TW209212B - Photoactive lactate liquid crystal - Google Patents

Abstract

A photoactive lactate liquid crystal having the following formula: (see claim 1) in which A is selected from the atom of O and S; B is selected from the group of -(CH2)m- and -(CH2)n-O-; R1 is selected from the group of aloxy, aryloxy, hydroxy with 2 to 8 carbons and halide; R2 is an alkyl group with 2 to 8 carbons; m=0-4, n=2-5, * is a chiral center.

Description

A6

ίί * * R1 ~ C ~ P h ~ AB-CH2-C H-R2 (la) CH3 CH3 where 4 is selected from the group including gas and sulfur atoms; β is selected from the group containing -Γ, one and -f C / y / nO, · \ is a group with 2 to S broken atoms of oxy, aryl radon, hydroxyl and halogen atoms in the case of self-corruption to 22 broken atoms; ^ is an integer of 0 to 4 ; N is an integer from 2 to 5 and * is the asymmetric center. Preferably, in the formula (Jaj, \ may be selected from a gas group, a gas group, a gas group, a butane group, a p-diphenol group, a 4,4′-biphenol group, a hydroxyl group or a gas atom, Or / horse oxygen, son, or β A- (CH2) m-and m is zero, or R2 is dagger group. The aforementioned light-active lactoprene derivatives can be synthetically produced by lactopyridine or thiolactar, which is the first Esterification of keratin or thiolactar, and then the m group or ^ • thio group in the keratin or thiolactar with the light-active halogen halide fc / 77 · ra 7 a 7 ”7 ha 7? · Desj is connected by mystery, and then becomes organic acid by saponification, and the acyl group can be obtained by reacting the corresponding organic compound. The organic compound or furnace-based halogen prepared according to the present invention is used to manufacture photoactive liquid crystals Material, which is obtained by combining the organic compound or compound with a m-based molecule whether or not having a liquid crystal phase by esterification. The photoactive liquid crystal material prepared according to this method is shown in the following formula ： (Please read the matters on the back first and then fill out this page) k. • Take ”• Line · Printed by the Central Bureau of Economic Affairs of the Ministry of Economic Affairs

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Ping 4 (2i〇X297 匁) Printed by the Central Bureau of Standards of the Ministry of Economic Affairs A6 ______B6 V. Description of the invention () The present invention relates to a photoactive lactoprene derivative, a liquid crystal composition and a liquid crystal device containing the photoactive papillary derivative . Since the 1960s, liquid crystal display technology has developed quite rapidly. This is due to the new nematic (the invention of nematicj liquid crystal materials, the new discovery of the liquid crystal photoelectric effect, and the progress of the electronics industry. Through these three different technologies The combination of science and technology in the field is a great expansion liquid; the application field of Jingyin display technology has developed from a simple display element as an electronic watch to a display element for a personal computer, and can be further developed into a On the display of high-definition TV, although the application level of liquid crystal display technology is very wasteful, it is inevitable that its contrast, viewing angle and speed of display all need further improvement; in order to eliminate these Disadvantages, many remedial measures need to be added to the circuit, so the production cost is increased, and the cost of the flat panel display used to manufacture TVs, oscilloscopes and computers increases, in addition, it also raises the technical layer :: the difficulty is not good. , In J975, Weyer et al discovered a strong dielectric ^^ (RBMeyer, L. Liebert, L. Strzeleckiand P. Keller " Ferroelectric L iquid Crystals " J. Physique Lett., 19/5,%, L-69J, which is a series of experiments on p-decylaminobenzylidene p’-amino t-methylcinnamon cinnamidine, It has been confirmed that the photoactive smectic liquid crystal is ferroelectric. Since then, the invention and application of this liquid crystal have become a challenging R & D topic. · In J9S0, C7ar / c and Lagerwan proposed the application of the liquid crystal Device, namely · SSfLC optical switch fSt / rface-Stabn / zec / ferroe / ectrfc L7.gu7_ c / Oysita7 / a bu e), this is a new basic device of photoelectric technology (NAClark, STLagerwall, Appl. Phys . Lett., 1980, 36, S99), because of the unique advantages of ferroelectric liquid crystals in terms of switching speed and memory, it is currently the biggest demand for flat panel displays. (Please listen first Read the precautions on the back and then fill out this page) • Installed • • Ordered •. Line • A 4 (210X297 public issue)

Printed by the Central Bureau of the Ministry of Economic Affairs. 5. Description of the invention (_) Strong dielectric properties "The strong dielectric properties of crystals mainly come from the photoactive molecular parts in the liquid crystal molecules. The parts are manufactured by asymmetric synthesis. In the application of displays, the mixture of ferroelectric liquid crystals is generally used, so that the photoactive compound, regardless of whether it has a photoactive layer or not, can be used as the photoactive filling rc of the ferroelectric liquid crystal material. / n > a7) > (y. Kuczynski, H. Stegemeyer, Chem. Phys. Lett., 1980.7〇, 123; F. Leenhouts, SM Kelly, A. Villiger, DTsp / ays, J99〇, Wj, Photoactive compounds include ferroelectric liquid crystals, which have recently become a material actively developed by nonlinear optical technology due to their asymmetric centers-(H. Kapitza, R. Zentel, RJ Twieg, C. Nguyen, SUVallerien, F. Kremer, CG Willson, Advanced Materials, 1990, 2_, 539) 〇Because it is a light-active natural substance that is readily available and contains chemically susceptible functional groups-hydroxyl and ketyl groups, it is often used by Siam as Synthesize objects that fit the desired molecular structure, as is known U.S. Patent Nos. 4,880,560: 4,852, 977; 4'S_Z2,259; 4,556,727, etc. are related to optically active milk derivatives and their application to liquid crystal compositions and liquid crystal devices. The light active milk disclosed in these conventional patents The derivative includes only one asymmetric center, and its performance on the escort device still needs to be improved. Therefore, the object island of the present invention provides a rutile derivative with two asymmetric centers and a novel ferroelectric liquid crystal • · When applied to liquid crystal materials and liquid crystal devices, it can exhibit excellent properties. The structural formula of the photoactive lactic acid derivative with two asymmetric centers of the present invention is 7 · (Please read the precautions on the back side before filling in this Page). Installed. • Ordered • • Green • A 4 (210X 297 public) Printed by the Central Bureau of Economic Affairs of the Ministry of Economic Development V. Description of invention () The second is the group that includes gas and sulfur atoms. —⑴Factory _ 2 ί / ~; η ~ 〇 '' ~ is an alkyl group with β _ broken atom, WL two integer, " is the integer H of Bu 5 or "is 0 or" and f is the same or Differently included in the gas and masculine atom groups, ~ ~ contains J to W Atoms have a straight bond burned group and * is an asymmetric center. In the formula, calibrated, ~ is a straight bond burned group containing 3 to 2 broken atoms, or 4 calibrated is a gas atom, or s can be a, rw, nn ^ Γ ^ ϋ r is ~ f Ch2, and m is zero, and f τ is gas or „, son, ^ 7 or g is j, and heart is ^ base. The liquid crystal composition of the present invention may be a mixture containing at least one of formula ⑽ or one of formulas or formula ⑼ and "6; a mixture of formula… domain formula ⑽ or… and a layer-containing C-phase liquid crystal or optical activity A layer of e-phase liquid crystal mixture. The liquid crystal device provided by the present invention is a liquid crystal composition formed by the formula (⑷ or formula or formula fiaj _) between two substrates. The liquid crystal composition of the present invention can also be made into a liquid crystal Liquid crystal composition, or non-linear optical material, and when the formula " phantom and f is selected from nitro, with excellent results, the liquid crystal composition prepared from the photoactive lactoplast derivative having two asymmetric centers of the present invention , Can have better properties of liquid crystal materials. The foregoing and other objects and features of the present invention will be more apparent through the following description of the preferred embodiments. It should be understood that these descriptions are only for illustrative purposes. The result of the operation of the invention in a better situation, rather than attempting to limit the scope of the invention, and other modifications and changes that do not detract from the spirit of the invention, are all protected by the present invention. f production type " aj 4 Bird oxygen, β is _ (C // 2 ~ —and ΛΪ is the cable, R j is 0 C $ // 5, /? $ Is C 2 ^ J (J.J8 gmmol)) (S) -Lactose G ester, 3.00 g

D Please read the notes on the back of the performance first and then fill out this page) • Pack.-Order. • Line · f 4 (210X297 Super)

Fifth, the instructions () millimoles of butyryl butyl iodide and 4 grams of 7J millimoles) vaporized silver, mixed in sot: heating and stirring for one hour, and then, add σg of a Glycidyl iodide and gram of silver oxide for a total of two times, and then heated and stirred for "3 hours (S0 ° C), the flask was cooled to room temperature, the product was eluted with 1 ether (4 x 50 ml>), mixed G ether solution, Wash twice with 50ml of / CO //, then wash twice with 5 £? Ml of fresh water, dry the organic layer with γ-magnesium sulfate, and evaporate to dryness to obtain j.3j grams of crude product, divided by color layer Method (5 / hexane / vinegar GS purpose 9: 』) purification to obtain 0.S4 grams of product, a yield of 45% 〇 / · α ~ J7 = -50.9. (C = _Z.OJ, C // £; 73), the results of WW /? Analysis are as follows: δ I 4.16 | 3.88 | 3.40 \ 3.05 \ 1.64 \ 1.36 | 1.25 | 1.13 [0.85 \ Painting: —— | —— | -1—— | —— | —— | —— | —— | ——Η .¾. N \ 2Η \ 1Η \ 1Η \ 1Η \ 1Η \ 4Η \ 3Η \ 1Η \ 6Η \ Example 2 In iJaJ, / 1 is gas and β is a f \ —and m Rj OH, R2 4 C2H5) · " · Dissolve the product of Example 1 of 0.1 g M. 5 mmole j in i 0 ml j · In the mixed solution with G%, heat at reflux for J hours, under ice water cooling and mixing, drip dredged drip into the solution dropwise to make it drastic, remove G drunk, and then use G ether 0X50 Milliliter J extracts the product in the water layer, mixes the resulting L ether solution, adds magnesium thiosulfate to dry, removes G ether, and obtains 0.70 grams of organic tartar product, with a production year of 95%, [a] D17 = -14.6. (C = 1.02, CHC13), I, X NMR analysis results are as follows. · Printed by the Central Bureau of Economics of the Ministry of Economic Affairs, 5 | 3.93 | 3.43 | 3.15 | 1.62 | 1.41 | 1.13 \ 0.86 | LHNMR: — | -1-1 -\ — \-1-1-1- H \ 1H \ 1H \ 1H \ 1H \ 4H \ 1H \ 6H \ f 4 (210X297 芨) A6 _________ B6 V. Description of invention () Example 2 (manufacturing type (A) In which, 4 is gas, β is _ (Μ ?, one is m and cable is β, β is argon, household and Q are all zero, the heart is c2 " 5 and /? 3 ^ cs / yJ7 >) will be 4.6 gm Ear ”uranium slices, put in 3 90 ml of mellow (9%) and stir until completely dissolved, and then add jJS grams of _ hydroxy hydroxy stupid U U millimolar) After the sample is pulled, add μ.3 grams ( j〇5mMole bromide_octane, reflux for 4 hours, add 30ml of "%" (0 ~ called) and then reflux for 2 hours, cool, degrade with strong Qizheng, meet J 9. g grams of solid, The yield is 79%, and then recrystallized with G yeast to obtain ^ • ^ grams of crystals with an eight yield of "%. Take 2.5 grams of millimoles) The product (jr) obtained in the previous step is dissolved in the milliliter. J5 millimole mellow was slowly added to the aforementioned solution during J〇 minutes, and then stirred at room temperature for 3 hours , Remove excess grass with a vacuum system of about buckle / nm / ygf, return to normal pressure with dry nitrogen and fluoride, and add 5 ml of difluoromethane to make a solution 4. Take another p-hydroxypandancarbyl ether (ij mmol) Bound) Dissolve in the solution of 2 ml of pyridine and j milli-juice two-gas embankment, and become solution 0. Solution β is slowly added to the solution in 5 minutes of sulfonium to see that Zhejiang and Zhejiang form a white solid, accelerated stirring, after 30 minutes , Remove the thorn, recrystallize with G alcohol to obtain 3.8 g of solid (18% yield is rib%). Mix 2.J6 g (5 mmol of J solid with 35 ml of G alcohol and 0.9 g of Pd / C Π MJ After the argonation reaction is complete, the M / C is filtered off and the crude product is obtained by removing the solvent. The crude product is recrystallized with ethyl acetate and ethyl acetate, the solid part is collected, and dried to obtain _Z.4 g of product HU), the yield is S2%. The printing is printed by the quasi-economic bureau of economics and fire ^ · (please read the precautions on the back and then fill out this page) • Order. Line. Will 0.6 g f 3.75 Laoqier J Example 2 The product was dissolved in J 0¾ outside stupid, another take the sugar gas (5 milligrams) in 5 minutes shovel level added to the aforementioned solution, with the declaration for 3 hours Sun Sun 30m / n // {7 Classic empty system-large-order multiple division -V-secret gas, return to Changen with dry nitrogen and fluoride, add 5¾ to open dichloroxanthine for backup 0 甲 4 (210X297 Gongchu) A6 B6 203312 V. Description of invention () Also dissolve the product ΠΒ j in Jml pyridine In the mixed solution of dichloromethane and milliliter, stir and dissolve evenly, add to the stirring solution mentioned in the previous paragraph within minutes, after stirring at room temperature for 2 hours, the reaction is completed, the solvent is removed, and the product is dissolved in Zhengji embankment In the column chromatography, the final product was obtained after removing the solvent (f2.78 millimoles), the yield was 74%, _ to .6. C // C73), w / VW /? The analysis results are as follows ·· lu, δ | 8.1 \ 7.2 \ 6.95 \ 4.17 \ 4.0 \ 3.55 \ 3.25 \ 1.9—1.65 |

Η ~ _: -π——I——I——I——h—η——I__L

H \ 2H \ 4H \ 2H \ 1H \ 2H \ 1H \ 1H \ 3H I

1 5 丨 j.6 ~ J.J I 0.9 I

H-NHR: —I --— I I

H \ 15H I 9 // I In the fourth embodiment, in the formula I, Z is gas, β-U-fc / ^ ~-and is said to be, 0 is argon, p is 彖, only C / 5 and / ^ is c 2H25) 1 According to the method of Example 2, replace the bromooctane with j-ododecane, and replace the p-hydroxybenzylamine with a benzylbenzyl ^ benzylpyridine, to prepare the desired gas-end inflammation product, [CX] 〇25 = · 27 4. (C = 1 〇〇, CHC13), u _ fractional prayer results are as follows: W · | 7.00 | 4.16 | J.99 | J.5S | 3.24 \ 1.9 ^ l.〇 | 〇g3 1 1 —I-1-1 — ~~-~~~ u_L „The Central Committee for Economics and Economics printed it as zero Μ 2H \ \ 4H 丨 2H 丨 w 丨 2ff 丨 lf / 丨 lf {Example 5 (In the production formula (ia), ^ is gas, 5 is one (, ~ is one < 2 > —0 // and the heart is

26H I 9H 2 and f 4 (210X297 ^ '^) 20 like 3 A6 __ B6 V. Description of invention () (please read the notices on the surface before filling in the hundred) According to the method of the third embodiment, it will be implemented by itself The organic compound obtained in Example 2 becomes acetyl chloride, and then 4-carbazinyl is added to the reaction, and the resulting product is subjected to argonation to remove the carbyl group to obtain the desired product, -M.3. (C = CHC13) 〇 Example 6 According to the light produced by the present invention, the liquid crystal phase of the active liquid crystal changes as shown in the following table

R3 P * Phase and phase change culmination c nr sc • k SA ^ 1 C ^ 17 0 s, s • 36.6 — (• 29.0). 2 C1 ^ 25 1 s, s * 81.8 • 137.1 • 149.0 · 3 C 1 (/ 121 1 S, s • 76.0 • 139.0 • 154.9 • 4 C ^ 19 1 S, s • 75.2 • 139.6 • 158.1. C represents the solid state, represents the photoactive smectic phase C, and represents light / 1 active smear / 1 The phase represents the liquid state, and () represents the single-variable liquid crystal phase. The Central Bureau of Economic Affairs of the Ministry of Economic Affairs printed 4 (210X297 Gongji)

Claims (1)

Af7c | Dl report six, apply for a patent model ® No. S0i (MSJ5 patent application model revisions J. Guanghao this life Rujiao derivatives, which is represented by the following formula: Date of amendment: .5 · 0 II * * Rj—C —CH—A—B—⑶ 一 CH—Ra (la) ch ch where / 1 is -Ο or -S '-, β is selected from the group containing —f. C Η 2 —and — 丨 C Η 2) ○ ** " one of the groups; /? Is selected from the group containing alkoxy groups, aryloxy groups, hydroxyl groups and halogen atoms containing ー to M breaking atoms; /? 2 is the group with 2 to S breaking atoms Embankment; m is an integer from 0 to 4, · η is an integer from 2 to 5 and * is an asymmetric center. 2. The photoactive lactoplast derivative according to item J of the patent application park, which is selected from the group consisting of methoxy, Goxy, propanyl, butanyl, p-dibenol, valerane 4, -One of the biphenol group, hydroxyl group and gas atom group. 3. The photoactive lactoprene derivative, which is represented by the following formula:… Bu:……… f ............ ..... Xiang. (Please flash the back first < precautions and then -t this W) .JiT. 〇-〇-γ-Α-Β ~~ 〇Η2 ~ 〇H-R2 (lb) CH3 [h3 where d is -0-. Or -S-; β is selected from the group containing one> (CH2-)- ^ One and one of the groups of ~ 代 Η ^ _Q; is an alkyl group with 2 to 8 broken atoms; the whole teaching of ^ ~ 4; / 7 is 2 ~ 5 and an integer, P is 〇 or 7; ^ is 〇 Electricity, D; and f are selected from the same or different groups including argon and the atomic group of atoms. A > 3 is a straight alkyl group containing J to 22 broken atoms and * is an asymmetric center. f * 1 (2l〇v 297. Itch .. The Ministry of Economic Affairs Central Rubbing Bureau Printing Disaster. A7 B7 C7 D7 VI. Application for a patent Fan Ji (Yi Fan Zhi Li Fan _ 3 Si Shuguang Guang (the material, which is Straight halo group containing 3 to 5 broken atoms. 5. According to the patent application, any of the items 3 or 4 of the patent-any of the light-active lactoprene derivatives, 4 of which are gas atoms. The light-active milk cunning ΛΪ * ilL i A ι Bio A described in item 3 or 4 is CH2 ~ ^ ~ m ', and ΛΙ is zero. According to any one of the items 3 or 4 of the patent application garden The light-active milk-derived derivative, wherein Z) and f are gas or gas atoms. The light-active milk-derived derivative described in any one of the patent application No. ^ 3 or 彳, whose towel ^ is hexyl. 9. According to the patent application patent range ^^, or 4 independent-miscellaneous photoactive lactoplast derivatives, where ^ is an oxygen atom, β is and \ is ethyl. According to item j of the patent application scope Photoactive lactic acid derivative, which is represented by the following formula: CH (please read the note on the back and fill in the dome page) • K.-定 · Hf2 ° ~ cC //-0- C // 2- c //-C ^ W5 CH. CH. 11 3 ^ " 3 where Table asymmetry center O According to the light miscellaneous milk contact object described in item 4 of the application 4 patent model, it is represented by the following formula. -° ^ 5 CH 3 73 f Ί (2) 〇 \ 〇97: · 'if \ Α7 Β7 C7 D7 VI. Application for special rules, where * represents the asymmetric center 12. According to the application of the patent application The light-active lactopie derivative, represented by the following formula, 0II * * C1—C ~ C H-0-CH2-CH-C ^ 5 CH 3 CH 3 where * represents the asymmetric center. -Z 3. Basis The light-active milk derivatives described in item 3 of the patent application range are represented by the following formula: Ο C00 〇II 9r * -0—C—CH—0—CH2-CH—C $ 5 ch3 ch3 where tablet 3 contains Straight atom groups with j to μ broken atoms and * represents an asymmetric center. (According to, please refer to the patent document No. ^ to describe the light miscellaneous bribe Wei n represented by the following formula: 〇 \ -0-C-CH -0-CH2-CH-C ^ s CH3 CH, which is a straight-chain alkyl group containing J to a broken atom, and * represents an asymmetric center. Privately represented by the following formula: (Read the notes on the back first and then sing & qu ot; 'this page) -Subscribe_ • Line ·· Printed by the Central Bureau of Economic Affairs of the Ministry of Economic Affairs 〇 ~ ^ 〇j-CT-0-CT ^ -C //-C / s. CH3 CH3, ruler 3 contains i A straight bond alkyl group with a broken atom and * represents wrong. 200 Χώ Α7 B? C7 D? Six, apply for a patent, the group called the center 〇16. Liquid crystal composition, which includes at least one photoactive milk derivative represented by the following formula: Rj-C-CH-AB ~ CH-CH -Rp (la) II CH. 17 '3 lh3 where 4 is -0- or -H is the green group of Siamese self-contained tens and one ^ c // ^ _ 〇 \ is selected from i to% Atomic gas group, aryloxy group, · ~ is an alkyl group with 2 to S broken atoms; Λ) is the whole teaching of 〇 ~ 4; ^ 7 is an integer of p ~ 5 and * is an asymmetric center . A crystal composition comprising at least one photoactive liquid crystal represented by the following formula I? * (Please read the precautions on the back before filling this page)% O—C—CH—A ~~ B—CH2—CH—R2 (lb) CH, CH. * 打--S '-, · β is one of the groups that avoid self-contained —f CH 2 ^ m and ^ Cf / 2 ~ ^ 1T · 0; a group with 2 to 8 broken atoms; m is an integer from 0 to 4; r) is Integers from 2 to 5; P is 0 or 7, · g is 0 or 7; fl and £ are the same or different, including argon and halogen atom groups; /? 3 is a straight-chain embankment containing 』to Μ broken atoms Base and * is the asymmetric center. The liquid crystal composition according to the patent application Paragraph No. 3, which includes: a photoactive lactoprene derivative represented by the formula aaj and one selected from the group consisting of a smectic c-phase liquid crystal and a photoactive smectic c-phase liquid crystal group mixture. A 4 (21 () X 2 Γ3 7 _ " Printed by the Ministry of Economic Affairs, Central Standardization Bureau " 18 .V A7 B7 C7 1.) 7… Patent Application Model J9 · Based on Item 7 of the Patent Application Profile A liquid crystal composition comprising a photoactive liquid crystal represented by the formula (I (I) and a mixture selected from the group consisting of a smectic C phase liquid crystal and a photoactive smectic C phase liquid crystal group. Ο • According to the patent application The liquid crystal composition described in item π can be used in a liquid crystal device including a pair of substrates and a liquid crystal compound interposed between the substrates. • According to the liquid crystal combination described in item J7 of the patent application scope It can be used in a liquid crystal device including a pair of substrates and a combination of crystals placed between the substrates. 22. The liquid crystal composition according to the application patent model W item can be used in A liquid crystal light-emitting device. It can be used for a liquid crystal optical switching device according to the liquid crystal composition described in item J7 of the patent application. It can be used for nonlinear optics according to the liquid crystal composition described in item Materials. Based on patent application Due to the liquid crystal composition described in Item J7, its linear optical material., (Please read the notes on the back of ^^ before filling in the evening book) • hit. · Ψ 4 (21〇Χ 297 i :, V)