TWI545182B

TWI545182B - Chiral compound for liquid crystal and liquid crystal mixture comprising the same

Info

Publication number: TWI545182B
Application number: TW104121976A
Authority: TW
Inventors: 李清田; 劉信呈; 王俊智
Original assignee: 達興材料股份有限公司
Priority date: 2015-07-07
Filing date: 2015-07-07
Publication date: 2016-08-11
Also published as: TW201702366A

Description

具光學活性的液晶添加物及含有此具光學活性的液晶添加物的液晶混合物 Optically active liquid crystal additive and liquid crystal mixture containing the optically active liquid crystal additive

本發明是有關於一種具光學活性的液晶添加物及含有此具光學活性的液晶添加物的液晶混合物。 The present invention relates to an optically active liquid crystal additive and a liquid crystal mixture containing the optically active liquid crystal additive.

液晶顯示器為利用液晶光電變化之顯示器，其具有體積小、重量輕、低電力消耗與顯示品質佳等優點，因此近年來已成為平面顯示器主流。隨著技術的進步，業界也不斷地利用各種方式來提高液晶顯示器的色彩飽和度，以符合使用者的需求。 The liquid crystal display is a display that utilizes liquid crystal photoelectric change, and has the advantages of small size, light weight, low power consumption, and good display quality, and thus has become a mainstream of flat display in recent years. With the advancement of technology, the industry is constantly using various methods to improve the color saturation of liquid crystal displays to meet the needs of users.

對於液晶顯示器中的液晶材料來說，具有高熱穩定性、高光穩定性、高穿透度、低旋轉黏度與高介電異方性的液晶化合物是符合目前需求的。特別是，當液晶材料具有高熱穩定性時，可以延長液晶顯示器的使用壽命。同時，具有高介電異方性、低旋轉黏度的液晶材料，可以使液晶顯示器具有較低的驅動電壓，因而可以達到省電的目的。 For liquid crystal materials in liquid crystal displays, liquid crystal compounds having high thermal stability, high light stability, high transparency, low rotational viscosity and high dielectric anisotropy are in line with current needs. In particular, when the liquid crystal material has high thermal stability, the life of the liquid crystal display can be extended. At the same time, the liquid crystal material with high dielectric anisotropy and low rotational viscosity can make the liquid crystal display have a lower driving voltage, thereby achieving the purpose of power saving.

具光學活性的手性添加劑是顯示用液晶材中重要的成份，早在20世紀便已發現在向列相液晶中添加少量的光學活性物質，可以誘導向列相轉變為膽固醇相，其中具光學活性的手性添加劑可在TN模式中使液晶分子取向扭轉90度，並抑制向錯的形成，而在STN模式則可使液晶分子取向扭轉180度至270度間；另在反射式膽固醇液晶顯示器中則可形成所需的短螺距(pitch)。另外，具光學活性的手性添加劑可補償閥值電壓(V_th)的溫度依存性。此外，適用於TFT液晶顯示器的具光學活性的手性添加劑，除要求具有較大的HTP值及良好的光穩定性和熱穩定性外，尚必須具有較高的電壓保持率(VHR)、與主體液晶材料有良好的相容性、低的溫度依存性、且不易被製程中的吸附劑(例如：分子篩)所吸附。 The optically active chiral additive is an important component in liquid crystal materials for display. It has been found in the 20th century that a small amount of optically active substance is added to the nematic liquid crystal to induce a nematic phase to a cholesterol phase, in which optical The active chiral additive can reverse the orientation of the liquid crystal molecules by 90 degrees in the TN mode and suppress the formation of the disclination, while in the STN mode, the liquid crystal molecules can be rotated by 180 to 270 degrees; the reflective cholesteric liquid crystal display The desired short pitch can be formed. In addition, optically active chiral additives compensate for the temperature dependence of the threshold voltage ( _Vth ). In addition, optically active chiral additives suitable for TFT liquid crystal displays, in addition to requiring a large HTP value and good light stability and thermal stability, must also have a high voltage holding ratio (VHR), and The host liquid crystal material has good compatibility, low temperature dependence, and is not easily adsorbed by the adsorbent (for example, molecular sieve) in the process.

有鑒於此，本發明之目的乃揭露一種新穎的具光學活性的液晶添加物，其不僅具有高HTP值、高光穩定性、高熱穩定性，且與主體液晶材料有良好的相容性、低的溫度依存性、且不易被製程中的吸附劑(例如、分子篩)所吸附。 In view of the above, the object of the present invention is to disclose a novel optically active liquid crystal additive which not only has high HTP value, high light stability, high thermal stability, but also has good compatibility with a host liquid crystal material and low. It is temperature-dependent and is not easily adsorbed by adsorbents (for example, molecular sieves) in the process.

根據本發明之一實施例，本發明提供一種具光學活性的液晶添加物，係該具光學活性的液晶添加物之結構式為A-B，該A為具有鏈狀之手性結構部分，該B具有至少兩個環狀結構，其中該環狀結構至少一個環為2,6-二氧雜二環[2,2,2]辛烷基、2,6,7-三氧雜二環[2,2,2]辛烷基或2,5-茚滿基，該A與該B以單鍵連接。 According to an embodiment of the present invention, the present invention provides an optically active liquid crystal additive having the structural formula AB of an optically active liquid crystal additive, wherein A is a chain-like chiral structure, and the B has At least two cyclic structures, wherein at least one ring of the cyclic structure is 2,6-dioxabicyclo[2,2,2]octyl, 2,6,7-trioxabicyclo[2, 2,2]octyl or 2,5-indanyl, which is linked to the B by a single bond.

根據本發明之某些實施例，本發明提供一種如上所述的具光學活性的液晶添加物，係具有式(I)所示之結構：其中，R¹為鹵素、CF₃、CN或為碳數1~10的烷基，且該碳數1~10的烷基為未經取代或任意-CH₂-可被O、S取代或至少一個-(CH₂)₂-可被-CH=CH-、-C≡C-取代，且該碳數為1~10的烷基，及/或任意碳上的氫原子為未經取代或被鹵素、CN或CF₃取代；R²為氫、C₁-C₁₀烷基或C₂-C₁₀烯基，且其中C₁-C₁₀烷基、C₂-C₁₀烯基為未經取代或任意-CH₂-被-O-、-S-、-O-CO-、-OC-O-或-O-CO-O-取代，且其中-O-、-S-、-O-CO-、-OC-O-或-O-CO-O-取代基彼此不直接相連接，及/或任意碳上的氫原子為未經取代或被鹵素、CN或CF₃取代；Q可為C、O、或S；Y為碳數1~10的烷基；環A1、環A2、環A3及環A4獨立地為2,6-二氧雜二環[2,2,2]辛烷基、2,6,7-三氧雜二環[2,2,2]辛烷基或2,5-茚滿基、1,4-伸環己基或1,4-伸苯基，及/或該1,4-伸苯基或1,4-伸苯基中為未經取代或至少一個氫被鹵素、CN、CF₃取代，且環A1、環A2、環A3及環A4至少之一為2,6-二氧雜二環[2,2,2]辛烷基、2,6,7-三氧雜二環[2,2,2]辛烷基或2,5茚滿基；Z₁、Z₂、及Z₃獨立地為單鍵、C₁-C₄伸烷基、C₂-C₄伸烯基、C₂-C₄伸炔基、-CO-O-、-O-CO-、-CF₂O-或-OCF₂-，且其中C₁-C₄伸烷基、C₂-C₄伸烯基、C₂-C₄伸炔基為未經取代或至少一個氫原子被鹵素取代，及/或任意-CH₂-被-O-或-S-取代，且其中-O-、-S-彼此不直接相連；n可為1或0。 According to some embodiments of the present invention, there is provided an optically active liquid crystal additive as described above having the structure of formula (I): Wherein R ¹ is halogen, CF ₃ , CN or an alkyl group having 1 to 10 carbon atoms, and the alkyl group having 1 to 10 carbon atoms is unsubstituted or any -CH ₂ - may be substituted by O, S or at least One -(CH ₂ ) ₂ - may be substituted by -CH=CH-, -C≡C-, and the alkyl group having a carbon number of 1 to 10, and/or the hydrogen atom on any carbon is unsubstituted or Halogen, CN or CF ₃ substituted; R ² is hydrogen, C ₁ -C ₁₀ alkyl or C ₂ -C ₁₀ alkenyl, and wherein C ₁ -C ₁₀ alkyl, C ₂ -C ₁₀ alkenyl is unsubstituted Or any -CH ₂ - is substituted by -O-, -S-, -O-CO-, -OC-O- or -O-CO-O-, and wherein -O-, -S-, -O-CO -, -OC-O- or -O-CO-O- substituents are not directly linked to each other, and/or the hydrogen atom on any carbon is unsubstituted or substituted by halogen, CN or CF ₃ ; Q can be C , O, or S; Y is an alkyl group having 1 to 10 carbon atoms; ring A1, ring A2, ring A3 and ring A4 are independently 2,6-dioxabicyclo[2,2,2]octyl , 2,6,7-trioxabicyclo[2,2,2]octyl or 2,5-indanyl, 1,4-cyclohexylene or 1,4-phenylene, and/or the 1,4-phenylene or 1,4-phenylene is unsubstituted in at least one hydrogen or halogen, CN, CF ₃ substituent, and ring A1, ring A2, ring A3, and ring A4 least One is 2,6-dioxabicyclo[2,2,2]octyl, 2,6,7-trioxabicyclo[2,2,2]octyl or 2,5 indanyl ; Z ₁ , Z ₂ , and Z _{3 are} independently a single bond, C ₁ -C ₄ alkylene, C ₂ -C ₄ alkylene, C ₂ -C ₄ alkynyl, -CO-O-, - O-CO-, -CF ₂ O- or -OCF ₂ -, and wherein C ₁ -C ₄ alkyl, C ₂ -C ₄ alkylene, C ₂ -C ₄ alkynyl are unsubstituted or at least One hydrogen atom is replaced by a halogen, and/or any -CH ₂ - is substituted by -O- or -S-, and wherein -O-, -S- are not directly connected to each other; n may be 1 or 0.

根據本發明之另一實施例，本發明提供一種如上所述的具光學活性的液晶添加物，其中環A1為2,6-二氧雜二環[2,2,2]辛烷基、2,6,7-三氧雜二環[2,2,2]辛烷基或2,5-茚滿基。 According to another embodiment of the present invention, there is provided an optically active liquid crystal additive as described above, wherein ring A1 is 2,6-dioxabicyclo[2,2,2]octyl, 2 6,7-Trioxabicyclo[2,2,2]octyl or 2,5-indanyl.

根據本發明之某些實施例，本發明提供一種如上所述的具光學活性的液晶添加物，其中環A2、環A3、環A4至少之一為1,4-伸苯基，且該1,4-伸苯基中至少一個氫被鹵素取代。 According to some embodiments of the present invention, the present invention provides an optically active liquid crystal additive as described above, wherein at least one of ring A2, ring A3, and ring A4 is 1,4-phenylene, and the 1, At least one hydrogen in the 4-phenylene group is replaced by a halogen.

根據本發明之某些實施例，本發明提供一種如上所述的具光學活性的液晶添加物，具選自以下式(II)、式(III)或式(IV)之結構式： According to some embodiments of the present invention, there is provided an optically active liquid crystal additive having a structural formula selected from the following formula (II), formula (III) or formula (IV):

其中，R²為氫、C₁-C₁₀烷基或C₂-C₁₀烯基，且其中C₁-C₁₀烷基、C₂-C₁₀烯基為未經取代或任意-CH₂-被-O-、-S-、-O-CO-、-OC-O-或-O-CO-O-取代，且其中-O-、-S-、-O-CO-、-OC-O-或-O-CO-O-取代基彼此不直接相連接，及/或任意碳上的氫原子為未經取代或被鹵素、CN或CF₃取代；Y為碳數1~10的烷基；環A2及環A3獨立地為1,4-伸環己基或1,4-伸苯基，及/或該1,4-伸苯基或1,4-伸苯基中為未經取代或至少一個氫被鹵素、CN、CF₃取代；Z₁、Z₂、及Z₃獨立地為單鍵、C₁-_C4伸烷基、C₂-C₄伸烯基、C₂-C₄伸炔基、-CO-O-、-O-CO-、-CF₂O-或-OCF₂-，且其中C₁-C₄伸烷基、C₂-C₄伸烯基、C₂-C₄伸炔基為未經取代或至少一個氫原子被鹵素取代，及/或任意-CH₂-被-O-或-S-取代，且其中-O-、-S-彼此不直接相連；Q為O；m為1至10。 Wherein R ² is hydrogen, C ₁ -C ₁₀ alkyl or C ₂ -C ₁₀ alkenyl, and wherein C ₁ -C ₁₀ alkyl, C ₂ -C ₁₀ alkenyl is unsubstituted or optionally -CH ₂ - Substituted by -O-, -S-, -O-CO-, -OC-O- or -O-CO-O-, and wherein -O-, -S-, -O-CO-, -OC-O - or -O-CO-O- substituents are not directly bonded to each other, and/or the hydrogen atom on any carbon is unsubstituted or substituted by halogen, CN or CF ₃ ; Y is an alkyl group having 1 to 10 carbon atoms Ring A2 and ring A3 are independently 1,4-cyclohexylene or 1,4-phenylene, and/or the 1,4-phenylene or 1,4-phenylene group is unsubstituted or at least one hydrogen is halogen, CN, CF ₃ substituent; Z _1, Z _2, and Z _{3 are} independently a single bond, _C ₁ - C 4 alkylene, C ₂ -C ₄ alkenylene group, C ₂ -C ₄ An alkynyl group, -CO-O-, -O-CO-, -CF ₂ O- or -OCF ₂ -, and wherein C ₁ -C _{4 is} alkyl, C ₂ -C _{4 is} alkenyl, C ₂ - The C ₄ alkynyl group is unsubstituted or at least one hydrogen atom is replaced by a halogen, and/or any -CH ₂ - is substituted by -O- or -S-, and wherein -O-, -S- are not directly bonded to each other; Q is O; m is from 1 to 10.

根據本發明之某些實施例，本發明提供一種如上所述的具光學活性的液晶添加物，具選自以下式(V)、式(VI)或式(VII)之結構式： According to some embodiments of the present invention, there is provided an optically active liquid crystal additive having a structural formula selected from the following formula (V), formula (VI) or formula (VII):

其中，R²為氫、C₁-C₁₀烷基或C₂-C₁₀烯基，且其中C₁-C₁₀烷基、C₂-C₁₀烯基為未經取代或任意-CH₂-被-O-、-S-、-O-CO-、-OC-O-或-O-CO-O-取代，且其中-O-、-S-、-O-CO-、-OC-O-或-O-CO-O-取代基彼此不直接相連接，及/或任意碳上的氫原子為未經取代或被鹵素、CN或CF₃取代；Y為碳數1~10的烷基；環A2為1,4-伸環己基或1,4-伸苯基，及/或該1,4-伸苯基或1,4-伸苯基中為未經取代或至少一個氫被鹵素、CN、CF₃取代；Z₁、Z₂、及Z₃獨立地為單鍵、C₁-C₄伸烷基、C₂-C₄伸烯基、C₂-C₄伸炔基、-CO-O-、-O-CO-、-CF₂O-或-OCF₂-，且其中C₁-C₄伸烷基、C₂-C₄伸烯基、C₂-C₄伸炔基為未經取代或至少一個氫原子被鹵素取代，及/或任意-CH₂-被-O-或-S-取代，且其中-O-、-S-彼此不直接相連；Q為O；m為1至10。 Wherein R ² is hydrogen, C ₁ -C ₁₀ alkyl or C ₂ -C ₁₀ alkenyl, and wherein C ₁ -C ₁₀ alkyl, C ₂ -C ₁₀ alkenyl is unsubstituted or optionally -CH ₂ - Substituted by -O-, -S-, -O-CO-, -OC-O- or -O-CO-O-, and wherein -O-, -S-, -O-CO-, -OC-O - or -O-CO-O- substituents are not directly bonded to each other, and/or the hydrogen atom on any carbon is unsubstituted or substituted by halogen, CN or CF ₃ ; Y is an alkyl group having 1 to 10 carbon atoms Ring A2 is 1,4-cyclohexylene or 1,4-phenylene, and/or the 1,4-phenylene or 1,4-phenylene group is unsubstituted or at least one hydrogen is halogen Substituting CN, CF ₃ ; Z ₁ , Z ₂ , and Z _{3 are} independently a single bond, a C ₁ -C ₄ alkylene group, a C ₂ -C ₄ alkylene group, a C ₂ -C ₄ alkynyl group, CO-O-, -O-CO-, -CF ₂ O- or -OCF ₂ -, and wherein C ₁ -C ₄ alkyl, C ₂ -C ₄ alkenyl, C ₂ -C ₄ alkynyl Is unsubstituted or at least one hydrogen atom is replaced by halogen, and/or any -CH ₂ - is substituted by -O- or -S-, and wherein -O-, -S- are not directly connected to each other; Q is O; m It is from 1 to 10.

根據本發明之某些實施例，本發明提供一種如上所述的具光學活性的液晶添加物，具以下結構式： According to some embodiments of the present invention, there is provided an optically active liquid crystal additive as described above having the following structural formula:

根據本發明之某些實施例，本發明提供一種如上所述的具光學活性的液晶添加物，其中Q為O；R¹為C_mH_2m+1；m=3-8。 According to some embodiments of the invention, the invention provides an optically active liquid crystal additive as described above, wherein Q is O; R ¹ is C _m H _2m+1 ; m=3-8.

根據本發明之另一實施例，本發明提供一種液晶組成物，包含至少一種如上所述之具光學活性的液晶添加物。 According to another embodiment of the present invention, there is provided a liquid crystal composition comprising at least one optically active liquid crystal additive as described above.

根據本發明之某些實施例，本發明提供一種如上所述的液晶組成物，其中該具光學活性的液晶添加物的含量可為0.1重量百分比至15重量百分比，較佳為小於1重量百分比，尤佳為0.1重量百分比至0.5重量百分比。 According to some embodiments of the present invention, there is provided a liquid crystal composition as described above, wherein the optically active liquid crystal additive is contained in an amount of from 0.1% by weight to 15% by weight, preferably less than 1% by weight, It is particularly preferably from 0.1% by weight to 0.5% by weight.

此外，前述液晶組成物中，除液晶以及上述的具光學活性的液晶添加物外，更可包括本領域熟知此技術者所熟知的UV穩定劑、抗氧化劑、自由基淨化劑、奈米粒子等添加劑，在此將不再贅述。 Further, the liquid crystal composition may include, in addition to the liquid crystal and the above-mentioned optically active liquid crystal additive, a UV stabilizer, an antioxidant, a radical scavenger, a nanoparticle, etc., which are well known to those skilled in the art. Additives will not be described here.

由於以下說明使用多種具光學活性的液晶添加物，為求表示的簡潔，下文將以代號組合來表示，其中以O代表氧原子，以正常字型顯示的數字代表碳數等於該數字的烷基，以及每一代號分別表示的結構單元整理於下表： Since a variety of optically active liquid crystal additives are used in the following description, for the sake of simplicity of the expression, the following will be represented by a combination of numbers, wherein O represents an oxygen atom, and a number displayed in a normal font represents an alkyl group having a carbon number equal to the number. And the structural units represented by each code are organized in the following table:

(S)3doPUO8代表結構式如下的化合物： (S) 3doPUO8 represents a compound of the formula:

(S)3toPUO8代表結構式如下的化合物： (S) 3toPUO8 represents a compound of the formula:

(S)2RIGUQUO8代表結構式如下的化合物： (S) 2RIGUQUO8 represents a compound of the formula:

(S)3RIGUO8代表結構式如下的化合物： (S) 3RIGUO8 represents a compound of the formula:

(S)3RIPUO8代表結構式如下的化合物 (S) 3RIPUO8 represents a compound of the following formula

具光學活性的液晶添加物： Optically active liquid crystal additive:

實施例1：(S)3doPUO8的合成： Example 1: Synthesis of ( S )3doPUO8:

首先，取1.15g(5.5mmol)的式(i)化合物於於250mL雙頸圓底瓶中，然後依序加入30mL二氯甲烷(CH₂Cl₂)、0.68g(5.2mmol)的(R)2-辛醇((R)-octanol)、2g(7.8mmol)的三苯基膦(PPh3)而形成一混合液。室溫下，慢慢加入1.6g(7.8mmol)的二異丙基偶氮二羧酸(DIAD)，使該混合液於室溫下攪拌1小時，以TLC片(層析液為乙酸乙酯)確認反應是否完全，待反應完全後進行減壓濃縮，最後利用管柱層析法(沖提液為乙酸乙酯及正己烷混合液，其中乙酸乙酯與正己烷的體積比例為1：10)純化獲得0.96g的無色液體，即為式(ii)化合物。上述反應之反應式，如下所示： First, 1.15 g (5.5 mmol) of the compound of formula (i) was placed in a 250 mL double neck round bottom bottle, followed by the addition of 30 mL of dichloromethane (CH ₂ Cl ₂ ), 0.68 g (5.2 mmol) of ( R ). 2-octanol ((R)-octanol), 2 g (7.8 mmol) of triphenylphosphine (PPh3) to form a mixed solution. 1.6 g (7.8 mmol) of diisopropylazodicarboxylic acid (DIAD) was slowly added at room temperature, and the mixture was stirred at room temperature for 1 hour to a TLC plate (yield ethyl acetate) Confirm that the reaction is complete. After the reaction is completed, concentrate under reduced pressure. Finally, use column chromatography (the extract is a mixture of ethyl acetate and n-hexane, wherein the volume ratio of ethyl acetate to n-hexane is 1:10). Purification afforded 0.96 g of a colorless liquid which is a compound of formula (ii). The reaction formula of the above reaction is as follows:

接著，於100ml雙頸瓶中加入0.96g(3mmol)式(ii)化合物以及20ml無水四氫呋喃，氮氣下，降溫至-70℃以下，開始滴加1.44mL(3.6mmol)正丁基鋰(n-BuLi)，滴完後-70℃下攪拌1小時；滴加1.25mL(6mmol)三甲基硼酯(B(OMe)3)，滴完後回0℃下攪拌1小時；加入HCL(1N,20mL)再攪拌一小時，以乙酸乙酯萃取該反應後的混合液，反覆進行三次萃取並收集有機層，再以無水硫酸鎂去除水份，最後進行過濾及減壓濃縮，獲得0.65g的黃色液體，即為式(iii)化合物。上述反應之反應式，如下所示： Next, 0.96 g (3 mmol) of the compound of the formula (ii) and 20 ml of anhydrous tetrahydrofuran were added to a 100 ml two-necked flask, and the temperature was lowered to -70 ° C or lower under nitrogen, and 1.44 mL (3.6 mmol) of n-butyllithium (n-) was added dropwise. BuLi), after the completion of the dropwise addition, the mixture was stirred at -70 ° C for 1 hour; 1.25 mL (6 mmol) of trimethylborate (B(OMe) 3) was added dropwise, and after the completion of the dropwise addition, the mixture was stirred at 0 ° C for 1 hour; HCL (1 N, 20 mL) was further stirred for one hour, and the mixture after the reaction was extracted with ethyl acetate. The mixture was extracted three times and the organic layer was collected, and then, water was removed with anhydrous magnesium sulfate, and finally filtered and concentrated under reduced pressure to obtain 0.65 g of yellow. The liquid is the compound of formula (iii). The reaction formula of the above reaction is as follows:

接著，於100ml雙頸瓶中加入0.65g(2.2mmol)的式(iii)化合物以及10ml無水四氫呋喃，降溫至0℃以下，開始滴加雙氧水(30%水溶液，2mL)，滴完後室溫下攪拌3小時；以乙酸乙酯萃取該反應後的混合液，反覆進行三次萃取並收集有機層，再以無水硫酸鎂去除水份，最後進行過濾及減壓濃縮，獲得0.5g的黃色液體，即為式(iv)化合物。上述反應之反應式，如下所示： Next, 0.65 g (2.2 mmol) of the compound of the formula (iii) and 10 ml of anhydrous tetrahydrofuran were added to a 100 ml two-necked flask, and the temperature was lowered to below 0 ° C, and hydrogen peroxide (30% aqueous solution, 2 mL) was added dropwise. After stirring for 3 hours, the reaction mixture was extracted with ethyl acetate, and extracted three times, and the organic layer was collected, then the water was removed with anhydrous magnesium sulfate, and finally filtered and concentrated under reduced pressure to obtain 0.5 g of a yellow liquid. Is a compound of formula (iv). The reaction formula of the above reaction is as follows:

2,6-二氧雜二環[2,2,2]辛烷環的合成方法如下：於250mL雙頸圓底瓶中，依序加入100mL二氯甲烷(CH₂Cl₂)、13.4g(0.1mol)的式(A)化合物、9.2g(0.15mol)的2,2-二甲氧基丙烷與0.1g對甲苯磺酸而形成一混合液。使該混合液於室溫下攪拌18小時，以TLC片(層析液為乙酸乙酯)確認反應是否完全，待反應完全後加入100mL的水中止反應。以二氯甲烷萃取該反應後的混合液，反覆進行三次萃取並收集有機層，再以無水硫酸鎂去除水份，最後進行過濾及減壓濃縮，獲得17.8 g的黃色液體，即為式(B)化合物，後續直接使用，不需純化。上述反應之反應式，如下所示： The synthesis method of 2,6-dioxabicyclo[2,2,2]octane ring is as follows: 100 mL of dichloromethane (CH ₂ Cl ₂ ) and 13.4 g are sequentially added to a 250 mL double neck round bottom bottle. 0.1 mol) of a compound of the formula (A), 9.2 g (0.15 mol) of 2,2-dimethoxypropane and 0.1 g of p-toluenesulfonic acid form a mixed liquid. The mixture was stirred at room temperature for 18 hours, and the reaction was confirmed to be complete with a TLC plate (the solvent was ethyl acetate). After the reaction was completed, the reaction was stopped by adding 100 mL of water. The mixture after the reaction was extracted with dichloromethane, and extracted three times, and the organic layer was collected, and then the water was removed with anhydrous magnesium sulfate, and finally filtered and concentrated under reduced pressure to obtain 17.8 g of a yellow liquid. Compounds, used directly afterwards, without purification. The reaction formula of the above reaction is as follows:

接著，於250mL雙頸圓底瓶中，依序加入20mL二氯甲烷、10.0g(0.058mol)的式(B)化合物、5.5mL的吡啶及10.1g(0.053mol)的4-甲苯基磺醯氯(4-toluenesulfonyl chloride)而形成一混合液。使該混合液於室溫下攪拌18小時，以TLC片(層析液為乙酸乙酯及正己烷混合液，其中乙酸乙酯與正己烷的體積比例為3：7)確認反應是否完全，待反應完全後加入100mL的水中止反應。以二氯甲烷萃取該反應後的混合液，反覆進行三次萃取並收集有機層，再以無水硫酸鎂去除水份、過濾及減壓濃縮，最後利用管柱層析法(沖提液為乙酸乙酯及正己烷混合液，其中乙酸乙酯與正己烷的體積比例為3：7)純化獲得14.3g的白色固體，即為化合物C。上述反應之反應式，如下所示： Next, 20 mL of dichloromethane, 10.0 g (0.058 mol) of the compound of the formula (B), 5.5 mL of pyridine and 10.1 g (0.053 mol) of 4-tolylsulfonate were sequentially added to a 250 mL double-necked round bottom flask. 4-toluenesulfonyl chloride forms a mixture. The mixture was stirred at room temperature for 18 hours, and the reaction was confirmed to be complete with a TLC plate (the mixture was a mixture of ethyl acetate and n-hexane, wherein the ratio of ethyl acetate to n-hexane was 3:7). After the reaction was completed, the reaction was stopped by adding 100 mL of water. The mixed solution was extracted with dichloromethane, and extracted three times to collect the organic layer, and then the water was removed with anhydrous magnesium sulfate, filtered, concentrated under reduced pressure, and finally purified by column chromatography (purified ethyl acetate) A mixture of ester and n-hexane in which the volume ratio of ethyl acetate to n-hexane was 3:7) was purified to obtain 14.3 g of a white solid, which was Compound C. The reaction formula of the above reaction is as follows:

接著，於250mL雙頸圓底瓶中，依序加入20mL丙酮、3.3g(0.01mol)的式(C)化合物及3.75g(0.025mol)的碘化鈉而形成一混合液。使該混合液於加熱迴流下攪拌18小時，以TLC片(層析液為乙酸乙酯及正己烷混合液，其中乙酸乙酯與正己烷的體積比例為1：9)確認反應是否完全，待反應完全後加入100mL的水中止反應。以二氯甲烷萃取該反應後的混合液，反覆進行三次萃取並收集有機層，再以無水硫酸鎂去除水份、過濾及減壓濃縮，最後利用管柱層析法(沖提液為乙酸乙酯及正己烷混合液，其中乙酸乙酯與正己烷的體積比例為1：9)純化獲得1.9g的淡黃色液體，即為式(D)化合物。上述反應之反應式，如下所示： Next, 20 mL of acetone, 3.3 g (0.01 mol) of the compound of the formula (C) and 3.75 g (0.025 mol) of sodium iodide were sequentially added to a 250 mL double-necked round bottom flask to form a mixed solution. The mixture was stirred under reflux with heating for 18 hours, and the reaction was confirmed to be complete with a TLC plate (the mixture was a mixture of ethyl acetate and n-hexane, wherein the ratio of ethyl acetate to n-hexane was 1:9). After the reaction was completed, the reaction was stopped by adding 100 mL of water. The mixed solution was extracted with dichloromethane, and extracted three times to collect the organic layer, and then the water was removed with anhydrous magnesium sulfate, filtered, concentrated under reduced pressure, and finally purified by column chromatography (purified ethyl acetate) A mixture of ester and n-hexane in which the volume ratio of ethyl acetate to n-hexane is 1:9) was purified to obtain 1.9 g of a pale yellow liquid, which is a compound of formula (D). The reaction formula of the above reaction is as follows:

接著，於250mL雙頸圓底瓶中，在氮氣存在下依序加入45mL的四氫呋喃(THF)及6.4mL的二異丙胺而形成一反應液。使該反應液溫度降至0℃，再慢慢滴入16mL的正丁基鋰(濃度為2.5M)，接著於0℃下攪拌30分鐘後，再加入9g(0.032mol)的N-環己基-溴苯基亞胺(式(v)化合物)並攪拌1小時後得到一烯胺試劑。使8.5g(0.03mol)之2,2-二甲基-5-丙基-5-碘甲基-1,3-二噁烷(式D)溶於10mL的THF中形成一混合液。將此混合液加入先前製備的烯胺試劑得到一混合物。使該混合物回溫至室溫，再加熱迴流攪拌反應18小時，以TLC片(層析液為乙酸乙酯及正己烷混合液，其中乙酸乙酯與正己烷的體積比例為1：10)確認反應是否完全，待反應完全後加入50mL的水中止反應。以乙酸乙酯萃取該反應後的混合物，反覆進行三次萃取並收集有機層，再以無水硫酸鎂去除水份、過濾及減壓濃縮，最後利用管柱層析法(沖提液為乙酸乙酯及正己烷混合液，其中乙酸乙酯與正己烷的體積比例為1：10)，純化獲得5.1g的棕色液體，即為2,2-二甲基-5-丙基-5-對溴苯甲醯乙基-1,3-二噁烷(式(E)化合物)。上述反應之反應式，如下所示： Next, 45 mL of tetrahydrofuran (THF) and 6.4 mL of diisopropylamine were sequentially added to a 250 mL double neck round bottom flask in the presence of nitrogen to form a reaction liquid. The temperature of the reaction solution was lowered to 0 ° C, and 16 mL of n-butyllithium (concentration: 2.5 M) was slowly added dropwise, followed by stirring at 0 ° C for 30 minutes, and then 9 g (0.032 mol) of N -cyclohexyl group was further added. -Bromophenylimine (compound of formula (v)) and stirred for 1 hour to give an enamine reagent. 8.5 g (0.03 mol) of 2,2-dimethyl-5-propyl-5-iodomethyl-1,3-dioxane (formula D ) was dissolved in 10 mL of THF to form a mixture. This mixture was added to the previously prepared enamine reagent to obtain a mixture. The mixture was warmed to room temperature, and the reaction was stirred and refluxed for 18 hours. The mixture was purified by TLC (yield: ethyl acetate and n-hexane mixture, ratio of ethyl acetate to n-hexane: 1:10). Whether the reaction is complete or not, after the reaction is completed, the reaction is stopped by adding 50 mL of water. The reaction mixture was extracted with ethyl acetate, and extracted three times, and the organic layer was collected. The organic layer was separated, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure, and finally purified by column chromatography (ethyl acetate) And a mixture of n-hexane, wherein the volume ratio of ethyl acetate to n-hexane is 1:10), and purified to obtain 5.1 g of a brown liquid, which is 2,2-dimethyl-5-propyl-5-p-bromobenzene. Formamidine-1,3-dioxane (compound of formula (E)). The reaction formula of the above reaction is as follows:

其中，上述反應所使用的式(v)化合物，其製備步驟包括先於250mL雙頸圓底瓶中，依序加入40mL甲苯、4g(0.02mol)的對溴苯乙酮(p-bromo acetophenone)、3g(0.03mol)的環己胺(cyclohexylamine)、0.04g的對甲苯磺酸及2g的分子篩而形成一混合物。使該混合物於加熱迴流下攪拌18小時，以矽藻土(celite)進行過濾並收集有機液，最後進行減壓濃縮而獲得4.8g的黃色固體，即為N-環己基-溴苯基亞胺(式(v)化合物)，後續直接使用，不需純化。上述反應之反應式，如下所示： Wherein, the compound of the formula (v) used in the above reaction comprises the steps of: adding 40 mL of toluene and 4 g (0.02 mol) of p- bromo acetophenone in a 250 mL double neck round bottom bottle. 3 g (0.03 mol) of cyclohexylamine, 0.04 g of p-toluenesulfonic acid and 2 g of molecular sieves form a mixture. The mixture was stirred under reflux with heating for 18 hours, filtered over Celite, and the organic liquid was collected, and finally concentrated under reduced pressure to give 4.8 g of a yellow solid as N -cyclohexyl-bromophenylimine. (Compound of formula (v)), used directly afterwards, without purification. The reaction formula of the above reaction is as follows:

接著，於250mL雙頸圓底瓶中，依序加入30mL的THF、2.9g(8mmol)之2,2-二甲基-5-乙基-5-對溴苯甲醯丙基-1,3-二噁烷(式(E)化合物)及30mL鹽酸水溶液(濃度為2N)而形成一混合液。使該混合液於室溫下攪拌2小時，以TLC片(層析液為乙酸乙酯及正己烷混合液，其中乙酸乙酯與正己烷的體積比例為1：10)確認反應是否完全，待反應完全後加入50mL的水中止反應。以乙酸乙酯萃取該反應後的混合物，反覆進行三次萃取並收集有機層，再以無水硫酸鎂去除水份、過濾及減壓濃縮，最後利用管柱層析法(沖提液為乙酸乙酯及正己烷混合液，其中乙酸乙酯與正己烷的體積比例為1：10)純化獲得1.9g的淡黃色固體，即為式(F)化合物。上述反應之反應式，如下所示： Next, 30 mL of THF and 2.9 g (8 mmol) of 2,2-dimethyl-5-ethyl-5-p-bromobenzylidenepropyl-1,3 were sequentially added to a 250 mL double-necked round bottom flask. - Dioxane (compound of formula (E)) and 30 mL of aqueous hydrochloric acid (concentration: 2N) to form a mixed liquid. The mixture was stirred at room temperature for 2 hours, and the TLC plate (the chromatographic solution was a mixture of ethyl acetate and n-hexane, wherein the volume ratio of ethyl acetate to n-hexane was 1:10) was confirmed to be complete. After the reaction was completed, the reaction was stopped by adding 50 mL of water. The reaction mixture was extracted with ethyl acetate, and extracted three times, and the organic layer was collected. The organic layer was separated, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure, and finally purified by column chromatography (ethyl acetate) And a mixture of n-hexane in which the volume ratio of ethyl acetate to n-hexane was 1:10) was purified to obtain 1.9 g of a pale yellow solid, which was a compound of formula (F). The reaction formula of the above reaction is as follows:

接著，於250mL雙頸圓底瓶中，依序加入15mL的THF、0.3g(0.1mmol)之(F)、0.26g(0.09mmol)的式(iii)化合物、3mL的碳酸鉀水溶液(濃度為1N)與0.05g的三苯基磷鈀鹽[Pd(PPh₃)₄]而形成一混合物。使該混合物於加熱迴流下攪拌18小時，以TLC片(層析液為乙酸乙酯及正己烷混合液，其中乙酸乙酯與正己烷的體積比例為1：10)確認反應是否完全，待反應完全後加入50mL的水中止反應。以乙酸乙酯萃取該反應後的混合物，反覆進行三次萃取並收集有機層，再以無水硫酸鎂去除水份、過濾及減壓濃縮，最後利用管柱層析法(沖提液為乙酸乙酯及正己烷混合液，其中乙酸乙酯與正己烷的體積比例為1：10)純化獲得0.3g的白色固體，即為(S)3doPUO8。上述反應之反應式，如下所示： Next, 15 mL of THF, 0.3 g (0.1 mmol) of (F), 0.26 g (0.09 mmol) of the compound of the formula (iii), and 3 mL of an aqueous potassium carbonate solution were added to a 250 mL double-necked round bottom flask (concentration was 1N) forms a mixture with 0.05 g of triphenylphosphine palladium salt [Pd(PPh ₃ ) ₄ ]. The mixture was stirred under reflux with heating for 18 hours, and the reaction was confirmed to be complete by a TLC plate (the mixture was a mixture of ethyl acetate and n-hexane, wherein the ratio of ethyl acetate to n-hexane was 1:10). After completely adding 50 mL of water, the reaction was stopped. The reaction mixture was extracted with ethyl acetate, and extracted three times, and the organic layer was collected. The organic layer was separated, dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure, and finally purified by column chromatography (ethyl acetate) And a mixture of n-hexane in which the volume ratio of ethyl acetate to n-hexane was 1:10) was purified to obtain 0.3 g of a white solid, which was ( S )3doPUO8. The reaction formula of the above reaction is as follows:

利用氣相沉積質譜儀(GCMS)以及核磁共振光譜(NMR)分析(S)3doPUO8，所得之質譜及光譜資訊如下：GCMS：m/z=472.3684[M]⁺；¹H-NMR(CDCl₃,400MHz),(ppm)：0.86-0.96(m,6H),1.14-2.25(m,25H),4.27-4.32(m,1H),7.102(d,J=9.2Hz,2H),7.473(d,J=8.4Hz,2H),7.572(d,J=8.8Hz,2H)。 The ( S )3doPUO8 was analyzed by vapor deposition mass spectrometry (GCMS) and nuclear magnetic resonance spectroscopy (NMR). The obtained mass spectrum and spectral information were as follows: GCMS: m/z = 472.3684 [M] ⁺ ; ¹ H-NMR (CDCl ₃ , 400MHz), (ppm): 0.86-0.96 (m, 6H), 1.14-2.25 (m, 25H), 4.27-4.32 (m, 1H), 7.102 (d, J = 9.2 Hz, 2H), 7.743 (d, J = 8.4 Hz, 2H), 7.572 (d, J = 8.8 Hz, 2H).

實施例2：(S)3toPUO8的合成 Example 2: Synthesis of ( S )3toPUO8

(S)3toPUO8的合成步驟是依據上述(S)3doPUO8的合成步驟及條件進行，除了將式(F)化合物置換為式(J)化合物以及依據莫耳數改變用量克數外，其餘合成步驟相同，最後製得(S)3toPUO8。 (S) 3toPUO8 synthesis step is carried out according to the synthesis step and the conditions 3doPUO8 (S), except that the compound of formula (F) is replaced with formula (J) based on number of moles of compound and the amount of change in grams, the same remaining synthetic steps Finally, ( S )3toPUO8 was obtained.

利用氣相沉積質譜儀(GCMS)以及核磁共振光譜(NMR)分析(S)3toPUO8，所得之質譜及光譜資訊如下：GCMS：m/z=474.4606[M]⁺；¹H NMR(400MHz,CDCl₃)：δ(ppm)0.80-0.91(m,6H),1.19-1.71(m,17H),4.108(s,6H),4.23-4.21(m,1H),7.085(d,J=9.2Hz,2H),7.471(d,J=8.8Hz,2H),7.652(d,J=8.8Hz,2H)。 Vapor deposition using a mass spectrometer (GCMS) and nuclear magnetic resonance spectroscopy (NMR) analysis (S) 3toPUO8, and the mass spectra obtained from the following information: GCMS: m / z = 474.4606 [M] +; 1 H NMR (400MHz, CDCl 3 ): δ (ppm) 0.80-0.91 (m, 6H), 1.19-1.71 (m, 17H), 4.108 (s, 6H), 4.23-4.21 (m, 1H), 7.085 (d, J = 9.2 Hz, 2H) ), 7.471 (d, J = 8.8 Hz, 2H), 7.652 (d, J = 8.8 Hz, 2H).

其中，上述式(J)化合物的製備步驟包括於250ml乾燥潔淨的三口瓶中加入12g的式(I)化合物以及90ml的二氯甲烷。在氮氣保護下攪拌前述混合物，並使用液氮降溫至0℃。控溫在0℃下，滴加1.4g的三氟化硼***，並在滴加完畢後，仍控溫在0℃且持續反應30min。之後，自然升溫至室溫，持續反應4小時。以薄層層析法(thin layer chromatography,TLC)確認反應的完成點，並當證實反應完成後，將前述混合物加入矽藻土進行抽氣過濾。接著，對濾液進行減壓濃縮，以得到一乾燥物。將前述乾燥物溶解於1倍重的二氯甲烷溶解中，並加入1倍重的矽膠混合後再進行減壓濃縮，以得到含有矽膠的一乾燥物。接著，將前述乾燥物置於裝有3~4倍重的矽膠的管柱中進行層析處理(沖提液為石油醚：乙酸乙酯=20：1，再加入總體積1%的三乙胺)。最後，收集層析液並濃縮，以得到7g呈白色固體的式(J)化合物。上述反應之反應式，如下所示： Wherein the preparation step of the above compound of the formula (J) comprises adding 12 g of the compound of the formula (I) and 90 ml of dichloromethane to 250 ml of a dry clean three-necked flask. The mixture was stirred under nitrogen and cooled to 0 °C using liquid nitrogen. Temperature control At 0 ° C, 1.4 g of boron trifluoride diethyl ether was added dropwise, and after the completion of the dropwise addition, the temperature was controlled at 0 ° C and the reaction was continued for 30 min. Thereafter, the temperature was naturally raised to room temperature, and the reaction was continued for 4 hours. The completion point of the reaction was confirmed by thin layer chromatography (TLC), and when it was confirmed that the reaction was completed, the above mixture was added to diatomaceous earth for suction filtration. Next, the filtrate was concentrated under reduced pressure to give a dried material. The dried product was dissolved in 1 part by weight of dichloromethane, and mixed with 1 time weight of yttrium gum, followed by concentration under reduced pressure to obtain a dried product containing guar gum. Next, the dried product was subjected to chromatography in a column containing 3 to 4 times by weight of tannin (the extract was petroleum ether: ethyl acetate = 20:1, and then a total volume of 1% triethylamine was added. ). Finally, the chromatography solution was collected and concentrated to give 7 g of the compound of formula (J) as a white solid. The reaction formula of the above reaction is as follows:

其中，上述的式(I)化合物，其製備步驟包括先於500ml乾燥潔淨的三口瓶中加入100g的1,1,1-三羥甲基丁烷、132g的碳酸二乙酯(diethyl carbonate，DEC)、0.25g的氫氧化鉀以及10ml的乙醇。接著，攪拌前述混合物，並加熱迴流2小時。之後，於150℃下常壓蒸除溶劑後，將溫度降至120℃。最後進行減壓蒸餾，以得到64g呈無色透明液體的式(H)化合物。然後，於2L潔淨的三口瓶中加入82g的式(H)化合物、111g吡啶以及400ml二氯甲烷。接著，在氮氣保護下攪拌前述混合物，並降溫至0℃~5℃。控溫在0℃~5℃下，滴加由163g的4-溴苯甲醯氯以及200ml的二氯甲烷組成的溶液。滴加完畢後，自然升溫並攪拌過夜。之後，向三口瓶中加入500ml的水，攪拌5min後進行分液得水相及有機相。接著，用100ml的二氯甲烷提取水相兩次，以及用100ml的氯化鈉水溶液洗滌合併後的有機相兩次至pH值接近中性。之後，對前述有機相用20g的無水硫酸鈉乾燥30min後進行抽氣過濾。接著，將濾液進行矽膠管柱層析(沖提液為石油醚：乙酸乙酯=9：1)收集層析液並濃縮後使用1倍量的乙醇進行再結晶，並將其放入冰箱冷凍8小時以上後取出以進行抽氣過濾。最後，使用少量凍乙醇淋洗以得到145g呈白色固體的式(I)化合物。上述反應之反應式，如下所示： Wherein the above compound of the formula (I) is prepared by adding 100 g of 1,1,1-trimethylolbutane and 132 g of diethyl carbonate (DEC) to a 500 ml dry clean three-necked bottle. ), 0.25 g of potassium hydroxide and 10 ml of ethanol. Next, the mixture was stirred and heated to reflux for 2 hours. Thereafter, after evaporating the solvent under normal pressure at 150 ° C, the temperature was lowered to 120 ° C. Finally, distillation under reduced pressure was carried out to obtain 64 g of a compound of the formula (H) as a colorless transparent liquid. Then, 82 g of the compound of the formula (H), 111 g of pyridine and 400 ml of dichloromethane were placed in a 2 L clean three-necked flask. Next, the mixture was stirred under a nitrogen atmosphere and cooled to 0 ° C to 5 ° C. The temperature control was carried out at 0 ° C to 5 ° C, and a solution consisting of 163 g of 4-bromobenzamide chloride and 200 ml of dichloromethane was added dropwise. After the addition was completed, the temperature was naturally raised and stirred overnight. Thereafter, 500 ml of water was added to the three-necked flask, and after stirring for 5 minutes, liquid separation and organic phase were carried out. Next, the aqueous phase was extracted twice with 100 ml of dichloromethane, and the combined organic phases were washed twice with 100 ml of an aqueous solution of sodium chloride until the pH was near neutral. Thereafter, the organic phase was dried with 20 g of anhydrous sodium sulfate for 30 min, and then suction filtered. Next, the filtrate was subjected to gel column chromatography (the extract was petroleum ether: ethyl acetate = 9:1). The chromatographic solution was collected, concentrated, and recrystallized using 1 time of ethanol, and placed in a refrigerator. After 8 hours or more, it was taken out for suction filtration. Finally, it was rinsed with a small amount of cold ethanol to give 145 g of the compound of formula (I) as a white solid. The reaction formula of the above reaction is as follows:

實施例3：(S)2RIGUQUO8的合成 Example 3: Synthesis of ( S )2RIGUQUO8

首先，於500ml三頸瓶中加入11.2g二異丙胺以及150ml無水四氫呋喃，在氮氣下降溫至-5℃，再滴加46ml的正丁基鋰(2.4M in 正己烷)，控制溫度在0℃以下，待滴加完畢後，持續控溫0℃，攪拌1小時；然後再降溫至-78℃，續滴加14.3g戊酸乙酯和10ml無水四氫呋喃的混合物，滴加完畢後，在-78℃下，攪拌30分鐘；續滴加25g對溴溴苄(4-Bromobenzyl bromide)和100ml四氫呋喃的混合物，滴加完畢後，控溫-78℃下攪拌1小時；移除低溫設備，待升至室溫後，再攪拌12小時；處理後可得淡黃色油狀物，將該油狀物用100ml乙醇溶解，加入到100ml 10%的氫氧化鈉水溶液中，加熱回流3小時，冷卻至室溫，得淡黃色固體，以石油醚再結晶得類白色固體18g，即為式(B1)化合物；產率為67%。上述反應的反應式如下所示： First, 11.2 g of diisopropylamine and 150 ml of anhydrous tetrahydrofuran were added to a 500 ml three-necked flask, and the temperature was lowered to -5 ° C under nitrogen, and then 46 ml of n-butyllithium (2.4 M in n-hexane) was added dropwise thereto, and the temperature was controlled at 0 ° C. After the completion of the dropwise addition, the temperature is continuously controlled at 0 ° C, and stirred for 1 hour; then, the temperature is further lowered to -78 ° C, and a mixture of 14.3 g of ethyl valerate and 10 ml of anhydrous tetrahydrofuran is continuously added dropwise, and after the addition is completed, at -78 Stir at °C for 30 minutes; continue to add 25g of a mixture of 4-Bromobenzyl bromide and 100ml of tetrahydrofuran. After the addition is completed, stir at a temperature of -78 ° C for 1 hour; remove the cryogenic equipment and wait until it is raised. After stirring at room temperature, stirring for further 12 hours; after treatment, a pale yellow oil was obtained. The oil was dissolved in 100 ml of ethanol, added to 100 ml of 10% aqueous sodium hydroxide solution, heated under reflux for 3 hours, and cooled to room temperature. A pale yellow solid was obtained which was recrystallized from petroleum ether to give 18 g of a white solid as a compound of formula (B1); yield 67%. The reaction formula of the above reaction is as follows:

接著，於250ml三頸瓶中加入18g的式(B1)化合物以及50ml亞硫醯氯，加熱迴流3小時，蒸除過量的亞硫醯氯；再加入120ml二氯甲烷溶解，在氮氣下降溫至0℃，分批加入共10g的無水三氯化鋁，然後迴流5小時；處理後得黃色固體14g，即為式(B2)化合物；產率為83%，純度(以氣相層析儀GC進行量測)99%。上述反應的反應式如下所示： Next, 18 g of the compound of the formula (B1) and 50 ml of sulfinium chloride were added to a 250 ml three-necked flask, and the mixture was heated under reflux for 3 hours to distill off excess sulfinium chloride; then dissolved in 120 ml of dichloromethane, and the temperature was lowered to nitrogen. At 0 ° C, a total of 10g of anhydrous aluminum trichloride was added in portions, and then refluxed for 5 hours; after treatment, 14 g of a yellow solid was obtained, which was a compound of the formula (B2); the yield was 83%, purity (by gas chromatography GC) Measure) 99%. The reaction formula of the above reaction is as follows:

接著，於250ml三頸瓶中加入14g的式(B2)化合物、23ml三乙基矽烷以及40ml三氟醋酸，室溫下攪拌12小時，將反應液倒入碳酸鈉水溶液中，調節pH值到7-8；得黃色油狀物，減壓蒸餾得無色透明液體12g，即為式(B3)化合物；產率為91%，純度(以氣相層析儀GC進行量測)97%。上述反應的反應式如下所示： Next, 14 g of the compound of the formula (B2), 23 ml of triethyldecane and 40 ml of trifluoroacetic acid were added to a 250 ml three-necked flask, and the mixture was stirred at room temperature for 12 hours, and the reaction solution was poured into an aqueous sodium carbonate solution to adjust the pH to 7. -8; obtained a yellow oil, distilled under reduced pressure to give a colorless transparent liquid 12 g, which is a compound of formula (B3); yield 91%, purity (measured by gas chromatograph GC) 97%. The reaction formula of the above reaction is as follows:

接著，於1000ml三頸瓶中加入12g化合物B3、7.9g 3，5-二氟苯硼酸、21.3g碳酸鈉、100ml水、100ml乙醇、200ml甲苯以及0.5g Pd(PPh₃)₄，在氮氣下加熱迴流6小時；處理得淡黃色油狀物，乙醇再結晶得白色固體10.2g，即為式(B4)化合物；產率為75%，純度(以氣相層析儀GC進行量測)99%。上述反應的反應式如下所示： Next, 12 g of compound B3, 7.9 g of 3,5-difluorophenylboronic acid, 21.3 g of sodium carbonate, 100 ml of water, 100 ml of ethanol, 200 ml of toluene and 0.5 g of Pd(PPh ₃ ) _{4 were} added to a 1000 ml three-necked flask under nitrogen. The mixture was heated under reflux for 6 hours; the residue was obtained as a pale yellow oil, and then recrystallized from ethanol to give a white solid: 10.2 g, which is a compound of formula (B4); yield: 75%, purity (measured by gas chromatograph GC) 99%. The reaction formula of the above reaction is as follows:

接著，於250ml三頸瓶中加入9.0g的式(B4)化合物、4.2g KOtBu及100ml無水四氫呋喃，氮氣保護下，降溫至-100℃，再滴加17ml的正丁基鋰(2.4M in正己烷)，滴加完畢後，控溫-100℃攪拌1小時，然後滴加9.5g硼酸三異丁酯和50ml無水四氫呋喃的混合物，滴加完畢後，控溫-100℃攪拌1小時，升至室溫水解；處理得6.9g黃色固體，即為式(B5)化合物；產率為65%。上述反應的反應式如下所示： Next, 9.0 g of the compound of the formula (B4), 4.2 g of KO t Bu and 100 ml of anhydrous tetrahydrofuran were added to a 250 ml three-necked flask, and the temperature was lowered to -100 ° C under nitrogen atmosphere, and then 17 ml of n-butyllithium (2.4 M) was added dropwise. In n-hexane), after the completion of the dropwise addition, the mixture was stirred at a temperature of -100 ° C for 1 hour, and then a mixture of 9.5 g of triisobutyl borate and 50 ml of anhydrous tetrahydrofuran was added dropwise, and after the completion of the dropwise addition, the mixture was stirred at a temperature of -100 ° C for 1 hour. Hydrolyzed to room temperature; 6.9 g of a yellow solid was obtained as a compound of formula (B5); The reaction formula of the above reaction is as follows:

接著，於1000ml三頸瓶中加入14.2g的式(B5)化合物、9.7g 3，5-二氟溴苯、21.3g碳酸鈉、100ml水、100ml乙醇、200ml甲苯以及0.5g Pd(PPh₃)₄，在氮氣保護下，加熱迴流6小時；處理得淡黃色固體，乙醇重結晶得白色固體12.8g，即為式(B6)化合物；產率為75%，純度(以氣相層析儀GC進行量測)99%。上述反應的反應式如下所示： Next, 14.2 g of the compound of the formula (B5), 9.7 g of 3,5-difluorobromobenzene, 21.3 g of sodium carbonate, 100 ml of water, 100 ml of ethanol, 200 ml of toluene and 0.5 g of Pd (PPh ₃ ) were placed in a 1000 ml three-necked flask. ₄ , under nitrogen protection, heated to reflux for 6 hours; treated to give a pale yellow solid, ethanol recrystallized to give a white solid 12.8 g, which is a compound of formula (B6); yield of 75%, purity (by gas chromatography GC Measure) 99%. The reaction formula of the above reaction is as follows:

接著，於500ml三頸瓶中加入35.2g化合物B6以及250ml無水四氫呋喃，在氮氣保護下，降溫至-70℃以下，開始滴加正丁基鋰46ml，滴完後於-70℃下攪拌2小時；再滴加含有二氟二溴甲烷84g/100ml無水四氫呋喃的溶液，滴完後於-70℃下攪拌1小時；水解、處理得黃色固體43g，即為式(B7)化合物。上述反應的反應式如下所示： Next, 35.2 g of the compound B6 and 250 ml of anhydrous tetrahydrofuran were added to a 500 ml three-necked flask, and the temperature was lowered to -70 ° C or lower under nitrogen atmosphere, and 46 ml of n-butyllithium was added dropwise, and the mixture was stirred at -70 ° C for 2 hours after the completion of the dropwise addition. Further, a solution containing 84 g of difluorodibromomethane/100 ml of anhydrous tetrahydrofuran was added dropwise, and after stirring, the mixture was stirred at -70 ° C for 1 hour; and hydrolyzed and treated to obtain 43 g of a yellow solid, which was a compound of the formula (B7). The reaction formula of the above reaction is as follows:

接著，於1000ml三頸瓶中加入3.6g化合物B7、50ml DMF、1.5g化合物iv、0.9g無水碳酸鉀以及0.1g碘化鉀，水浴90℃攪拌0.5小時；冷卻後倒入水中，處理後得2.1g白色固體，即為化合物(S)2RIGUQUO8。上述反應的反應式如下所示： Next, 3.6 g of Compound B7, 50 ml of DMF, 1.5 g of compound iv, 0.9 g of anhydrous potassium carbonate and 0.1 g of potassium iodide were added to a 1000 ml three-necked flask, and the mixture was stirred at 90 ° C for 0.5 hour in a water bath; after cooling, it was poured into water, and 2.1 g was obtained after the treatment. A white solid is the compound ( S ) 2RIGUQUO8. The reaction formula of the above reaction is as follows:

利用氣相沉積質譜儀(GCMS)以及核磁共振光譜(NMR)分析(S)2RIGUQUO8，所得之質譜及光譜資訊如下：GC-MS：m/z=658.6720[M]⁺；¹H-NMR(CDCl₃,400MHz),(ppm)：0.85-0.99(m,6H),1.23-1.77(m,14H),1.69-1.77(m,1H),2.37-2.44(m,1H),2.58-2.66(m,2H),3.04-3.12(m,2H),4.19-4.24(m,1H),6.885(d,J=8.4Hz,2H),7.22-7.45(m,8H)。 The mass spectrometry and spectral information obtained by vapor phase deposition mass spectrometry (GCMS) and nuclear magnetic resonance spectroscopy (NMR) analysis of ( S )2RIGUQUO8 were as follows: GC-MS: m/z = 658.6720 [M] ⁺ ; ¹ H-NMR (CDCl) _{3, 400MHz), (ppm)} : 0.85-0.99 (m, 6H), 1.23-1.77 (m, 14H), 1.69-1.77 (m, 1H), 2.37-2.44 (m, 1H), 2.58-2.66 (m , 2H), 3.04-3.12 (m, 2H), 4.19-4.24 (m, 1H), 6.885 (d, J = 8.4 Hz, 2H), 7.22 - 7.45 (m, 8H).

實施例4：(S)3RIGUO8的合成 Example 4: Synthesis of ( S )3RIGUO8

(S)3RIGUO8的合成是依據(S)3doPUO8的步驟及條件進行，除了將式(F)化合物置換為式(B8)化合物，並將式(iii)化合物置換成式(ii)化合物以及依據莫耳數改變用量克數外，其餘合成步驟相同，最後製得(S)3RIGUO8。上述式(B8)化合物製備步驟與製備式(B5)化合物的步驟相同，除了將戊酸乙酯置換為己酸乙酯以及將依據莫耳數改變用量克數外，其餘合成步驟是依據式(B5)化合物的步驟及條件進行，最後製得該式(B8)化合物。上述反應的反應式如下所示： (S) is carried out according to the synthetic 3RIGUO8 (S) 3doPUO8 steps and conditions, in addition to the compound of formula (F) is replaced with formula (B8), compounds (iii) and replaced with a compound of formula of formula (ii) and based on Mo The number of ears was changed by the number of grams, and the other synthetic steps were the same. Finally, ( S )3RIGUO8 was obtained. The preparation step of the compound of the above formula (B8) is the same as the step of preparing the compound of the formula (B5), except that the ethyl valerate is replaced with ethyl hexanoate and the amount of the gram is changed according to the molar number, and the other synthetic steps are based on the formula ( The step (5) of the compound is carried out, and finally the compound of the formula (B8) is obtained. The reaction formula of the above reaction is as follows:

用氣相沉積質譜儀(GCMS)以及核磁共振光譜(NMR)分析(S)3RIGUO8，所得之質譜及光譜資訊如下：GC-MS：m/z=494.4746[M]⁺。¹H-NMR(CDCl₃,400MHz),(ppm)：0.88-0.97(m,6H),1.23-1.77(m,16H),1.66-1.85(m,1H),2.47-2.67(m,3H),3.05-3.12(m,2H),4.31-4.38(m,1H),7.183(d,J=8.8Hz,2H),7.27-7.45(m,6H)。 The ( S )3RIGUO8 was analyzed by vapor deposition mass spectrometry (GCMS) and nuclear magnetic resonance spectroscopy (NMR), and the obtained mass spectrum and spectral information were as follows: GC-MS: m/z = 494.4746 [M] ⁺ . ¹ H-NMR (CDCl ₃ , 400 MHz), (ppm): 0.88-0.97 (m, 6H), 1.23-1.77 (m, 16H), 1.66-1.85 (m, 1H), 2.47-2.67 (m, 3H) , 3.05-3.12 (m, 2H), 4.31-4.38 (m, 1H), 7.183 (d, J = 8.8 Hz, 2H), 7.27-7.45 (m, 6H).

實施例5：(S)3RIPUO8的合成 Example 5: Synthesis of ( S )3RIPUO8

依據(S)3RIGUO8的合成步驟，使用合適的起始物，即可製得(S)3RIPUO8。 Based on (S) 3RIGUO8 of synthetic steps, using appropriate starting materials, can be prepared (S) 3RIPUO8.

用氣相沉積質譜儀(GCMS)以及核磁共振光譜(NMR)分析(S)3RIPUO8，所得之質譜及光譜資訊如下：GC-MS：m/z=476.5169[M]⁺。¹H-NMR(CDCl₃,400MHz),(ppm)：0.87-0.97(m,6H),1.25-1.65(m,17H),2.45-2.67(m,3H),3.04-3.12(m,2H),4.28-4.36(m,1H),7.13-7.20(m,3H)7.391(d,J=8.0Hz,1H),7.445(s,1H),7.567(d,J=8.4Hz,2H),7.641(d,J=8.4Hz,2H)。 The ( S )3RIPUO8 was analyzed by vapor deposition mass spectrometry (GCMS) and nuclear magnetic resonance spectroscopy (NMR), and the obtained mass spectrum and spectral information were as follows: GC-MS: m/z = 476.5169 [M] ⁺ . ¹ H-NMR (CDCl ₃ , 400 MHz), (ppm): 0.87-0.97 (m, 6H), 1.25-1.65 (m, 17H), 2.45-2.67 (m, 3H), 3.04-3.12 (m, 2H) , 4.28-4.36 (m, 1H), 7.13-7.20 (m, 3H) 7.391 (d, J = 8.0 Hz, 1H), 7.445 (s, 1H), 7.567 (d, J = 8.4 Hz, 2H), 7.641 (d, J = 8.4 Hz, 2H).

具光學活性的液晶添加物的性質量測：表1顯示的具光學活性的液晶添加物，包括習知的S1011(Merck)、S2011(Merck)以及根據本發明實施例所揭露的(S)3RIGUO8、(S)3RIPUO8、(S)3doPUO8及(S)3toPUO8，該等具光學活性的液晶添加物性質量測，其步驟主要是先將各具光學活性的添加物的調配於母液中以製備待測樣品，然後再以下面各段落所敘述的方法量測各項性質，所得結果分別如表2、表3及表4所示。 Sexual mass measurement of optically active liquid crystal additives: optically active liquid crystal additives shown in Table 1, including conventional S1011 (Merck), S2011 (Merck), and (S) 3RIGUO8 according to embodiments of the present invention. , (S) 3RIPUO8, (S) 3doPUO8 and (S) 3toPUO8, the optically active liquid crystal additive physical property measurement, the steps of which are mainly to first prepare each optically active additive in the mother liquor to prepare The samples were tested and the properties were measured by the methods described in the following paragraphs. The results are shown in Table 2, Table 3 and Table 4, respectively.

澄清點(Tni，單位：℃)：Clarification point (Tni, unit: °C):

使用差示掃描量熱儀(DSC；廠商：TA；型號：Q200)，將待測樣品置於鋁盤中精秤0.5mg至10mg，並在鋁盤壓錠後以DSC進行相變溫度測試，即藉由待測樣品因相變化而出現的吸熱峰及放熱峰的起始點來得到相變化溫度。由於待測樣品中的母液為向列相(nematic phase)，因此由室溫升溫的圖譜上會出現向列相轉變為液相的吸熱峰，可讀出澄清點的溫度。 Using a differential scanning calorimeter (DSC; manufacturer: TA; model: Q200), the sample to be tested is placed in an aluminum pan with a scale of 0.5 mg to 10 mg, and the phase change temperature test is performed by DSC after pressing the aluminum pan. The phase change temperature is obtained by the endothermic peak of the sample to be tested due to the phase change and the starting point of the exothermic peak. Since the mother liquor in the sample to be tested is a nematic phase, an endothermic peak which changes from a nematic phase to a liquid phase occurs on the spectrum of the temperature rise from room temperature, and the temperature of the clearing point can be read.

介電常數異向性(Δε)：Dielectric anisotropy (Δε):

將待測樣品裝入液晶盒中，於溫度25℃下，對該液晶盒施加0V至20V的電壓，並量測得電容對電壓的曲線(C-V curve)。在C-V curve中，高電壓區及低電壓區皆會呈現水平，在低電壓區讀取電容C⊥、在高電壓區讀取電容C∥，並可藉公式由C⊥、C∥換算為ε⊥、ε∥，介電常數異向性(Δε)=ε∥-ε⊥。 The sample to be tested is placed in a liquid crystal cell, and a voltage of 0 V to 20 V is applied to the liquid crystal cell at a temperature of 25 ° C, and the capacitance versus voltage curve is measured (C-V) Curve). In the CV curve, both the high voltage region and the low voltage region will be horizontal. The capacitor C⊥ is read in the low voltage region and the capacitor C∥ is read in the high voltage region, and can be converted to C by C⊥ and C∥ by the formula. ⊥, ε∥, dielectric anisotropy (Δε) = ε ∥ - ε ⊥.

光學異向性(Δn)：Optical anisotropy (Δn):

利用一目鏡上安裝有偏光板的阿貝(Abbe)折射儀(廠商：ATAGO；型號：DR-M2)對各個待測樣品進行量測。首先，在阿貝折射儀的主稜鏡表面以單方向刷上配向液，並以無塵布沿同一方向擦拭配向，接著在主稜鏡上滴加少量待測樣品，在測試溫度25℃，使用波長為589nm的濾光片進行光學異向性的測量。當偏光方向與擦拭方向平行時，測得的折射率為n∥；當偏光方向與擦拭方向垂直時，測得的折射率為n⊥；光學異向性(Δn)=n∥-n⊥。 Each sample to be tested was measured using an Abbe refractometer (manufacturer: ATAGO; model: DR-M2) on which a polarizing plate was attached. First, the alignment liquid is brushed in a single direction on the main surface of the Abbe refractometer, and the alignment is wiped in the same direction with a dust-free cloth, and then a small amount of the sample to be tested is dropped on the main crucible at a test temperature of 25 ° C. The optical anisotropy was measured using a filter having a wavelength of 589 nm. When the polarizing direction is parallel to the wiping direction, the measured refractive index is n∥; when the polarizing direction is perpendicular to the wiping direction, the measured refractive index is n⊥; optical anisotropy (Δn)=n∥-n⊥.

轉動黏度(γ1，單位：mPa．s)：Rotational viscosity (γ1, unit: mPa.s):

如前述測得介電常數異向性(Δε)之後，軟體即可由Δε值進行轉動黏度(γ1)的換算。 After the dielectric anisotropy (Δε) is measured as described above, the soft body can be converted from the rotational viscosity (γ1) by the Δε value.

螺距(pitch，單位：μm)：Pitch (unit: μm):

將待測樣品裝入楔型盒(KCRK-07，EHC)中，置於加熱平台上，加熱至實驗所需的溫度，再以電子顯微鏡(Tomas,M21+LX3000)觀測，量測兩條平形線間距，即為待測樣品在此溫度下之pitch值。 The sample to be tested was placed in a wedge-shaped box (KCRK-07, EHC), placed on a heating platform, heated to the temperature required for the experiment, and then observed by an electron microscope (Tomas, M21+LX3000) to measure two flat shapes. The line spacing is the pitch value of the sample to be tested at this temperature.

溫度依存性(μm/℃)Temperature dependence (μm/°C)

待測樣品分別在25℃、30℃、40℃、50℃、60℃、 70℃、80℃下量測螺距值，將數據作線性回歸，求得此回歸線之斜率即為螺距對於溫度的變化量。 The samples to be tested are at 25 ° C, 30 ° C, 40 ° C, 50 ° C, 60 ° C, The pitch value is measured at 70 ° C and 80 ° C, and the data is linearly regressed. The slope of the regression line is obtained as the variation of the pitch with respect to temperature.

吸附實驗Adsorption experiment

將液晶組成物與10%重量百分比的3分子篩，在室溫下，混合攪拌一小時，過濾去除分子篩後，量測液晶組成物螺距值，實驗前後螺距值的改變量百分比，即為具光學活性的液晶添加物被吸附量的重量百分比。 Liquid crystal composition with 10% by weight of 3 The molecular sieve was mixed and stirred at room temperature for one hour, and after removing the molecular sieve by filtration, the pitch value of the liquid crystal composition was measured, and the percentage change of the pitch value before and after the experiment was the weight percentage of the optically active liquid crystal additive adsorbed.

表2係顯示母液添加根據本發明實施例的具光學活性的液晶添加物(S)3RIGUO8、(S)3RIPUO8、(S)3doPUO8、(S)3toPUO8後所形成的液晶組成物A、B、C、D與未添加具光學活性的液晶添加物的母液之特性量測結果。 Table 2 shows the liquid crystal compositions A, B, and C formed by adding the optically active liquid crystal additives (S) 3RIGUO8, (S) 3RIPUO8, (S) 3doPUO8, (S) 3toPUO8 according to an embodiment of the present invention. , D and the characteristics of the mother liquor without the addition of optically active liquid crystal additives.

如表2所示，在添加0.2wt%~0.25wt%不等的根據本發明之具光學活性的液晶添加物(S)3RIGUO8、(S)3RIPUO8、(S)3doPUO8、(S)3toPUO8至母液後，可誘導其向列相形成螺旋狀排列，螺距約為50μm。本發明之具光學活性的液晶添加物並不會破壞母液原本之液晶光電特性，添加後所形成的液晶組成物，其澄清點(Tni)、介電常數異向性(Δε)、光學異向性(Δn)、轉動黏度(γ1，單位：mPa．s)均與母液添加前的數值相當。此外，本發明之具光學活性的液晶添加物(S)3RIGUO8、(S)3RIPUO8、(S)3doPUO8、(S)3toPUO8，其HTP(helical twisting power)值約為8~10，在實際應用上，可依液晶顯示器的規格需求，加入合適的比例以調整所需的螺距。 As shown in Table 2, optically active liquid crystal additives (S) 3RIGUO8, (S) 3RIPUO8, (S) 3doPUO8, (S) 3toPUO8 to mother liquor according to the present invention are added in an amount of 0.2 wt% to 0.25 wt%. After that, it can induce its nematic phase to form a spiral Arranged, the pitch is about 50 μm. The optically active liquid crystal additive of the present invention does not destroy the original liquid crystal photoelectric characteristics of the mother liquid, and the liquid crystal composition formed after the addition has a clearing point (Tni), a dielectric anisotropy (Δε), and an optical anisotropy. The properties (Δn) and rotational viscosity (γ1, unit: mPa.s) are equivalent to the values before the mother liquor is added. In addition, the optically active liquid crystal additives (S) 3RIGUO8, (S) 3RIPUO8, (S) 3doPUO8, (S) 3toPUO8 of the present invention have a HTP (helical twisting power) value of about 8 to 10, which is practically used. According to the specifications of the liquid crystal display, the appropriate ratio can be added to adjust the required pitch.

表3係顯示在相同母液中分別添加根據本發明實施例的手性添加物(S)3RIGUO8、(S)3toPUO8及習知的手性添加物S1011、S2011，所得到的四個含有不同手性添加物的液晶組成物A、D、E和F，經過分子篩吸附實驗後，螺距變化量的量測結果以及在25℃、30℃、40℃、50℃、60℃、70℃、80℃下實驗所得到的溫度依存性量測結果。 Table 3 shows that the chiral additives (S) 3RIGUO8, (S) 3toPUO8 and the conventional chiral additives S1011, S2011 according to the examples of the present invention are respectively added to the same mother liquor, and the four obtained have different chiralities. The liquid crystal compositions A, D, E and F of the additive were measured by the molecular sieve adsorption test, and the measurement results of the pitch variation were at 25 ° C, 30 ° C, 40 ° C, 50 ° C, 60 ° C, 70 ° C, 80 ° C. The temperature dependence measurement results obtained from the experiment.

如表3結果所示，在母液中分別添加根據本發明實施例的具光學活性的液晶添加物(S)3RIGUO8、(S)3toPUO8所得到的液晶組成物A和D，其通過分子篩後，該具光學活性的液晶添加物被吸附掉的吸附損失率分別為0.1%與0.8%，低於在相同母液中分別添加習知的具光學活性的液晶添加物S1011、S2011所得到的液晶組成物E和F通過分子篩後的吸附損失率2.8%以及1%。換言之，添加根據本發明實施例的具光學活性的液晶添加物(S)3RIGUO8、(S)3toPUO8所得到的液晶組成物，該具光學活性的液晶添加物較不易被分子篩吸附，對於各種液晶生產製程，如果可有效減低具光學活性的液晶添加物因為被吸附所造成的損失量，可降低成本。同時，對於液晶組成物而言，也具有穩定的螺距的優點。此外，液晶組成物A和D對溫度的正依存性，也遠低於液晶組成物F，代表本發明之具光學活性的液晶添加物(S)3RIGUO8、(S)3toPUO8具有較低的溫度依存性，故添加具光學活性的液晶添加物(S)3RIGUO8、(S)3toPUO8所得到的液晶組成物A和D，其螺距受到外在溫度的影響較低。 As shown in the results of Table 3, the liquid crystal compositions A and D obtained by optically active liquid crystal additives (S) 3RIGUO8 and (S) 3toPUO8 according to the examples of the present invention were respectively added to the mother liquid, and after passing through the molecular sieve, Optically active liquid crystal The adsorption loss rates of the adsorbed materials are 0.1% and 0.8%, respectively, which are lower than the liquid crystal compositions E and F obtained by adding the conventional optically active liquid crystal additives S1011 and S2011 to the same mother liquor. The adsorption loss rate was 2.8% and 1%. In other words, a liquid crystal composition obtained by optically active liquid crystal additives (S) 3RIGUO8 and (S) 3toPUO8 according to an embodiment of the present invention is added, and the optically active liquid crystal additive is less likely to be adsorbed by molecular sieves, and is produced for various liquid crystals. The process can reduce the cost if it can effectively reduce the amount of loss of the optically active liquid crystal additive due to adsorption. At the same time, for the liquid crystal composition, it also has the advantage of a stable pitch. In addition, the positive dependence of the liquid crystal compositions A and D on temperature is also much lower than that of the liquid crystal composition F, representing that the optically active liquid crystal additives (S) 3RIGUO8 and (S) 3toPUO8 of the present invention have low temperature dependence. Therefore, the liquid crystal compositions A and D obtained by adding the optically active liquid crystal additives (S) 3RIGUO8 and (S) 3toPUO8 have a lower pitch which is less affected by the external temperature.

表4係顯示在母液內添加根據本發明實施例之具光學活性的液晶添加物(S)3RIGUO8、(S)3RIPUO8及習知的具光學活性的液晶添加物S1011、S2011所形成的液晶組成物之可信賴度特性量測結果。其中，可信賴度量測包括光穩定性量測以及熱穩定性量測。其中，光穩定性量測主要是利用UV光照射比較在母液內添加各種具光學活性的添加劑後所形成的液晶組成物30分鐘，然後再比較UV光照射前、後液晶組成物的螺距變化。 Table 4 shows liquid crystal compositions formed by adding optically active liquid crystal additives (S) 3RIGUO8, (S) 3RIPUO8 and conventional optically active liquid crystal additives S1011, S2011 according to an embodiment of the present invention to a mother liquor. The reliability characteristic measurement result. Among them, the reliability measurement includes light stability measurement and thermal stability measurement. Among them, the photostability measurement mainly uses a UV light irradiation to compare the liquid crystal composition formed by adding various optically active additives to the mother liquid for 30 minutes, and then compares the pitch variation of the liquid crystal composition before and after the UV light irradiation.

如表4所示，液晶組成物A和B，在UV光照射30分鐘後的螺距變化率，均遠低於液晶組成物E和F的螺距變化率，顯示添加根據本發明實施例的具光學活性的液晶添加物(S)3RIGUO8、(S)3RIPUO8所形成的液晶組成物，其光穩定性較佳。此外，添加根據本發明實施例的具光學活性的液晶添加物(S)3RIGUO8、3RIPUO8的液晶組成物，在溫度150度C加熱1小時後，其螺距變化率均遠低於添加習知的具光學活性的液晶添加物S1011、S2011所形成的液晶組成物的螺距變化率，顯示添加根據本發明實施例的具光學活性的液晶添加物(S)3RIGUO8、(S)3RIPUO8所形成的液晶組成物，其熱穩定性較佳。 As shown in Table 4, the pitch change rates of the liquid crystal compositions A and B after 30 minutes of UV light irradiation were far lower than the pitch change ratio of the liquid crystal compositions E and F, showing the addition of optical according to an embodiment of the present invention. The liquid crystal composition formed by the active liquid crystal additives (S) 3RIGUO8 and (S) 3RIPUO8 has better photostability. Further, the liquid crystal composition of the optically active liquid crystal additives (S) 3RIGUO8 and 3RIPUO8 according to the embodiment of the present invention is added, and after heating at 150 ° C for 1 hour, the pitch change rate is much lower than that of the conventionally known one. The pitch change rate of the liquid crystal composition formed by the optically active liquid crystal additives S1011 and S2011 shows the liquid crystal composition formed by adding the optically active liquid crystal additives (S) 3RIGUO8 and (S) 3RIPUO8 according to the embodiment of the present invention. Its thermal stability is better.

綜上所述，根據本發明所揭示的具光學活性的液晶添加物，其不僅具有合適的HTP值、高光穩定性、高熱穩定性，且與主體液晶材料有良好的相容性、低的溫度依存性，且不易被吸附劑所吸附等多項優點。 In summary, the optically active liquid crystal additive disclosed in the present invention not only has a suitable HTP value, high light stability, high thermal stability, but also has good compatibility with a host liquid crystal material and a low temperature. Dependence, and not easy to be adsorbed by the adsorbent and many other advantages.

雖然本發明己以實施例揭露如上，然其並非用以限定本發明，任何所屬技術領域中具有通常知識者，在不脫離本發明的精神和範圍內，當可作些許的更動與潤飾，故本發明的保護範圍當視後附的申請專利範圍所界定者為準。 Although the present invention has been disclosed above by way of example, it is not intended to limit the present invention. The scope of the present invention is defined by the scope of the appended claims, which are defined by the scope of the appended claims, without departing from the spirit and scope of the invention. quasi.

Claims

一種具光學活性的液晶添加物，其結構式為A-B，該A為具有鏈狀之手性結構部分，該B具有至少兩個環狀結構，其中該環狀結構至少一個環為2,6-二氧雜二環[2,2,2]辛烷基、2,6,7-三氧雜二環[2,2,2]辛烷基或2,5-茚滿基，該A與該B以單鍵連接。 An optically active liquid crystal additive having the structural formula AB, wherein A is a chain-like chiral structural moiety, and B has at least two cyclic structures, wherein at least one ring of the cyclic structure is 2,6- Dioxabicyclo[2,2,2]octyl, 2,6,7-trioxabicyclo[2,2,2]octyl or 2,5-indanyl, the A and B is connected by a single button.

如申請專利範圍第1項之具光學活性的液晶添加物，係具有式(I)所示之結構：其中，R¹為鹵素、CF₃、CN或為碳數1~10的烷基，且該碳數1~10的烷基為未經取代或任意-CH₂-可被O、S取代或至少一個-(CH₂)₂-可被-CH=CH-、-C≡C-取代，且該碳數為1~10的烷基，及/或任意碳上的氫原子為未經取代或被鹵素、CN或CF₃取代；R²為氫、C₁-C₁₀烷基或C₂-C₁₀烯基，且其中C₁-C₁₀烷基、C₂-C₁₀烯基為未經取代或任意-CH₂-被-O-、-S-、-O-CO-、-OC-O-或-O-CO-O-取代，且其中-O-、-S-、-O-CO-、-OC-O-或-O-CO-O-取代基彼此不直接相連接，及/或任意碳上的氫原子為未經取代或被鹵素、CN或CF₃取代；Q可為C、O、或S；Y為碳數1~10的烷基；環A1、環A2、環A3及環A4獨立地為2,6-二氧雜二環[2,2,2]辛烷基、2,6,7-三氧雜二環[2,2,2]辛烷基或2,5-茚滿基、1,4-伸環己基或1,4-伸苯基，及/或該1,4-伸苯基或1,4-伸苯基中為未經取代或至少一個氫被鹵素、CN、CF₃取代，且環A1、環A2、環A3及環A4至少之一為2,6-二氧雜二環[2,2,2]辛烷基、2,6,7-三氧雜二環[2,2,2]辛烷基或2,5茚滿基；Z₁、Z₂、及Z₃獨立地為單鍵、C₁-C₄伸烷基、C₂-C₄伸烯基、C₂-C₄伸炔基、-CO-O-、-O-CO-、-CF₂O-或-OCF₂-，且其中C₁-C₄伸烷基、C₂-C₄伸烯基、C₂-C₄伸炔基為未經取代或至少一個氫原子被鹵素取代，及/或任意-CH₂-被-O-或-S-取代，且其中-O-、-S-彼此不直接相連；n可為1或0。 An optically active liquid crystal additive as claimed in claim 1 has the structure represented by the formula (I): Wherein R ¹ is halogen, CF ₃ , CN or an alkyl group having 1 to 10 carbon atoms, and the alkyl group having 1 to 10 carbon atoms is unsubstituted or any -CH ₂ - may be substituted by O, S or at least One -(CH ₂ ) ₂ - may be substituted by -CH=CH-, -C≡C-, and the alkyl group having a carbon number of 1 to 10, and/or the hydrogen atom on any carbon is unsubstituted or Halogen, CN or CF ₃ substituted; R ² is hydrogen, C ₁ -C ₁₀ alkyl or C ₂ -C ₁₀ alkenyl, and wherein C ₁ -C ₁₀ alkyl, C ₂ -C ₁₀ alkenyl is unsubstituted Or any -CH ₂ - is substituted by -O-, -S-, -O-CO-, -OC-O- or -O-CO-O-, and wherein -O-, -S-, -O-CO -, -OC-O- or -O-CO-O- substituents are not directly linked to each other, and/or the hydrogen atom on any carbon is unsubstituted or substituted by halogen, CN or CF ₃ ; Q can be C , O, or S; Y is an alkyl group having 1 to 10 carbon atoms; ring A1, ring A2, ring A3 and ring A4 are independently 2,6-dioxabicyclo[2,2,2]octyl , 2,6,7-trioxabicyclo[2,2,2]octyl or 2,5-indanyl, 1,4-cyclohexylene or 1,4-phenylene, and/or the 1,4-phenylene or 1,4-phenylene is unsubstituted in at least one hydrogen or halogen, CN, CF ₃ substituent, and ring A1, ring A2, ring A3, and ring A4 least One is 2,6-dioxabicyclo[2,2,2]octyl, 2,6,7-trioxabicyclo[2,2,2]octyl or 2,5 indanyl ; Z ₁ , Z ₂ , and Z _{3 are} independently a single bond, C ₁ -C ₄ alkylene, C ₂ -C ₄ alkylene, C ₂ -C ₄ alkynyl, -CO-O-, - O-CO-, -CF ₂ O- or -OCF ₂ -, and wherein C ₁ -C ₄ alkyl, C ₂ -C ₄ alkylene, C ₂ -C ₄ alkynyl are unsubstituted or at least One hydrogen atom is replaced by a halogen, and/or any -CH ₂ - is substituted by -O- or -S-, and wherein -O-, -S- are not directly connected to each other; n may be 1 or 0.

如申請專利範圍第2項所述之具光學活性的液晶添加物，其中環A1為2,6-二氧雜二環[2,2,2]辛烷基、2,6,7-三氧雜二環[2,2,2]辛烷基或2,5-茚滿基。 An optically active liquid crystal additive as described in claim 2, wherein ring A1 is 2,6-dioxabicyclo[2,2,2]octyl, 2,6,7-trioxane Heterobicyclo[2,2,2]octyl or 2,5-indanyl.

如申請專利範圍第2項所述之具光學活性的液晶添加物，其中n為1。 An optically active liquid crystal additive as described in claim 2, wherein n is 1.

如申請專利範圍第3項所述之具光學活性的液晶添加物，其中環A2、環A3、環A4至少之一為1,4-伸苯基，且該1,4-伸苯基中至少一個氫被鹵素取代。 The optically active liquid crystal additive according to claim 3, wherein at least one of the ring A2, the ring A3 and the ring A4 is 1,4-phenylene, and the 1,4-phenylene group is at least One hydrogen is replaced by a halogen.

如申請專利範圍第5項所述之具光學活性的液晶添加物，具選自以下式(II)、式(III)或式(IV)之結構式：其中，R²為氫、C₁-C₁₀烷基或C₂-C₁₀烯基，且其中C₁-C₁₀烷基、C₂-C₁₀烯基為未經取代或任意-CH₂-被-O-、-S-、-O-CO-、-OC-O-或-O-CO-O-取代，且其中-O-、-S-、-O-CO-、-OC-O-或-O-CO-O-取代基彼此不直接相連接，及/或任意碳上的氫原子為未經取代或被鹵素、CN或CF₃取代； Y為碳數1~10的烷基；環A2及環A3獨立地為1,4-伸環己基或1,4-伸苯基，及/或該1,4-伸苯基或1,4-伸苯基中為未經取代或至少一個氫被鹵素、CN、CF₃取代；Z₁、Z₂、及Z₃獨立地為單鍵、C₁-C₄伸烷基、C₂-C₄伸烯基、C₂-C₄伸炔基、-CO-O-、-O-CO-、-CF₂O-或-OCF₂-，且其中C₁-C₄伸烷基、C₂-C₄伸烯基、C₂-C₄伸炔基為未經取代或至少一個氫原子被鹵素取代，及/或任意-CH₂-被-O-或-S-取代，且其中-O-、-S-彼此不直接相連；Q為O；m為1至10。 An optically active liquid crystal additive according to claim 5, which has a structural formula selected from the following formula (II), formula (III) or formula (IV): Wherein R ² is hydrogen, C ₁ -C ₁₀ alkyl or C ₂ -C ₁₀ alkenyl, and wherein C ₁ -C ₁₀ alkyl, C ₂ -C ₁₀ alkenyl is unsubstituted or optionally -CH ₂ - Substituted by -O-, -S-, -O-CO-, -OC-O- or -O-CO-O-, and wherein -O-, -S-, -O-CO-, -OC-O - or -O-CO-O-substituents are not directly bonded to each other, and/or the hydrogen atom on any carbon is unsubstituted or substituted by halogen, CN or CF ₃ ; Y is an alkyl group having 1 to 10 carbon atoms Ring A2 and ring A3 are independently 1,4-cyclohexylene or 1,4-phenylene, and/or the 1,4-phenylene or 1,4-phenylene group is unsubstituted or At least one hydrogen is substituted by halogen, CN, CF ₃ ; Z ₁ , Z ₂ , and Z _{3 are} independently a single bond, a C ₁ -C ₄ alkyl group, a C ₂ -C ₄ alkylene group, a C ₂ -C _{4 group} An alkynyl group, -CO-O-, -O-CO-, -CF ₂ O- or -OCF ₂ -, and wherein C ₁ -C _{4 is} alkyl, C ₂ -C _{4 is} alkenyl, C ₂ - The C ₄ alkynyl group is unsubstituted or at least one hydrogen atom is replaced by a halogen, and/or any -CH ₂ - is substituted by -O- or -S-, and wherein -O-, -S- are not directly bonded to each other; Q is O; m is from 1 to 10.

如申請專利範圍第6項所述之具光學活性的液晶添加物，具以下結構式： The optically active liquid crystal additive as described in claim 6 has the following structural formula:

如申請專利範圍第2項所述之具光學活性的液晶添加物，其中n為0。 An optically active liquid crystal additive as described in claim 2, wherein n is zero.

如申請專利範圍第8項所述之具光學活性的液晶添加物，其中環A2、環A4至少之一為1,4-伸苯基，且該1,4-伸苯基中至少一個氫被鹵素取代。 The optically active liquid crystal additive according to claim 8, wherein at least one of the ring A2 and the ring A4 is 1,4-phenylene, and at least one hydrogen of the 1,4-phenylene group is Halogen substitution.

如申請專利範圍第9項所述之具光學活性的液晶添加物，具選自以下式(V)、式(VI)或式(VII)之結構式：其中，R²為氫、C₁-C₁₀烷基或C₂-C₁₀烯基，且其中C₁-C₁₀烷基、C₂-C₁₀烯基為未經取代或任意-CH₂-被-O-、-S-、-O-CO-、-OC-O-或-O-CO-O-取代，且其中-O-、-S-、-O-CO-、-OC-O-或-O-CO-O-取代基彼此不直接相連接，及/或任意碳上的氫原子為未經取代或被鹵素、CN或CF₃取代；Y為碳數1~10的烷基；環A2為1,4-伸環己基或1,4-伸苯基，及/或該1,4-伸苯基或1,4-伸苯基中為未經取代或至少一個氫被鹵素、CN、CF₃取代；Z₁、Z₂、及Z₃獨立地為單鍵、C₁-C₄伸烷基、C₂-C₄伸烯基、C₂-C₄伸炔基、-CO-O-、-O-CO-、-CF₂O-或-OCF₂-，且其中C₁-C₄伸烷基、C₂-C₄伸烯基、C₂-C₄伸炔基為未經取代或至少一個氫原子被鹵素取代，及/或任意-CH₂-被-O-或-S-取代，且其中-O-、-S-彼此不直接相連；Q為O；m為1至10。 An optically active liquid crystal additive according to claim 9 which has a structural formula selected from the following formula (V), formula (VI) or formula (VII): Wherein R ² is hydrogen, C ₁ -C ₁₀ alkyl or C ₂ -C ₁₀ alkenyl, and wherein C ₁ -C ₁₀ alkyl, C ₂ -C ₁₀ alkenyl is unsubstituted or optionally -CH ₂ - Substituted by -O-, -S-, -O-CO-, -OC-O- or -O-CO-O-, and wherein -O-, -S-, -O-CO-, -OC-O - or -O-CO-O- substituents are not directly bonded to each other, and/or the hydrogen atom on any carbon is unsubstituted or substituted by halogen, CN or CF ₃ ; Y is an alkyl group having 1 to 10 carbon atoms Ring A2 is 1,4-cyclohexylene or 1,4-phenylene, and/or the 1,4-phenylene or 1,4-phenylene group is unsubstituted or at least one hydrogen is halogen Substituting CN, CF ₃ ; Z ₁ , Z ₂ , and Z _{3 are} independently a single bond, a C ₁ -C ₄ alkylene group, a C ₂ -C ₄ alkylene group, a C ₂ -C ₄ alkynyl group, CO-O-, -O-CO-, -CF ₂ O- or -OCF ₂ -, and wherein C ₁ -C ₄ alkyl, C ₂ -C ₄ alkenyl, C ₂ -C ₄ alkynyl Is unsubstituted or at least one hydrogen atom is replaced by halogen, and/or any -CH ₂ - is substituted by -O- or -S-, and wherein -O-, -S- are not directly connected to each other; Q is O; m It is from 1 to 10.

如申請專利範圍第10項所述之具光學活性的液晶添加物，具以下結構式： An optically active liquid crystal additive as described in claim 10, having the following structural formula:

如申請專利範圍第6項或第9項之具光學活性的液晶添加物，其中Q為O；R¹為C_mH_2m+1；m=3-8。 An optically active liquid crystal additive according to claim 6 or claim 9, wherein Q is O; R ¹ is C _m H _2m+1 ; m=3-8.

一種液晶組成物，包含至少一種如申請專利範圍第1項至第12項中任一項所述之具光學活性的液晶添加物。 A liquid crystal composition comprising at least one optically active liquid crystal additive as described in any one of claims 1 to 12.

如申請專利範圍第13項之液晶組成物，其中該具光學活性的液晶添加物的含量小於1重量百分比。 The liquid crystal composition of claim 13, wherein the optically active liquid crystal additive is contained in an amount of less than 1% by weight.