TW300915B - Chiral organic alcohol and liquid crystal composition containing same - Google Patents

Abstract

A chiral organic compound having a structural formula as shown,where A is selected from H and S, R1 is C2-8 alkyl, m is inter 0-5, n is 0 or 1, *and** are chiral center, r is 0 or 1, when r=0, R2 is selected from H, C1-22 alkyl, aryl, hydroxyl-containing alkyl, phenol and biphenyl, when r=1, R2 is selected from C1-22 straight chain alkyl, m is inter 0-5, n is 0 or 1, p is 0 or 1, q is 0 or 1, and D and E which may be the same or different are selected from H and halide.

Description

Printed by the Central Sample Bureau of the Ministry of Economic Affairs, Zhengong Consumer Cooperative 300915 V. Description of the invention (1) The present invention relates to a photoactive organic alcohol and its derivative with two asymmetric centers' liquid crystal composition containing the photoactive compound And liquid crystal devices. Since the 1960s, liquid crystal displays have developed quite rapidly. This is due to the invention of new nematic liquid crystal materials, the discovery of the liquid crystal photoelectric effect, and the progress of the electronics industry. It has been developed from a simple display element used as an electronic watch to a display element used as a personal mold brain and can be further developed into a high-definition television (HDTV) display. Although the application level of liquid crystal display technology is very wide, it is undeniable that its contrast, viewing angle and display speed must be further improved. In practice, Meyer et al. Discovered a strong dielectric liquid crystal (RBMeyer, L. Strzelecki and P. Keller "Ferroelectric. Liquid Crystals" J. Physique Lett., 1975, 36, L-69 ), Which is a series of experiments on P-decyloxybenzylidene P'-amino 2-methylbutylcinnamate, confirming that the photoactive smectic C-phase liquid crystal is a strong dielectric. Since then, regarding The invention and application of this kind of liquid crystal became a challenging issue; in 1980, Clark and Lagerwall proposed a device that uses this liquid crystal, SSFLC optical switch (Surface-Stablized · Ferroelectric Liquid Crystal Light Valve), which is A new basic device of photoelectric technology (1 ^. 八 .0: 1 & partner, 8.1’.1 ^ 61 ^ 311, eight sub-chapters 1.?11>^ 丄 成., 1980,36,899), due to forced introduction Electrical liquid crystals have unique advantages in terms of switching speed and memorability. Therefore, the application of flat panel displays is currently the biggest demand. The ferroelectric properties of the ferroelectric liquid crystal mainly come from the liquid crystal molecules containing the paper. The size of the paper is suitable. China's sleepy family (CNS) grid (21〇X29) 7 male ϋ 83.3.10,000 (please read the notes on the back first (Consume this page) Order 〇00915 _ V. Description of the invention (2 The light active molecular part is printed by the Beigong Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. This part is manufactured by asymmetric synthesis and is used in display applications. Generally, a mixture of ferroelectric liquid crystals is used, so that a photoactive compound, regardless of whether it has a photoactive smectic C phase (Chiral Sc Phase), can be used as a photoactive substrate of a ferroelectric liquid crystal material Filler (Chiral Dopant), (W. Kuczynski, H. Stegemeyer, Chem. Phys. Lett., 1980, 70, 123; SMKelly, A. VilUger, Displays, 1990, 41), the photoactive compound contains a strong dielectric Liquid crystals, because of their asymmetric centers, have recently become one of the materials actively developed by nonlinear optical technology. Since lactic acid is a photoactive natural substance that is readily available and contains chemically easily changed functional groups: hydroxyl and carboxyl, Is It is often selected as a synthetic object that can meet the desired molecular structure, such as the conventional U.S. Patent Nos. 4,880,560; 4,852,977; 4,812,259; 4,556,727, etc. are related to photoactive lactic acid derivatives and their application to liquid crystal compositions and liquid crystal devices, The photoactive lactic acid derivatives disclosed in these conventional patents only include one asymmetric center, and their performance on the display still needs to be improved. The main object of the present invention is to provide a photoactive organic alcohol having two asymmetric centers and its Derivatives and novel ferroelectric liquid crystals; when they are applied to liquid crystal materials and liquid crystal devices, they can exhibit excellent properties. The reason is to achieve the above purpose, the structural formula of the photoactive organic matter with two asymmetric centers in the present invention for:

D

(Please read the note $ item on the back before filling this page) R2 C〇C> O ^^ r〇CH2-j ^ -A- (CH2) ir (〇VCH 中 -ί where Α is selected from the group consisting of oxygen and sulfur Atomic group; Ri is with -R. This paper scale uses Chinese national rubbing rate (CNS) A4 specification (2 丨 〇Χ25Ϊmm) 83. 3.10,000 A7 _ B7_____ V. Invention description (3) 2 to 8 Alkyl groups of carbon atoms; m is an integer of 0-5: η is 0 or 1 and * and ** are asymmetric centers; r is 0 or 1, and when r = 0, R2 is selected from the group consisting of hydrogen atoms, containing Alkyl, aryl, hydroxyl-containing alkyl, phenol or biphenol groups with 1 to 22 carbon atoms; when r = 1, R2 is a linear alkyl group with 1 to 22 carbon atoms and m is 0-5 Integer; η is 0 or 1: p is 0 or 1: q is 0 or 1; D and E are the same or different from the group including hydrogen and halogen atoms. When r = 0, the photoactive organic compound The structural formula is: R2OCH2-CH—A— (CH2) — (0) —CHj-CH—R, (ia) ch3 ch3 where A is selected from the group including oxygen and sulfur atoms; Ri is having 2 to 8 Alkyl group with carbon atom; R2 is selected from hydrogen atom, alkyl group with 1 to 22 carbon atoms, aryl group, hydroxyl-containing alkyl group, phenol group Or biphenol group: m is an integer of 0-5; η is 0 or 1; p is 0 or 1; q is 0 or 1 ,; D and E are the same or different from the group including hydrogen and halogen atoms》 When r = l, the structural formula of the photoactive organic compound is: (please read the notes on the back before filling this page)

Printed CH, CH by the Beigong Consumer Cooperative of the Central Bureau of Economic Affairs of the Ministry of Economic Affairs, where A is selected from the group including oxygen and sulfur atoms; Ri is an alkyl group having 2 to 8 carbon atoms; R2 is 1 to 22 carbon atoms Linear alkyl group of atoms, m is an integer of 0-5; η is 0 or 1; p is 0 or 1; q is 0 or 1; D and E are the same or different from the group including hydrogen and halogen atoms And * and ** are asymmetric centers. ίΊ 83. 3.10,000 This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (21〇X297 mm) Printed by the Ministry of Economic Affairs Central Bureau of Industry and Commerce MC Industrial and Consumer Cooperatives A7 B7 V. Description of invention (4) Structural formula (la ) Is a photoactive organic alcohol synthesized by synthesizing lactic acid and thiolactic acid; it is to first esterify lactic acid or thiolactate 'and then the hydroxyl group or hydrogenthio group in the lactate or thiolactic acid and the photoactive alkyl group Chiral alkly halides or alkyl sulfonates are connected by etherification and then reduced to organic alcohols. Monohenyl ether of hydroquinone or 4,4'-biphenol and the light produced The combination of active organic alcohols can be achieved through a substitution reaction, where the sulfonate of the photoactive organic alcohol is reacted with hydroquinone or 4,4'-biphenol monobenzyl ether respectively, and after hydrogenation, it can be prepared A photoactive compound containing hydroquinone and 4,4 '· biphenol is obtained. The photoactive organic compound containing hydroquinone and 4,4'-biphenol prepared according to the present invention can be used to manufacture a strong dielectric Liquid crystal, which uses esterification to combine the photoactive organic compounds containing hydroquinone with 4,4'-biphenol It is obtained by combining molecules of organic acids or acetyl halides with or without liquid crystal phase. The liquid crystal composition of the present invention may be a mixture containing formula (la) and / or formula (lb), or formula (la) And / or formula (lb) and other mixtures of smectic C phase liquid crystal or photoactive smectic C phase liquid crystal; the liquid crystal device provided by the present invention is arranged between two substrates by formula (la) and / or (lb) The formed liquid crystal composition, the liquid crystal material of the present invention can also be made into a liquid crystal optical switching element, an optical computing element or a non-linear optical material; the liquid crystal prepared by the organic compound with two asymmetric centers of the present invention can have Good liquid crystal material properties. The following 'this invention will be explained in detail with examples. Example 1: Synthesis of p-decyloxybenzoic acid Dissolve 2-11 g of potassium hydroxide in 50 ml of ethanol, add 2.6 g of p-hydroxyl silver paper The standard applies to the Chinese standard (CNS> A4 specification (210X297 mm) 83. 3.10,000 (please read the precautions on the back before filling in this page) Order A7 B7 5. Description of invention (5) • Benzoic acid, Add 5.8ml of bromodecane and heat at reflux for 15 hours, After adding 25ml of 10% aqueous sodium hydroxide solution and refluxing for 2 hours to cool, adding concentrated hydrochloric acid to make acid, filtering and recrystallizing with ethanol to obtain the product 3.8g (yield 73%). Example 2: p-dodecyloxybenzene Synthesis of formic acid Dissolve 4.17 g of potassium hydroxide in 100 mL of ethanol, then add 5.03 g of p-hydroxybibenzoic acid and 12.2 ml of dodecane bromide, reflux for 15 hours, then add 50 mL of 10% aqueous sodium hydroxide solution and reflux After heating for 2 hours and cooling, concentrated hydrochloric acid was added to make it acidic, then filtered, and recrystallized from ethanol to obtain 7.66 g of product (yield 70%). Example 3: Synthesis of 4,4'-octyloxybibenzoic acid Dissolve 1.15 g of potassium hydroxide in 100 ml of ethanol, add 2 g of 4,4'-hydroxybibenzoic acid, then add 2.45 ml of octane bromide, Heat at reflux for 16 hours, then add 50 ml of 10% aqueous sodium hydroxide solution and heat at reflux for 2 hours to cool, add concentrated hydrochloric acid to make acid, then filter, recrystallize with ethanol to obtain 1.95 g of product (64% yield). Printed by the Central Sample Standardization Bureau of the Ministry of Economic Affairs-Industrial and Consumer Cooperatives (please read the $ item on the back and fill in this page) Example 4: Synthesis of 4,4'_nonoxybibenzoic acid dissolve 1.12 grams of potassium hydroxide 100ml of ethanol, add 2g of 4,4'-hydroxybibenzoic acid, then add 2.3ml of nonane bromide, heat at reflux for 19 hours, then add 50ml of 10% aqueous sodium hydroxide solution and reflux for 2 hours to cool, add concentrated hydrochloric acid After acidification, it is filtered and recrystallized with ethanol to obtain the product 2.18 g (yield —-? ---:-The paper size is based on the standard (CNS) A4 specification (210X297mm) 83 . 3.10,000 A7 _______B7_ V. Description of the invention (6) 69%) °

I Example 5: Synthesis of 2 (S)-[2 (S) _methylbutoxy] ethyl propionate Combine 7.2 g of ethyl lactate, add 14.14 g (S) -l-iodo-2-methyl A mixture of butyl butyl oxide and 17 g of silver oxide was heated and stirred at 70 ° C. for 12 hours, taken out for filtration, and the liquid was purified by distillation under reduced pressure to obtain 4.8 g of product (yield 52%). [a] S = -56.3. , (C = 1.05, C2H5〇H) Example 6: Preparation of formula (la), where A = 0, m and η and 0, RpH »R2 = C2H5 4.8 g 2 (S)-[2 (S)- Methylbutoxy] ethyl propionate was dissolved in ether, and then a solution of lithium aluminum hydride in ether was added dropwise with stirring. After stirring for 7 hours, a little water was added and extracted with dichloromethane. The organic layer was concentrated after Purification by column chromatography gave 2.8 g of the final product (yield 77%). [a] S = 20.2. , (C = 1.01, C2H5〇H) Example 7: Preparation of formula (la), where A = 0, m and η are 0, ---------- \ ------ 1Τ ------ ^-* (Read the interim $ item on the back and then fill in this page)

0.3g of 2 (S)-[2 (S) -methylbutoxy] propanol was dissolved in pyridine, and 0.73g of tosylate was added at 0 ° C. After the reaction is complete, add a small amount of water and stir for 1 hour, then extract with ether, then wash the ether phase with 10% hydrochloric acid solution, saturated sodium bicarbonate solution and water, and then dry and concentrate with sodium sulfate to obtain the product 0.68 g (yield 95 %). [a] i > ° = -1.5. , (C = 1.04 'C2H5OH) Example 8: Preparation of formula (la), where A = 0, m and η are 0' K2H5, this paper scale uses the Chinese National Standard (CNS) Α4 present grid (210X297 public %) 83. 3.10,000 Printed by the Central Ministry of Economic Affairs, Central Economic and Trade Consumer Cooperative A7 ___B7 __ 5. Description of the invention (7_) R2 = © -CH ^ °-< 0 > 0.46 grams of hydroquinone T ether Dissolve in sodium hydroxide (0.2 g) in ethanol solution, add 0.68 g of the sulfonate prepared in Example 7 under reflux for 24 hours, t. Extract with dichloromethane and water, concentrate the extract and purify by column chromatography 0.18 g of the final product was obtained (yield 70%). [a] g = -2.0 °, (C = 1.00, c2H5〇H) Example 9: Preparation of formula (la), where A = 0, m and η are 0, R1 =: C2H5, r2 = h〇- © -Dissolve 1.21 g of the product from Example 8 in an ethanol solution. After the hydrogenation reaction, purify by column chromatography to obtain the final product 0.72 g (yield 76%). [α] ί ?, = -2.2. , (C = 0.98 > C2H5〇H) Example 10: Preparation of formula (lb), where A = 0, m, n, p and q are Ο, Κ2Η5, R2 = Cl〇H21 in 98.5 mg Example 9 The resulting product, 105 mg of p-decyloxycarboxylic acid, 6.1 mg of p-dimethylaminopyridine and 85.5 mg of 1,3-biscyclohexylcarbodiimide, were added 4 ml of methylene chloride at room temperature After stirring, after the reaction was completed, it was filtered and concentrated, and then purified by column chromatography to obtain the final product 118 mg (yield 62%). [a] S = -2.5. , (C = 0.48, C2H5OH) Example 11: Preparation of formula (lb), where A = 0, D = H, m, η, p and q are 〇,

Rl = C2H5, R2 = C 丨 2Η25 -9 ----- This paper scale uses Chinese National Standard (CNS) A4 said grid (210X297mm) 83.3.! 〇, 〇〇〇 (please read the note on the back first Please fill in this page again) -Subscribe J—Zhongwei Sample Preparatory Bureau of the Ministry of Economic Affairs; A7 B7 Printed by Industrial and Consumer Cooperatives 5. Description of Invention (8) According to the method of Example 10, from 0.26 g of p-dodecyloxybenzoic acid With 0.21 g of the product obtained in Example 9, 0.32 g of product (yield 70%) was prepared ^ '1: [α] $ = -2.2. , (C = 1.01, C2H5OH) Example 12: Preparation of formula (lb), where A = 0, D = H, m, η and q are 〇, p = l > Rl = C2Hs > R2 = C8Hl7 According to the example In the method of 10, 0.11 g of product (60% yield) was prepared from 0.1 g of 4,4′-octyloxybiphenyl, acid and 82 mg of the product obtained in Example 9. [a] 2D. = -4_5. , (C = 0.1l, CH3C13) Example 13: Preparation of formula (I b), where a = 0, D = H, m, η and q are Ο, ρ = 1 * Rl = C2Hs · R2 = C9Hl9 According to the example In the method 10, 0.31 g of product (72% yield) was prepared from 0.27 g of 4,4′-anyoxybibenzoic acid and 0.2 g of the product obtained in Example 9. [a] 2 ». = -8.30, (C = 1.0, CH3CI3) Example 14. Preparation of formula (lb) where A = 0, D = H, m, η and q are Ο, P = 1 1 Rl = C2H5 > R2 = Cl 〇H2l According to the method of Example 10, 0.2 g of the product obtained in Example 9 was prepared from 0.23 g of 4,4′-decoxybibenzoic acid and 0.17 g of the product obtained in Example 9 (yield 53%). [a] g = -5.40, (C = 1.09, CHCI3) Example 15: Preparation of formula (lb), where A = 0, D = H, m, η and q are 0, P = 1 * Rl = C2Hs' R2 = Cl2H25 According to the method of Example 10, 0.25 g of product was prepared from 0.23 g of 4,4'-dodecyloxybenzoic acid and 0.16 g of the product obtained in Example 9 CNS) A4 specification (2 丨 0> < 2 to mm) 83. 3.10,000 ------------ ^ ------ SET ------ ^ • > * (Please read the note $ item on the back of Jing Jing first and then fill in this page) A7 300915 _b7_ Printed by the Central Ministry of Economic Affairs Consumer Cooperatives of the Ministry of Economic Affairs A5 300915 _b7_ V. Description of invention (9) 69%) 〇 [α] Include = -11 -60, (C = 1.00, CHCI3) The crystal phase change of the photoactive liquid crystal prepared above is shown in Table 1 below: Table 1 R2 P 氺 氺 氺 氺 相 和 相 变 温度 (° C) C Sb Sc * Sa I C.〇H2! 0 SS • 28-(· 17) (· 22) • (Example 10) C12H25 0 SS • 34 — (· 19) (· 30) (Example 11) GH.7 1 SS • 64 — • 121 • 158 (Example 12) C9H19 1 SS • 74-• 130 • 151 (Example 13) C10H21 1 SS • 61 — • 121 • 140 (Example 14) C12H25 1 SS • 09-• 127 • 137 (Example 15) C stands for solid. Sb represents the smectic B phase, S3 represents the photoactive smectic C phase, Sa represents the smectic A phase, I represents the liquid, and () represents the single-variable liquid crystal phase. In summary, I believe that your review committee has a fairly detailed understanding of the present invention, and the present invention can indeed achieve the desired effect as disclosed by the disclosed embodiments. It is in line with practical use, and has not been publicly disclosed before the application for this case. New patent applications, such as novelty, practicality, progress, etc., file patent applications in accordance with the law. However, the above is only one of the preferred embodiments of the present invention, and various changes and modifications made by those who are familiar with this skill in accordance with the spirit of the present invention should still be included in the patent scope of this case. -Η- This paper scale is applicable to the Chinese National Standard (CNS) Α4 said grid (210X297mm) 83.3.10,000 (please read the $ item on the back and fill in this page)

Claims (1)

ABCD r2 Patent application range No. 8110353 The second amendment to the patent application range ~ A photoactive organic compound, which has the following general formula: DE coo ^^ O ^ rwH2 ^ HA- (cH2) ~ (〇)! RCH3'ifH ~ Ri Guang tH, CH3 where A is selected from the group including oxygen and sulfur atoms; Ri is an alkyl group having 1 to 2 carbon atoms; m is an integer of 0-5; η is 0 or 1 and * and ** are asymmetric centers; r is 0 or 1, and when r = 0, R2 is selected from hydrogen atoms, alkyl groups containing 1 to 22 carbon atoms, aryl groups, and hydroxyl groups When the alkyl, phenol or biphenol r = l, R2 is a linear alkyl group containing 1 to 22 carbon atoms, m is an integer of 0-5; η is 0 or 1; p is 〇 or 1: q is 0 or 1; D and E are the same or different and are selected from the group including hydrogen and halogen atoms. 2. The photoactive organic compound as described in item 1 of the patent application, where r is 0. 3. The photoactive organic compound as described in item 2 of the patent application, wherein Rl is a hydrogen atom, hydroquinone group and 4,4′-biphenol group. 4. The photoactive organic compound as described in item 2 of the patent application, where A is an oxygen atom. 5. The photoactive organic compound as described in item 3 of the patent application, wherein A is an oxygen atom. 6. The photoactive organic compound as described in item 2 of the patent application, where m and η are 0. 7. The photoactive organic compound as described in item 3 of the patent application scope, where αχ. The paper size is applicable to the Chinese National Standard (CNS > Α4 present grid (210Χ297mm) (Please read the precautions on the back before filling in this Page) Τ The Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs printed the ABCD. The Employee Consumer Cooperative of the Central Bureau of Economic Affairs of the Ministry of Economic Affairs printed π and the patent application ranges m and η are 0. 8. Light activity as described in item 2 of the patent application Organic compound, where Ri is ethyl. 9. The photoactive organic compound as described in item 3 of the patent application, where Ri is ethyl. 10. The photoactive organic compound as described in item 1 of the patent application, wherein Γ is 1. 11. The photoactive organic compound as described in item 10 of the patent application scope, wherein Rl is a hydrogen atom, hydroquinone group and 4,4'-biphenol group. 12. As the patent application section The photoactive organic compound according to item 10, wherein A is an oxygen atom. 13. The photoactive organic compound according to item 11 of the patent application, where A is an oxygen atom. 14. As described in item 10 of the patent application Recount The photoactive organic compound, where m and η are 0. 15. The photoactive organic compound as described in item 11 of the patent application, where m and η are 0. 16_ The light as described in item 10 of the patent application Active organic compound, where Ri is ethyl. 17. The photoactive organic compound as described in item 11 of the patent application, where Rl is ethyl. 1 8. The photoactive organic compound as described in item 1 of the patent application , With the following molecular formula: --η- This paper scale is applicable to the Chinese National Standard (CNS) Α4 specification (210Χ297mm) (please read the precautions on the back before filling this page), νβ A8 B8 C8 D8 1 ^ 0915, apply Patent scope HOCHf-CH-OCH2-CH-C2H5 CH3 CH3 19 · The photoactive organic compound as described in item 1 of the patent application scope has the following molecular formula: H〇-och2-ch-och2-ch-c2h5 ch3 ch3 2Q · The photoactive organic compound as described in item 1 of the patent application has the following molecular formula: — CH-och2-ch—c2h5 CH3 CH3 21 · The photoactive organic compound as described in item 1 of the patent application has the following molecular formula (Please read the precautions on the back before filling out this page) • ΙΊ 汉 2〇c〇〇 ~ 《〉 — OCH2 ~ CH—OCH, < fH-C2H5 CH, printed by the Central Consumer Agency of the Ministry of Economic Affairs, Consumer Cooperative 22 · The photoactive organic compound as described in item 1 of the patent application has the following molecular formula: COO OCH2-CH-OCH2-^ H—c2h5 CH3 ch3 23 · $ α The photoactive organic compound as described in item 1 of the patent application , With the following molecular formula: r2o coo Hj-CH—OCH2-CH—C2H5 CH, CH, AJL · This paper scale is applicable to the Chinese standard (CNS> A4 present format (210 X 297 mm) A8 B8 C8 D8 〇〇09ίδ, the scope of patent application 24.-A photoactive liquid crystal composition, the composition containing 1 to 35% by weight of the following formula of the photoactive organic compound, 'Lh3 ch3 where A is selected from the group consisting of oxygen and A group of sulfur atoms; Ri is an alkyl group having 2 to 8 carbon atoms; m is an integer of 0-5; η is 0 or 1 and * and ** are asymmetric centers; r is 0 or 1, and r = At 0, R2 is selected from hydrogen atoms, alkyl groups containing 1 to 22 carbon atoms, aryl groups, hydroxyl-containing alkyl groups, phenol groups or biphenol groups; when r = 1, R2 is 1 to 22 carbon atoms Straight chain alkyl, m is an integer of 0-5; η is 0 or 1; p is 0 or 1; q is 0 or 1; D and E are the same or different from the group including hydrogen and halogen atoms: And the composition can be selectively added to the liquid crystal compound containing smectic C phase or the liquid crystal compound containing photoactive smectic C phase. (Please read the precautions on the back before filling in this page) Order Printed by the Staff Consumer Cooperative of the Central Bureau of Economic Development of the Ministry of Economic Affairs This paper standard is applicable to the Chinese National Standard (CNS) A4 (210X297mm)