• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Crystalline-liquid substances comprise compounds of the general formulae <IMAGE> wherein R<1> = Br-, C1-, CnH2n+1-, CnH2n+10- with n = 1 to 10, R<2> = CnH2n+1- with n = 2 to 10, R<3> = CnH2n+1-, CnH2n+10- with n = 1 to 10 R<4> = CnH2n+1-, CnH2n+10- with n = 1 to 10 They are obtained by reactions involving the formation of the tetrazine ring. Further crystalline-liquid or non- crystalline-liquid substances, especially colouring substances, can be mixed with the substances according to the invention. They are useful in electro- optical devices.
    公开号:SU956536A1
    申请号:SU787770395
    申请日:1978-12-19
    公开日:1982-09-07
    发明作者:Херманн Шуберт；Диетрих Цашке；Диетрих Демус；Франк Кушел；Герхард Пелцл；Виллибалд Шлиеманн；Ханс-Улрих Нотник
    申请人:Феб Верк Фюр Фернзеэлектроник Им Феб Комбинат Микроэлектроник (Инопредприятие)；
    IPC主号:
    专利说明:

    (approximately + l / u-m). In addition, the observed interference colors are often very sensitive to fluctuations in the applied voltage and temperature.
    These drawbacks can be partially circumvented by using the already well-known nematic method. In this case, electro-optical cells with twisted or cholesterol layers of weak twist are used for color modulation of light. For this, a suitable dye in the form of a non-liquid crystal nematic, smectic, or cholesterol compound is added to a crystalline liquid having as high a positive dielectric anisotropy as possible. Between crossed polarizers, these cells give colored light in transmitted or reflected light and after applying an electric field extinguishing (F.Kuschel, D.Demus, G.Pelzl: DDR WP 1 6tl6). Although using this method, the dependence of the resulting color on thickness Layer and voltage can significantly reduce the disadvantage caused by the use of two polarizers, remains.
    A method is known that allows modulation of colored light using a liquid crystal cell using only one polarizer. This guest-host effect method (G.H.Heilmeier. L.A.Zanoni: Applied Physics Letters 13.91 (1968)) uses a positive dichroism dye that is dissolved in a nematic liquid.
    If this liquid crystal mixture of rb detects a positive dielectric anisotropy, then layer P is obtained from it. This layer P appears in polarized light to be colored if the direction of the transition moment of the embedded dye molecules coincides with the direction of light oscillation. After switching on the electrical voltage, a change from
    a colored state to a slightly colored or colorless state. For visual reasons, it is more advantageous if the liquid crystal mixture detects negative dielectric anisotropy and comes from layer N. Then this layer in a state without voltage appears colorless or slightly colored, and vice versa, this layer becomes colored if it is reoriented in the same direction as using an electric floor. Using this method, the goal of creating an electro-optical system in which areas or areas induced by electricity (numbers, letters, etc.) are brightly colored and stand out against the floor-free space is also not achieved or is achieved not completely. This is due to the fact that the known nematic liquids with negative anisotropy, suitable for circuit elements, require too high operating voltage (10 V and above). Another disadvantage of the known methods for color modulation of light is that the dyes used are soluble in nematic liquid, often only very poorly. In these cases only weak color contrasts are achieved. In addition, there is a danger that at lower temperatures the dye will crystallize. In addition, the resistance to light of the dyes used so far is insufficient, as a result of which the color contrast decreases with increasing duration of operation.
    The aim of the invention is to expand the range of tetrazine derivatives used as components of liquid crystal display and information processing systems.
    The goal is achieved by tetrazine derivatives of the general formula
    or
    where R BrVCr, SPN ,, ,, p 1-10
    R ;; CnHan + i; n 2-10
    R SpNgp41-; SpNs p4-10-; n 1-10
    R CnHan + t; n i-io
    The proposed compounds are characterized by high chemical and thermal stability, intense intrinsic coloration and pronounced dichroism in the visible region of the spectrum, with a satisfactory high. points of clarification at sufficiently low melting points, and that "e sufficient resistance to the action of light. They can be used in an electro-optical system of modulation. transmitted or incident light, as well as to reproduce numbers, characters and images. By preparing mixtures of several such substances, or of such substances and other liquid-crystalline compounds, the melting point can be further reduced and the working range increased even more significantly. sneeze temperatures. The transformation temperatures of substances in accordance with the inventive shadow are shown in Tables 1 and 2, where K is a solid-crystalline state; S - smectic modification |; K - nematic modification; I is the isotropic-liquid state. The dots under these symbols indicate the relevant modifications that existed, the dashes indicate the absence of modifications. The data enclosed in brackets denote the transformation to unstable, OC2H5 MH-HCl
    ifH,
    2nd option.
    3,6-Fig- (4-substituted.-phenyl) -, 2,4,5 tetrazines.
    OCjHs K2
    uaHOj / CH-sCooH
    I l
    R4oV, f. j-B2
    0
    112Н4.-НгО
    KaNO./ solmal acid
    W
    HCl
     ) -R KaHOf (ucheusmvlie varied region. Conversion temperatures are given in degrees Celsius. Synthesis of the proposed substances can occur according to the following reaction schemes. 3- (4-substituted. -Phenyl} -6-p-alkyl-1, 2, 4,5-tetrazines. 1st variant. 20 WK
    7-956536
    3- (4-p-alkyloxy-phenyl) -6- (4-substituent,
    u
    KChOM KNOW
    MKOZ / y / ss smil acid
    - /,
    eight
    -phenyl) -1, 2, 4, 5-tetraziv y K-i -
    n n
    | T a 6 l and c a 1
    Melting unstable solid modification at 53.5 ° C. Nematic monotrope.
    Melting unstable solid modification at 43 ° C. In the smectic region, a transition is observed at 65-68 ° C. Example 1. 3- (4-substituted. -Pheny-6-p-alkyl-1,2,4,5-tetrazines (1st to riant) ... In a three-neck flask equipped with a thermometer, a stirrer, and a reflux condenser, 0 , 03 mol N-alkanoyl-.H- (4-for | Mesh-benzoyl-hydrazine) are mixed with 20 g (0.09 mol) PClj and under vacuum and heated to 140 ° C with stirring. The reaction mixture liquefies both POClj and PClg The reaction is completed if POClj is no longer formed. After cooling, the contents of the flask are taken up in ether and carefully cooled with ice, removed. The ether extract is then washed with water and bicarbonate solution, dried over NaijSOi and removed Solvent on a rotary evaporator. 1,4-dichloro-1- (4-substituted.-phenyl) -4-alkylazines precipitate out as yellow-brown oils and are processed further as raw materials. The oil is suspended in 50-80 ml of absolute ethanol and cooled. to -5 ° C. Then add as much ether until a clear solution is obtained (about 20 ml) With stirring, add 4 g of 80% hydrazine hydrate in 20 ml of ethanol so that the temperature does not exceed 0 ° C. The mixture is then stirred for another two hours at room temperature. The resulting dihydrotetrazine is aspirated and oxidized to tetrazine with NaNdrj / acetic acid. Purification of the product is carried out by recrystallization or chromatography on a column. Output 10-20% of theoretical. Example 2. 3- (4-substituted.-phenyl) -6-p-alkyl-1, 2,4,5-tetrazines (2nd variant). 0.005 mol of 4-substitution. -Benzimidoether hydrochloride, 0.015 mol of amidine hydrochloride and 10-30 mg of hydrazine hydrate (80%) are stirred at room temperature for 2-5 hours. Then the contents of the flask are poured into water, the precipitate is sucked off and washed. The precipitate is suspended in 30-40 Ml of a 10% NaNOi solution, coated with a layer of ether in an amount of 70 ml and oxidized with stirring in small portions of a 10% aqueous solution of acetic acid to tetrazine. The ether extract is washed, dried with Na.2.S04 and the solvent is removed on a company; 1iok iOM evaporator. The precipitate is purified by chromatography using silica gel, with methylene chloride being the solvent for leaching. Output 20-50% of theoretical. Example .3. 3,6-5is- (4-substituted.-Phenyl) -, 2,4,5-tetrazines. 0.02 mol of 4-substitution. -Benzimidoether hydrochloride is heated from 10 g of 85% hydrazine hydrate to 1 h in a water bath. After cooling, the yellow crystalline mass of the substituted dihydro-3-tetrazine is filtered off with suction and washed with ether. The precipitate is suspended in 30-40 ml of a 10% NaNOi solution, coated with a layer of ether in an amount of 70 ml and oxidized with stirring to s-tetrazine using small portions of 10% acetic acid. The tetraein formed is dissolved in ether, the acidification is complete if the starting yellow product is consumed. The ether phase is separated, scrubbed, dried with Na and then the solvent is distilled off on a rotary evaporator. The precipitate is recrystallized from dioxane or a mixture of ethyl alcohol / dioxane (7: 1). Output 40-70% of theoretical. Example 4. 3- (4-p-alkyloxy-phenyl) -6- (4-substituted.-phenyl) -1,2,4,5-tetrazines. 0.005 mol of 4-p-alkyl-6-hydroxy-benzimide ester-hydrochloride, 0.015 mol of 4-substitution.-Benzamidine-hydrochloride and 8 ml of 80% hydrazine hydrate are heated for 3 hours in a water bath at 80 ° C and with stirring, and left be at night. The precipitate is sucked off and washed with water and ether. For oxidation, the precipitate (dihydro-s-tetrazines) is suspended in 30-40 ml of a 10% sodium nitrite solution, covered with a layer of ether in an amount of 70 ml, and small peerations of 10% acetic acid are added with stirring. The oxidation is complete if the initial yellow product is consumed and the tetrazines are dissolved in ether. The ether phase is separated, washed with water, dried with Na, and the solvent is distilled off with a rotary evaporator. The residue is chromatographed on silica gel (grain size O, 05-0, 2, Merck Company) using a mixture of benzcyclohexane (1: 1). On the separation column of cm size, the three tetrazines obtained are completely separated. The yield of asymmetric tetrazine is 10–50% of theoretical. P i me R 5. Between transparent electrically conducting electrodes of substance no. 2/18. An oriented layer (layer P) is prepared with a thickness of about 10 / ht. When it is illuminated with white polarized light, this layer appears to be colored yellowish if the direction of light oscillation coincides with the preferred direction of the layer P. After applying an electrical voltage of 15 V at 163 ° C, the layer is reoriented, which then becomes colored in an intense red-violet color. Switching can be performed as many times as desired. EXAMPLE 6 Analogously to Example 5, a layer P of substance No. 1/4 is prepared. This layer without an electric field seems to be colorless if the direction of the oscillations of the directed polarized light coincides with the preferred direction of the P layer. If an electric voltage of 15 V is applied at 56 ° C, then after the reorientation the layer becomes red-violet. The switching time is 30 ms, the time is off. 90 ms. The color change from slightly pink to red-violet and vice versa can also be observed in a white, not polarized light. If a green filter is turned on in the beam path, then after applying an electric floor, a light green color changes to black. Example 7. A blend of the following composition, mol%, is prepared: 4-p-propyl-cyclohexanecarboxylic acid, (4-cyano-phenyl ester) 25.5; 4-p-butyl-cyclohexanecarboxylic acid (4-cyano-phenyl ester) 24; 4-p-pentyl-cyclohexanecarboxylic acid (4-cyano-phenyl ester) 25.5; substance f 1/4 25. This mixture of substances at room temperature. is nematic and colored red. It detects negative dichroism. Between the transparent electrodes of the mixture. A layer P of about 20 / u.m is prepared. In white, linearly polarized light, the direction of oscillation of which coincides with the preferred direction of the layer P, the transmitted or reflected light appears colored in pale pink. After switching on the electrical voltage of 3 V, an intense red color appears. This system has been exposed to daylight for 600 hours. Compared with the initial state after that, in the visible region of the spectrum, a decrease in extinction was not noticeable. Example 8. In the mixture according to Example 7, 0.9 wt.% Of the yellow dye Wolfen 6, having the desired chemical structure, was dissolved: (; Hs- (O / - 1 "oV and exhibiting positive dichroism. The layer prepared from this mixture is P in transmitted or - reflected light appears yellow if the preferred direction of the layer P and the direction of oscillation of the directed polarized light are the same. After switching on the electric voltage of 3 V (50 Hz), the color change to red is set. , still in addition Indophenol blue is a dye with positive dichroism and is obtained from a mixture obtained in this way, a layer of thickness 20 ui-rp is produced. If the preferred direction of this layer and the direction of oscillation of the incident polarized light coincide The transmitted or reflected light appears green.
    After switching on the alternating voltage of 3 V, the layer turns red.
    权利要求:
    Claims (1)
    [1]
    Tetrazine derivatives of the general formula
    2 go EMO
    CnhartffO
    R Br, Cl
    : ,, n
    in-m
    n 1-10;
    R CnHin .., n 2-10;
    ,, CpH, g, 0-, n 1-10;
    ., .n 1-10;
    This R3 and R4 are different quality components of the liquid crystal materials for the electro-optical display systems and
    10 information processing. . .
    Recognized as an invention according to the results of the examination carried out by Be, by the residence of the German Democratic Republic.
    类似技术:
    公开号 | 公开日 | 专利标题
    US4077260A|1978-03-07|Optically active cyano-biphenyl compounds and liquid crystal materials containing them
    GB2035303A|1980-06-18|2,3-dicyano-hydroquinone derivatives
    US4293434A|1981-10-06|Liquid crystal compounds
    EP0263843B1|1992-12-02|Liquid crystal compounds, mixtures and devices
    US4358393A|1982-11-09|Nematic liquid crystals of 5-cyano-2-[4-acyloxyphenyl]-pyrimidines and mixtures containing the same
    SU956536A1|1982-09-07|Tetrazine derivatives as components of liquid=crystal materials for optoelectronic data display and processing systems
    US4382012A|1983-05-03|Liquid crystalline diketones
    GB2065158A|1981-06-24|Anthraquinone Dichroic Dyes
    US4391730A|1983-07-05|Nematic liquid crystal compounds and use and device for using the same
    US4358589A|1982-11-09|Nematic liquid crystal compounds
    JP2525214B2|1996-08-14|Ferroelectric liquid crystal composition
    US3984344A|1976-10-05|Positive dielectric anisotropy liquid crystal compositions
    US4814476A|1989-03-21|Liquid crystalline compound
    GB2200912A|1988-08-17|Terphenyl derivatives and liquid crystal materials containing them
    US4058475A|1977-11-15|Liquid crystal compositions containing cyanocinnamic acid esters
    EP0334845B1|1992-05-06|Liquid crystal compounds, mixtures and devices
    US4457859A|1984-07-03|Mesomorphic material containing 2,2&#39;-azoimidazole compounds containing 1,1&#39;-benzylideneamino substituents
    JP3073795B2|2000-08-07|Benzofuranoquinone compounds
    JP3073780B2|2000-08-07|Benzofuranoquinone compounds
    JP2822550B2|1998-11-11|Azulene derivative, liquid crystal composition and liquid crystal device using the same
    EP0259423B1|1993-04-21|Liquid crystal compounds, mixtures and devices
    KR100553514B1|2006-02-20|Triphenodioxazine compound, Method for preparing the same, Use of the compound as dichroic dye, and Liquid crystal composition
    US4879061A|1989-11-07|Liquid crystalline materials and method of making same
    GB2091753A|1982-08-04|Use of 1,4-b15 | anthraquinos as dyes in the smetic layers of a liquid crystal cell
    JP2580254B2|1997-02-12|Novel optically active ester compound and method for producing the same
    同族专利:
    公开号 | 公开日
    JPS6133824B2|1986-08-04|
    DE2841245C2|1986-04-30|
    FR2422707A1|1979-11-09|
    HU186345B|1985-07-29|
    JPS59112974A|1984-06-29|
    GB2014130B|1982-07-28|
    JPS6121274B2|1986-05-26|
    DD137117A1|1979-08-15|
    GB2014130A|1979-08-22|
    CH640257A5|1983-12-30|
    DD137117B1|1980-10-01|
    JPS54110185A|1979-08-29|
    DE2841245A1|1979-07-26|
    FR2422707B1|1984-02-03|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3863010A|1973-09-28|1975-01-28|American Cyanamid Co|Compositions of matter and method of use of phenyl and substituted phenyl tetrazines|
    SU498300A1|1973-11-27|1976-01-05|Институт Органической Химии Ан Украинской Сср|The method of obtaining derivatives of 3,6-diaryl-simm-tetrazine|DD137118B1|1978-02-06|1980-10-01|Hermann Schubert|ELECTROOPTICAL ARRANGEMENT FOR LIGHT MODULATION OR SYMBOL INDICATION|
    DD137242B1|1978-06-16|1980-10-29|Dietrich Demus|NEMATIC CRYSTALLINE-FLUID MIXTURES|
    US4358589A|1979-02-02|1982-11-09|Veb Werk Fur Fernsehelektronik Im Veb Kombinat Mikroelektronik|Nematic liquid crystal compounds|
    US4273929A|1979-02-05|1981-06-16|Hoffmann-La Roche Inc.|Heterocyclic compounds|
    CH645102A5|1980-10-14|1984-09-14|Hoffmann La Roche|DISUBSTITUTED PYRIMIDINE.|
    FR3085912B1|2018-09-19|2020-11-27|Psa Automobiles Sa|VEHICLE INCLUDING A STRENGTH DISTRIBUTION SYSTEM MOUNTED ON THE BUMPER SYSTEM|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    DD20336178A|DD137117B1|1978-01-23|1978-01-23|NEMATIC CRYSTALLINE-LIQUID SUBSTANCES|
    [返回顶部]