TWI301151B - Chiral swallow-tailed liquid crystal and its fabrication method - Google Patents

Description

1301151

V. INSTRUCTION DESCRIPTION OF THE INVENTION (1) - Technical Field of the Invention The present invention relates to an antiferroelectric liquid crystal material and its manufacture, and in particular to an optically active dovetail type liquid crystal material and a t-reforming method thereof /, clothing manufacturing method 2, [prior art] eye shovel in optical liquid crystal (chira 1 1 iquidcrysta 1 ) ψ & 夕丁户 /]"

The current antiferroelectric phase (3111: 丨{6]: 1'〇6160:1; 1^心七7) is a tristable switching property, meaning that the crystal is in addition to the general In addition to the bistable state of ferroelectric liquid crystal (ferr 〇e 1 ectric 1 iquid crystal), it has the characteristics of another antiferroelectric optical smectic C phase, which is abbreviated as S CA. * Phase, this is the so-called third stable state (th ird stable state).

In general, both an antiferroelectric liquid crystal and a ferroelectric liquid c r y s t a 1 have similar helical structures. However, the main difference between the two is that the former helix structure (he 1 ica 1 structure) is composed of zigzag bilayers, as shown in the first figure, the liquid crystals of two adjacent layers in the structure. The molecular systems are arranged in reverse. In the latter ferroelectric liquid crystal structure, liquid crystal molecules of two adjacent layers are arranged in the same direction, as shown in the second figure.

Page 5 1301151 V. Description of the invention (2) Due to the anti-ferroelectric liquid crystal, the spiral propagation +, the ^W field ^ Λ. ^ U冓 can be used to solve the effect between the liquid crystal molecules and the interface, and ferroelectricity LCD c + 01 . Ί . j, d, μ 丄 dog 1 with a fixed surface (surface 3 seven 81311126 (1) state, in this shape

Rl i, 广曰八1, 儿门A factory, generally ferroelectric liquid crystal, the liquid crystal molecules of the mouth are arranged in the same direction, as shown in Figure 2, and in the same direction. Molecular dipole, and let it produce a net Φ av θ > π (1) at the spontaneous polarization value; otherwise, the reverse, 夂 闰斛 甘 - Gan ^ U,, / night crystal molecular system is a sawtooth double-layer structure J. 0 C ^ /rb lU ^ The alignment direction of liquid crystal molecules in the mouth, ?, I born # spontaneous extreme value. Such molecules are in opposite order, that is, anti-ferroelectric liquid ^ # ^ ^ , ^ A three-day steady state. This third stable sorrow can be converted by loyalty to the pen and the slogan. ” ” and Xiacheng ferroelectricity, the so-called “field induced antiferroelectricity to ferroelectricity (field i +.f , \ uuced Anti ferroelectric to ferroelectric)!:^鳇施0户$〇" & conversion under the action of an electric field, the three stable states of antiferroelectric liquid crystal, showing a special photoelectric effect (eleCtr〇〇ptiCal eifect), such as: DC Features such as critical \ field and hysteresis can make full use of these characteristics to effectively improve the design constraints of viewing angles and contrasts (c〇ntrast rati〇).

In addition, the 'anti-ferroelectric liquid crystal has the following advantages: 1 · The optical axis of the anti-ferroelectric liquid SB molecule is arranged along the direction of the alignment (a ignment direction), which is advantageous for the stability of alignment and alignment; The electro-optical liquid crystal has a third stable state in the unwinding state, so that the ghost effect (g 〇st effect) and the memory effect (mem 〇ry effect) can be effectively avoided;

Page 6 1301151 V. Description of Invention (3) 3 · Antiferroelectric liquid crystal has a critical electric field and hysteresis under the action of an electric field, and has a matrix addressing capacity to improve the resolution of the liquid crystal display; 4. Anti-ferroelectric liquid crystals are easy to get the matching of the book-like bookcase (叩仏丨b〇〇kshelf), "the σ structure can be ordered to have a fairly high contrast value, about 20 ~ 3 0; 5 · anti Ferroelectric liquid crystal has a fast response time (resp〇nse time), so it can fully utilize the driving technology of the current liquid crystal display without separately developing a new driving technology; and 6 · antiferroelectric liquid crystal has automatic alignment repair Its characteristics can improve the ability of liquid crystal display to resist mechanical and thermal shock. Since 'anti-ferroelectric liquid crystal has such an important position and potential in the actual manufacture and application of photovoltaic devices, how to anti-iron The relationship between the molecular structure and the liquid crystal phase in the electro-optic liquid crystal material is researched and developed to design a low-cost and good-effect antiferroelectric liquid crystal material, and to effectively master the liquid crystal display. The key technology of the device has obviously become the goal of the current optoelectronic manufacturers and research units. The antiferroelectric liquid crystal materials developed by various optoelectronic manufacturers and research units now have their molecular chemical structures and ferroelectric liquid crystals. The molecules are similar. As shown in the fifth figure, the system consists of a terminal chirai alkyl chain, a rigid core 2, a linking group 3, and an achiral alkyl ch a. In)4

Page 7 1301151 V. INSTRUCTIONS (4) Cheng, the molecular structure of the first three parts is anti-ferroelectric: an important key component of liquid crystal production.

The terminal optical chain structure in the molecular structure of the antiferroelectric liquid crystal can be roughly classified into four types as shown in the sixth figure, in which the polarity and the molecule of the substituent (Ri) on the chira center (C*) Size, the most important factor affecting the formation of antiferroelectric liquid crystal. The structural change of hard core (rigidc 〇re) has little effect on the formation of antiferroelectric liquid crystal. In the materials of different hard core structures, as shown in the seventh figure, the hard core structure is changed from aromatic ring to heterogeneous When an aromatic ring or a substituent is present, it does not affect the formation of an antiferroelectric liquid crystal phase. In addition, most of the hard cores are composed of three or more aromatic rings or heteroaromatic rings, and there are fewer antiferroelectric liquid crystal materials having a two-ring structure.

The linking group in the molecular structure of the antiferroelectric liquid crystal is generally the most common in the ester group and the ketone group. As shown in Fig. 8, the linking structure of the hard core and the terminal optical chain is particularly important. The X-ray diffraction and FT IR spectroscopy (Fourier transform infrared spectroscopy) of the ester materials were analyzed. It was found that the optical chain at the end of the optical rotation was linked by -C00-, which easily caused a bent structure, thus making the molecules in phase. Two adjacent layers form a sawtooth double layer structure that is arranged in reverse pairs. Such a -C00-method linkage can simultaneously increase the co-consumption of electrons in the liquid crystal molecules on the molecular long axis (c ο njugati ο η ), and contributes to antiferroelectricity S CA * The generation of liquid crystal phase. 1301151

V. INSTRUCTIONS (5): The antiferroelectric liquid crystal is considered to be capable of being made into a high-quality liquid crystal display = E d bond material because of its three stable state transition, j) C critical electric field and hysteresis. However, traditionally, these antiferroelectric liquid crystal materials have limited the high Ed and the pre-transformation effect (pretransiti〇nai effec1:), which has not been used as expected in the production of liquid crystal displays. The characteristics of the second and high contrast. Male seeing the corner

Until 1996, Japanese scientist I nu丨 mixed the three antiferroelectric liquid crystal materials I, II and III shown in the ninth figure to investigate the E and pre-transformation effects of the mixing ratio on the antiferroelectric liquid crystal. The effect of this result shows that changing the mixing ratio of these liquid crystal materials can effectively reduce the E straightness of the antiferroelectric liquid crystal. But the 'pre-transformation effect is even more pronounced. At the same time, the Japanese scientist I nui found that the antiferroelectric liquid crystal did not have E "straight existence" when the mixing ratio was I : II : III = 4 0 : 4 0 : 2 0. More specifically, its field induced antiferroelectric The transition from ferroelectricity to ferroelectricity is a continuous V-shaped transition (v-shaped switching). I nui combines this kind of antiferroelectric liquid crystal into a valveless antiferroelectric liquid crystal (T Hresh ο 1 d 1 ess ant i ferroe1ectr ic liquid crystals; TLAFLCs), such valveless antiferroelectric liquid crystal materials have the following characteristics on the display:

(1) Large tilt angle (> 3 5 degrees); (2) Low drive voltage (<2V//z m_l ); (3) Ideal gray scale; (4) Fast Antiferroelectric to ferroelectric conversion time (< 5 0// s ); (5) high contrast value (> 1 〇〇);

- Page 1 1301151 V. INSTRUCTIONS (6) (6) Wide viewing angle (> 6 twist). These features not only overcome the gray scale problem that occurs when fabricating a passive matrix-driven surface-stabilized ferroelectric liquid crystal display, but also effectively improve the active matrix or thin film. Thin film transistor-driven spiral structure change (def ormed-helix) ferroelectric liquid crystal display and passive matrix-driven antiferroelectric liquid crystal display are not easy to obtain high contrast value. At the same time, in the case of increasing the contrast value, high-speed responsiveness can still be maintained. Production of displays with a wide viewing angle and fast display of gray levels is possible. [Invention] In view of the many excellent characteristics of the above-mentioned valveless antiferroelectric liquid crystal material, the main object of the present invention is to provide an optically active dovetail type liquid crystal material. It is a guanamine-containing optically active dovetail liquid crystal material having a molecular structure of (s)-2-{6 - [4-(4'-pyroxybenzene)benzoquinoneoxy]-2-naphthyl} ( Compound or molecule of N,N '-diethyl (s)-2-{6_[ 4-(4, -alkoxyphenyl)benzoyloxy]-2-naphthyl}propionamide) The structure is (s) - 2 - { 6 - [ 4 - ( 4 '-alkoxybenzene) benzhydryloxy]-2-naphthyl} (Ν, Ν'-dipropyl) propionate decyl N, Ν a compound of '-dipropyl (s)-2-{6-[4-(4'-alkoxyphenyl)benzoyloxy]-2-naphthyl} propi ο nanamide ); in the optical rotation of the liquid crystal material of the present invention

Page 10 1301151 V. Description of invention (7) The heart (chrial cent er) is directly connected, on its hard core (· · s 1 ac 〇re ), and the tail end of the optical rotation is connected with a dovetail base (swal l〇w — Tai led ' and this optical rotation center and dovetail base are in the liquid crystal material of the present invention, HQup > 'Knife structure

On one side, this structural feature not only makes the liquid crystal material of the present invention have the characteristics of =i N ferroelectric, but also has a simple manufacturing process and a high yield, and has excellent application effects on the surface of the film. Another object of the present invention is to provide a guanamine-containing optically active dovetail type liquid crystal material having photoelectric properties such as antiferroelectricity and Thresholdless V-shaped switching. It is advantageous to optimize the preparation of mixed liquid crystal for the production of V-type thin film transistor liquid crystal device (TFT-V mode LCD). Still another object of the present invention is to provide a method for producing a guanamine-containing optically active dovetail type liquid crystal material which can provide a rapid reaction liquid crystal material for an active driving liquid crystal display. According to the above objects, the present invention provides an optically active dovetail type liquid material which is synthesized from an optically active material. The optically active, tail-type liquid crystal material of the present invention is (s) _ 2 - 丨 6 - [ 4 - ( 4 , _ alkoxybenzene) benzene | A & oxygen] 1-2 Ny[N}N (N, N ,-Diethyl) decylamine propionate (N,N,-diethy 1 (s) 2 {6 [4-(4'-aikoxyphenyl)benzoyloxy]-2-naphthy 1}0 二〇?1〇1^11 ^(1〇 or (3)-2-{6-[4-(4'-Alkoxybenzene)benzoquinoneoxy]- 2-nyl}(N,N'~dipropyl)propanoic acid decylamine (N, N, a dipr〇pyl(s) one 2 -

Page 11 1301151 V. Inventive Note (8) - {6 - [4 -(4' -al,koxyphenyl)benzoyloxy] - 2-naphthyl} p r op ion amide). The chrial center of the liquid crystal material of the present invention is directly connected to the hard core (r丨g丨dc 〇re ), and the tail end of the optical rotation is connected with a dovetail base (swa 1 1 〇w — tai 1 edgroup ). The optical rotation center and the dovetail base are on the same side. This structural feature makes the liquid crystal material of the invention have valveless antiferroelectric characteristics, and has a simple manufacturing process and high yield, and has excellent application effects on the liquid crystal display. 4. [Embodiment] The present invention provides a guanamine-containing optically active dovetail liquid crystal material having valveless antiferroelectricity, which is composed of a molecular structure of (s) - ( + ) - 2 - (6 Anthraquinone-2 ~naphthyl}propionic acid ((s)~( + )- 2-(6-meth〇xy-2 -naphthyl)pr 〇pi 〇nicacid) synthesized by an optically active material. The optical rotation center of the optically active dovetail type liquid crystal material is directly connected to the hard core thereof, and the tail end of the light-emitting tail is connected with a tail group, and its general formula is as shown in the following chemical formula (I):

Ch3 〇

Page 12 1301151 V. Description of invention (9) Both n and m are integers, when m = 6~ hard core. The hard core includes the following: where Rl - CmH2m + l, R2 = - N (CnH "n + 1) 2 16, n = 3, and when m = i 〇 ~ 15, n = 2, a is the molecular structure: JQrJQr

It can be seen from the above chemical formula (I) that the optical rotation center and the dovetail group of the fluorene-containing optically active dovetail type liquid crystal material of the present invention are on the same side of the molecular structure, and this structural feature makes the guanamine-containing optically active dovetail type of the present invention. The liquid crystal material has the characteristics of valveless antiferroelectricity. The method for synthesizing the fluorene-containing optically active dovetail type liquid crystal material of the present invention will be described in detail in the following preferred embodiment in conjunction with the flow chart of the synthesis steps shown in the tenth embodiment. The optically active material used in the synthesis of the fluorene-containing optically active dovetail type liquid crystal material of the present invention is (s) -( + )- 2 -(6-decyloxy-2-naphthyl}propionic acid ((s) one (+ Λ - 2-(6iethoxy - 2-naphthyl)propionic acid), which is based on Tokyo Chemical Industry Co., Ltd. (Tokyo Chemical Industry C ο. LTD.), and has an optical purity of over 99%. The dichloromethane (CH2Cl 2 ) used in the preferred embodiment is used,

Page 13 1301151__ V. INSTRUCTIONS (10) The former was dried and hydrogenated by hydrogenation (L i A 1 Η 4). In a first preferred embodiment of the present invention, 285 ml, 325 mmol of ethylene dioxane ((C0C1) 2) is gradually added to 3 of dichloromethane in 3 ml.克, 13 mM (s)-(+)-2-(6-methoxy-2-naphthyl}propionic acid ((s)-( + )- 2-(6-methoxy-2-naphthyl In propionic acid), the final solution is heated at the first reflux temperature (firstref ux temperature) for two hours. Then, under reduced pressure, the remaining ethane chloride is removed by evaporation. (s)-2-(6-methoxy-2-naphthylpropionic acid chloride) (5-methoxy-2-naphthylpropionic acid chloride) in 5 ml of dichlorodecane Add 3 · 36 ml of 3,5 mmol of N,N'-diethylamine (N, N'- dissolved in 10 ml of dichloromethane, stirred in an ice bath (about 0 ° C). Diethylamine) (HN(CH2CH3)2) and 5 ml of triethylamine (TEA) solution. Finally, some solids are produced and this mixture is placed in the refrigerator overnight, ie at a temperature of -5 ° C 1 2 Hour. Under reduced pressure, the mixture is dried by evaporation and used as a gelatin (ASTM) 'Screen number 70~230' column chromatography over silica gel (70-230 mesh ASTM), using dichloromethane/ethyl acetate (V: V = 8: 2) as the eluate, The residue after evaporation drying was purified to obtain 70% white (S)-2-(6-methoxy-2-naphthyl}propionic acid N,N '-diethyl hydrazine (N) , N'-diethyl (s) - 2 -( 6-methoxy-2-naphthyl)propionate), which is the first intermediate for synthesizing the fluorene-containing optically active dovetail type liquid crystal material of the first preferred embodiment of the present invention Body (I).

Page 14 1301151 V. INSTRUCTIONS (11) White (s) -2-(6-methoxy-2-naphthyl}propionic acid N, Ν'-diethyl ester, (Ν,Ν' -diethyl The results of nuclear magnetic resonance spectroscopy (1H-NMR spectrum) analysis of (s)-2-(6-methoxy-2_naphthyl) propionate): 5 (CDC13, ppm) 7.7 to 7.1 (m, 6H, ArH), 7.25 (s, CDC13), 4.0 to 3.9 (q, 1H, ArC*H), 3.9 (s, 3H, CH30), 3.6 to 3·0 (ιη, 4H, NCH2CH3), 1.6 (d, 3H, C*H (CH3) ), 1·卜〇·9( m,6H,NCH2CH3). Next, it is dissolved in 66.5 g of 68.65 ml of dry di-methane.

1 7. 54 millimoles of (s) -2 -(6-methoxy-2-naphthyl}propionic acid N,Ν'-diethyl ester (Ν,Ν' -die thyl(s)-2 -(6 - methoxy-2 - naphthyl) propionate) at -20 ° C with 3 · 4 ml of tribrominated stone pennone (boron

t r i brom i de ) ( BBr3) mixed. The mixture was stirred at -0 °C for 5 minutes and at 0 t for 40 minutes. After diluting with 137 ml of dichloromethane, the solution was poured into 137 ml of saturated ammonium chloride (amm ο niumch 1). 〇ride ) and a mixture of 100 g of crushed ice, wherein the organic layer was separated, washed with brine-ice, dried over anhydrous sodium sulfate (Na 2 SO 4 ), and concentrated under vacuum. After recrystallization from acetonitrile (acet ο nitri 1 e ), (S)_2-(6-hydroxy-2-naphthyl}propionic acid N,N,-diethylhydrazine (N) can be collected in 71% yield. , N-diethyl (s)*~2-(6-hydroxy-2-naphthyl) propionate), which is the second intermediate for synthesizing the ammine-containing optically active dovetail liquid crystal material of the first preferred embodiment of the present invention (S)-2-(6-hydroxy-2-naphthyl}propionic acid N,N,-diethyl ester (N,N, one

Page ι 1301151 V. Description of invention (12)

The results of 1H-NMR spectrum analysis of diethyl (s) - 2-(6-hydroxy - 2-naphthyl )propionate): 6 (CDC13, ppm) 7.8 ~ 7.0 (m, 6H, ArH), 7.25 (s, CDC13), 5.8 to 5.7 (s, 1H, OH), 4. 0-3. 9 (q, 1H, ArC*H), 3.7-3.0 (m, 4H, NCH 2CH3), 1.6 (d, 3H, C*H(CH3)), 1.2-0.9(m, 6H, NCH2CH3 Next, slowly add 0. 4 ml, 4.634 mmol of ethylene dichloride ((C0C1) 2) to 0. · 76 g, 0·185 mmol of 4-(4'-alkoxyphenyl)benzoic acid (mPBA, m=10 ～ 15, m is an integer, In the case of the alkoxy Cin H2m+1 0-carbon number, the final solution was stirred at the second reflux temperature for two hours. The remaining ethylene dichloride was evaporated under reduced pressure. The crude product 4-(4,-alkoxyphenyl)benzoic acid chloride was dissolved in 5 ml of dichloromethane and added to the ice bath (temperature approx. °C) 0.5 g of 0.185 mmol (s)-2-(6-hydroxy-2-naphthyl}propionic acid N,Ν'-diethyl ester dissolved in 5 ml of anhydrous dichloromethane. N, N, -die Thyl(s)-2-(6-hydr〇xy-2-naphthyl) propionate) and 5 ml of pyridine mixture. After the precipitation is produced, the mixture is placed in the refrigerator overnight, that is, at room temperature. After 1 hour at 5 ° C. Thereafter, the mixture was evaporated to dryness under reduced pressure, and a colloidal gel (ASTM, Division 70 to 230) column chromatography method (column chromatography over silica gel (70 to 230 mesh ASTM)) was used. ), using dioxane / ethyl acetate (V : V = 8 · · 2 ) as the eluant, after evaporation and drying

Page 16 1301151 V. INSTRUCTIONS (13) . The residue is purified to obtain (s)-2-{6_[4-(4,-alkoxy)benzoquinone]-2 with 60% white yield. -naphthyl}N,N,'~diethyl(s)-2-{6-[4-(4,-alkoxyphenyl)benzoyloxy]-2 -naphthyl }propionamide)(DEmPBNPA, m=10~15, m is an integer which is alkoxy (8111〇\7) (:|11}12111+10-carbon number), this is the hair: Amidino-based optically active dovetail liquid crystal material series (I), its molecular structure, as shown in the tenth figure. Also '4-(4'-:1: oxyphenyl) benzoic acid (mPBA, 111 = 9~ 15, m is an integer, is alkoxy (alkoxy) CmH2m + 10 - carbon number of the synthesis method of the pansystem is 3.62 grams, 17 亳 Mo 4' - thiodiphenyl-4 - Wei Acid (4, _ hydroxybipheny b 4_carboxylic acid) and 250 ml of ethanol were added to a 1000 ml three-necked round bottle. One of the necks of the three-necked round bottle was equipped with a condenser. The other neck is fitted with a feed tube' and the other neck is plugged with a rubber stopper. 2. grams, 36.07 millimoles of potassium hydroxide (ΚΟΗ) & 〇 · 5 grams, 3 〇 1 millimol of potassium moth (Κ I) and 50 ml of distilled water are added from the feed tube In a neck-shaped round bottle, the mixture was heated to reflux and stirred for a few hours. Thereafter, j 〇 ml, 51 mmol of alkyl bromide (CniH2m + iBr, ~15, m is an integer) was added dropwise. In this mixture, and heating under reflux | stirring for about 12 hours. Then, 1 〇〇 ml of 丨〇% potassium hydroxide ▲ solution was added to the mixture and heated under reflux for 2 hours. The mixture was acidified with a 5 % aqueous hydrochloric acid solution and filtered, and the crude product was washed with cold water and glacial acetic acid was used.

1301151_ V. Description of invention (14). The crude product was washed with ice water (c ο 1 dwater) and recrystallized using glacial acetic acid (CH3C00Η) and absolute ethanol (C2H50H) to obtain a yield of 60-77%. - (4, monoalkoxyphenyl) benzoic acid (mPBA, m = 9 to 15). In a second preferred embodiment of the present invention, 9.5 ml, 108.573⁄4 mol of a brewing gas ((C0C1) 2) is gradually added to 10 g, 43.4 dissolved in 1 ml of dichloromethane. 3 millimolar of (S)-2-(6-methoxy-2-naphthyl) propionic acid ((s)-(+)-2-(6-methoxy-2-naphthyl) propionic acid) 'The final solution was heated at the first reflux temperature for two hours. Then, the remaining ethylene dichloride was removed by evaporation under reduced pressure. (s)-2-(6-methoxy-2-naphthylpropionic acid ch 1 oride ) crude product in alkane Add 22.3 3 ml, 126.8 5 mmol of N,N,-dipropylamine dissolved in 30 ml of anhydrous dichloromethane in an ice bath (temperature about 〇 °c). (HN(CH2CH 2CH 3)2) and 10 ml of triethylamine (TEA) solution. Finally, some solids are produced, and the mixture is placed in the refrigerator overnight, that is, at a temperature of -5°. C under 1 2 hours. Under reduced pressure, this mixture The product was evaporated to dryness, and a column chromatography over silica gel (70~2 3 0 mesh ASTM) was used as the dichloromethane/ethyl acetate (ASTM, 70-230 mesh ASTM). V : V = 8 : 2) As an eluant, the residue after evaporation and purification is purified to obtain a yield of 70% white (s)

Page 18 1301151 V. INSTRUCTIONS (15) -2-(6-decyloxy-2-, naphthyl}propionic acid N,N,-dipropyl ester (N,N,-dipropyl(s)-2 -(6-methoxy-2-naphthyl)propionate) which is the first intermediate (I) for synthesizing the fluorene-containing optically active dovetail type liquid crystal material of the second preferred embodiment of the present invention. White (s) N,N'-dipropyl(s)-2-(6-methoxy-2-naphthyl) propionate -2-(6-methoxy-2-naphthyl propionate) The results of nuclear magnetic resonance spectroscopy (1H-NMR spectrum) analysis were: 5 (CDC13, ppm) 7.7 to 7.1 (m, 6H, ArH), 7.25 (s, CDC13), 4.0 to 3.9 (q, 1H, ArC*H) , 3.9 (s, 3H, CH30), 3·6 to 3. 0 (m, 4H, NCH2CH2CH3), 1. 5 to 1. 4 (m, 4H, NCH2CH2 CH3), 1.6 (d, 3H, C*H (CH3)), ll-0.9 (m, 6H, NCH2CH, then 8 g, 26.76 mmol (s)-2-(6-) dissolved in 5 2. 36 mL of dry dichloromethane.曱 -2 - -naphthyl} propionate, Ν'-dipropyl(s) - 2 -(6 -methoxy-2 -naphthyl) propionate at -20 °C With 5·24 ml of boron tribride (boron tribr 〇mide) (B B r3) Mixing. Mix the mixture at -0 °C for 5 minutes and at 0 °C for 40 minutes. After diluting with 104.73⁄4 liters of dioxins, the solution is poured into 104. 7 ml of a mixture of saturated ammonium chloride (ammonium ch 1 〇ride ) and 10 g of crushed ice 'where the organic layer is separated, washed with ice brine (ice-ice) and using anhydrous sodium sulfate (N a S 〇4 ) Dry and concentrate under vacuum. Re-knot via acetonitrile tri le

Page 19 1301151 V. INSTRUCTIONS (16) After the crystallization, (1) - 2 - ( 6 ~ hydroxy-2-naphthyl} propionic acid N, N' - dipropyl ester can be collected (Ν,Ν,-dipropyl (s) -2-(6-hydroxy -2-

Naphthyl )propionate), which is a second intermediate (I (s) - 2-(6 - mercapto-2-) containing a S&-amine-based optically active dovetail liquid crystal material according to a second preferred embodiment of the present invention N,N'-dipropyl(n)-dipropyl(s)-2-(6-hydroxy-2-naphthyl)pr〇pi〇nate 2 Nuclear Magnetic Resonance Spectroscopy (1H NMR spectrum) Analysis results are: ppm) 7.8~7.0 (m, 6H, ArH), 7.25 (s, CDCl3), 5.8~5.7 (s, 1H, OH), 4.0 to 3.9 (q, 1H, ArC*H), 3.7 ~ 3·0 (πι, 4H, NCH 2CH3), 1.6 (d, 3H, C*H(CH3)), 1. 5 to 1.4 (m, 4H, NCH2CH2 CH3), 1·2 to 0·9 (m, 6H, NCH2CH3) Next, slowly add 35·35 ml, 1.58 mmol of ethanedichloride ((c〇Cl)2) to 〇·58 g, 1.00 mmol. -(4'-alkoxyphenyl)benzoic acid (mPBA, m = 9~13, m is an integer, alkoxy (aik〇xy) Cmu carbon In the atomic number, the final solution was stirred at the second reflux temperature for two hours. The remaining ethylene dioxane was removed by evaporation under reduced pressure. The crude product was 4-(4,-alkyloxybenzene)benzoquinone. acid The compound (4-(4,-alkoxyphenyl)benzoic acid chloride) was dissolved in 3 ml of di-methane and added to an ice bath (temperature about 〇.〇) and stirred in 0.3 ml of 5 ml of anhydrous dichloromethane. 1.05 millimoles (s)-2-(6-carbyl-2-naphthyl}propionic acid n,n,-dipropyl ester (N,N,-dipropyl(s)

Page 20 1301151 V. INSTRUCTIONS (17) β -2-(6-hydroxy-2-naphthyl)propionate) and 5 ml 卩 σ ( p y r i d i n e ) in a mixture. After the sulphate was produced, the mixture was placed in a _ refrigerator overnight at a temperature of -5 °C for 12 hours. Thereafter, the ice solution is dried under reduced pressure, and a colloidal gel (ASTM, sieve number 70 to 23 0) column chromatography method (column chromatography over silica gei: (70 to 230 mesh AS D)) is used. Dichloromethane/ethyl acetate (v:v = 8:2) was used as the eluate, and the residue after evaporation and purification was purified to obtain (s)-2-{6. -[4-(4,-Alkoxybenzene) alum oxy]-2-naphthyl}(N,N-propyl)propanoic acid decylamine (n,N'-dipropyl (s)-2-{ 6-[4-(4,

-alkloxyphenyl)benzoyloxy]-2-naphthy 1 }propionamide F )(DPmPBNPA,m = 9~1 3 ), which is a guanamine-containing optically active dovetail type liquid crystal material series (Π), its molecular structure, The tenth picture. The first intermediate embodiment (1) and the second intermediate ((1) obtained in the first preferred embodiment and the second preferred embodiment of the present invention have the following chemical formula: h3co

CH—C—N. 〇

CnH2n+l CH3

CnH2n+l

First intermediate (I)

1301151

Intermediate (11) ϋ 1 In a preferred embodiment, n of the first intermediate (I) and the intermediate (II) is 2, and in the case of 坌一^矛矛, continuation rn ^ In the preferred embodiment, 11 of the middle (I) and the intermediate (11) of the third is 3 . The chemical formula < 〇 of these intermediates, the optical rotation center and the dovetail base are on the same side, so that the final product also has the same characteristics, that is, has valveless antiferroelectricity.

The guanamine-containing optically active dovetail type liquid crystal material provided by the invention has photoelectric properties such as antiferroelectricity and valveless v-type switching behavior, and is favorable for optimizing the preparation of mixed liquid crystal, and can be used for V-type film electricity. Production of a crystal liquid crystal display (TFT-V mode LCD). The above is only the preferred embodiment of the present invention, and is not intended to limit the scope of the present invention; all other equivalent changes or modifications which are not departing from the spirit of the present invention should be included in the following. Within the scope of the patent application.

1301151 Schematic description of the simple five. [The schematic diagram briefly illustrates the molecular structure of the spiral state antiferroelectric liquid crystal in the first figure. The second figure is the molecular structure of the spiral state ferroelectric liquid crystal; the third figure is ferroelectricity. Schematic diagram of the arrangement of the dissolving molecules of the liquid crystal, the fourth picture is a schematic diagram of the arrangement of the anti-ferroelectric liquid crystals; the fifth picture is a schematic diagram of the conjugate system of the antiferroelectric liquid crystal molecules; Figure; The structure of the anti-ferroelectric liquid crystal molecule terminal optical chain is shown in Figure 7. The various antiferroelectric liquid crystals with different hard core structures are not included in the seventh figure. The eighth figure shows the various reversed bases shown in Figure IX. Is a ferroelectric liquid enthalpy diagram; and a molecular structure of an antiferroelectric material. The tenth figure is a flow chart of the synthesis steps of the liquid crystal material compound of the present invention.

1301151

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Claims (1)

1301151__ VI. Patent application scope 1. 1. An optically active dovetail liquid crystal material, which is a compound synthesized by an optically active material. The optical rotation center of the compound is directly connected to the hard core, and the optical rotation end is connected. There is a dovetail base with the following formula: CH 3 RiO— A ~coo where R, -CmH2m+1, R2 = -N(CnH2n+1 )2, m = 6~16, η二卜4, m and η are integers, and A represents a hard core structure , is selected from the following structures: 2. The optically active dovetail type liquid crystal material according to claim 1, wherein m=10~15 and η=2. 3. The optically active dovetail type liquid crystal material according to claim 1, wherein m = 9 to 13 and η = 3 above. Page 25 1301151 VI. Scope of Application 4 · A method for manufacturing an optically active dovetail liquid crystal material, which comprises the following steps: (1) Ethylene dichloride ((C0C1)2) and optically active (s)-(+)-2-(6-methoxy-2-cacoyl}propionic acid ((s)-(+ - 2-(6-methoxy-2-naphthyl)propionic acid) to give (s)-2 -(6-methoxy-naphthyl}propanoic acid chloride ((s)-2-(6) - methoxy-2-naphthyl) propionic acid chloride); (s) - 2 -(6-methoxy-naphthyl}propanoic acid chloride ((s) - 2 -(6-methoxy-2-naphthyl ) propionic acid chloride) is reacted with a mixed solution of hydrazine, Ν'-diethylamine (HN(CH2CH3)2) and triethy 1 amine (TEA) to obtain the first Intermediate (I)(s)-2 -(6-methoxy-2-naphthyl}propionic acid N,N'-diethyl ester (N,N'-diethyl (s)-2-(6iethoxy- 2~naphthyl)propionate), (2) reacting the first intermediate (I) obtained in the above step (1) with boron tribromide (BBr3) to obtain a second intermediate (II) (s) - 2 -(6-Pyryl-2-naphthyl}propionic acid N,N'-diethyl fluorene (N,N'-diethyl (s)-2-(6-hydroxy-2-naphthyl )propionate); and (3) Ethylene dichloride ((C0C1)2) and 4-(4'-alkoxyphenyl)benzoic acid (mPBA, m=10~15, m Reaction to alkoxy Cm H2m+i 0 -the number of carbon atoms) to give the crude product 4 - ( 4 '-alkoxyphenyl)benzoic acid chloride (4-(4'-alkoxyphenyl)benzoic acid ch 1 Oride), the crude product obtained from the above step (2), the second intermediate (II) (s)-2-(6-hydroxy-2-naphthyl}propionic acid N, Ν'-diethyl ester Page 26 1301151 VI. Application of the patent (N, Ν'-diethyl (s)-2-(6-hydroxy-2-:naphthyl) propionate) to obtain the optically active dovetail liquid crystal material (s)-2 - {6 - [4-(4,-Alkoxyphenyl)benzoquinoneoxy]-2-naphthyl}anthracene, Ν'-diethylpropionate oxime (Ν,Ν' -diethyl(s)- 2-{6-[4-(4'-alkoxyphenyl) benzoyloxy]-2-naphthyl}propi〇namide) (m=10~15, m is an integer, alkoxy CmH2H1+1〇- The number of carbon atoms). 5. The method for producing an optically active dovetail type liquid crystal material according to claim 4, wherein the step (3) of 4-(4'-alkoxyphenyl)benzoic acid (4-(4'- alkoxyphenyl) Benzoic acids can be prepared by the following steps: 4'-hydroxybiphenyl-4-carboxylic acid and alky 1 bromide (CmH2m+1Br, m = 9 to 15, m is an integer) reaction to give 4-(4'-pyroxyphenyl)benzoic acid. 6 - A method for producing an optically active dovetail type liquid crystal material, comprising the steps of: (1) converting ethylene dichloride ((C0C1)2) with optically active (s)-(+)-2-(6- Methoxy-2-naphthylpropionic acid ((s) -( + )- 2 -(6-methoxy-2-naphthyl)propionic acid) to give (s)-2-(6-decyloxy- a crude product of (s)-2-(6-methoxy-2-naphthyl) propionic acid chloride; the (s)-2-(6-methoxy-naphthyl}propionic acid Chloride ((s)-2-(6-methoxy-2-naphthyl) propionic acid chloride) crude product with hydrazine, Ν'-dipropylamine (Ν,Ν' Page 27 1301151 VI. Application of a mixed solution of dipropylamine (HN(CH2CH2CH3)2) and triethy 1 amine (TEA) to obtain the first intermediate (I) (s)-2 -(6-oxime-2-naphthyl} propionate, N, Ν'-dipropyl (s)-2-(6-meth〇xy-2-naphthyl) propionate (2) The first intermediate (I) (s)-2-(6-decyloxy-2-naphthyl}propionic acid hydrazide, Ν'-dipropyl ester obtained in the above step (1) (N, Ν'-dipropyl (s) - 2 -(6 - methoxy - 2-naphthyl) propionate)) is reacted with boron tribromide (BBr3) to give a second intermediate (II) (s -2-(6-hydroxy-2-naphthyl}propionic acid N,Ν'-dipropyl(s)-2-(6-hydroxy-2-naphthyl)propionate; And (3) ethylene bismuth ((: 0 (: 1) 2) and 4- (4'-alkoxyphenyl) benzoic acid) (mPBA, m = 9~13, m· — an integer, alkoxy (8 11^(^7)(] Having a carbon number of 111+10-) is reacted to obtain a crude product 4-(4'-pyroxybenzene) Benzoic acid chloride (4-(4'-alkoxyphe) Nyl )benzoic acid chloride), the crude product and the second intermediate (II )(s)-2-(6-hydroxy-2-naphthyl}propionic acid N,Ν'-dipropyl ester (N, N , -dipropy1(s)-2-(6_hydroxy-2-naphthyl) propionate) reaction to obtain the optically active dovetail liquid crystal material (s)-2-{6-[4-(4,-alkoxybenzene)benzene (N,N,-dipropy1(s)-2-{6-[4-(4,-alkoxyphenyl)benzoyloxy]N,N,-dipropy1(s)-2-{6-[4-(4,-alkoxyphenyl)benzoyloxy ]-2 -naphthyl } propanamide ) (DP, „P BNP A, m = 9 〜13, m is an integer, which is the number of carbon atoms of alkoxy CmH2m+10-). Page 28 1301151 6. Patent application scope 7. The method for producing an optically active dovetail liquid crystal material according to claim 6, wherein the above step (3) of 4-(4'-alkoxybenzene)benzene 4-(4'-alkoxyphenyl)benzoic acids can be prepared by the following steps: 4'-hydroxybiphenyl-4-carboxylic acid and alkyl bromide ( Alkyl bromide) (CmH2m+1 Br, m = 9~15, m is an integer) to give 4-(4'-alkoxyphenyl)benzoic acid 0 8 · A method for producing an optically active dovetail type liquid crystal material, comprising the following steps: (1) 2·85 ml, 32·5 mmol of ethylene dichloride ((C0C1) 2) Add 3 g, 1 3 mmol of optically active (s) _ (+ ) 2- 2-(6-methoxy-2-naphthyl}propionic acid ((s)-((s)-(()) In the +(6-methoxy-2-naphthyl)propionic acid), the final solution was heated and stirred at the first reflux temperature for two hours to obtain (s) -2-(6- (曱)-(6-methoxy-2-naphthy 1 propionic acid chloride); (s)-2 dissolved in 5 ml of dichlorosilane -(6-methoxy-naphthyl}propi〇nic acid chloride) is added to dissolve at a temperature of about 0 ° C. l · 36 ml of dichloromethane, 32. 5 mmol of N, N' -diethylamine (HN (CH2CH3) 2) and 5 ml of triethylamine (triethylamine) (TEA) solution; the mixed solution is statically placed at a temperature of 1301151. The patent application range is about -5 °C for a first predetermined time of about 12 hours, and then dried to obtain a first intermediate (I). (s)-2-(6-decyloxy-2-naphthyl}propionic acid N, Ν'-diethyl ester (Ν,Ν' -diethyl (s)-2-(6- Methoxy-2-naphthyl) propionate); (2) 5 g, 7.5 mM of the first intermediate (I) obtained in the above step (1) is dissolved in 68. 65 ml of dichloromethane It was mixed with 3.4 ml of boron tribromide (BBr3) at -20 ° C, and the mixture was stirred at -20 ° C for 5 minutes and at 0 t for 40 minutes. After diluting with 137 ml of dichloromethane, the solution was poured into a mixture of [3 7 ml of saturated chlorinated (ammon i um ch 1 or i de ) and 100 g of crushed ice. The layer is separated and washed with brine-ice, followed by dehydration and concentration, and then recrystallized to obtain a second intermediate (II)(s) 2-(6-hydroxy-2-naphthyl}propionic acid N. Ν'-diethyl ester (Ν,Ν' -diethyl (s) - 2 -(6-hydroxy -2-naphthyl)propionate); and (3) will be 0.4 ml, 4 · 634 millimoles of B Dioxane ((c〇ci) 2) added 0·76 g, 0·185 mmol of 4-(4'-alkoxyphenyl)benzoic acid (4-(4, -a lkoxy phenyl) benzoic acids) (mPBA, m 2 10~15, m is alkoxy c, n H2m+1 〇-carbon number), the final solution is stirred at the second reflux temperature for two hours' The crude product 4-(4'-alkoxyphenyl)benz〇ic acid chloride is obtained, and the crude product > valley is burned in a house. Adding the first intermediate (II)(s) - 2 obtained in the above step (2) by dissolving 〇·5 g dissolved in 5 ml of methylene chloride at a temperature of about 〇. -(6_Phenyl-2-naphthyl}propionic acid ν,ν,-diethyl Ν(Ν,Ν' -die thyl(s)-2-(6-hydroxy-2-naphthyl) Page 30 1301151 Sixth, the scope of application for patents propionate) and 5 ml D ratio. In the pyridine mixture, the mixture is allowed to stand at a temperature of about -5 ° C for a second predetermined time of about 12 hours, and then dried to obtain the optically active dovetail type liquid crystal material (s ) - 2 - { 6 - [ 4 - ( 4,-Oxygenated) benzamidine]-2 -naphthyl}anthracene, Ν'-diethylpropionic acid amide (N,Ν' - diethyl(s)-2-{6 -[4-(4' -alkoxyphenyl)benzoyloxy]-2-naphthyl}propionamide) (m = 10 〜15, m is an integer, alkoxy CmH2m+10-carbon number). 9. The method for producing an optically active dovetail type liquid crystal material according to claim 8, wherein the organic layer of the above step (2) is separated and washed with ice brine to form sodium sulphate (N a2 S 04) Go to the water. The manufacturing method of the optically active dovetail type liquid crystal material according to Item 8 of the patent application, wherein the organic layer of the above step (2) is dehydrated and concentrated, and then acetonitrile (acet ο nitri 1 e ) Crystallization to obtain the second intermediate (II) 〇 11. The method for producing an optically active dovetail type liquid crystal material according to claim 8, wherein the above step (3) is 4-(4'-alkoxyphenyl)benzoic acid (4-(4,-alkoxyphenyl) The benzoic acids can be obtained by the following steps: 3.62 g, 17 亳 molar 4'-hydroxybiphenyl-4-carboxylic acid and 250 ml of ethanol and 2. 02 g, 36. 07 mmol of potassium hydroxide (Κ0Η) and 0·5 g, 3.01 mmol of potassium iodide (KI) and 50 ml of distilled water, the mixture is added Page 31 1301151 VI. The patent application range is hot reflux for 1 hour; after that, 1 〇 ml, 51 1 mmol of alkyl bromide (CmH2m+1Br, m = 9~15, m is an integer) is added. The mixed mixture was heated and refluxed for about 12 hours; then, 1 % ml of a 10% aqueous potassium hydroxide solution was added to the mixture and heated to reflux for two hours. After cooling, it was acidified by adding a 5 % aqueous hydrochloric acid solution. A mixture is obtained by filtration to obtain a crude product which is washed with ice water (c ο 1 dwater) and recrystallized to give 4-(4,-alkyloxyphenyl) azo acid. The method for producing an optically active dovetail type liquid crystal material according to the above aspect, wherein the recrystallization step uses glacial acetic acid and absolute thanol. The method for producing an optically active dovetail type liquid crystal material according to the above, wherein the first intermediate (I) of the above step (1) can be separated by a chromatography method (c〇lumri chromatography over silica gel) ◦~2 30 mesh ASTM)) It is obtained by purifying methylene chloride/ethyl acetate (volume ratio of 8:2) as an eluate (e 1 uant ). 1 4. The optically active dovetail type liquid crystal material as described in claim 8 of the patent application_ The manufacturing method of the material, wherein the second intermediate (π) of the above step (2) can be passed through a c〇lumrl chromatography over silica gei (70~230 mesh ASTM), The gas decane/acetic acid B (the volume ratio of 8 : 2 ) was obtained as an eluate (e 1 uant) purification. Page 32 1301151___ VI. Patent Application No. 1 5 · A method for producing an optically active dovetail liquid crystal material, comprising the following steps: (1) 9.5 ml, 108·57 mmol of ethylene dichloride ( (C0C1) 2) Add 10 g of light-emitting (s)-(+)-2-(6-methoxy-2-naphthyl}propionic acid (10 g, 43.43 mmol) dissolved in 10 ml of dichlorohydrazine. (s)-( + )-2-(6-methoxy - 2-naphthyl )propionic acid), the final solution is stirred at the first reflux temperature for two hours to obtain (s -2-(6-methoxy-naphthyl}propionic acid chloride ((s)- 2-(6-methoxy-2-naphthyl) pr〇pionic acid chloride) crude product; dissolved in 10 ml of dichloro The crude product of (s)-2-(6-methoxy-2-naphthylpropionic acid chloride) in methane is added at a temperature of about 0. 22.33 ml, 126.8 5 mmol of N,Ν'-dipropylamine (HN(CH2CH2CH3)2) and 10 ml of triethyl ether dissolved in 30 ml of dichloromethane at °C. In a solution of triethylamine (TEA), the mixture is placed in warm After about 1 hour of the first predetermined time at about 5 ° C, it is dried and purified to obtain the first intermediate (I) (s)-2-(6-decyloxy-2-naphthyl}propionic acid. Ν,Ν'-dipropyl ester (Ν,Ν'-dipropyl (s)-2-(6-methoxy-2-naphthyl) propionate); (2) 8 g, 26.76 mmoles of the above steps ( 1) The obtained first intermediate (I)(s) - 2-(6-decyloxy-2-cacoyl}propionic acid N,N'-dipropyl hydrazine (N, Ν'-dipropyl (s)-2-(6-methoxy-2-naphthyl) propionate)) dissolved in 52.36 ml of methylene chloride and at -20 ° C with 5.24 ml of boron tribromide (BBrq: ^l, this Page 33 1301151___ VI. Scope of application The mixture is stirred at -20 °C for 5 minutes and at 0 °C for 40 minutes. After diluting with 1 0 4 · 7 ml of dioxane, the solution is poured. 1 〇 4 · 7 ml of saturated ~ mixture of ammonium chloride and 100 g of crushed ice, the organic layer is separated and washed with brine-ice, dehydrated and concentrated, then Crystallization to give the second intermediate (II)(s)-2-(6-carbyl-2-naphthyl}propanoate, Ν'-dipropyl ester (Ν,Ν'-dipropyl(s)-2 -(6-hydroxy-2-naphthyl)propionate ); and (3) 0.35 ml, 1.58 mmol of ethylene dichloride ((c〇C丨) 2) was added to 0.58 g, 1.05 mmol of 4- (4'-alkoxyphenyl benzoic acids) (mPBA, m = 9 〜13, m is an integer ·, alkoxy CinH2m+10- In the number of carbon atoms, the final solution was stirred at the second reflux temperature for two hours, and the remaining ethylene dichloride was removed by evaporation to obtain the crude product 4 - ( 4 ' - alkoxybenzene) benzoic acid chloride (4 — ( 4,-alkoxyphenyl)benzoic a Cid chloride), the crude product was dissolved in 3 ml of dichloromethane, and added to a solution of 0.3 g, 1.05 mmol, dissolved in 5 ml of dichlorohydrazine, stirred at a temperature of about 〇 ° C. Intermediate (h)(s) -2-(6-hydroxy-2-naphthyl}propionic acid N,N,-dipropyl ester (n,N,-dipropyl (s)-2-(6-hydroxy- 2-naphthyl) prop i〇nate) and 5 ml of a pyridine mixture, the mixture is placed at a temperature of about -5. After a second predetermined time of about 12 hours, the optically active yan is obtained by evaporation drying. 0 Tail type liquid crystal material (s) -2 - {6 - [4-(4'-pyroxybenzene) benzhydrazide] 2-naphthyl}(1^,N _propyl) propionate (N,Ν' - dipropyl(s) - 2-{6 - [4- (4' -alkoxyphenyl ) benzoyl oxy]-2-naphthyl }propanani id · e)(DPmPBNPA,m = 9~13, m is one Integer, which is alkoxy (aik〇xy) Page 34 1301151 VI. Patent application scope CmH2m+1〇-the number of carbon atoms) ° 1 6 · The manufacturing method of the optically active dovetail type liquid crystal material as described in claim 15 wherein the above step (1) After the organic layer was dehydrated and concentrated, it was recrystallized from acetonitrile (acet ο nitri 1 e) to know the first intermediate (II). 1 7 - The method for producing an optically active dovetail type liquid crystal material according to claim 15, wherein the above step (3) is 4 - (4'-pyroxybenzene)-benzoic acid (4-(4, -alkoxyphenyl)benzoic acids can be prepared by the following procedure: 3.62 g, 17 亳 molar 4,-hydroxydiphenyl-4-carboxylic acid and 250 love: Elevated ethanol Mixing with 2.02 g, 36.0 0 mmol of potassium hydroxide (K0H) and 0.5 gram, 3.2 mM potassium iodide (KI) and 50 ml of distilled water' The mixture was heated to reflux for 1 hour. After that, 10 ml of 51 lmol of alkyl bromide (Cm H2in+1 Br, m = 9 〜1 5, m is an integer) is added to the mixture and heated to reflux about 1 2 After that, 2 (10) ml of a 1% by weight aqueous solution of potassium hydroxide was added to the mixture to heat and reflux for two hours. After cooling, the mixture was acidified by adding a 5% aqueous hydrochloric acid solution, and filtered to obtain a crude product. c ο 1 dwater ) The crude product is recrystallized to give 4-(4'-alkoxyphenyl)benzoic acid. Page 35 (1) The method for producing a material, wherein the recrystallization step is glacial acetic acid. The optically active dovetail liquid crystal 1301151_____ according to claim 17 of the patent application scope, glacial acetic acid and Absolute ethane (absolute tha η ο 1) 〇1 9 · The method for producing an optically active dovetail type liquid crystal material according to claim 15, wherein the first intermediate (I) of the above step (1) is Through the column chromatography over silica gel (70~230 mesh ASTM), using dichlorohydrazine/ethyl acetate (volume ratio 8 ·· 2 ) as the eluate (e 1 uant) It is obtained by purification. The manufacturing method of the optically active dovetail type liquid crystal material according to Item 15 of the patent application, wherein the second intermediate (11) of the above step (2) can be separated by a color separation method of the Shixi rubber column ( Column chromatography over silica gel (70~230 mesh A STM)) was obtained by purifying eluant with dichlorohydrazine/ethyl acetate (volume ratio: 8:2).