TW202305096A - Liquid crystal compound with negative dielectric anisotropy, liquid crystal composition and liquid crystal display device - Google Patents
Liquid crystal compound with negative dielectric anisotropy, liquid crystal composition and liquid crystal display device Download PDFInfo
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Abstract
Description
本發明涉及液晶顯示材料領域，具體涉及具有負介電各向異性的液晶化合物、液晶組合物及液晶顯示器件。The invention relates to the field of liquid crystal display materials, in particular to a liquid crystal compound with negative dielectric anisotropy, a liquid crystal composition and a liquid crystal display device.
目前，液晶化合物的應用範圍拓展的越來越廣，其可應用於多種類型的顯示器、電光器件、傳感器等中。用於上述顯示領域的液晶化合物的種類繁多，其中向列相液晶應用最為廣泛。向列相液晶已經應用在無源TN、STN矩陣顯示器和具有TFT有源矩陣的系統中。At present, the application range of liquid crystal compounds is expanding more and more widely, and it can be applied to various types of displays, electro-optic devices, sensors, and the like. There are various types of liquid crystal compounds used in the above-mentioned display fields, among which nematic liquid crystals are most widely used. Nematic liquid crystals have been used in passive TN, STN matrix displays and systems with TFT active matrix.
對於薄膜晶體管技術(TFT-LCD)應用領域，近年來市場雖然已經非常巨大，技術也逐漸成熟，但人們對顯示技術的要求也在不斷的提高，尤其是在實現快速響應，降低驅動電壓以降低功耗等方面。液晶材料作為液晶顯示器重要的光電子材料之一，對改善液晶顯示器的性能發揮重要的作用。For the application field of thin film transistor technology (TFT-LCD), although the market has been huge in recent years and the technology has gradually matured, people's requirements for display technology are also constantly improving, especially in achieving fast response and reducing driving voltage to reduce power consumption etc. As one of the important optoelectronic materials of liquid crystal display, liquid crystal material plays an important role in improving the performance of liquid crystal display.
隨著TFT-LCD的不斷發展，寬視角模式已成為行業內追求的目標，目前主流的寬視角技術主要採用VA垂直取向、IPS面內開關及FFS邊緣場開關等顯示類型。這些顯示模式，廣泛採用具有負介電各向異性的液晶介質。對於用於這些模式的液晶介質，對其響應時間的要求越來越高。而液晶介質的響應時間受到粘度、清亮點T NI(℃)、彈性係數、折光率等多個因素的影響，如何獲得這些因素綜合作用下的響應時間提高的液晶化合物是本領域亟待解決的問題之一。 With the continuous development of TFT-LCD, the wide viewing angle mode has become the goal pursued by the industry. At present, the mainstream wide viewing angle technology mainly adopts display types such as VA vertical orientation, IPS in-plane switching and FFS fringe field switching. For these display modes, liquid crystal media with negative dielectric anisotropy are widely used. The demands on the response time of the liquid-crystalline media used in these modes are increasingly higher. However, the response time of liquid crystal media is affected by multiple factors such as viscosity, clearing point T NI (°C), elastic coefficient, and refractive index. How to obtain liquid crystal compounds with improved response time under the combined effects of these factors is an urgent problem to be solved in this field. one.
本發明針對上述現有技術存在的問題，進行了深入的研究後發現，採用本發明的式I所示的以二苯並噻吩或二苯並呋喃為核心結構，並且通過連接基團在二苯並噻吩或二苯並呋喃的兩側鍵合有數量相等的環己基、芳香環、雜芳基等環狀基團的液晶化合物，能夠獲得在維持一定水平的負型介電常數的基礎上具有提高的響應時間的新型液晶化合物，由此完成了本發明。The present invention aims at the problems existing in the above-mentioned prior art. After in-depth research, it is found that the core structure of dibenzothiophene or dibenzofuran shown in the formula I of the present invention is used, and the dibenzothiophene or dibenzofuran is used as the core structure through the linking group. Liquid crystal compounds with an equal number of cyclic groups such as cyclohexyl, aromatic rings, and heteroaryl groups bonded to both sides of thiophene or dibenzofuran can obtain a certain level of negative dielectric constant on the basis of improved The novel liquid crystal compound of the response time of , thus completed the present invention.
對於液晶介質，根據顯示模式的不同，液晶介質的響應時間與G1/K 11或者G1/K 33相關。進一步，本發明人等研究發現，除了G1、K 11、K 33等因素之外，液晶介質的響應時間還與清亮點T NI(℃)、折光率Δn相關，具體地，在VA（vertical alignment，垂直取向）或者PS-VA（Polymer stabilized vertical alignment,聚合物穩定垂直取向）模式下，液晶介質的響應時間與G1/(K 33*△n*△n*T NI)的值相關，而在FFS（Fringe Field Switching，邊緣場開關）、IPS（In-Plane Switching，平面轉換）、PS-FFS（Polymer stabilized Fringe Field Switching，聚合物穩定邊緣場開關）、PS-IPS（Polymer stabilized In-Plane Switching，聚合物穩定平面轉換）等模式下，液晶介質的響應時間與G1/(K 11*△n*△n*T NI)的值相關。在本申請中，將G1/(K 33*△n*△n*T NI)、G1/(K 11*△n*△n*T NI)的值稱為響應指標值。前述響應指標值越小，表明液晶介質的響應時間越快。本發明的具有負介電各向異性的液晶化合物在維持一定水平的負型介電常數的基礎上具有小的響應指標值從而具有提高的響應時間。 For liquid crystal media, according to different display modes, the response time of liquid crystal media is related to G1/K 11 or G1/K 33 . Further, the inventors of the present invention have found that, in addition to G1, K 11 , K 33 and other factors, the response time of the liquid crystal medium is also related to the clearing point T NI (°C) and the refractive index Δn, specifically, in VA (vertical alignment , vertical alignment) or PS-VA (Polymer stabilized vertical alignment, polymer stabilized vertical alignment) mode, the response time of the liquid crystal medium is related to the value of G1/(K 33 *△n*△n*T NI ), while in FFS (Fringe Field Switching, fringe field switching), IPS (In-Plane Switching, plane switching), PS-FFS (Polymer stabilized Fringe Field Switching, polymer stabilized fringe field switching), PS-IPS (Polymer stabilized In-Plane Switching , polymer stabilized in-plane switching) and other modes, the response time of the liquid crystal medium is related to the value of G1/(K 11 *△n*△n*T NI ). In the present application, the values of G1/(K 33 *Δn*Δn*T NI ) and G1/(K 11 *Δn*Δn*T NI ) are referred to as response index values. The smaller the aforementioned response index value, the faster the response time of the liquid crystal medium. The liquid crystal compound with negative dielectric anisotropy of the present invention has a small response index value and thus an improved response time on the basis of maintaining a certain level of negative dielectric constant.
本發明包括下述的技術方案：The present invention comprises following technical scheme:
一方面，本發明提供一種具有負介電各向異性的液晶化合物，所述化合物具有下述的式Ⅰ所示的結構：
式I中，R 1、R 2各自獨立地表示氫原子、C1～C8的直鏈烷基、C1～C8的直鏈烷氧基、C2～C8的直鏈烯基、C2～C8的直鏈烯氧基,其中一個或兩個不相鄰的-CH 2-任選被-O-取代,任意H任選被F原子取代； In Formula I, R 1 and R 2 each independently represent a hydrogen atom, C1-C8 straight-chain alkyl, C1-C8 straight-chain alkoxy, C2-C8 straight-chain alkenyl, C2-C8 straight-chain Alkenyloxy, wherein one or two non-adjacent -CH 2 -s are optionally substituted by -O-, and any H is optionally substituted by an F atom;
Z 1、Z 2各自獨立地表示-C 2H 2-、-C 2H 4-、-C 2H 2CH 2O-、-OCH 2C 2H 2-、-CH 2O-、-OCH 2-、-C 2H 2CH 2S-、-SCH 2C 2H 2-、-CH 2S-、-SCH 2-、-O-、-S-、-CF 2O-、-OCF 2-、-C≡C-、-OOC-、或者-COO-、當Z 1、Z 2表示-CH 2O-、-C 2H 2-、-C 2H 4-、-C 2H 2CH 2O-、或者-OCH 2C 2H 2-時，任意H任選被F取代； Z 1 and Z 2 each independently represent -C 2 H 2 -, -C 2 H 4 -, -C 2 H 2 CH 2 O-, -OCH 2 C 2 H 2 -, -CH 2 O-, -OCH 2 -, -C 2 H 2 CH 2 S-, -SCH 2 C 2 H 2 -, -CH 2 S-, -SCH 2 -, -O-, -S-, -CF 2 O-, -OCF 2 -, -C≡C-, -OOC-, or -COO-, when Z 1 and Z 2 represent -CH 2 O-, -C 2 H 2 -, -C 2 H 4 -, -C 2 H 2 CH 2 O-, or -OCH 2 C 2 H 2 -, any H is optionally substituted by F;
Y 1、Y 2表示-F-、-OCH 2F-、-OCHF 2-、-OCF 3-或者不同時表示-F-； Y 1 and Y 2 represent -F-, -OCH 2 F-, -OCHF 2- , -OCF 3 - or -F- at the same time;
n表示0、1、2或者3。n represents 0, 1, 2 or 3.
本發明另一方面提供一種液晶組合物，其含有前述的本發明的具有負介電各向異性的液晶化合物。Another aspect of the present invention provides a liquid crystal composition, which contains the aforementioned liquid crystal compound with negative dielectric anisotropy of the present invention.
本發明的又一方面提供一種液晶顯示器件，其含有前述的本發明的具有負介電各向異性的液晶化合物或者前述的本發明的液晶組合物。Still another aspect of the present invention provides a liquid crystal display device, which contains the aforementioned liquid crystal compound with negative dielectric anisotropy of the present invention or the aforementioned liquid crystal composition of the present invention.
發明效果Invention effect
與現有技術相比，本發明的具有負介電各向異性的液晶化合物在維持一定水平的負型介電常數的基礎上具有小的響應指標值從而具有更快的響應時間。通過在本發明的液晶組合物中使用本發明的具有負介電各向異性的液晶化合物，在本發明的液晶顯示器件中含有使用了本發明的液晶化合物的液晶組合物，能夠使得顯示裝置的響應時間更快。Compared with the prior art, the liquid crystal compound with negative dielectric anisotropy of the present invention has a small response index value on the basis of maintaining a certain level of negative dielectric constant and thus has a faster response time. By using the liquid crystal compound with negative dielectric anisotropy of the present invention in the liquid crystal composition of the present invention, and containing the liquid crystal composition using the liquid crystal compound of the present invention in the liquid crystal display device of the present invention, the display device can be made Response time is faster.
以下將結合具體實施方案來說明本發明。需要說明的是，下面的實施例為本發明的示例，僅用來說明本發明，而不用來限制本發明。在不偏離本發明主旨或範圍的情況下，可進行本發明構思內的其他組合和各種改良。The present invention will be described below in combination with specific embodiments. It should be noted that the following examples are examples of the present invention, and are only used to illustrate the present invention, not to limit the present invention. Other combinations and various modifications within the concept of the present invention can be made without departing from the spirit or scope of the present invention.
[具有負介電各向異性的液晶化合物][Liquid Crystal Compounds with Negative Dielectric Anisotropy]
本發明的具有負介電各向異性的液晶化合物具有下述的式Ⅰ所示的結構：
式I中，R 1、R 2各自獨立地表示氫原子、C1～C8的直鏈烷基、C1～C8的直鏈烷氧基、C2～C8的直鏈烯基、或者C2～C8的直鏈烯氧基，其中一個或兩個不相鄰的-CH 2-任選被-O-取代，任意H任選被F原子取代； In formula I, R 1 and R 2 each independently represent a hydrogen atom, C1-C8 straight-chain alkyl, C1-C8 straight-chain alkoxy, C2-C8 straight-chain alkenyl, or C2-C8 straight-chain Alkenyloxy, wherein one or two non-adjacent -CH 2 -s are optionally substituted by -O-, and any H is optionally substituted by an F atom;
Z 1、Z 2各自獨立地表示-C 2H 2-、-C 2H 4-、-C 2H 2CH 2O-、-OCH 2C 2H 2-、-CH 2O-、-OCH 2-、-C 2H 2CH 2S-、-SCH 2C 2H 2-、-CH 2S-、-SCH 2-、-O-、-S-、-CF 2O-、-OCF 2-、-C≡C-、-OOC-或者-COO-，當Z 1、Z 2表示-CH 2O-、-C 2H 2-、-C 2H 4-、-C 2H 2CH 2O-、或者-OCH 2C 2H 2-時，其中任意H任選被F取代； Z 1 and Z 2 each independently represent -C 2 H 2 -, -C 2 H 4 -, -C 2 H 2 CH 2 O-, -OCH 2 C 2 H 2 -, -CH 2 O-, -OCH 2 -, -C 2 H 2 CH 2 S-, -SCH 2 C 2 H 2 -, -CH 2 S-, -SCH 2 -, -O-, -S-, -CF 2 O-, -OCF 2 -, -C≡C-, -OOC- or -COO-, when Z 1 and Z 2 represent -CH 2 O-, -C 2 H 2 -, -C 2 H 4 -, -C 2 H 2 CH 2 O-, or -OCH 2 C 2 H 2 -, wherein any H is optionally substituted by F;
Y 1、Y 2表示-F-、-OCH 2F-、-OCHF 2-、-OCF 3-或者不同時表示-F-； Y 1 and Y 2 represent -F-, -OCH 2 F-, -OCHF 2- , -OCF 3 - or -F- at the same time;
n表示0、1、2或3。n represents 0, 1, 2 or 3.
作為前述的“C1～C8的直鏈烷基”，可以列舉出例如，甲基、乙基、正丙基、正丁基、正戊基、正己基、正庚基、正辛基等。Examples of the "C1-C8 linear alkyl group" include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl and the like.
作為前述的“C1～C8的直鏈烷氧基”，可以列舉出例如，甲氧基、乙氧基、正丙氧基、正丁氧基、正戊氧基、正己氧基、正庚氧基、正辛氧基等。Examples of the aforementioned "C1-C8 linear alkoxy group" include methoxy, ethoxy, n-propoxy, n-butoxy, n-pentyloxy, n-hexyloxy, n-heptyloxy base, n-octyloxy group, etc.
作為前述的“C2～C8的直鏈烯基”，可以列舉出例如，乙烯基、1-丙烯基、2-丙烯基、1-丁烯基、2-丁烯基、3-丁烯基、1-戊烯基、2-戊烯基、1-己烯基、2-己烯基、3-己烯基、1-庚烯基、2-庚烯基、3-庚烯基、1-辛烯基、2-辛烯基、3-辛烯基。Examples of the aforementioned "C2-C8 linear alkenyl group" include vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 1-heptenyl, 2-heptenyl, 3-heptenyl, 1- Octenyl, 2-octenyl, 3-octenyl.
作為前述的“C2～C8的直鏈烯氧基”，可以列舉出例如，乙烯氧基、1-丙烯氧基、2-丙烯氧基、1-丁烯氧基、2-丁烯氧基、3-丁烯氧基、1-戊烯氧基、2-戊烯氧基、1-己烯氧基、2-己烯氧基、3-己烯氧基、1-庚烯氧基、2-庚烯氧基、3-庚烯氧基、1-辛烯氧基、2-辛烯氧基、3-辛烯氧基等。Examples of the aforementioned "C2-C8 linear alkenyloxy group" include ethyleneoxy, 1-propyleneoxy, 2-propyleneoxy, 1-butenyloxy, 2-butenyloxy, 3-butenyloxy, 1-pentenyloxy, 2-pentenyloxy, 1-hexenyloxy, 2-hexenyloxy, 3-hexenyloxy, 1-heptenyloxy, 2 -heptenyloxy, 3-heptenyloxy, 1-octenyloxy, 2-octenyloxy, 3-octenyloxy and the like.
前述的“一個或兩個不相鄰的-CH 2-任選被-O-取代”是指，前述的C1～C8的直鏈烷基、C1～C8的直鏈烷氧基、C2～C8的直鏈烯基、C2～C8的直鏈烯氧基中的任意-CH 2-任選被取代為-O-，但是相鄰的-CH 2-不會同時被取代。 The aforementioned "one or two non-adjacent -CH 2 - optionally substituted by -O-" refers to the aforementioned C1-C8 straight-chain alkyl, C1-C8 straight-chain alkoxy, C2-C8 Any -CH 2 - in the straight-chain alkenyl group and C2-C8 straight-chain alkenyloxy group can be optionally substituted with -O-, but the adjacent -CH 2 - will not be substituted at the same time.
前述的“任意H任選被F原子取代”，是指，對於F取代的個數沒有任何的限定，可以為單氟取代、多氟取代、或者全氟取代。The aforementioned "any H is optionally substituted by an F atom" means that there is no limitation on the number of F substitutions, which may be monofluoro, polyfluoro, or perfluoro substituted.
優選地，前述R 1、R 2各自獨立地表示氫原子、C1～C5的直鏈烷基、C1～C5的直鏈烷氧基、C2～C5的直鏈烯基、或者、C2～C5的直鏈烯氧基，其中一個或兩個不相鄰的-CH 2-任選被-O-取代，任意H任選被F原子取代。 Preferably, the aforementioned R 1 and R 2 each independently represent a hydrogen atom, a C1-C5 straight-chain alkyl group, a C1-C5 straight-chain alkoxy group, a C2-C5 straight-chain alkenyl group, or a C2-C5 Straight-chain alkenyloxy, wherein one or two non-adjacent -CH 2 -s are optionally substituted by -O-, and any H is optionally substituted by F atoms.
前述的“C1～C5的直鏈烷基”，可以列舉出例如，甲基、乙基、正丙基、正丁基、正戊基。優選為甲基、乙基或者正丙基。The aforementioned "C1-C5 linear alkyl group" includes, for example, methyl group, ethyl group, n-propyl group, n-butyl group, and n-pentyl group. Preferred is methyl, ethyl or n-propyl.
作為前述的“C1～C5的直鏈烷氧基”，可以列舉出例如，甲氧基、乙氧基、正丙氧基、正丁氧基、正戊氧基。優選為甲氧基、乙氧基或者正丙氧基。Examples of the "C1-C5 linear alkoxy group" include methoxy, ethoxy, n-propoxy, n-butoxy, and n-pentoxy. Preference is given to methoxy, ethoxy or n-propoxy.
作為前述的“C2～C5的直鏈烯基”，可以列舉出例如，乙烯基、1-丙烯基、2-丙烯基、1-丁烯基、2-丁烯基、3-丁烯基、1-戊烯基、2-戊烯基、3-戊烯基。優選為乙烯基、1-丙烯基、3-丁烯基、或者、3-戊烯基。Examples of the aforementioned "C2-C5 linear alkenyl group" include vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl. Preferred is vinyl, 1-propenyl, 3-butenyl, or 3-pentenyl.
作為前述的“C2～C5的直鏈烯氧基”，可以列舉出例如，乙烯氧基、1-丙烯氧基、2-丙烯氧基、1-丁烯氧基、2-丁烯氧基、3-丁烯氧基、1-戊烯氧基、2-戊烯氧基、3-戊烯氧基。優選為乙烯氧基、1-丙烯氧基、3-丁烯氧基、或者、3-戊烯氧基。Examples of the aforementioned "C2-C5 linear alkenyloxy group" include ethyleneoxy, 1-propyleneoxy, 2-propyleneoxy, 1-butenyloxy, 2-butenyloxy, 3-butenyloxy, 1-pentenyloxy, 2-pentenyloxy, 3-pentenyloxy. Preferably, it is ethyleneoxy, 1-propyleneoxy, 3-butenyloxy, or 3-pentenyloxy.
前述的C1～C5的直鏈烷基、C1～C5的直鏈烷氧基、C2～C5的直鏈烯基、或者、C2～C5的直鏈烯氧基中，一個或兩個不相鄰的-CH2-任選被-O-取代，任意H任選被F原子取代。One or two of the aforementioned C1-C5 straight-chain alkyl, C1-C5 straight-chain alkoxy, C2-C5 straight-chain alkenyl, or C2-C5 straight-chain alkenyloxy are not adjacent The -CH2- is optionally substituted by -O-, and any H is optionally substituted by an F atom.
式I中，n表示0、1、2、或者3，從獲得更小的響應指標值從而具有更快的響應時間等方面考慮，n優選為0、1或者2，進一步優選為n=0或者2。In formula I, n represents 0, 1, 2, or 3, and from aspects such as obtaining a smaller response index value and thus having a faster response time, n is preferably 0, 1 or 2, and is more preferably n=0 or 2.
本發明的具有負介電各向異性的液晶化合物中，優選地，其選自下述的式IA~IZK、Ia-Izk所示化合物組成。
其中，R 1、R 2的定義與前述相同。 Wherein, the definitions of R 1 and R 2 are the same as above.
進一步，本發明的具有負介電各向異性的液晶化合物優選為選自下述的式IA-1~IZK-4、Ia-1~Izk-4所示的化合物組成的組，其中，Alkyl各自獨立地表示C1～C8的直鏈烷基、Alkenyl各自獨立地表示C2～C8的直鏈烯基，
[液晶化合物的製備方法][Preparation method of liquid crystal compound]
下面，對本發明的具有負介電各向異性的液晶化合物的製備方法進行說明。Next, the preparation method of the liquid crystal compound having negative dielectric anisotropy of the present invention will be described.
需要理解的是，本發明的具有負介電各向異性的液晶化合物的製備方法，並非限於下述說明的製備方法。本領域技術人員可以採用其他的適宜的方法進行製備。It should be understood that the preparation method of the liquid crystal compound with negative dielectric anisotropy of the present invention is not limited to the preparation method described below. Those skilled in the art can use other suitable methods for preparation.
另外，下述的說明中對於式I所述的部分化合物進行說明，對於其他的化合物，本領域技術人員可以參照下述的說明並結合本領域的常規技術手段來獲得。In addition, part of the compounds described in formula I are described in the following descriptions, and other compounds can be obtained by those skilled in the art by referring to the following descriptions in combination with conventional technical means in the field.
採用包括如下製備步驟的方法製備前述式ⅠA所示的液晶化合物，其中，R
1、R
2的定義與前述相同。
步驟IA1：溴苯酚與R
1取代苯硼酸進行鈴木反應，生成聯苯化合物(A)；
步驟IA2：將前述的聯苯化合物(A)於強鹼下反應，生成單邊R
1氧基取代的三氟甲氧基化氟化氧芴(B)；
步驟IA3：將前述步驟IA2獲得的單邊R
1氧基取代的三氟甲氧基化氟化氧芴 (B)與鋰試基反應，後續與硼酸酯反應、水解、氧化生成酚基，獲得帶有酚基的單邊R
1氧基取代的三氟甲氧基化氟化氧芴(C)；
步驟IA4：將酚基的單邊R
1氧基取代的三氟甲氧基化氟化氧芴 (C)與帶有R
2溴(或碘)化合物於鹼性條件反應生成兩邊對稱或不對稱的氧基三氟甲氧基化氟化氧芴(IA)；
採用包括如下製備步驟的方法製備前述式Ⅰa所示的液晶化合物，其中，R
1、R
2的定義與前述相同。
步驟Ia1：三氟甲氧基苯硼酸與帶有R
1氧基取代溴苯進行鈴木反應，得到聯苯化合物(A)；
步驟Ia2：將前述的聯苯化合物(A)、三級胺與三氟甲磺酸酐反應，把酚基轉換成三氟甲磺酸基生成聯苯化合物 (B)；
步驟Ia3：將前述步驟Ia2獲得的聯苯化合物(B)與硫醇反應，在鈀金屬催化下進行耦合反應，得到具有硫醚的聯苯化合物 (C-2)；
步驟Ia4：將前述步驟Ia3獲得的具有硫醚的聯苯化合物(C-2)在強鹼下反應，獲得單邊對位R
1氧基取代的三氟甲氧基化氟化硫芴(D)；
步驟Ia5：將單邊對位R
1氧基取代的三氟甲氧基化氟化硫芴(D)與鋰試劑反應，後續與硼酸酯反應、水解、氧化合成出酚基，獲得帶有酚基的單邊R
1氧基取代的三氟甲氧基化氟化硫芴(E)；
步驟Ia6：將帶有酚基的單邊R
1氧基取代的三氟甲氧基化氟化硫芴(E)與帶有R
2溴(或碘)化合物於鹼性條件反應生成兩邊對稱或不對稱的甲氧基三氟甲氧基化氟化硫芴(Ia)。
以上，示出了前述的式IA、式Ia所示化合物的製備方法。對於其他化合物的製備，本領域技術人員能夠參照前述製備方法，根據本領域的技術常識，改變前述製備方法中的反應原料進行製備，沒有特別的限定。Above, the preparation method of the compound represented by the aforementioned formula IA and formula Ia is shown. For the preparation of other compounds, those skilled in the art can refer to the above-mentioned preparation methods, and according to the technical knowledge in the field, change the reaction raw materials in the above-mentioned preparation methods for preparation, without special limitation.
[液晶組合物][Liquid Crystal Composition]
本發明液晶組合物中含有本發明的具有負介電各向異性的液晶化合物。The liquid crystal compound of the present invention having negative dielectric anisotropy is contained in the liquid crystal composition of the present invention.
本發明的液晶組合物中，可以含有一種或者多種本發明的負介電各向異性的液晶化合物，每一種本發明的負介電各向異性的液晶化合物的含量按照重量百分含量計算可以為例如20%以下。從低溫溶解性、可靠性等方面考慮，優選為15%以下的範圍。含有多種本發明的負介電各向異性的液晶化合物時，本發明的負介電各向異性的液晶化合物的含量的總和以重量百分含量計算可以為例如50%以下。In the liquid crystal composition of the present invention, one or more liquid crystal compounds with negative dielectric anisotropy of the present invention can be contained, and the content of each liquid crystal compound with negative dielectric anisotropy of the present invention can be calculated by weight percentage. For example, below 20%. From the viewpoint of low-temperature solubility, reliability, etc., it is preferably in the range of 15% or less. When multiple liquid crystal compounds with negative dielectric anisotropy of the present invention are contained, the total content of the liquid crystal compounds with negative dielectric anisotropy of the present invention may be, for example, 50% or less in weight percent.
本發明的液晶組合物中，除了前述的具有負介電各向異性的液晶化合物之外，本領域技術人員還可以在不破壞其期望的液晶組合物的性能的基礎上添加其他液晶化合物。In the liquid crystal composition of the present invention, in addition to the aforementioned liquid crystal compound with negative dielectric anisotropy, those skilled in the art can also add other liquid crystal compounds on the basis of not destroying the desired properties of the liquid crystal composition.
本發明的液晶組合物中，可選的，還可以加入各種功能的摻雜劑，這些摻雜劑可以列舉出例如抗氧化劑、紫外線吸收劑、手性劑。Optionally, various functional dopants may be added to the liquid crystal composition of the present invention, and these dopants include, for example, antioxidants, ultraviolet absorbers, and chiral agents.
如前所述，本發明的液晶組合物中雖然含有本發明的具有負性介電各向異性的液晶化合物，但是本發明的組合物並非一定為負性介電各向異性，其也可以為正性介電各向異性。本領域技術人員能夠根據需要調節組合物各組分的組成及配比來獲得具有需要的各向異性的組合物。As mentioned above, although the liquid crystal composition of the present invention contains the liquid crystal compound with negative dielectric anisotropy of the present invention, the composition of the present invention does not necessarily have negative dielectric anisotropy, and it can also be Positive dielectric anisotropy. A person skilled in the art can adjust the composition and proportion of each component of the composition as required to obtain a composition with desired anisotropy.
對於本發明的液晶組合物的製備，沒有特別的限定。在含有本發明的液晶化合物的基礎上，本領域技術人員能夠根據需要，選擇適宜的其他組分進行調製。The preparation of the liquid crystal composition of the present invention is not particularly limited. On the basis of containing the liquid crystal compound of the present invention, those skilled in the art can select appropriate other components for preparation as required.
[液晶顯示器件][Liquid crystal display device]
本發明的第三方面提供一種液晶顯示器件，其只要包含前述的本發明的具有負介電各向異性的液晶化合物，或者前述的液晶組合物，就沒有特別的限定。本發明的液晶顯示器件可以為有源矩陣顯示器件，也可以為無源矩陣顯示器件。本領域技術人員能夠根據所需的性能選擇合適的液晶顯示組件、液晶顯示器的結構。The third aspect of the present invention provides a liquid crystal display device, which is not particularly limited as long as it contains the aforementioned liquid crystal compound with negative dielectric anisotropy of the present invention, or the aforementioned liquid crystal composition. The liquid crystal display device of the present invention may be an active matrix display device or a passive matrix display device. Those skilled in the art can select a suitable liquid crystal display component and structure of the liquid crystal display according to the required performance.
實施例Example
實施例1Example 1
B(S)[F,OT]-2O-O5
合成路線:
取0.5g 6-溴代-3-乙氧基-2-氟苯酚(2.13mmole)與0.44g 碳酸鉀於氮氣下以6ml THF與4ml水溶解後，加入含有0.48g (2-氟-3-(三氟甲氧基)苯基)硼酸 (2.13mmole)、0.036g 雙(二亞苄基丙酮)鈀(0)(0.06 mmole)與32.0mg CataCXium A (Di(1-adamantyl)-n-butylphosphine, 二(1-金剛烷基)-正丁基膦, C 24H 39P, 0.09 mmole)的8ml THF溶液，接著進行回流反應至隔日。隔日待反應溫度回到室溫後，將反應液以乙酸乙酯-水進行萃取、收集有機層，隨後將有機層以無水硫酸鎂除水、減壓濃縮。將濃縮物進行管柱層析，得到0.49g透明液體狀的化合物A1。 After taking 0.5g of 6-bromo-3-ethoxy-2-fluorophenol (2.13mmol) and 0.44g of potassium carbonate dissolved in 6ml of THF and 4ml of water under nitrogen, add 0.48g of (2-fluoro-3- (Trifluoromethoxy)phenyl)boronic acid (2.13mmole), 0.036g bis(dibenzylideneacetone)palladium(0) (0.06 mmole) and 32.0mg CataCXium A (Di(1-adamantyl)-n-butylphosphine , bis(1-adamantyl)-n-butylphosphine, C 24 H 39 P, 0.09 mmole) in 8 ml THF solution, followed by reflux reaction until next day. The next day, after the reaction temperature returned to room temperature, the reaction solution was extracted with ethyl acetate-water, and the organic layer was collected. Then, the organic layer was dehydrated with anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate was subjected to column chromatography to obtain 0.49 g of compound A1 as a transparent liquid.
1H-NMR(500MHz, CD 2Cl 2, ppm)：9.58 (s, 1H)、7.43 (d, 1H)、7.37 (d, 1H)、7.21 (t, 1H)、7.04 (d, 1H)、6.87 (d, 1H)、4.07 (q, 2H)、1.34 (t, 3H)。 1 H-NMR (500MHz, CD 2 Cl 2 , ppm): 9.58 (s, 1H), 7.43 (d, 1H), 7.37 (d, 1H), 7.21 (t, 1H), 7.04 (d, 1H), 6.87 (d, 1H), 4.07 (q, 2H), 1.34 (t, 3H).
取0.5g 化合物A1(1.50 mmole)於氮氣下以8ml THF溶解後，將反應瓶放入冰浴中冷卻，之後加入0.12g DMAP (1.65 mmole)與0.42g 三氟甲磺酸酐 (1.50 mmole) 。在冰浴下反應30分鐘後，接著在室溫下反應至隔日。反應完畢後，將反應液進行減壓濃縮，得到的濃縮液進行管柱層析，得到0.42g微黃色液體狀化合物B1。After dissolving 0.5g of compound A1 (1.50 mmole) in 8ml THF under nitrogen, the reaction bottle was cooled in an ice bath, and then 0.12g DMAP (1.65 mmole) and 0.42g trifluoromethanesulfonic anhydride (1.50 mmole) were added. After reacting in an ice bath for 30 minutes, it was then reacted at room temperature until the next day. After the reaction was completed, the reaction solution was concentrated under reduced pressure, and the obtained concentrated solution was subjected to column chromatography to obtain 0.42 g of compound B1 as a light yellow liquid.
1H-NMR(500MHz, CD 2Cl 2, ppm)：7.61 (d, 1H)、7.43 (d, 1H)、7.3 (d, 1H)、7.21 (t, 1H)、7.04 (d, 1H)、4.07 (q, 2H)、1.34 (t, 3H)。 1 H-NMR (500MHz, CD 2 Cl 2 , ppm): 7.61 (d, 1H), 7.43 (d, 1H), 7.3 (d, 1H), 7.21 (t, 1H), 7.04 (d, 1H), 4.07 (q, 2H), 1.34 (t, 3H).
取0.6g 化合物B1(1.28 mmole)、0.17g 3-巰基丙酸乙酯(1.28mmole)、0.18g 碳酸鉀(1.28mmole)、64mg 雙[(2-二苯基膦基)苯基]醚(0.12mmole)與35mg 雙（二亞苄基丙酮）鈀(0) (0.06mmole)於反應瓶內，並且將氣體置換成氮氣，之後加入甲苯進行回流反應至隔天。反應完畢後降溫，將反應液以矽膠短管柱過濾、減壓濃縮，得到化合物C1。Take 0.6g compound B1 (1.28 mmole), 0.17g ethyl 3-mercaptopropionate (1.28 mmole), 0.18 g potassium carbonate (1.28 mmole), 64 mg bis[(2-diphenylphosphino)phenyl]ether ( 0.12 mmole) and 35 mg bis(dibenzylideneacetone) palladium (0) (0.06 mmole) in the reaction flask, and the gas was replaced with nitrogen, and then added toluene for reflux reaction until the next day. After the reaction was completed, the temperature was lowered, the reaction solution was filtered through a short silica gel column, and concentrated under reduced pressure to obtain compound C1.
1H-NMR(500MHz, CDCl 3, ppm)：7.44 (m, 2H)、7.21 (t, 1H)、7.07 (m, 2H) 、4.05 (m, 4H)、3.17 (t, 2H)、2.61 (t, 2H)、1.34 (t, 3H)、1.07 (t, 3H)。 1 H-NMR (500MHz, CDCl 3 , ppm): 7.44 (m, 2H), 7.21 (t, 1H), 7.07 (m, 2H), 4.05 (m, 4H), 3.17 (t, 2H), 2.61 ( t, 2H), 1.34 (t, 3H), 1.07 (t, 3H).
將化合物C1的濃縮液加入含有0.158g 叔丁醇鉀(1.4mmole)的12ml 甲苯溶液，之後加熱回流反應至隔夜。反應完畢、待溫度降溫後，使用乙酸乙酯與水進行萃取、收集有機層減壓濃縮。將得到的濃縮液進行管柱層析，得到白色固體狀化合物D1。The concentrated solution of compound C1 was added to a solution of 0.158 g potassium tert-butoxide (1.4 mmole) in 12 ml of toluene, and then heated under reflux to react overnight. After the reaction was completed and the temperature dropped, ethyl acetate and water were used for extraction, and the collected organic layer was concentrated under reduced pressure. The obtained concentrate was subjected to column chromatography to obtain Compound D1 as a white solid.
1H-NMR(500MHz, CDCl 3, ppm)：8.13 (d, 1H)、7.82 (d, 1H)、7.41 (t, 1H)、7.11 (d, 2H)、4.07 (q, 2H)、1.34 (t, 3H)。 1 H-NMR (500MHz, CDCl 3 , ppm): 8.13 (d, 1H), 7.82 (d, 1H), 7.41 (t, 1H), 7.11 (d, 2H), 4.07 (q, 2H), 1.34 ( t, 3H).
取0.6g化合物D1 (1.81mmole)與0.2g t-BuOK (1.81mmole)溶解在12ml THF中，將反應瓶降溫至-78℃後加入1.26ml的含有1.5M 己烷的正丁基鋰 (1.9mmole)，之後回溫至0℃反應30分鐘。接著在-78℃下加入0.197g 硼酸三甲酯 (1.9mmole)後，將反應溫度回到室溫反應1hr。之後加入1ml 醋酸與0.5ml 30% H 2O 2，接著繼續攪拌至隔日。反應液用乙酸乙酯與水進行萃取、收集有機層減壓濃縮，將得到的濃縮液進行管柱層析，得到0.53g白色固體狀化合物E1。 Take 0.6g compound D1 (1.81mmole) and 0.2g t-BuOK (1.81mmole) and dissolve in 12ml THF, after cooling the reaction flask to -78°C, add 1.26ml of n-butyllithium containing 1.5M hexane (1.9 mmole), and then return to 0°C for 30 minutes. Next, 0.197 g of trimethyl borate (1.9 mmole) was added at -78° C., and the reaction temperature was returned to room temperature for 1 hr. Afterwards, 1 ml of acetic acid and 0.5 ml of 30% H 2 O 2 were added, and the stirring was continued until the next day. The reaction solution was extracted with ethyl acetate and water, the collected organic layer was concentrated under reduced pressure, and the obtained concentrated solution was subjected to column chromatography to obtain 0.53 g of compound E1 as a white solid.
1H-NMR(500MHz, CDCl 3, ppm)：9.48 (s, 1H)、7.82 (d, 1H)、7.56 (d, 1H)、7.11 (d, 1H)、6.98 (d, 1H)、4.07 (q, 2H)、1.34 (t, 3H)。 1 H-NMR (500MHz, CDCl 3 , ppm): 9.48 (s, 1H), 7.82 (d, 1H), 7.56 (d, 1H), 7.11 (d, 1H), 6.98 (d, 1H), 4.07 ( q, 2H), 1.34 (t, 3H).
取0.6g化合物E1 (1.73mmole)、0.29g 1-溴戊烷 (1.9mmole)與0.26g 碳酸鉀 (1.9mmole)溶解在15ml THF中，接著加熱至回流反應到隔天。反應完成後，用乙酸乙酯與水進行萃取、收集有機層減壓濃縮、進行管柱層析，得到0.63g白色固體狀化合物F。0.6g of compound E1 (1.73mmole), 0.29g of 1-bromopentane (1.9mmole) and 0.26g of potassium carbonate (1.9mmole) were dissolved in 15ml of THF, then heated to reflux for the next day. After the reaction was completed, extraction was performed with ethyl acetate and water, the collected organic layer was concentrated under reduced pressure, and column chromatography was performed to obtain 0.63 g of compound F as a white solid.
製備得到的化合物F的質譜、核磁共振譜數據如下。根據測試結果，化合物F為B(S)[F,OT]-2O-O5所示結構。將得到的B(S)[F,OT]-2O-O5的
1H核磁共振光譜圖、
13C核磁共振光譜圖分別示於附圖1附圖2中。
The mass spectrum and nuclear magnetic resonance spectrum data of the prepared compound F are as follows. According to the test results, compound F has the structure shown in B(S)[F,OT]-2O-O5. The 1 H nuclear magnetic resonance spectrum and the 13 C nuclear magnetic resonance spectrum of B(S)[F,OT]-2O-O5 obtained are respectively shown in accompanying drawing 1 and accompanying
MS(EI, m/z): 304, 387, 416。MS (EI, m/z): 304, 387, 416.
1H-NMR(500MHz, CDCl3, ppm)：7.82 (d, 1H)、7.73 (d, 1H)、7.13 (d, 2H)、4.06 (m, 4H)、1.77 (m, 2H)、1.39 (m, 4H)、1.34 (t, 3H)、0.90 (t, 3H)。 1 H-NMR (500MHz, CDCl3, ppm): 7.82 (d, 1H), 7.73 (d, 1H), 7.13 (d, 2H), 4.06 (m, 4H), 1.77 (m, 2H), 1.39 (m , 4H), 1.34 (t, 3H), 0.90 (t, 3H).
13C-NMR(500MHz, CDCl3, ppm)：146.0、145.5、141.8、129.6、126.5、126.1、123.0、122.4、119.4、116.1、69.0、64.6、29.3、28.1、22.7、14.8、14.1。 13 C-NMR (500MHz, CDCl3, ppm): 146.0, 145.5, 141.8, 129.6, 126.5, 126.1, 123.0, 122.4, 119.4, 116.1, 69.0, 64.6, 29.3, 28.1, 22.7, 14.8, 14.1.
實施例2Example 2
B[F,OT]-2O-O5
合成路線:
取0.5g 6-溴代-3-乙氧基-2-氟苯酚(2.13mmole)與0.44g 碳酸鉀於氮氣下以6ml THF與 4ml 水溶解後，加入含有0.48g (2-氟-3-(三氟甲氧基)苯基)硼酸 (2.13mmole)、0.036g 雙(二亞苄基丙酮)鈀(0) (0.06 mmole)與32mg CataCXium A (Di(1-adamantyl)-n-butylphosphine, 二(1-金剛烷基)-正丁基膦, C 24H 39P, 0.09 mmole)的8ml THF溶液，接著進行回流反應至隔日。隔日待反應溫度回到室溫後，將反應液以乙酸乙酯(EA)-水進行萃取、收集有機層，隨後將有機層以無水MgSO 4除水、減壓濃縮。將濃縮物進行管柱層析，得到0.49g透明液體狀化合物A2。 1H-NMR(500MHz, CD 2Cl 2)：9.58 (s, 1H)、7.43 (d, 1H)、7.37 (d, 1H)、7.21 (t, 1H)、7.04 (d, 1H)、6.87 (d, 1H)、4.07 (q, 2H)、1.34 (t, 3H)。 After taking 0.5g of 6-bromo-3-ethoxy-2-fluorophenol (2.13mmol) and 0.44g of potassium carbonate dissolved in 6ml of THF and 4ml of water under nitrogen, add 0.48g of (2-fluoro-3- (Trifluoromethoxy) phenyl) boronic acid (2.13 mmole), 0.036 g bis(dibenzylideneacetone) palladium (0) (0.06 mmole) and 32 mg CataCXium A (Di(1-adamantyl)-n-butylphosphine, Bis(1-adamantyl)-n-butylphosphine, C 24 H 39 P, 0.09 mmole) in 8 ml of THF, followed by reflux reaction until next day. After the reaction temperature returned to room temperature the next day, the reaction solution was extracted with ethyl acetate (EA)-water, and the organic layer was collected. Then, the organic layer was dehydrated with anhydrous MgSO 4 and concentrated under reduced pressure. The concentrate was subjected to column chromatography to obtain 0.49 g of compound A2 as a transparent liquid. 1 H-NMR (500MHz, CD 2 Cl 2 ): 9.58 (s, 1H), 7.43 (d, 1H), 7.37 (d, 1H), 7.21 (t, 1H), 7.04 (d, 1H), 6.87 ( d, 1H), 4.07 (q, 2H), 1.34 (t, 3H).
將0.49 g化合物A2(1.47 mmole)加入含有0.18 g 叔丁醇鉀 (1.61mmole)的15ml 甲苯溶液，之後加熱回流反應至隔夜。反應完畢、待溫度降溫後，使用乙酸乙酯與水進行萃取、收集有機層減壓濃縮。將得到的濃縮液進行管柱層析，得到白色固體狀化合物B2。0.49 g of compound A2 (1.47 mmole) was added to a solution of 0.18 g of potassium tert-butoxide (1.61 mmole) in 15 ml of toluene, and then heated under reflux to react overnight. After the reaction was completed and the temperature dropped, ethyl acetate and water were used for extraction, and the collected organic layer was concentrated under reduced pressure. The obtained concentrate was subjected to column chromatography to obtain Compound B2 as a white solid.
1H-NMR(500MHz, CDCl 3, ppm)：7.15 (d, 1H)、7.05 (d, 1H)、6.70 (t, 1H)、6.62 (d, 2H)、3.98 (q, 2H)、1.33 (t, 3H)。 1 H-NMR (500MHz, CDCl 3 , ppm): 7.15 (d, 1H), 7.05 (d, 1H), 6.70 (t, 1H), 6.62 (d, 2H), 3.98 (q, 2H), 1.33 ( t, 3H).
取0.6g化合物B2 (1.91mmole)溶解在13ml THF中，將反應瓶降溫至-78℃後加入1.34ml的含1.5M 正丁基鋰的己烷(2.01mmole) ，之後回溫至0℃反應30分鐘。接著在-78℃下加入0.209g 硼酸三甲酯 (2.01mmole)後，將反應溫度回到室溫反應1hr。之後加入1ml 醋酸與0.5ml 30% H
2O
2，接著繼續攪拌至隔日。反應液用乙酸乙酯與水進行萃取、收集有機層減壓濃縮，將得到的濃縮液進行管柱層析，得到0.53g白色固體狀化合物C2。
1H-NMR(500MHz, CDCl
3, ppm)：9.48 (s, 1H)、7.61 (d, 1H)、7.35 (d, 1H)、6.96 (d, 1H)、6.83 (d, 1H)、4.07 (q, 2H)、1.34 (t, 3H)。
Dissolve 0.6g of compound B2 (1.91mmole) in 13ml of THF, cool the reaction bottle to -78°C, add 1.34ml of hexane (2.01mmole) containing 1.5M n-butyllithium, and return to 0°C for
取0.6g化合物C2(1.82mmole)、0.30g 1-溴戊烷 (2.0mmole)與0.27g 碳酸鉀 (2.0mmole)溶解在15ml THF中，接著加熱至回流反應到隔天。反應完成後，用乙酸乙酯與水進行萃取、收集有機層減壓濃縮、進行管柱層析，得到0.63g白色固體狀化合物D2。0.6g of compound C2 (1.82mmole), 0.30g of 1-bromopentane (2.0mmole) and 0.27g of potassium carbonate (2.0mmole) were dissolved in 15ml of THF, then heated to reflux for the next day. After the reaction was completed, extraction was performed with ethyl acetate and water, the collected organic layer was concentrated under reduced pressure, and column chromatography was performed to obtain 0.63 g of compound D2 as a white solid.
製備得到的化合物D2進行質譜、核磁共振譜測試，測試得到的數據如下。根據測試結果，化合物D2為B[F,OT]-2O-O5所示結構。The prepared compound D2 was subjected to mass spectrometry and nuclear magnetic resonance spectrometry tests, and the data obtained from the tests are as follows. According to the test results, compound D2 has the structure shown as B[F,OT]-2O-O5.
MS(EI, m/z): 300, 372, 401。MS (EI, m/z): 300, 372, 401.
1H-NMR(500MHz, CDCl 3, ppm)：7.61 (d, 1H)、7.52 (d, 1H)、6.96 (d, 2H)、4.06 (m, 4H)、1.77 (m, 2H)、1.39 (m, 4H)、1.34 (t, 3H)、0.90 (t, 3H)。 1 H-NMR (500MHz, CDCl 3 , ppm): 7.61 (d, 1H), 7.52 (d, 1H), 6.96 (d, 2H), 4.06 (m, 4H), 1.77 (m, 2H), 1.39 ( m, 4H), 1.34 (t, 3H), 0.90 (t, 3H).
13C-NMR(500MHz, CDCl 3, ppm)：146.7、145.1、145.0、141.9、131.1、130.3、128.8、120.0、117.1、113.8、113.0、112.4、106.4、69.0、64.6、29.3、28.1、22.7、14.8、14.1。 13 C-NMR (500MHz, CDCl 3 , ppm): 146.7, 145.1, 145.0, 141.9, 131.1, 130.3, 128.8, 120.0, 117.1, 113.8, 113.0, 112.4, 106.4, 69.0, 64.6, 29.3, 28.1, 22.7, 14.8 , 14.1.
實施例3Example 3
B(S)[OT,OT]-2O-O5
合成路線:
取0.6g化合物1-乙氧基-2-氟-3- (三氟甲氧基)苯(2.68mmole) 溶解在18ml THF中，將反應瓶降溫至-78℃後加入1.9ml的1.5M 正丁基鋰的己烷 (2.81mmole)，之後回溫至0℃反應30分鐘。接著在-78℃下加入0.292g 硼酸三甲酯 (2.81mmole)後，將反應溫度回到室溫反應1hr。接著在0℃ 下加入3.2ml的1.0M HCl，室溫下攪拌半小時。反應液用乙酸乙酯與水進行萃取，收集有機層減壓濃縮，將得到的濃縮液進行管柱層析，得到0.65g產物A3。Dissolve 0.6g of compound 1-ethoxy-2-fluoro-3-(trifluoromethoxy)benzene (2.68mmol) in 18ml of THF, cool the reaction bottle to -78°C and add 1.9ml of 1.5M normal Butyllithium in hexane (2.81 mmole), then returned to 0° C. for 30 minutes to react. Then, after adding 0.292 g of trimethyl borate (2.81 mmole) at -78°C, the reaction temperature was returned to room temperature for 1 hr. Then, 3.2ml of 1.0M HCl was added at 0°C, and stirred at room temperature for half an hour. The reaction solution was extracted with ethyl acetate and water, the collected organic layer was concentrated under reduced pressure, and the obtained concentrated solution was subjected to column chromatography to obtain 0.65 g of product A3.
1H-NMR(500MHz, CDCl 3, ppm)：7.41 (m, 1H)、6.73 (d, 1H) 、4.2(s, 2H)、4.13 (m, 2H)、1.42(m, 3H)。 1 H-NMR (500MHz, CDCl 3 , ppm): 7.41 (m, 1H), 6.73 (d, 1H), 4.2(s, 2H), 4.13 (m, 2H), 1.42 (m, 3H).
取0.5g2-溴-6-(三氟甲氧基)苯酚(1.95mmole)與0.4g 碳酸鉀 (2.92mmol)於氮氣下以5ml THF與 4ml 水溶解後，加入含有0.52g A3 (2.13mmole)、0.034g 雙(二亞苄基丙酮)鈀(0) (0.058 mmole)與58mg CataCXium A (Di(1-adamantyl)-n-butylphosphine, 二(1-金剛烷基)-正丁基膦, C 24H 39P, 0.162 mmole)的7ml THF溶液，接著進行回流反應至隔日。隔日待反應溫度回到室溫後，將反應液以EA-水進行萃取、收集有機層，隨後將有機層以無水硫酸鎂除水、減壓濃縮。將濃縮物進行管柱層析，得到0.55g產物B3。 Take 0.5g of 2-bromo-6-(trifluoromethoxy)phenol (1.95mmol) and 0.4g of potassium carbonate (2.92mmol) and dissolve them in 5ml of THF and 4ml of water under nitrogen, add 0.52g of A3 (2.13mmole) , 0.034g bis(dibenzylideneacetone)palladium(0) (0.058 mmole) and 58mg CataCXium A (Di(1-adamantyl)-n-butylphosphine, two(1-adamantyl)-n-butylphosphine, C 24 H 39 P, 0.162 mmole) in 7 ml THF solution, followed by reflux reaction until next day. After the reaction temperature returned to room temperature the next day, the reaction solution was extracted with EA-water, and the organic layer was collected. Then, the organic layer was dehydrated with anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate was subjected to column chromatography to obtain 0.55 g of product B3.
1H-NMR(500MHz, CD 2Cl 2, ppm)：10.44 (s, 1H)、7.50 (m, 2H)、7.00 (m, 3H)、4.13 (q, 2H)、1.42 (t, 3H)。 1 H-NMR (500MHz, CD 2 Cl 2 , ppm): 10.44 (s, 1H), 7.50 (m, 2H), 7.00 (m, 3H), 4.13 (q, 2H), 1.42 (t, 3H).
取0.5g 化合物B3 (1.25 mmole)於氮氣下以6ml DCM溶解後，將反應瓶放入冰浴中冷卻，之後加入0.17g DMAP(1.38 mmole)與0.35g 三氟甲磺酸酐 (1.25 mmole)。在冰浴下反應30分鐘後，接著在室溫下反應至隔日。反應完畢後，將反應液進行減壓濃縮，得到的濃縮液進行管柱層析，得到0.4g產物C3。After 0.5g of compound B3 (1.25 mmole) was dissolved in 6ml of DCM under nitrogen, the reaction bottle was cooled in an ice bath, and then 0.17g of DMAP (1.38 mmole) and 0.35g of trifluoromethanesulfonic anhydride (1.25 mmole) were added. After reacting in an ice bath for 30 minutes, it was then reacted at room temperature until the next day. After the reaction was completed, the reaction solution was concentrated under reduced pressure, and the obtained concentrate was subjected to column chromatography to obtain 0.4 g of product C3.
1H-NMR(500MHz, CD 2Cl 2, ppm)：7.74 (d, 1H)、7.43 (m, 2H)、7.11 (d, 1H)、6.77 (d, 1H)、4.13 (q, 2H)、1.42 (t, 3H)。 1 H-NMR (500MHz, CD 2 Cl 2 , ppm): 7.74 (d, 1H), 7.43 (m, 2H), 7.11 (d, 1H), 6.77 (d, 1H), 4.13 (q, 2H), 1.42 (t, 3H).
取0.6g 化合物C3 (1.13 mmole) 、0.15g Ethyl 3-mercaptopropionate (1.13mmole)、0.16g 碳酸鉀(1.138mmole) 、57mg 雙[ (2-二苯基膦基)苯基]醚 (0.106mmole)與32mg 雙(二亞苄基丙酮)鈀(0) (0.056mmole)於反應瓶內，並且將氣體置換成氮氣，之後加入甲苯進行回流反應至隔天，生成化合物D3。反應完畢後降溫，將反應液以矽膠短管柱過濾、減壓濃縮，後續直接進行下一步反應。 1H-NMR(500MHz, CDCl 3, ppm)：7.35 (m, 3H)、7.20 (dd, 1H)、6.77 (d, 1H) 、4.13 (m, 4H)、3.17 (t, 2H)、2.61 (t, 2H)、1.42 (t, 3H)、1.07 (t, 3H) 。 Take 0.6g compound C3 (1.13 mmole), 0.15g Ethyl 3-mercaptopropionate (1.13mmole), 0.16g potassium carbonate (1.138mmole), 57mg bis[(2-diphenylphosphino)phenyl]ether (0.106mmole) Put 32mg of bis(dibenzylideneacetone)palladium(0) (0.056mmole) in the reaction flask, and replace the gas with nitrogen, then add toluene to carry out the reflux reaction until the next day to generate compound D3. After the reaction was completed, the temperature was lowered, and the reaction solution was filtered through a short silica gel column, concentrated under reduced pressure, and then proceeded directly to the next step of reaction. 1 H-NMR (500MHz, CDCl 3 , ppm): 7.35 (m, 3H), 7.20 (dd, 1H), 6.77 (d, 1H), 4.13 (m, 4H), 3.17 (t, 2H), 2.61 ( t, 2H), 1.42 (t, 3H), 1.07 (t, 3H).
將0.5 g化合物D3 (0.97 mmole)加入含有0.12 g 叔丁醇鉀 (1.07mmole)的10ml 甲苯溶液，之後加熱回流反應至隔夜。反應完畢、待溫度降溫後，使用乙酸乙酯與水進行萃取、收集有機層減壓濃縮。將得到的濃縮液進行管柱層析，得到白色固體狀化合物E3。0.5 g of compound D3 (0.97 mmole) was added to a solution of 0.12 g of potassium tert-butoxide (1.07 mmole) in 10 ml of toluene, and then heated under reflux to react overnight. After the reaction was completed and the temperature dropped, ethyl acetate and water were used for extraction, and the collected organic layer was concentrated under reduced pressure. The obtained concentrate was subjected to column chromatography to obtain compound E3 as a white solid.
1H-NMR(500MHz, CDCl 3, ppm)：7.66 (d, 1H)、7.52 (d, 1H)、7.32 (dd, 1H)、7.04 (d, 1H)、6.89 (d, 1H)、4.14 (q, 2H)、1.42 (t, 3H)。 1 H-NMR (500MHz, CDCl 3 , ppm): 7.66 (d, 1H), 7.52 (d, 1H), 7.32 (dd, 1H), 7.04 (d, 1H), 6.89 (d, 1H), 4.14 ( q, 2H), 1.42 (t, 3H).
取0.6g化合物E3 (1.56mmole)溶解在11ml THF中，將反應瓶降溫至-78℃後加入1.1ml的1.5M 正丁基鋰的己烷 (1.58mmole)，之後回溫至0℃反應30分鐘。接著在-78℃下加入0.16g 硼酸三甲酯 (1.58mmole)後，將反應溫度回到室溫反應1hr。之後加入1ml 醋酸與0.5ml 30% H 2O 2，接著繼續攪拌至隔日。反應液用乙酸乙酯與水進行萃取、收集有機層減壓濃縮，將得到的濃縮液進行管柱層析，得到0.4g產物F3。 Dissolve 0.6g of compound E3 (1.56mmole) in 11ml of THF, cool the reaction bottle to -78°C, add 1.1ml of 1.5M n-butyllithium in hexane (1.58mmole), then return to 0°C for 30 minute. Next, 0.16 g of trimethyl borate (1.58 mmole) was added at -78°C, and the reaction temperature was returned to room temperature for 1 hr. Afterwards, 1 ml of acetic acid and 0.5 ml of 30% H 2 O 2 were added, and the stirring was continued until the next day. The reaction solution was extracted with ethyl acetate and water, the collected organic layer was concentrated under reduced pressure, and the obtained concentrated solution was subjected to column chromatography to obtain 0.4 g of product F3.
1H-NMR(500MHz, CDCl 3, ppm)：9.48 (s, 1H)、7.61 (d, 1H)、7.35 (d, 1H) 、6.96 (d, 1H)、6.83 (d, 1H)、4.07 (q, 2H)、1.34 (t, 3H)。 1 H-NMR (500MHz, CDCl 3 , ppm): 9.48 (s, 1H), 7.61 (d, 1H), 7.35 (d, 1H) , 6.96 (d, 1H), 6.83 (d, 1H), 4.07 ( q, 2H), 1.34 (t, 3H).
取0.6g化合物F3 (1.46mmole)、0.24g 1-溴己烷 (1.46mmole)及0.22g 碳酸鉀(1.61mmole)溶解在15ml THF中，回流8小時。反應液用乙酸乙酯與水進行萃取、收集有機層減壓濃縮，將得到的濃縮液進行管柱層析，得到0.49g產物G3。0.6g of compound F3 (1.46mmole), 0.24g of 1-bromohexane (1.46mmole) and 0.22g of potassium carbonate (1.61mmole) were dissolved in 15ml of THF and refluxed for 8 hours. The reaction solution was extracted with ethyl acetate and water, the collected organic layer was concentrated under reduced pressure, and the obtained concentrated solution was subjected to column chromatography to obtain 0.49 g of product G3.
製備得到的化合物G3進行質譜、核磁共振譜測試，測試得到的數據如下。根據測試結果，化合物G3為B(S)[OT,OT]-2O-O5所示結構。The prepared compound G3 was tested by mass spectrometry and nuclear magnetic resonance spectrum, and the data obtained by the test are as follows. According to the test results, compound G3 has the structure shown in B(S)[OT,OT]-2O-O5.
MS(EI. m/z): 382, 411, 482。MS (EI. m/z): 382, 411, 482.
1H-NMR(500MHz, CDCl3, ppm)：7.73 (d, 2H)、7.13 (d, 2H)、4.13 (m, 4H)、1.82 (m, 2H)、1.39 (m, 7H)、1.03 (t, 3H)。 1 H-NMR (500MHz, CDCl3, ppm): 7.73 (d, 2H), 7.13 (d, 2H), 4.13 (m, 4H), 1.82 (m, 2H), 1.39 (m, 7H), 1.03 (t , 3H).
13C-NMR(500MHz, CDCl3)：146.0、145.5、141.8、137.1、129.6、126.8、126.5、122.4、116.1、69.0、64.9、29.3、28.1、22.7、14.8、13.8。 13 C-NMR (500MHz, CDCl3): 146.0, 145.5, 141.8, 137.1, 129.6, 126.8, 126.5, 122.4, 116.1, 69.0, 64.9, 29.3, 28.1, 22.7, 14.8, 13.8.
實施例4Example 4
B[OT,OT]-2O-O5
合成路線:
取0.6g化合物1-乙氧基-2-氟-3- (三氟甲氧基)苯 (2.68mmole) 溶解在18ml THF中，將反應瓶降溫至-78℃後加入1.9ml的含1.5M 正丁基鋰的己烷 (2.81mmole) ，之後回溫至0℃反應30分鐘。接著在-78℃下加入0.292g 硼酸三甲酯 (2.81mmole)後，將反應溫度回到室溫反應1hr 。接著在0℃ 下加入3.2ml的1.0M HCl，室溫下攪拌半小時。反應液用乙酸乙酯與水進行萃取，收集有機層減壓濃縮，將得到的濃縮液進行管柱層析，得到0.65g產物A4。Take 0.6g of the compound 1-ethoxy-2-fluoro-3-(trifluoromethoxy)benzene (2.68mmole) and dissolve it in 18ml of THF, cool the reaction bottle to -78°C and add 1.9ml of 1.5M n-Butyllithium in hexane (2.81 mmole), and then return to 0° C. for 30 minutes to react. Next, 0.292 g of trimethyl borate (2.81 mmole) was added at -78°C, and the reaction temperature was returned to room temperature for 1 hr. Then, 3.2ml of 1.0M HCl was added at 0°C, and stirred at room temperature for half an hour. The reaction solution was extracted with ethyl acetate and water, the collected organic layer was concentrated under reduced pressure, and the obtained concentrated solution was subjected to column chromatography to obtain 0.65 g of product A4.
1H-NMR(500MHz, CDCl 3, ppm)：7.41 (m, 1H)、6.73 (d, 1H)、4.2(s, 2H)、4.13 (m, 2H)、1.42(m, 3H)。 1 H-NMR (500 MHz, CDCl 3 , ppm): 7.41 (m, 1H), 6.73 (d, 1H), 4.2 (s, 2H), 4.13 (m, 2H), 1.42 (m, 3H).
取0.5g 2-溴-6- (三氟甲氧基)苯酚(1.95mmole)與0.4g 碳酸鉀 (2.92mmol)於氮氣下以5ml THF與 4ml 水溶解後，加入含有0.52g (2-氟-3- (三氟甲氧基)苯基)硼酸 (2.13mmole)、0.034g 雙(二亞苄基丙酮)鈀(0) (0.058 mmole)與58mg CataCXium A (Di(1-adamantyl)-n-butylphosphine, 二(1-金剛烷基)-正丁基膦, C 24H 39P, 0.162 mmole)的7ml THF溶液，接著進行回流反應至隔日。隔日待反應溫度回到室溫後，將反應液以EA-水進行萃取、收集有機層，隨後將有機層以無水MgSO 4除水、減壓濃縮。將濃縮物進行管柱層析，得到0.55g產物B4。 1H-NMR(500MHz, CD 2Cl 2, ppm)：10.44 (s, 1H)、7.50 (m, 2H)、7.00 (m, 3H)、4.13 (q, 2H)、1.42 (t, 3H)。 Take 0.5g 2-bromo-6-(trifluoromethoxy)phenol (1.95mmol) and 0.4g potassium carbonate (2.92mmol) in 5ml THF and 4ml water under nitrogen, add 0.52g (2-fluoro -3-(trifluoromethoxy)phenyl)boronic acid (2.13mmole), 0.034g bis(dibenzylideneacetone)palladium(0) (0.058 mmole) and 58mg CataCXium A (Di(1-adamantyl)-n -butylphosphine, bis(1-adamantyl)-n-butylphosphine, C 24 H 39 P, 0.162 mmole) in 7 ml THF solution, followed by reflux reaction until next day. After the reaction temperature returned to room temperature the next day, the reaction solution was extracted with EA-water, the organic layer was collected, and then the organic layer was dehydrated with anhydrous MgSO 4 and concentrated under reduced pressure. The concentrate was subjected to column chromatography to obtain 0.55 g of product B4. 1 H-NMR (500MHz, CD 2 Cl 2 , ppm): 10.44 (s, 1H), 7.50 (m, 2H), 7.00 (m, 3H), 4.13 (q, 2H), 1.42 (t, 3H).
將0.5 g化合物B4 (1.25 mmole)加入含有0.15 g 叔丁醇鉀 (1.37mmole)的13ml 甲苯溶液，之後加熱回流反應至隔夜。反應完畢、待溫度降溫後，使用乙酸乙酯與水進行萃取、收集有機層減壓濃縮。將得到的濃縮液進行管柱層析，得到產物C4。 1H-NMR(500MHz, CDCl 3)：7.66 (d, 1H)、7.52 (d, 1H)、7.32 (t, 1H)、6.89 (d, 1H)、4.13 (q, 2H)、1.42 (t, 3H)。 0.5 g of compound B4 (1.25 mmole) was added to a solution of 0.15 g of potassium tert-butoxide (1.37 mmole) in 13 ml of toluene, and then heated under reflux to react overnight. After the reaction was completed and the temperature dropped, ethyl acetate and water were used for extraction, and the collected organic layer was concentrated under reduced pressure. The obtained concentrate was subjected to column chromatography to obtain product C4. 1 H-NMR (500MHz, CDCl 3 ): 7.66 (d, 1H), 7.52 (d, 1H), 7.32 (t, 1H), 6.89 (d, 1H), 4.13 (q, 2H), 1.42 (t, 3H).
取0.6g化合物C(1.58mmole)溶解在11ml THF中，將反應瓶降溫至-78℃後加入1.1ml的含1.5M 正丁基鋰的己烷(1.66mmole) ，之後回溫至0℃反應30分鐘。接著在-78℃下加入0.17g 硼酸三甲酯 (1.66mmole)後，將反應溫度回到室溫反應1hr。之後加入1ml 醋酸與0.5ml 30% H
2O
2，接著繼續攪拌至隔日。反應液用乙酸乙酯與水進行萃取、收集有機層減壓濃縮，將得到的濃縮液進行管柱層析，得到0.44g產物D4。
Dissolve 0.6g of compound C (1.58mmole) in 11ml of THF, cool the reaction bottle to -78°C, add 1.1ml of hexane (1.66mmole) containing 1.5M n-butyllithium, and then return to 0°C for
1H-NMR(500MHz, CDCl 3, ppm)：9.48 (s, 1H)、7.52 (d, 1H)、7.35 (d, 1H)、6.89 (m, 2H)、4.13 (q, 2H)、1.42 (t, 3H)。 1 H-NMR (500MHz, CDCl 3 , ppm): 9.48 (s, 1H), 7.52 (d, 1H), 7.35 (d, 1H), 6.89 (m, 2H), 4.13 (q, 2H), 1.42 ( t, 3H).
取0.6g化合物D4 (1.51mmole)、0.25g 1-溴己烷 (1.51mmole)及0.23g 碳酸鉀(1.66mmole)溶解在15ml THF中，回流8小時。反應液用乙酸乙酯與水進行萃取、收集有機層減壓濃縮，將得到的濃縮液進行管柱層析，得到0.42g產物E4。0.6g of compound D4 (1.51mmole), 0.25g of 1-bromohexane (1.51mmole) and 0.23g of potassium carbonate (1.66mmole) were dissolved in 15ml of THF and refluxed for 8 hours. The reaction solution was extracted with ethyl acetate and water, the collected organic layer was concentrated under reduced pressure, and the obtained concentrated solution was subjected to column chromatography to obtain 0.42 g of product E4.
製備得到的化合物E4進行質譜、核磁共振譜測試，測試得到的數據如下。根據測試結果，化合物E4為B[OT,OT]-2O-O5所示結構。The prepared compound E4 was subjected to mass spectrometry and nuclear magnetic resonance spectrometry tests, and the data obtained from the tests are as follows. According to the test results, the compound E4 has the structure shown as B[OT,OT]-2O-O5.
MS(EI, m/z): 380, 395, 466。MS (EI, m/z): 380, 395, 466.
1H-NMR(500MHz, CDCl 3, ppm)：7.52 (m, 2H)、6.89 (m, 2H)、4.13 (m, 4H)、1.77 (m, 2H)、1.42 (m, 7H)、1.1 (t, 3H)。 1 H-NMR (500MHz, CDCl 3 , ppm): 7.52 (m, 2H), 6.89 (m, 2H), 4.13 (m, 4H), 1.77 (m, 2H), 1.42 (m, 7H), 1.1 ( t, 3H).
13C-NMR(500MHz, CDCl 3)：150.0、146.7、145.1、130.3、128.8、120.0、113.8、112.4、106.4、69.0、64.9、29.3、28.1、22.7、15.1、14.3。 13 C-NMR (500 MHz, CDCl 3 ): 150.0, 146.7, 145.1, 130.3, 128.8, 120.0, 113.8, 112.4, 106.4, 69.0, 64.9, 29.3, 28.1, 22.7, 15.1, 14.3.
實施例5Example 5
COB(S)[F,OT]OIC-3-3
合成路線:
取0.5g 2-溴-6-氟苯酚 (2.62mmole)與0.54g 碳酸鉀 (3.93mmol)於氮氣下以7ml THF與 5ml 水溶解後，加入含有0.99g (2-氟-4- ((4-丙基環己基)甲氧基) -3- (三氟甲氧基)苯基)硼酸 (2.62mmole)、45mg 雙(二亞苄基丙酮)鈀(0) (0.079 mmole)與77mg CataCXium A (Di(1-adamantyl)-n-butylphosphine, 二(1-金剛烷基)-正丁基膦, C 24H 39P, 0.215 mmole)的7ml THF溶液，接著進行回流反應至隔日。隔日待反應溫度回到室溫後，將反應液以EA-水進行萃取、收集有機層，隨後將有機層以無水硫酸鎂除水、減壓濃縮。將濃縮物進行管柱層析，得到0.93g產物A5。 Take 0.5g of 2-bromo-6-fluorophenol (2.62mmol) and 0.54g of potassium carbonate (3.93mmol) and dissolve it in 7ml of THF and 5ml of water under nitrogen, add 0.99g of (2-fluoro-4-((4 -propylcyclohexyl)methoxy)-3-(trifluoromethoxy)phenyl)boronic acid (2.62 mmole), 45 mg bis(dibenzylideneacetone)palladium(0) (0.079 mmole) and 77 mg CataCXium A (Di(1-adamantyl)-n-butylphosphine, bis(1-adamantyl)-n-butylphosphine, C 24 H 39 P, 0.215 mmole) in 7 ml THF, followed by reflux reaction until next day. After the reaction temperature returned to room temperature the next day, the reaction solution was extracted with EA-water, and the organic layer was collected. Then, the organic layer was dehydrated with anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate was subjected to column chromatography to obtain 0.93 g of product A5.
1H-NMR(500MHz, CD 2Cl 2, ppm)：9.58 (s, 1H)、7.59 (d, 1H)、7.43 (d, 1H)、7.08 (m, 2H)、6.77 (d, 1H)、3.86 (d, 2H)、1.94 (m, 1H)、1.64~1.21 (m, 13H)、0.98 (t, 3H)。 1 H-NMR (500MHz, CD 2 Cl 2 , ppm): 9.58 (s, 1H), 7.59 (d, 1H), 7.43 (d, 1H), 7.08 (m, 2H), 6.77 (d, 1H), 3.86 (d, 2H), 1.94 (m, 1H), 1.64~1.21 (m, 13H), 0.98 (t, 3H).
取0.5g 化合物A5 (1.12 mmole)於氮氣下以6ml DCM溶解後，將反應瓶放入冰浴中冷卻，之後加入0.15g DMAP (1.23 mmole)與0.31g 三氟甲磺酸酐 (1.12 mmole)。在冰浴下反應30分鐘後，接著在室溫下反應至隔日。反應完畢後，將反應液進行減壓濃縮，得到的濃縮液進行管柱層析，得到0.58g產物B5。After 0.5g of compound A5 (1.12 mmole) was dissolved in 6ml of DCM under nitrogen, the reaction bottle was cooled in an ice bath, and then 0.15g of DMAP (1.23 mmole) and 0.31g of trifluoromethanesulfonic anhydride (1.12 mmole) were added. After reacting in an ice bath for 30 minutes, it was then reacted at room temperature until the next day. After the reaction was completed, the reaction solution was concentrated under reduced pressure, and the obtained concentrate was subjected to column chromatography to obtain 0.58 g of product B5.
1H-NMR(500MHz, CD 2Cl 2, ppm)：7.83 (d, 1H)、7.513 (m, 3H)、6.77 (d, 1H)、3.86 (d, 2H)、1.94 (m, 1H)、1.63~1.20 (m, 13H)、0.89 (t, 3H)。 1 H-NMR (500MHz, CD 2 Cl 2 , ppm): 7.83 (d, 1H), 7.513 (m, 3H), 6.77 (d, 1H), 3.86 (d, 2H), 1.94 (m, 1H), 1.63~1.20 (m, 13H), 0.89 (t, 3H).
取0.6g 化合物B5 (1.04mmole) 、0.14g 3-巰基丙酸乙酯 (1.04mmole)、0.14g 碳酸鉀(1.04mmole) 、53mg 雙[ (2-二苯基膦基)苯基]醚 (0.098mmole)與30mg 雙(二亞苄基丙酮)鈀(0) (0.052mmole)於反應瓶內，並且將氣體置換成氮氣，之後加入甲苯進行回流反應至隔天，生成化合物D5。反應完畢後降溫，將反應液以矽膠短管柱過濾、減壓濃縮，後續直接進行下一步反應。 1H-NMR(500MHz, CDCl 3, ppm)：7.44 (m, 2H)、7.28 (m, 2H)、4.01 (q, 2H)、3.86 (d, 2H)、3.17 (t, 2H)、2.61 (t, 2H)、1.94 (m, 1H)、1.62~1.21 (m, 13H)、1.07 (t , 3H)、0.92 (t, 3H)。 Take 0.6g compound B5 (1.04mmole), 0.14g ethyl 3-mercaptopropionate (1.04mmole), 0.14g potassium carbonate (1.04mmole), 53mg bis[(2-diphenylphosphino)phenyl]ether ( 0.098 mmole) and 30 mg bis(dibenzylideneacetone) palladium (0) (0.052 mmole) in the reaction flask, and the gas was replaced with nitrogen, and then added toluene for reflux reaction until the next day to generate compound D5. After the reaction was completed, the temperature was lowered, and the reaction solution was filtered through a short silica gel column, concentrated under reduced pressure, and then proceeded directly to the next step of reaction. 1 H-NMR (500MHz, CDCl 3 , ppm): 7.44 (m, 2H), 7.28 (m, 2H), 4.01 (q, 2H), 3.86 (d, 2H), 3.17 (t, 2H), 2.61 ( t, 2H), 1.94 (m, 1H), 1.62~1.21 (m, 13H), 1.07 (t , 3H), 0.92 (t, 3H).
將0.5 g化合物C5 (0.89 mmole)加入含有0.11 g 叔丁醇鉀 (0.98mmole)的9ml 甲苯溶液，之後加熱回流反應至隔夜。反應完畢、待溫度降溫後，使用乙酸乙酯與水進行萃取、收集有機層減壓濃縮。將得到的濃縮液進行管柱層析，得到白色固體D5。0.5 g of compound C5 (0.89 mmole) was added to a solution of 0.11 g of potassium tert-butoxide (0.98 mmole) in 9 ml of toluene, and then heated under reflux to react overnight. After the reaction was completed and the temperature dropped, ethyl acetate and water were used for extraction, and the collected organic layer was concentrated under reduced pressure. The obtained concentrate was subjected to column chromatography to obtain white solid D5.
1H-NMR(500MHz, CDCl 3, ppm)：8.22 (d, 1H)、7.73 (d, 1H)、7.49 (m, 1H)、7.13 (m, 2H)、3.86 (d, 2H)、1.94 (m, 1H)、1.61~1.18 (m, 13H)、0.89 (t, 3H)。 1 H-NMR (500MHz, CDCl 3 , ppm): 8.22 (d, 1H), 7.73 (d, 1H), 7.49 (m, 1H), 7.13 (m, 2H), 3.86 (d, 2H), 1.94 ( m, 1H), 1.61~1.18 (m, 13H), 0.89 (t, 3H).
取0.6g化合物D5(1.36mmole)溶解在9ml THF中，將反應瓶降溫至-78℃後加入1.0ml的含1.5M 正丁基的己烷 (1.43mmole) ，之後回溫至0℃反應30分鐘。接著在-78℃下加入0.15g 硼酸三甲酯 (1.43mmole)後，將反應溫度回到室溫反應1hr。之後加入1ml 醋酸與0.5ml 30% H 2O 2，接著繼續攪拌至隔日。反應液用乙酸乙酯與水進行萃取、收集有機層減壓濃縮，將得到的濃縮液進行管柱層析，得到0.43g產物E5。 Dissolve 0.6g of compound D5 (1.36mmole) in 9ml of THF, cool the reaction bottle to -78°C, add 1.0ml of 1.5M n-butyl-containing hexane (1.43mmole), then return to 0°C for 30 minute. Next, 0.15 g of trimethyl borate (1.43 mmole) was added at -78°C, and the reaction temperature was returned to room temperature for 1 hr. After that, 1 ml of acetic acid and 0.5 ml of 30% H 2 O 2 were added, and the stirring was continued until the next day. The reaction solution was extracted with ethyl acetate and water, the collected organic layer was concentrated under reduced pressure, and the obtained concentrated solution was subjected to column chromatography to obtain 0.43 g of product E5.
1H-NMR(500MHz, CDCl 3, ppm)：9.0 (s, 1H)、7.73 (m, 2H)、7.13 (d, 1H)、6.96 (d, 1H)、3.86 (d, 2H)、1.94 (m, 1H)、1.61~1.18 (m, 13H)、0.86 (t, 3H) 。 1 H-NMR (500MHz, CDCl 3 , ppm): 9.0 (s, 1H), 7.73 (m, 2H), 7.13 (d, 1H), 6.96 (d, 1H), 3.86 (d, 2H), 1.94 ( m, 1H), 1.61~1.18 (m, 13H), 0.86 (t, 3H).
取0.6g化合物E5 (1.31mmole)、0.29g 1-(溴甲基) -4-丙基環己烷 (1.31mmole)及0.20g 碳酸鉀 (1.45mmole)溶解在13ml THF中，回流8小時。反應液用乙酸乙酯與水進行萃取、收集有機層減壓濃縮，將得到的濃縮液進行管柱層析，得到0.55g產物F5。0.6g of compound E5 (1.31mmole), 0.29g of 1-(bromomethyl)-4-propylcyclohexane (1.31mmole) and 0.20g of potassium carbonate (1.45mmole) were dissolved in 13ml of THF and refluxed for 8 hours. The reaction solution was extracted with ethyl acetate and water, the collected organic layer was concentrated under reduced pressure, and the obtained concentrated solution was subjected to column chromatography to obtain 0.55 g of product F5.
製備得到的化合物F5進行質譜、核磁共振譜測試，測試得到的數據如下。根據測試結果，化合物F5為COB(S)[F,OT]OIC-3-3所示結構。The prepared compound F5 was subjected to mass spectrometry and nuclear magnetic resonance spectrometry tests, and the data obtained from the tests are as follows. According to the test results, compound F5 has the structure shown as COB(S)[F,OT]OIC-3-3.
MS(EI, m/z): 316, 455, 594。MS (EI, m/z): 316, 455, 594.
1H-NMR(500MHz, CDCl 3, ppm)：7.82 (d, 1H)、7.73 (d, 1H)、7.11 (d, 2H)、3.86 (d, 4H)、1.94 (m, 2H)、1.62~1.28 (m, 26H)、0.89 (t, 6H)。 1 H-NMR (500MHz, CDCl 3 , ppm): 7.82 (d, 1H), 7.73 (d, 1H), 7.11 (d, 2H), 3.86 (d, 4H), 1.94 (m, 2H), 1.62~ 1.28 (m, 26H), 0.89 (t, 6H).
13C-NMR(500MHz, CDCl 3, ppm)：146.0、141.9、141.7、137.1、135.1、129.6、127.5、126.8、123.0、122.4、119.4、116.1、75.2、74.9、38.7、37.1、29.3、27.7、26.5、20.5、14.4。 13 C-NMR (500MHz, CDCl 3 , ppm): 146.0, 141.9, 141.7, 137.1, 135.1, 129.6, 127.5, 126.8, 123.0, 122.4, 119.4, 116.1, 75.2, 74.9, 38.7, 37.1, 29.3, 2 7.7, 26.5 , 20.5, 14.4.
實施例6Example 6
CVOB(S)[F,OT]OIC-3-3
取0.6g實施例5的化合物E5 (1.31mmole)、0.32g 1- (3-溴丙-1-烯-1-基) -4-丙基環己烷 (1.31mmole)及0.20g 碳酸鉀(1.45mmole)溶解在13ml THF中，回流8小時。反應液用乙酸乙酯與水進行萃取、收集有機層減壓濃縮，將得到的濃縮液進行管柱層析，得到0.57g產物。Get the compound E5 (1.31mmole) of 0.6g embodiment 5, 0.32g 1-(3-bromoprop-1-en-1-yl)-4-propylcyclohexane (1.31mmole) and 0.20g potassium carbonate ( 1.45 mmole) was dissolved in 13 ml THF and refluxed for 8 hours. The reaction solution was extracted with ethyl acetate and water, the collected organic layer was concentrated under reduced pressure, and the obtained concentrated solution was subjected to column chromatography to obtain 0.57 g of the product.
製備得到的化合物進行質譜、核磁共振譜測試，測試得到的數據如下。根據測試結果，化合物為CVO(S)[F,OT]OIC-3-3所示結構。The prepared compound was tested by mass spectrometry and nuclear magnetic resonance spectrum, and the data obtained by the test are as follows. According to the test results, the compound has the structure shown as CVO(S)[F,OT]OIC-3-3.
MS(EI, m/z): 316, 475 ,614。MS (EI, m/z): 316,475,614.
1H-NMR(500MHz, CDCl 3, ppm)：7.76 (m, 2H)、7.13 (d, 1H)、7.04 (d, 1H)、5.77 (m, 1H)、5.52 (m, 1H) 4.68 (d, 2H)、4.01 (d, 2H)、2.48 (m, 1H)、1.94 (m, 1H)、1.65~1.24 (m, 26H)、0.91 (t, 6H)。 1 H-NMR (500MHz, CDCl 3 , ppm): 7.76 (m, 2H), 7.13 (d, 1H), 7.04 (d, 1H), 5.77 (m, 1H), 5.52 (m, 1H) 4.68 (d , 2H), 4.01 (d, 2H), 2.48 (m, 1H), 1.94 (m, 1H), 1.65~1.24 (m, 26H), 0.91 (t, 6H).
13C-NMR(500MHz, CDCl 3, ppm)：148.0、144.9、141.8、137.1、135.8、134.2、129.6、129.1、127.9、126.8、122.9、119.8、116.1、75.2、64.3、38.7、37.1、33、29.7、27.7、26.5、21.1 、15.5。 13 C-NMR (500MHz, CDCl 3 , ppm): 148.0, 144.9, 141.8, 137.1, 135.8, 134.2, 129.6, 129.1, 127.9, 126.8, 122.9, 119.8, 116.1, 75.2, 64.3, 38.7, 37.1, 33, 29.7 , 27.7, 26.5, 21.1, 15.5.
實施例7Example 7
POB(S)[F,OT]OIC-3-3
取0.6g實施例5化合物E5 (1.31mmole)、0.28g 1-(溴甲基)-4-丙苯(1.31mmole)及0.20g 碳酸鉀(1.45mmole)溶解在13ml THF中，回流8小時。反應液用乙酸乙酯與水進行萃取、收集有機層減壓濃縮，將得到的濃縮液進行管柱層析，得到0.54g產物。0.6 g of Example 5 compound E5 (1.31 mmole), 0.28 g of 1-(bromomethyl)-4-propylbenzene (1.31 mmole) and 0.20 g of potassium carbonate (1.45 mmole) were dissolved in 13 ml of THF and refluxed for 8 hours. The reaction solution was extracted with ethyl acetate and water, the collected organic layer was concentrated under reduced pressure, and the obtained concentrated solution was subjected to column chromatography to obtain 0.54 g of the product.
製備得到的化合物進行質譜、核磁共振譜測試，測試得到的數據如下。根據測試結果，化合物為POB(S)[F,OT]OIC-3-3所示結構。The prepared compound was tested by mass spectrometry and nuclear magnetic resonance spectrum, and the data obtained by the test are as follows. According to the test results, the compound has the structure shown as POB(S)[F,OT]OIC-3-3.
MS(EI, m/z): 316, 449, 588。MS (EI, m/z): 316, 449, 588.
1H-NMR(500MHz, CDCl 3, ppm)：7.86 (m, 1H)、7.76 (d, 1H)、7.38 (d, 2H)、7.13 (m, 4H)、5.16 (s, 1H)、3.86 (d, 2H)、2.61 (t, 2H)、1.94 (m, 1H)、1.64-1.29 (m, 15H)、0.86 (m, 3H)。 1 H-NMR (500MHz, CDCl 3 , ppm): 7.86 (m, 1H), 7.76 (d, 1H), 7.38 (d, 2H), 7.13 (m, 4H), 5.16 (s, 1H), 3.86 ( d, 2H), 2.61 (t, 2H), 1.94 (m, 1H), 1.64-1.29 (m, 15H), 0.86 (m, 3H).
13C-NMR(500MHz, CDCl 3, ppm)：149.2、146.2、141.9、140.9、134.0、129.6、128.3、172.7、126.9、126.1、123、122.3、119.4、116.5、74.9、71.1、38.7、37.1、29.3、28.3、27.2、24.1、20.5、14.4、13.3。 13 C-NMR (500MHz, CDCl 3 , ppm): 149.2, 146.2, 141.9, 140.9, 134.0, 129.6, 128.3, 172.7, 126.9, 126.1, 123, 122.3, 119.4, 116.5, 74.9, 71.1, 38.7, 3 7.1, 29.3 , 28.3, 27.2, 24.1, 20.5, 14.4, 13.3.
實施例8Example 8
CQ(S)[F,OT]QIC-3-3
合成路線:
取0.6g 1-(二氟(4-丙基環己基)甲氧基)-3-氟-2-(三氟甲氧基)苯(1.62mmole) 溶解在11ml THF中，將反應瓶降溫至-78℃後加入1.1ml的含1.5M 正丁基鋰的環己烷 (1.7mmole) ，之後回溫至0℃反應30分鐘。接著在-78℃下加入0.17g 硼酸三甲酯 (1.7mmole)後，將反應溫度回到室溫反應1hr 。接著在0℃ 下加入2ml的1.0M HCl，室溫下攪拌半小時。反應液用乙酸乙酯與水進行萃取，再用碳酸氫鈉水溶液調至鹼性、收集有機層減壓濃縮，將得到的濃縮液進行管柱層析，得到0.61g產物A8。Get 0.6g 1-(difluoro(4-propylcyclohexyl)methoxy)-3-fluoro-2-(trifluoromethoxy)benzene (1.62mmol) and dissolve it in 11ml THF, and cool the reaction flask to After -78°C, 1.1ml of cyclohexane (1.7mmole) containing 1.5M n-butyllithium was added, and then returned to 0°C for 30 minutes. Next, 0.17 g of trimethyl borate (1.7 mmole) was added at -78°C, and the reaction temperature was returned to room temperature for 1 hr. Then 2ml of 1.0M HCl was added at 0°C, and stirred at room temperature for half an hour. The reaction solution was extracted with ethyl acetate and water, adjusted to alkaline with aqueous sodium bicarbonate solution, the collected organic layer was concentrated under reduced pressure, and the obtained concentrated solution was subjected to column chromatography to obtain 0.61 g of product A8.
1H-NMR(500MHz, CDCl 3, ppm)：7.41 (m, 1H)、6.73 (d, 1H)、4.2(s, 2H)、3.34(m, 1H)、1.63~1.20 (m, 14H)、0.89 (t, 3H)。 1 H-NMR(500MHz, CDCl 3 , ppm): 7.41 (m, 1H), 6.73 (d, 1H), 4.2(s, 2H), 3.34(m, 1H), 1.63~1.20 (m, 14H), 0.89 (t, 3H).
取0.5g 2-溴-6-氟苯酚 (2.62mmole)與0.54g 碳酸鉀 (3.93mmol)於氮氣下以7ml THF與 5ml 水溶解後，加入含有1.09g 化合物A8 (2.62mmole)、45mg 雙(二亞苄基丙酮)鈀(0) (0.079 mmole)與77mg CataCXium A (Di(1-adamantyl)-n-butylphosphine, 二(1-金剛烷基)-正丁基膦, C 24H 39P, 0.215 mmole)的7ml THF溶液，接著進行回流反應至隔日。隔日待反應溫度回到室溫後，將反應液以EA-水進行萃取、收集有機層，隨後將有機層以無水硫酸鎂除水、減壓濃縮。將濃縮物進行管柱層析，得到1.00g產物B8。 1H-NMR(500MHz, CD 2Cl 2)：9.58 (s, 1H)、7.59 (d, 1H)、7.43 (d, 1H)、7.08 (m, 1H)、6.77 (d, 1H)、3.34 (m, 1H)、1.61~1.28 (m, 13H)、1.02 (t, 3H)。 After taking 0.5g of 2-bromo-6-fluorophenol (2.62mmol) and 0.54g of potassium carbonate (3.93mmol) and dissolving them in 7ml of THF and 5ml of water under nitrogen, add 1.09g of compound A8 (2.62mmol), 45mg of bis( Dibenzylideneacetone)palladium(0) (0.079 mmole) with 77mg CataCXium A (Di(1-adamantyl)-n-butylphosphine, bis(1-adamantyl)-n-butylphosphine, C 24 H 39 P, 0.215 mmole) of 7ml THF solution, followed by reflux reaction to the next day. After the reaction temperature returned to room temperature the next day, the reaction solution was extracted with EA-water, and the organic layer was collected. Then, the organic layer was dehydrated with anhydrous magnesium sulfate and concentrated under reduced pressure. The concentrate was subjected to column chromatography to obtain 1.00 g of product B8. 1 H-NMR (500MHz, CD 2 Cl 2 ): 9.58 (s, 1H), 7.59 (d, 1H), 7.43 (d, 1H), 7.08 (m, 1H), 6.77 (d, 1H), 3.34 ( m, 1H), 1.61~1.28 (m, 13H), 1.02 (t, 3H).
取0.5g 化合物B (1.04 mmole)於氮氣下以6ml DCM溶解後，將反應瓶放入冰浴中冷卻，之後加入0.14g DMAP (1.14 mmole)與0.29g 三氟甲磺酸酐 (1.04 mmole)。在冰浴下反應30分鐘後，接著在室溫下反應至隔日。反應完畢後，將反應液進行減壓濃縮，得到的濃縮液進行管柱層析，得到0.57g產物C8。After 0.5g of compound B (1.04 mmole) was dissolved in 6ml of DCM under nitrogen, the reaction bottle was cooled in an ice bath, and then 0.14g of DMAP (1.14 mmole) and 0.29g of trifluoromethanesulfonic anhydride (1.04 mmole) were added. After reacting in an ice bath for 30 minutes, it was then reacted at room temperature until the next day. After the reaction was completed, the reaction solution was concentrated under reduced pressure, and the obtained concentrate was subjected to column chromatography to obtain 0.57 g of product C8.
1H-NMR(500MHz, CD 2Cl 2, ppm)：7.83 (d, 1H)、7.513 (m, 3H)、6.77 (d, 1H)、3.34 (m, 1H)、1.63~1.20 (m, 13H)、0.89 (t, 3H)。 1 H-NMR (500MHz, CD 2 Cl 2 , ppm): 7.83 (d, 1H), 7.513 (m, 3H), 6.77 (d, 1H), 3.34 (m, 1H), 1.63~1.20 (m, 13H ), 0.89 (t, 3H).
取0.6g 化合物C8 (0.98mmole) 、0.13g 3-巰基丙酸乙酯(0.98mmole)、0.14g 碳酸鉀(0.98mmole) 、50mg 雙[ (2-二苯基膦基)苯基]醚(0.092mmole)與28mg雙(二亞苄基丙酮)鈀(0) (0.049mmole)於反應瓶內，並且將氣體置換成氮氣，之後加入甲苯進行回流反應至隔天，生成化合物D8。反應完畢後降溫，將反應液以矽膠短管柱過濾、減壓濃縮，後續直接進行下一步反應。 1H-NMR(500MHz, CDCl 3, ppm)：7.44 (m, 2H)、7.28 (m, 2H)、6.77 (d, 1H)、4.01 (q, 2H)、3.34 (m, 1H)、3.17 (t, 2H)、2.61 (t, 2H)、1.61~1.28 (m, 13H)、1.07 (t , 3H)、0.91 (t, 3H)。 Take 0.6g compound C8 (0.98mmole), 0.13g ethyl 3-mercaptopropionate (0.98mmole), 0.14g potassium carbonate (0.98mmole), 50mg bis[(2-diphenylphosphino)phenyl]ether ( 0.092 mmole) and 28 mg bis(dibenzylideneacetone) palladium (0) (0.049 mmole) in the reaction flask, and the gas was replaced with nitrogen, and then added toluene for reflux reaction until the next day to generate compound D8. After the reaction was completed, the temperature was lowered, and the reaction solution was filtered through a short silica gel column, concentrated under reduced pressure, and then proceeded directly to the next step of reaction. 1 H-NMR (500MHz, CDCl 3 , ppm): 7.44 (m, 2H), 7.28 (m, 2H), 6.77 (d, 1H), 4.01 (q, 2H), 3.34 (m, 1H), 3.17 ( t, 2H), 2.61 (t, 2H), 1.61~1.28 (m, 13H), 1.07 (t , 3H), 0.91 (t, 3H).
將0.5 g化合物D8 (0.84 mmole)加入含有0.10 g 叔丁醇鉀(0.94mmole)的9ml 甲苯溶液，之後加熱回流反應至隔夜。反應完畢、待溫度降溫後，使用乙酸乙酯與水進行萃取、收集有機層減壓濃縮。將得到的濃縮液進行管柱層析，得到白色固體E8。0.5 g of compound D8 (0.84 mmole) was added to a solution of 0.10 g of potassium tert-butoxide (0.94 mmole) in 9 ml of toluene, and then heated under reflux to react overnight. After the reaction was completed and the temperature dropped, ethyl acetate and water were used for extraction, and the collected organic layer was concentrated under reduced pressure. The obtained concentrate was subjected to column chromatography to obtain white solid E8.
1H-NMR(500MHz, CDCl 3, ppm)：8.22 (d, 1H)、7.73 (d, 1H)、7.49 (m, 1H)、7.13 (m, 2H)、3.36 (m, 1H)、1.61~1.19 (m, 13H)、0.93 (t, 3H)。 1 H-NMR (500MHz, CDCl 3 , ppm): 8.22 (d, 1H), 7.73 (d, 1H), 7.49 (m, 1H), 7.13 (m, 2H), 3.36 (m, 1H), 1.61~ 1.19 (m, 13H), 0.93 (t, 3H).
取0.6g化合物E8(1.05mmole)溶解在7ml THF中，將反應瓶降溫至-78℃後加入0.74ml的含1.5M正丁基鋰的己烷(1.1mmole) ，之後回溫至0℃反應30分鐘。接著在-78℃下加入0.12g 硼酸三甲酯 (1.1mmole)後，將反應溫度回到室溫反應1hr。之後加入1ml 醋酸與0.5ml 30% H
2O
2，接著繼續攪拌至隔日。反應液用乙酸乙酯與水進行萃取、收集有機層減壓濃縮，將得到的濃縮液進行管柱層析，得到0.36g產物F8。
Dissolve 0.6g of compound E8 (1.05mmole) in 7ml of THF, cool the reaction bottle to -78°C, add 0.74ml of hexane (1.1mmole) containing 1.5M n-butyllithium, and then return to 0°C for
1H-NMR(500MHz, CDCl 3, ppm)：9.0 (s, 1H)、7.73 (m, 1H)、7.65 (d, 1H)、7.13 (d, 1H)、6.96 (d, 1H)、3.34 (m, 1H)、1.61~1.19 (m, 13H)、0.89 (t, 3H)。 1 H-NMR (500MHz, CDCl 3 , ppm): 9.0 (s, 1H), 7.73 (m, 1H), 7.65 (d, 1H), 7.13 (d, 1H), 6.96 (d, 1H), 3.34 ( m, 1H), 1.61~1.19 (m, 13H), 0.89 (t, 3H).
取0.6g化合物F8 (1.22mmole)、0.31g 1- (溴二氟甲基) -4-丙基環己烷 (1.22mmole)及0.19g 碳酸鉀 (1.34mmole)溶解在12ml THF中，回流8小時。反應液用乙酸乙酯與水進行萃取、收集有機層減壓濃縮，將得到的濃縮液進行管柱層析，得到0.57g產物G8。Get 0.6g compound F8 (1.22mmole), 0.31g 1-(bromodifluoromethyl)-4-propylcyclohexane (1.22mmole) and 0.19g potassium carbonate (1.34mmole) and dissolve in 12ml THF, reflux 8 Hour. The reaction solution was extracted with ethyl acetate and water, the collected organic layer was concentrated under reduced pressure, and the obtained concentrated solution was subjected to column chromatography to obtain 0.57 g of product G8.
製備得到的化合物G8進行質譜、核磁共振譜測試，測試得到的數據如下。根據測試結果，化合物為CQB(S)[F,OT]QIC-3-3所示結構。The prepared compound G8 was subjected to mass spectrometry and nuclear magnetic resonance spectrometry tests, and the data obtained from the tests are as follows. According to the test results, the compound has the structure shown in CQB(S)[F,OT]QIC-3-3.
MS(EI, m/z): 316, 491, 666。MS (EI, m/z): 316, 491, 666.
1H-NMR(500MHz, CDCl 3, ppm)：7.82 (d, 1H)、7.73 (d, 1H) 、7.11 (m, 2H) 、3.34 (m, 2H)、1.63~1.21 (m, 26H)、0.92 (m, 6H)。 1 H-NMR (500MHz, CDCl 3 , ppm): 7.82 (d, 1H), 7.73 (d, 1H) , 7.11 (m, 2H) , 3.34 (m, 2H), 1.63~1.21 (m, 26H), 0.92 (m, 6H).
13C-NMR(500MHz, CDCl 3, ppm)：146.0、145.5、141.9、141.2、130.7、130.4、129.6、126.5、126.1、123.0、122.4、119.4、116.1、42.2、37.1、29.3、26.5、20.5 、15.2、14.1。 13 C-NMR (500MHz, CDCl 3 , ppm): 146.0, 145.5, 141.9, 141.2, 130.7, 130.4, 129.6, 126.5, 126.1, 123.0, 122.4, 119.4, 116.1, 42.2, 37.1, 29.3, 26.5, 20.5, 15.2 , 14.1.
對於下述的表1所示的前述實施例及對比例的各化合物，在下述條件下測定T NI、Δn、Δε、K 11、K 33、G1等，其物理性能測試結果示於後述的表2中，根據這些測試結果計算得到的響應指標值G1/(K 11*△n*△n*T NI)、G1/(K 33*△n*△n*T NI)示於後述的表3中，在VA（vertical alignment，垂直取向）或者PS-VA（Polymer stabilized vertical alignment,聚合物穩定垂直取向）模式下，液晶介質的響應時間與指標G1/(K 33*△n*△n*T NI)相關，而在FFS（Fringe Field Switching，邊緣場開關）、IPS（In-Plane Switching，平面轉換）、PS-FFS（Polymer stabilized Fringe Field Switching，聚合物穩定邊緣場開關）、PS-IPS（Polymer stabilized In-Plane Switching，聚合物穩定平面轉換）等模式下，液晶介質的響應時間與響應指標值G1/(K 11*△n*△n*T NI)相關。前述的響應指標值越小，表明響應時間越快。 For each compound of the preceding examples and comparative examples shown in the following Table 1, T NI , Δn, Δε, K 11 , K 33 , G1, etc. were measured under the following conditions, and the physical property test results are shown in the following table In 2, the response index values G1/(K 11 *△n*△n*T NI ) and G1/(K 33 *△n*△n*T NI ) calculated based on these test results are shown in Table 3 below In VA (vertical alignment, vertical alignment) or PS-VA (Polymer stabilized vertical alignment, polymer stabilized vertical alignment) mode, the response time of the liquid crystal medium and the index G1/(K 33 *△n*△n*T NI ) correlation, while in FFS (Fringe Field Switching, fringe field switch), IPS (In-Plane Switching, plane switching), PS-FFS (Polymer stabilized Fringe Field Switching, polymer stabilized fringe field switch), PS-IPS ( In the Polymer stabilized In-Plane Switching mode, the response time of the liquid crystal medium is related to the response index value G1/(K 11 *△n*△n*T NI ). The smaller the aforementioned response index value, the faster the response time.
T NI代表液晶單體由向列相相變至澄清相的溫度，通過MP-90設備測量； T NI represents the temperature at which the liquid crystal monomer changes from a nematic phase to a clear phase, measured by MP-90 equipment;
Δn表示光學各向異性，Δn=n e-n o，其中，n o為尋常光的折射率，n e為非尋常光的折射率，測試條件：589 nm、25±0.2℃。 Δn represents optical anisotropy, Δn=n e -n o , where n o is the refractive index of ordinary light, and ne is the refractive index of extraordinary light. Test conditions: 589 nm, 25±0.2°C.
Δε表示介電各向異性，Δε＝ε ∥-ε ⊥，其中，ε ∥為平行于分子軸的介電常數，ε ⊥為垂直于分子軸的介電常數，測試條件：25℃、INSTEC:ALCT-IR1、18微米垂直盒； Δε represents dielectric anisotropy, Δε=ε ∥ -ε ⊥ , where ε ∥ is the dielectric constant parallel to the molecular axis, ε ⊥ is the dielectric constant perpendicular to the molecular axis, test conditions: 25°C, INSTEC: ALCT-IR1, 18 micron vertical cell;
K 11為扭曲彈性常數，K 33為展曲彈性常數，測試條件為：25℃、INSTEC:ALCT-IR1、18微米垂直盒。 K 11 is the torsional elastic constant, K 33 is the splay elastic constant, and the test conditions are: 25°C, INSTEC: ALCT-IR1, 18 micron vertical box.
Gamma1(mPa.s) 為旋轉粘滯係數，簡寫為“G1”，測試條件為：25℃、INSTEC:ALCT-IR1、18微米垂直盒。Gamma1(mPa.s) is the coefficient of rotational viscosity, abbreviated as "G1", and the test conditions are: 25°C, INSTEC: ALCT-IR1, 18 micron vertical box.
表1：實施例及對比例的各化合物
表2：實施例及對比例的各化合物的物理性能測試結果
表3：實施例及對比例的各化合物的響應指標值
通過表3中實施例1~8以及對比例的響應指標指的對比可以看出，實施例1~10的液晶化合物的響應指標值G1/(K 11*△n*△n*T NI)、G1/(K 33*△n*△n*T NI)相對於對比例降低，尤其是G1/(K 11*△n*△n*T NI)降低顯著。 From the comparison of the response indicators of Examples 1-8 and Comparative Examples in Table 3, it can be seen that the response indicators of the liquid crystal compounds of Examples 1-10 are G1/(K 11 *Δn*Δn*T NI ), G1/(K 33 *△n*△n*T NI ) decreased compared to the comparative example, especially G1/(K 11 *△n*△n*T NI ) decreased significantly.
從表2可以看出，實施例的1~8的液晶化合物的G1值雖然要高於對比例，但是由於其清亮點T NI(℃)相對於對比例1顯著提高，並且彈性係數K11(pN)、K33（pN）相對於對比例1顯著提高，從而有助於響應指標值的降低。 As can be seen from Table 2, although the G1 value of the liquid crystal compounds of Examples 1 to 8 is higher than that of the Comparative Example, the clearing point T NI (° C.) is significantly improved compared to Comparative Example 1, and the elastic coefficient K11 (pN ), K33 (pN) were significantly increased compared with Comparative Example 1, which contributed to the reduction of the response index value.
本發明可用其他的不違背本發明的精神或主要特徵的具體形式來概述。因此，無論從哪一點來看，本發明的上述實施方案都只能認為是對本發明的說明而不能限制本發明，權利要求書指出了本發明的範圍，而上述的說明並未指出本發明的範圍，因此，在與本發明的權利要求書相當的含義和範圍內的任何改變，都應認為是包括在本發明的權利要求書的範圍內。The present invention may be embodied in other specific forms without departing from the spirit or main characteristics of the invention. Therefore, no matter from which point of view, the above-mentioned embodiments of the present invention can only be regarded as descriptions of the present invention and cannot limit the present invention, and the claims have pointed out the scope of the present invention, and the above description does not point out the scope of the present invention. Therefore, any changes within the meaning and scope equivalent to the claims of the present invention should be considered to be included in the scope of the claims of the present invention.
無none
圖1為本發明的實施例1中製備的化合物B(S)[F,OT]-2O-O5溶於CDCl 3的 1H核磁共振光譜圖。 Fig. 1 is the 1 H nuclear magnetic resonance spectrum of compound B(S)[F,OT]-2O-O5 dissolved in CDCl 3 prepared in Example 1 of the present invention.
圖2為本發明的實施例1中製備的化合物B(S)[F,OT]-2O-O5的溶於CDCl 3的 13C核磁共振光譜圖。 Fig. 2 is the 13 C nuclear magnetic resonance spectrum of the compound B(S)[F,OT]-2O-O5 prepared in Example 1 of the present invention dissolved in CDCl 3 .
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| CN114394953A (en) * | 2022-01-13 | 2022-04-26 | 烟台显华科技集团股份有限公司 | Polymerizable compound, composition, and liquid crystal display device |
| CN114381279B (en) * | 2022-01-17 | 2024-01-30 | 烟台显华科技集团股份有限公司 | Polymerizable compound, composition, and liquid crystal display device |
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| EP3085753B1 (en) * | 2015-04-13 | 2019-04-24 | Merck Patent GmbH | Fluorinated dibenzofurane derivatives and dibenzothiophene derivatives |
| EP3323873B9 (en) * | 2015-07-15 | 2021-05-19 | JNC Corporation | Liquid crystal composition and liquid crystal display device |
| TWI744458B (en) * | 2017-02-27 | 2021-11-01 | 日商捷恩智股份有限公司 | Compound with dibenzofuran ring, liquid crystal composition and liquid crystal display element |
| JP2021028299A (en) * | 2017-11-30 | 2021-02-25 | Jnc株式会社 | Compound having dibenzothiophene ring, liquid crystal composition and liquid crystal display element |
| EP3898891A1 (en) * | 2018-12-19 | 2021-10-27 | Merck Patent GmbH | Liquid-crystalline medium and liquid-crystal display comprising the same and compounds |
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| CN113913193A (en) | 2022-01-11 |
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