prepared in Preparation Example 1 in 100 ml of dichloromethane. , DPTS 19.0 g (64.4 mmol) and DCC 13.3 g (64.4 mmol) were added and reacted for about 10 minutes. 1.0 g (8.1 mmol) of methylhydroquinone dissolved in 10 ml of dichloromethane was added dropwise. After the reaction was quenched in excess distilled water, extracted and dried. Column separation with a solvent of hexane: ethyl acetate (8: 1) afforded the desired compound (yield = 41%).
1H NMR(300 MHz, CDCl3) δ 1.4~1.8(28H, m), δ 2.27(3H, s), δ 3.35(4H, m), δ 3.78(4H, m), δ 3.98(4H, t), δ 4.55(2H, m), δ 6.80(1H, d), δ 7.39(2H, m), δ 7.66(4H, d), δ 8.19(4H, d).
1 H NMR (300 MHz, CDCl3 ) δ 1.4 to 1.8 (28H, m), δ 2.27 (3H, s), δ 3.35 (4H, m), δ 3.78 (4H, m), δ 3.98 (4H, t ), δ 4.55 (2H, m), δ 6.80 (1H, d), δ 7.39 (2H, m), δ 7.66 (4H, d), δ 8.19 (4H, d).
단계 2: 2-Step 2: 2-메틸methyl-1,4--1,4-페닐렌Phenylene 비스(3-(4-((6- Bis (3- (4-((6-하이드록시헥실Hydroxyhexyl))옥시Oxy))페닐Phenyl))프로피올레이트Propiolate)의 제조Manufacturing
메탄올 50 ml에 상기 단계 1에서 수득한 화합물인 2-메틸-1,4-페닐렌 비스(3-(4-((6-((테트라하이드로-2H-파이란-2-일)옥시)헥실)옥시) 페닐)프로피올레이트) 2.5(3.2mmol)을 녹인 후 10% HCl 10ml를 넣어 상온에서 반응시켰다. 반응 종료 후 용매를 제거하고 물에 퀀칭하여 디클로로메탄으로 추출하여 MgSO4로 건조시킨 후 농축하고 헥산:에틸아세테이트(4:1)의 용매로 컬럼 분리하여 목적 화합물을 수득하였다(수율=81%).2-methyl-1,4-phenylene bis (3- (4-((6-((tetrahydro-2H-pyran-2-yl) oxy) hexyl) which is a compound obtained in step 1 in 50 ml of methanol) Oxy) phenyl) propiolate) 2.5 (3.2 mmol) was dissolved, and 10 ml of 10% HCl was added to react at room temperature. After completion of the reaction, the solvent was removed, quenched in water, extracted with dichloromethane, dried over MgSO4 , concentrated, and column separated with a solvent of hexane: ethyl acetate (4: 1) to obtain the target compound (yield = 81%). .
1H NMR(300 MHz, CDCl3) δ 1.4~1.8(16H, m), δ 2.27(3H, s), δ 3.72(4H, t), δ 3.98(4H, t), δ 4.55(2H, m), δ 6.82(1H, d), δ 7.41(2H, m), δ 7.63(4H, d), δ 8.16(4H, d).
1 H NMR (300 MHz, CDCl3 ) δ 1.4 to 1.8 (16H, m), δ 2.27 (3H, s), δ 3.72 (4H, t), δ 3.98 (4H, t), δ 4.55 (2H, m ), δ 6.82 (1H, d), δ 7.41 (2H, m), δ 7.63 (4H, d), δ 8.16 (4H, d).
단계 3: (((((2-Step 3: (((((2-메틸methyl-1,4--1,4-페닐렌Phenylene))비스Vis((옥시Oxy))))비스Vis(3-(3-옥소프로Oxopro-1-핀-3,1--1-pin-3,1-디D일))Work))비스Vis(4,1-(4,1-페닐렌Phenylene))))비스Vis((옥시Oxy))))비스Vis((헥산Hexane-6,1--6,1-디일Dill))디아크릴레이트의Diacrylate 제조 Produce
디클로로메탄 30 ml에 상기 단계 2에서 수득한 화합물인 2-메틸-1,4-페닐렌 비스(3-(4-((6-하이드록시헥실)옥시)페닐)프로피올레이트) 1.6 g(2.6 mmol), 트리에틸아민 3.8 ml(26.1 mmol) 및 아크로일 클로라이드 0.64 ml(7.8 mmol)을 넣고 상온에서 반응시켰다. 반응 종료 후 과량의 물로 퀀칭하여 디클로로메탄으로 추출, 분리하였다. MgSO4로 건조시킨 후 농축하였다. 헥산:에틸아세테이트(6:1)의 용매로 컬럼 분리하여 목적 화합물을 수득하였다(수율=49%).1.6 g (2.6) of 2-methyl-1,4-phenylene bis (3- (4-((6-hydroxyhexyl) oxy) phenyl) propiolate), the compound obtained in step 2, in 30 ml of dichloromethane mmol), triethylamine 3.8 ml (26.1 mmol) and 0.64 ml (7.8 mmol) of acroyl chloride were added and reacted at room temperature. After the reaction was quenched with excess water, extracted with dichloromethane and separated. After drying over MgSO4 , it was concentrated. Column separation with a solvent of hexane: ethyl acetate (6: 1) gave the desired compound (yield = 49%).
1H NMR(300 MHz, CDCl3) δ 1.4~1.8(16H, m), δ 2.27(3H, s), δ 3.72(4H, t), δ 3.98(4H, t), δ 5.82(2H, dd), δ 6.15(2H, dd), δ 6.41(2H, dd), δ 6.81(1H, d), δ 7.43(2H, m), δ 7.67(4H, d), δ 8.21(4H, d),1 H NMR (300 MHz, CDCl3 ) δ 1.4 to 1.8 (16H, m), δ 2.27 (3H, s), δ 3.72 (4H, t), δ 3.98 (4H, t), δ 5.82 (2H, dd ), δ 6.15 (2H, dd), δ 6.41 (2H, dd), δ 6.81 (1H, d), δ 7.43 (2H, m), δ 7.67 (4H, d), δ 8.21 (4H, d),
Fab MS m/z 720(M+) IR max(cm-1) 1628(-C=C-), 1720(-COO-), 2216(-C≡C-), 2998(-CH-)Fab MS m / z 720 (M+ ) IR max (cm-1 ) 1628 (-C = C-), 1720 (-COO-), 2216 (-C≡C-), 2998 (-CH-)
UV(nm) 287UV (nm) 287
Elemental analysis: calc. for C43H44O10, C 71.65, H 6.15, O 22.20 ; found. C 71.68, H 6.14, O 21.91% DSC & POM: I 114 ℃ N
Elemental analysis: calc. for C43 H44 O10 , C 71.65, H 6.15, O 22.20; found. C 71.68, H 6.14, O 21.91% DSC & POM: I 114 ° C N
<<실시예Example 2> (((((9,9- 2> (((((9,9-디에틸Diethyl-9H--9H-플루오렌Fluorene-2,7--2,7-디일Dill))비스Vis((옥시Oxy))))비스Vis(3-(3-옥소Oxo프로-1-핀-3,1-Pro-1-pin-3,1-디일Dill))))비스Vis(4,1-(4,1-페닐렌Phenylene))))비스Vis((옥시Oxy))))비스Vis((헥산Hexane-6,1--6,1-디일Dill))디아크릴레이트Diacrylate((1b)의1b) 제조 Produce
단계 1: 9,9-Step 1: 9,9-디에틸Diethyl-9H--9H-플루오렌Fluorene-2,7--2,7-디일Dill 비스(3-(4-((6-(( Bis (3- (4-((6-((테트라하이드로Tetrahydro-2H-파이란-2-일)-2H-pyran-2-yl)옥시Oxy))헥실Hexyl))옥시Oxy))페닐Phenyl))프로피올레이트Propiolate)의 제조Manufacturing
디클로로메탄 100 ml에 상기 제조예 1에서 수득한 화합물인 3-(4-(6-(테트라하이드로-2H-파이란-2-일옥시)헥실옥시)페닐)프로피올린산 11 g(31.7 mmol), DPTS 9.33 g(31.7 mmol) 및 DCC 6.54 g(31.7 mmol)을 넣고 약 10분 동안 반응시킨 후 디클로로메탄 10 ml에 녹인 제조예 2에서 수득한 화합물인 9,9-디에틸-9H-플루오렌-2,7-디올 1.0 g(4.0 mmol)을 적가하였다. 반응 종료 후 과량의 증류수에 퀀칭하고 추출하여 건조시켰다. 헥산:에틸아세테이트(8:1)의 용매로 컬럼 분리하여 목적 화합물을 수득하였다(수율=51.4%).11 g (31.7 mmol) of 3- (4- (6- (tetrahydro-2H-pyran-2-yloxy) hexyloxy) phenyl) propolinic acid as a compound obtained in Preparation Example 1 in 100 ml of dichloromethane. , 9.33 g (31.7 mmol) of DPTS and 6.54 g (31.7 mmol) of DCC were reacted for about 10 minutes and dissolved in 10 ml of dichloromethane to obtain 9,9-diethyl-9H-fluorene. 1.0 g (4.0 mmol) of -2,7-diol was added dropwise. After the reaction was quenched in excess distilled water, extracted and dried. Column separation with a solvent of hexane: ethyl acetate (8: 1) gave the desired compound (yield = 51.4%).
1H NMR(300 MHz, DMSO-d6) δ 0.20(6H, t), δ 1.4~1.8(28H, m), δ 1.84(4H, quart), δ 3.37(4H, m), δ 3.85(4H, m), δ 3.98(4H, t), δ 4.57(2H, m), δ 7.13(4H, d), δ 7.24(2H, dd), δ 7.36(2H, d), δ 7.90(2H, d), δ 8.11(4H, d).
1 H NMR (300 MHz, DMSO-d6 ) δ 0.20 (6H, t), δ 1.4 to 1.8 (28H, m), δ 1.84 (4H, quart), δ 3.37 (4H, m), δ 3.85 (4H , m), δ 3.98 (4H, t), δ 4.57 (2H, m), δ 7.13 (4H, d), δ 7.24 (2H, dd), δ 7.36 (2H, d), δ 7.90 (2H, d ), δ 8.11 (4H, d).
단계 2: 9,9-Step 2: 9,9-디에틸Diethyl-9H--9H-플루오렌Fluorene-2,7--2,7-디일Dill 비스(3-(4-((6- Bis (3- (4-((6-하이드록시헥실Hydroxyhexyl))옥시Oxy))페닐Phenyl))프로피올레이트의Propiolate 제조 Produce
메탄올 50 ml에 상기 단계 1에서 수득한 9,9-디에틸-9H-플루오렌-2,7-디일 비스(3-(4-((6-((테트라하이드로-2H-파이란-2-일)옥시)헥실)옥시) 페닐)프로피올레이트) 1.84 g(2.0 mmol)을 녹인 후 10% HCl 5 ml를 넣어 상온에서 반응시켰다. 반응 종료 후 용매를 제거한 후 물에 퀀칭하여 디클로로메탄으로 추출하고 MgSO4로 건조시킨 후 농축하였다. 헥산:에틸아세테이트(3:1)의 용매로 컬럼 분리하여 목적 화합물을 수득하였다(수율=86.7%).9,9-diethyl-9H-fluorene-2,7-diyl bis (3- (4-((6-((tetrahydro-2H-pyran-2-yl) obtained in step 1 above in 50 ml of methanol ) Oxy) hexyl) oxy) phenyl) propiolate) 1.84 g (2.0 mmol) was dissolved, 5 ml of 10% HCl was added and reacted at room temperature. After completion of the reaction, the solvent was removed, quenched in water, extracted with dichloromethane, dried over MgSO4 and concentrated. Column separation with a solvent of hexane: ethyl acetate (3: 1) afforded the desired compound (yield = 86.7%).
1H NMR(300 MHz, DMSO-d6) δ 0.20(6H, t), δ 1.4~1.8(16H, m), δ 1.82(4H, quart), δ 4.12(8H, m), δ 4.42(2H, m), δ 7.10(4H, d), δ 7.23(2H, dd), δ 7.32(2H, d), δ 7.84(2H, d), δ 8.10(4H, d)
1 H NMR (300 MHz, DMSO-d6 ) δ 0.20 (6H, t), δ 1.4 to 1.8 (16H, m), δ 1.82 (4H, quart), δ 4.12 (8H, m), δ 4.42 (2H , m), δ 7.10 (4H, d), δ 7.23 (2H, dd), δ 7.32 (2H, d), δ 7.84 (2H, d), δ 8.10 (4H, d)
단계 3: (((((9,9-Step 3: (((((9,9-디에틸Diethyl-9H--9H-플루오렌Fluorene-2,7--2,7-디일Dill))비스Vis((옥시Oxy))))비스Vis(3-(3-옥소프로Oxopro-1-핀-3,1--1-pin-3,1-디일Dill))))비스Vis(4,1-(4,1-페닐렌Phenylene))))비스Vis((옥시Oxy))))비스Vis((헥산Hexane-6,1--6,1-디일Dill))디아크릴레이트의Diacrylate 제조 Produce
디클로로메탄 20 ml에 상기 단계 2에서 수득한 화합물 9,9-디에틸-9H-플루오렌-2,7-디일 비스(3-(4-((6-하이드록시헥실)옥시)페닐)프로피올레이트 1.3 g(1.75 mmol), 트리에틸아민 2.5 ml(17.5 mmol) 및 아크릴로일 클로라이드 0.43 ml(5.2 mmol)을 넣고 상온에서 반응시켰다. 반응 종료 후 과량의 물에 퀀칭하여 디클로로메탄으로 추출, 분리하고 MgSO4로 건조시킨 후 농축시켰다. 헥산:에틸아세테이트(5:1)의 용매로 컬럼 분리하여 목적 화합물을 수득하였다.In 20 ml of dichloromethane, the compound 9,9-diethyl-9H-fluorene-2,7-diyl bis (3- (4-((6-hydroxyhexyl) oxy) phenyl) propionol obtained in the above step 2 1.3 g (1.75 mmol) of triethylamine, 2.5 ml (17.5 mmol) of triethylamine, and 0.43 ml (5.2 mmol) of acryloyl chloride were added and reacted at room temperature After completion of the reaction, the mixture was quenched with excess water and extracted with dichloromethane. It was then dried over MgSO4 and concentrated, and the resulting compound was separated by column separation with a solvent of hexane: ethyl acetate (5: 1).
1H NMR(300 MHz, DMSO-d6) δ 0.20(6H, t), δ 1.4~1.8(16H, m), δ 1.84(4H, quart), δ 4.12(8H, m), δ 5.91(2H, dd), δ 6.12(2H, dd), δ 6.29(2H, dd), δ 7.11(4H, d), δ 7.21(2H, dd), δ 7.36(2H, d), δ 7.87(2H, d), δ 8.08(4H, d)1 H NMR (300 MHz, DMSO-d6 ) δ 0.20 (6H, t), δ 1.4 to 1.8 (16H, m), δ 1.84 (4H, quart), δ 4.12 (8H, m), δ 5.91 (2H , dd), δ 6.12 (2H, dd), δ 6.29 (2H, dd), δ 7.11 (4H, d), δ 7.21 (2H, dd), δ 7.36 (2H, d), δ 7.87 (2H, d ), δ 8.08 (4H, d)
Fab MS m/z 850(M+)Fab MS m / z 850 (M+ )
IR max(cm-1) 1638(-C=C-), 1724(-COO-), 2218(-C≡C-), 2912(-CH-)IR max (cm-1 ) 1638 (-C = C-), 1724 (-COO-), 2218 (-C≡C-), 2912 (-CH-)
UV(nm) 277UV (nm) 277
Elemental analysis: calc. for C53H54O10, C 74.80, H 6.40, O 18.80 ; found. C 74.80, H 6.40, O 18.80%Elemental analysis: calc. for C53 H54 O10 , C 74.80, H 6.40, 0 18.80; found. C 74.80, H 6.40, O 18.80%
DSC & POM: I 40 ℃ N
DSC & POM: I 40 ℃ N
<<실험예Experimental Example 1> 1>실시예Example 1의 화합물의 필름 특성, 코팅, 배향 및 복굴절 측정 Film Properties, Coating, Orientation and Birefringence Measurement of Compound 1
본 발명에 따른 상기 실시예 1에서 제조한 화합물인 6,6’-(4,4’(3,3’-(2-메틸-1,4-페닐렌)비스(옥시)비스(3-옥소프로-1-핀-3,1-디일))비스(4,1-페닐렌)) 비스(옥시)비스(헥산-6,1-디일) 디아크릴레이트의 필름 특성, 코팅, 배향 및 복굴절을 측정하였다.
6,6 '-(4,4' (3,3 '-(2-methyl-1,4-phenylene) bis (oxy) bis (3-oxo) which is a compound prepared in Example 1 according to the present invention. The film properties, coatings, orientations and birefringence of the pro-1-pin-3,1-diyl)) bis (4,1-phenylene)) bis (oxy) bis (hexane-6,1-diyl) diacrylate Measured.
<1-1> 액정 조성물의 제조<1-1> Preparation of Liquid Crystal Composition
먼저 상기 6,6’-(4,4’(3,3’-(2-메틸-1,4-페닐렌)비스(옥시)비스(3-옥소프로-1-핀-3,1-디일))비스(4,1-페닐렌)) 비스(옥시)비스(헥산-6,1-디일) 디아크릴레이트 100 mg (30 wt%)과 광개시제로서 3-{4-[2.4-비스(트리클로로메틸)-s-트리아진-6-일]페닐티오}프로피온산 3 mg (반응성 액정의 3 wt%)을 사이클로헥사논(cyclohexanone) 용매에 완전히 녹여 액정 조성물을 제조하였다.
First 6,6 '-(4,4' (3,3 '-(2-methyl-1,4-phenylene) bis (oxy) bis (3-oxoprop-1-pin-3,1-diyl )) Bis (4,1-phenylene)) 100 mg (30 wt%) bis (oxy) bis (hexane-6,1-diyl) diacrylate and 3- {4- [2.4-bis (trichloro) as photoinitiator 3 mg (3 wt% of the reactive liquid crystal) of romethyl) -s-triazin-6-yl] phenylthio} propionic acid was completely dissolved in a cyclohexanone solvent to prepare a liquid crystal composition.
<1-2> 코팅-배향-경화<1-2> coating-orientation-curing
유리기판 위에 폴리이미드 배향막을 코팅하고 1회 러빙 처리하여 제조한 배향막 위에 상기 <1-1>에서 제조한 반응성 액정 조성물 용액을 스핀 코팅하고 100 ℃에서 배향한 후 100 ℃에서 1 J/cm2의 자외선을 조사하여 경화하여 1 μm의 필름 (P-1) 을 제조하였다.
After coating the polyimide alignment layer on the glass substrate and rubbing treatment, the reactive liquid crystal composition solution prepared in the above <1-1> was spin-coated and oriented at 100 ° C, followed by 1 J / cm2 at 100 ° C. Irradiation with ultraviolet rays cured to prepare a 1 μm film (P-1).
<1-3> 배향 확인<1-3> Check the orientation
편광 광학현미경을 이용하여 균일 배향을 가지는 것을 확인하였고 도 2에 나타난 바와 같이 필름이 편광자 사이에 0도와 45도로 위치할 때 각각 검정색과 흰색을 나타났다.
It was confirmed to have a uniform orientation using a polarizing optical microscope, and as shown in FIG. 2, the film was black and white when the film was positioned between 0 and 45 degrees between the polarizers, respectively.
<1-4> 위상차 측정<1-4> Phase difference measurement
위상차를 측정하기 위하여 도 3에 나타난 바와 같이 PEM 장비를 이용하였다. 90도 직교된 편광자와 분석자 사이에 액정의 배향 방향이 편광자와 분석자의 편광축에 각각 45도가 되도록 고정시킨 다음 평면상에서 360도 회전시켜 빛의 투과도를 전압 변화량으로 측정하였다. 상기 전압 변화량을 하기 수학식 1을 통해 위상차로 환산하고 액정의 두께로 나누어 복굴절을 계산하여 하기 표 1에 나타내었다.PEM equipment was used as shown in FIG. 3 to measure the phase difference. The transmittance of the light was measured as a change in voltage by fixing the alignment direction of the liquid crystal between the polarizer and the analyzer 90 degrees orthogonal to the polarization axis of the polarizer and the analyzer. The voltage change amount is converted into a phase difference through Equation 1 below, and the birefringence is calculated by dividing by the thickness of the liquid crystal.
(여기서, V는 전압변화량이다.)Where V is the voltage change.
이때, 비교예 1로 사용한 화합물은 상기 실시예 1과 동일한 모핵과 치환기를 가지되 아세틸렌기가 없는 2-메틸-1,4-페닐렌 비스(4-(6-(아크릴로일옥시)헥실옥시)벤조에이트) 화합물이고, 상기와 동일한 방법으로 필름을 제조하여 제조된 필름(P-2)을 이용하여 계산된 복굴절 또한 하기 표 1에 나타내었다.In this case, the compound used in Comparative Example 1 has the same parent nucleus and substituent as in Example 1, but 2-methyl-1,4-phenylene bis (4- (6- (acryloyloxy) hexyloxy without acetylene group) Benzoate) compound, and the birefringence calculated using the film (P-2) prepared by the same method as described above is also shown in Table 1 below.
표 1에 나타난 바와 같이, 아세틸렌이 도입된 실시예 1의 화합물로 제조된 필름의 경우 아세틸렌이 도입되지 않은 비교예 1의 화합물로 제조된 필름보다 복굴절 값이 더 큰 것을 확인할 수 있다.As shown in Table 1, it can be seen that the birefringence value of the film prepared with the compound of Example 1 in which acetylene was introduced is greater than that of the film prepared with the compound of Comparative Example 1 without acetylene.
따라서, 본 발명에 따른 아세틸렌이 도입된 화합물은 아세틸렌이 없는 비교예 1의 화합물에 비하여 복굴절의 편차가 더 크므로 광학 이방성이 더 우수한 것을 확인할 수 있다.
Therefore, it can be confirmed that the compound in which the acetylene is introduced according to the present invention has better optical anisotropy since the deviation of birefringence is larger than that of the compound of Comparative Example 1 without acetylene.
<<실험예Experimental Example 2> 2>실시예Example 2의 화합물의 필름 특성, 코팅, 배향 및 복굴절 측정 Film Properties, Coating, Orientation and Birefringence Measurement of Compound 2
본 발명에 따른 상기 실시예 2에서 제조한 화합물인 (6,6‘-(4,4’-(3,3‘-(9,9-디에틸-9H-플루오렌-2,7-디일)비스(옥시)비스(3-옥소프로-1-핀-3,1-디일))비스(4,1-페닐렌))비스(옥시)비스(헥산-6,1-디일)디아크릴레이트의 필름 특성, 코팅, 배향 및 복굴절을 측정하였다.(6,6 '-(4,4'-(3,3 '-(9,9-diethyl-9H-fluorene-2,7-diyl), which is a compound prepared in Example 2, according to the present invention. Of bis (oxy) bis (3-oxoprop-1-pin-3,1-diyl)) bis (4,1-phenylene)) bis (oxy) bis (hexane-6,1-diyl) diacrylate Film properties, coatings, orientations and birefringence were measured.
<1-1> 액정 조성물의 제조<1-1> Preparation of Liquid Crystal Composition
실시예 2의 화합물을 50 mg(15 wt%) 및 광개시제를 1.5 mg 사용한 것을 제외하고는 상기 실험예 1의 <1-1>과 동일한 방법으로 액정 조성물을 제조하였다.
A liquid crystal composition was manufactured in the same manner as in <1-1> of Experimental Example 1, except that 50 mg (15 wt%) of the compound of Example 2 and 1.5 mg of the photoinitiator were used.
<1-2> 코팅-배향-경화<1-2> coating-orientation-curing
스핀 코팅온도 75 ℃, 5 J/cm2의 자외선을 조사하여 790 nm의 필름(P-3)을 제조하는 것을 제외하고는 상기 실험예 2의 <1-2>와 동일한 방법으로 제조하였다.
A spin coating temperature of 75 ° C. was prepared in the same manner as in <1-2> of Experimental Example 2, except that 790 nm film (P-3) was prepared by irradiation with ultraviolet rays at 5 J / cm2 .
<1-3> 배향 확인<1-3> Check the orientation
상기 실시예 1의 <1-3>과 동일한 방법으로 확인하였다.
It confirmed by the same method as <1-3> of Example 1.
<1-4> 위상차 측정<1-4> Phase difference measurement
상기 실시예 1의 <1-4>와 동일한 방법으로 계산하여 하기 표 2에 나타내었고, 이때, 비교예 2로 사용한 화합물은 상기 실시예 2와 동일한 모핵과 치환기를 가지되 삼중결합이 없는 9,9-디에틸-9H-플루오렌-2,7-디일 비스(4-(6-(아크릴로일옥시)헥실옥시) 벤조에이트) 화합물이고, 상기와 동일한 방법으로 필름을 제조하여 제조된 필름(P-4)을 이용하여 계산된 복굴절 또한 하기 표 2에 나타내었다.Calculated in the same manner as in <1-4> of Example 1 shown in Table 2, wherein, the compound used in Comparative Example 2 has the same parent nucleus and substituents as in Example 2 but no triple bond 9, 9-diethyl-9H-fluorene-2,7-diyl bis (4- (6- (acryloyloxy) hexyloxy) benzoate) compound, a film prepared by producing a film in the same manner as described above The birefringence calculated using (P-4) is also shown in Table 2 below.
표 2에 나타난 바와 같이, 아세틸렌이 도입된 실시예 2의 화합물로 제조된 필름의 경우 아세틸렌이 도입되지 않은 비교예 2의 화합물로 제조된 필름보다 복굴절 값이 더 큰 것을 확인할 수 있다.As shown in Table 2, it can be seen that the birefringence value of the film prepared with the compound of Example 2 in which acetylene was introduced is greater than that of the film prepared with the compound of Comparative Example 2 without acetylene.
따라서, 본 발명에 따른 아세틸기가 도입된 화합물은 삼중결합이 도입되지 않은 비교예 2의 화합물에 비하여 복굴절의 편차가 더 크므로 광학 이방성이 더 우수한 것을 확인할 수 있다.
Therefore, it can be confirmed that the compound in which the acetyl group is introduced according to the present invention has better optical anisotropy because the deviation of birefringence is larger than that of the compound of Comparative Example 2 in which triple bond is not introduced.
Claims (9)
Translated fromKorean[화학식 1]
(상기 화학식 1에서,
Ar은 C6~C30의 방향족 또는 비방향족의 고리화합물이고, 이때 상기 방향족 또는 비방향족의 고리화합물은 비치환되거나 1 내지 5개의 할로겐 또는 C1~C8의 직쇄, 측쇄 또는 고리형 알킬로 치환되며;
A는
R은 C1~C7의 알킬렌이고, 상기 알킬렌기 중 1 이상의 메틸렌기는 O로 치환될 수 있고, 이때 치환된 O가 2 이상인 경우, O는 서로 인접하여 치환되지 않고;
X는 -O-이고;
Y는
n은 2 내지 6의 정수이다.).
A compound represented by the following formula (1):
[Formula 1]
(In Formula 1,
Ar is a C6 to C30 aromatic or non-aromatic cyclic compound, wherein the aromatic or non-aromatic cyclic compound is unsubstituted or substituted with 1 to 5 halogens or C1 to C8 straight, branched or cyclic alkyl. Substituted;
A is
R is C1 to C7 alkylene, wherein at least one methylene group of the alkylene group may be substituted with O, wherein when the substituted O is 2 or more, O is not substituted adjacent to each other;
X is -O-;
Y is
n is an integer from 2 to 6).
The compound of claim 1, wherein Ar is an aromatic or non-aromatic cyclic compound of C6 -C30 , wherein the aromatic or non-aromatic cyclic compound is unsubstituted or one or more of F, Cl, Br or methyl, ethyl, propyl, Isopropyl, butyl substituted compound.
3. The compound of claim 2, wherein Ar is phenylene, fluorene, triphenylene, coronene.
상기 Ar은
A는
R은 C1~C7의 알킬렌이고, 상기 알킬렌기 중 1 이상의 메틸렌기는 O로 치환될 수 있고, 이때 치환된 O가 2 이상인 경우, O는 서로 인접하여 치환되지 않고;
X는 -O- 이고;
Y는
n은 2 내지 6인 것을 특징으로 하는 화합물.
The method of claim 1,
The Ar
A is
R is C1 to C7 alkylene, wherein at least one methylene group of the alkylene group may be substituted with O, wherein when the substituted O is 2 or more, O is not substituted adjacent to each other;
X is -O-;
Y is
n is 2 to 6, characterized in that.
출발물질인 화학식 2의 화합물을 유기용매 및 염기하에서 화학식 3의 화합물과 반응시켜 화학식 4의 화합물을 제조하는 단계(단계 1);
상기 단계 1에서 제조된 화학식 4의 화합물을 유기 용매 및 산 존재하에 반응시켜 화학식 5의 화합물을 제조하는 단계(단계 2);
상기 단계 2에서 제조된 화학식 5의 화합물을 유기 용매 및 염기 존재하에 화학식 6의 화합물과 반응시켜 화학식 1의 화합물을 제조하는 단계(단계 3)를 포함하는 제1항의 화합물의 제조방법:
[반응식 1]
(상기 반응식 1에서,
Ar, A, R, X, Y 및 n은 상기 화학식 1에서 정의한 바와 같고,
THP는 테트라하이드로파이란이다.).
As shown in Scheme 1 below,
Preparing a compound of formula 4 by reacting a compound of formula 2, which is a starting material, with a compound of formula 3 in an organic solvent and a base (step 1);
Preparing a compound of Chemical Formula 5 by reacting the compound of Chemical Formula 4 prepared in Step 1 in the presence of an organic solvent and an acid (Step 2);
Method of preparing a compound of claim 1 comprising the step of preparing a compound of formula 1 by reacting the compound of formula 5 prepared in step 2 with a compound of formula 6 in the presence of an organic solvent and a base:
[Reaction Scheme 1]
(In the above Reaction Scheme 1,
Ar, A, R, X, Y and n are as defined in Formula 1,
THP is tetrahydroparan).
화학식 7의 화합물을 유기 용매 하에서 화학식 8의 화합물과 반응시켜 화학식 9의 화합물을 제조하는 단계(단계 i);
상기 단계 i에서 제조된 화학식 9의 화합물을 유기 용매 및 염기하에서 화학식 10의 DHP와 반응시켜 화학식 11의 화합물을 제조하는 단계(단계 ii);
상기 단계 ii에서 제조된 화학식 11의 화합물을 화학식 12의 화합물과 반응시켜 화학식 13의 화합물을 제조하는 단계(단계 iii);
상기 단계 iii에서 제조된 화학식 13의 화합물을 NaH와 반응시켜 화학식 14의 화합물을 제조하는 단계(단계 iv);
상기 단계 iv에서 제조된 화학식 14의 화합물을 유기 용매 하에서 메틸클로로카보네이트와 반응시켜 화학식 15의 화합물을 제조하는 단계(단계 v); 및
상기 단계 v에서 제조된 화학식 15의 화합물을 KOH와 반응시켜 화학식 3의 화합물을 제조하는 단계(단계 vi)를 포함하는 제1항의 화합물의 제조방법:
[반응식 2]
(상기 반응식 2에서,
A, R 및 X는 상기 화학식 1에서 정의한 바와 같고,
상기 DHP는 디하이드로파이란이고, THP는 테트라하이드로파이란이다.).
The method of claim 5, wherein the compound represented by the formula (3) is shown in Scheme 2,
Reacting a compound of formula 7 with a compound of formula 8 in an organic solvent to prepare a compound of formula 9 (step i);
Preparing a compound of formula 11 by reacting the compound of formula 9 prepared in step i with DHP of formula 10 in an organic solvent and a base (step ii);
Preparing a compound of formula 13 by reacting the compound of formula 11 prepared in step ii with a compound of formula 12 (step iii);
Preparing a compound of formula 14 by reacting the compound of formula 13 prepared in step iii with NaH (step iv);
Reacting the compound of Formula 14 prepared in step iv with methylchlorocarbonate in an organic solvent to prepare a compound of Formula 15 (step v); And
Method of preparing a compound of claim 1 comprising the step (step vi) of preparing a compound of formula 3 by reacting the compound of formula 15 prepared in step v with KOH:
[Reaction Scheme 2]
(In the above Reaction Scheme 2,
A, R and X are as defined in Formula 1,
The DHP is dihydroparan and THP is tetrahydroparan).
A polymerizable liquid crystal composition comprising the compound of claim 1.
A polymer film comprising the polymer of the compound of claim 1.
An optically anisotropic film using the polymer film of claim 8.
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|---|---|---|---|---|
| CN111171048A (en)* | 2020-01-20 | 2020-05-19 | 畅的新材料科技（上海）有限公司 | Spirooxazine photochromic compound and preparation method thereof |
| CN111808120A (en)* | 2020-06-11 | 2020-10-23 | 畅的新材料科技（上海）有限公司 | Photochromic compound of colorless-to-blue spirooxazine and preparation method and application thereof |
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| CN111788505B (en)* | 2018-03-19 | 2022-10-04 | 三菱化学株式会社 | Composition for forming anisotropic dye film, anisotropic dye film and optical element |
| JP7272022B2 (en)* | 2018-03-19 | 2023-05-12 | 三菱ケミカル株式会社 | Composition for forming anisotropic dye film, anisotropic dye film, and optical element |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008050440A (en) | 2006-08-23 | 2008-03-06 | Fujifilm Corp | Polymerizable monomer, polymer compound, optical anisotropic film, optical compensation sheet, polarizing plate and liquid crystal display device, and method for producing optical compensation sheet |
| WO2008061606A1 (en) | 2006-11-24 | 2008-05-29 | Merck Patent Gmbh | Cyclohexylene reactive mesogens and their applications |
| KR20100003716A (en)* | 2008-07-01 | 2010-01-11 | 주식회사 엘지화학 | Pressure-sensitive adhesive composition, polarizer and liquid crystal display |
- 2011
- 2011-06-17KRKR1020110059223Apatent/KR101308544B1/ennot_activeExpired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008050440A (en) | 2006-08-23 | 2008-03-06 | Fujifilm Corp | Polymerizable monomer, polymer compound, optical anisotropic film, optical compensation sheet, polarizing plate and liquid crystal display device, and method for producing optical compensation sheet |
| WO2008061606A1 (en) | 2006-11-24 | 2008-05-29 | Merck Patent Gmbh | Cyclohexylene reactive mesogens and their applications |
| KR20100003716A (en)* | 2008-07-01 | 2010-01-11 | 주식회사 엘지화학 | Pressure-sensitive adhesive composition, polarizer and liquid crystal display |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111171048A (en)* | 2020-01-20 | 2020-05-19 | 畅的新材料科技（上海）有限公司 | Spirooxazine photochromic compound and preparation method thereof |
| CN111808120A (en)* | 2020-06-11 | 2020-10-23 | 畅的新材料科技（上海）有限公司 | Photochromic compound of colorless-to-blue spirooxazine and preparation method and application thereof |
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