WO2013189171A1 - 苯并菲衍生物及其应用 - Google Patents

苯并菲衍生物及其应用 Download PDF

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WO2013189171A1
WO2013189171A1 PCT/CN2013/000642 CN2013000642W WO2013189171A1 WO 2013189171 A1 WO2013189171 A1 WO 2013189171A1 CN 2013000642 W CN2013000642 W CN 2013000642W WO 2013189171 A1 WO2013189171 A1 WO 2013189171A1
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formula
liquid crystal
group
compound
optical compensation
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PCT/CN2013/000642
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English (en)
French (fr)
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孔翔飞
严铭
谭玉东
陈昭远
游石枝
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江苏和成显示科技股份有限公司
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Priority to US14/410,144 priority Critical patent/US9273246B2/en
Publication of WO2013189171A1 publication Critical patent/WO2013189171A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/32—Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems
    • C09K19/322—Compounds containing a naphthalene ring or a completely or partially hydrogenated naphthalene ring
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/32—Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C07C69/84—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of monocyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of a six-membered aromatic ring
    • C07C69/92—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of monocyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of a six-membered aromatic ring with etherified hydroxyl groups
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3016—Polarising elements involving passive liquid crystal elements
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K2019/0425—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a specific unit that results in a functional effect
    • C09K2019/0429—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a specific unit that results in a functional effect the specific unit being a carbocyclic or heterocyclic discotic unit
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/32—Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems
    • C09K2019/328—Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems containing a triphenylene ring system
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/13363—Birefringent elements, e.g. for optical compensation
    • G02F1/133633—Birefringent elements, e.g. for optical compensation using mesogenic materials

Definitions

  • TECHNICAL FIELD The present invention relates to compounds as components of liquid crystal media and uses thereof.
  • Background Art In current TFT liquid crystal displays, a rod-like liquid crystal material having a positive birefringence ( ⁇ ⁇ ⁇ ⁇ ⁇ ) is used. The anisotropy of the rod-like liquid crystal material causes light leakage of the display and causes its viewing angle to be narrow.
  • an optical compensation film having a negative birefringence ( ⁇ ⁇ 0) is used to compensate for the optical path difference after the linearly polarized light passes through the liquid crystal cell, which is an effective method.
  • the optical compensation film materials that have been reported so far are uniaxially or biaxially stretched polymer films, main chain type liquid crystal polymers, polymers having rigid chain links, photopolymerized rod-like liquid crystal polymers, and discotic liquid crystal compounds.
  • a benzophenanthrene-like discotic liquid crystal having a single optical axial phase phase has a birefringence value of a negative value, and its absolute value is similar to that of a rod-like liquid crystal generally used for a liquid crystal display, and thus can be used as an optical compensation film (box) material. Used to compensate for the optical path difference after the line is polarized through the liquid crystal cell.
  • Patent No. 5,518,783 the use of a hexaaryl benzophenanthrene compound having a phase orientation as an optical film material is reported. Such materials have been reported to have a higher melting point (above 100'C) and a clearing point of around 20 (TC). When preparing an optical compensation film, it must be heated above the clearing point of the material, and then slowly cooled to control The orientation of the discotic molecules. Therefore, in order to ensure that the liquid crystal phase temperature range is within a suitable range, reducing the clearing point of the material can save energy and reduce the preparation process. When used as an optical compensation box material, the melting point of the material must be lower than room temperature.
  • the object of the present invention is to overcome the problem of high melting point of nematic phase benzophenanthrene-like discotic liquid crystals, such as by introducing three The alkoxy side chain lowers the melting point of the material while maintaining a sufficiently wide liquid crystal temperature range, and even makes the melting point below room temperature.
  • the present invention provides a discotic molecule having the general formula (I) or the general formula ( ⁇ ). a compound, and a nematic phase discotic liquid crystal medium comprising the composition of the discotic molecular compound.
  • R 1 is selected from H, F, Cl, Br, -CN, -SCN, OR 2 or SR 2 , wherein R 2 is a straight having 1 to 20 C atoms which may be substituted by one or more F, CI or Br a chain or branched alkyl group, wherein one or more of the non-adjacent CH 2 groups of the linear or branched fluorenyl group having 1 to 20 C atoms may be -0-, -CO-0- , -0-CO- or -0-CO-0- instead, provided that 0 atoms are not directly connected;
  • L is a group that conforms to the following formula:
  • A1 end is linked to the benzophenanthrene nucleus
  • A1 is -0-CO-
  • A2 is phenylene
  • A3 is -0-, -0-CO-, -CO-0-
  • A4 is an alkylene group of 1 to 12 carbon atoms
  • A5 is -0-
  • A6 is -CO-
  • a 0, 1 or
  • L is selected from the group consisting of the following formulas. Wherein, the left end of the formula is attached to the benzophenanthrene nucleus.
  • Another aspect of the invention also provides a liquid crystal medium comprising one or more discotic molecular compounds of the invention.
  • Another aspect of the present invention provides an optical compensation film of a liquid crystal display comprising the above liquid crystal medium and an optical compensation box of the liquid crystal display comprising the liquid crystal medium.
  • the o-dimethoxybenzene is first prepared by refluxing guaiacol, bromine oxime and potassium carbonate in ethanol (or acetone) for 24 hours.
  • the o-dimethoxybenzene is oxidized with ferric chloride in a solution of dichloromethane, and a mixture of hexamethylene benzophenanthrene 1 and 2 is obtained by reacting for 1 to 2 hours, and the pure substance of 1 and 2 is obtained by separation and purification.
  • Compound 1 is added with thiophenol and potassium carbonate, and refluxed in N, N,-dimethylformamide for 1 to 2 hours to obtain tridecyloxytrihydroxybenzophenanthrene 3, further with a benzoic acid derivative at room temperature.
  • the target product 4 can be obtained by reacting with hydrazine, ⁇ '-dicyclohexylcarbodiimide (DCC) and 4'-fluorene, hydrazine-dimethylaminopyridine (DMAP) for 6-8 hours.
  • the reaction of the compound 2 is referred to the compound 1.
  • Synthetic route 2 firstly reacting catechol, alkyl bromide and potassium carbonate in ethanol for 24 to 48 hours to prepare o-dialkoxybenzene; o-dialkoxybenzene in trichloroethane in dichloromethane solution The iron is oxidized, and the reaction is carried out for about 1 to 2 hours to obtain hexa-alkoxybenzophenanthrene 5, and then reacted with B-bromo-9-boronbicyclo[3.3.1]nonane at room temperature for 30 to 48 hours to obtain a trialkoxy group.
  • Hydroxybenzophenanthrene 3 and 6, 3 are further refluxed with 5-chloro-1-phenyl-1H-tetrazole and potassium carbonate in acetone for 12-18 h; then palladium carbon (0.35 g) is used as a catalyst at 40 ° C. Hydrogen is introduced into the reduction reaction for 24 ⁇ 48h to form tridecyloxybenzophenanthrene 7; and then reacted with boron tribromide at room temperature for 4 ⁇ 8h, and an alkyl group is removed to form dihydroxybenzophenanthrene 8; Method (synthesis
  • FIG. 1 is a texture diagram of a compound of Formula 7 taken during cooling.
  • Fig. 2 is a texture diagram of a compound of Formula 12 taken during temperature rise.
  • DETAILED DESCRIPTION OF THE INVENTION The present invention will be described below in conjunction with specific embodiments. It should be noted that the following examples are merely illustrative of the invention and are not intended to limit the invention. Various other combinations and modifications within the inventive concept can be made without departing from the spirit and scope of the invention. In the examples below, all percentages represent weight percentages. The temperatures described below are degrees Celsius. Mp represents the melting point, Cp represents the clearing point, h represents the hour, min represents the minute, ⁇ represents the crystal phase, Ne represents the nematic phase and Is represents the isotropic phase. The number between these symbols indicates the temperature at which the phase transition occurs.
  • an alkyl group means a n-decyl group.
  • the apparatus used for 1H NMR was Varian 300 MHz, or Bruker 300 MHz, and the internal standard was trimethylsilyl (TMS).
  • TMS trimethylsilyl
  • the solvent was deuterated chloroform (CDC1 3 ), except as indicated.
  • Physical, physicochemical and electro-optical parameters are determined by generally known methods, as in "Merck Liquid Crystals - Physical Properties of Liquid Crystals - Description of the Measurement Methods ( Merck Liquid Crystals)
  • the compound of formula 3 (0.83 g, 1.34 mmol), thiophenol (0.88 g, 8 mmol) and potassium carbonate (1.66 g, 12 mmol) were refluxed in dimethylformamide (DMF) (6 ml) 1.5 h. Cool to room temperature and acidify by adding dilute hydrochloric acid (30 ml). The resulting precipitate was filtered off, and the crude product was purified using silica gel column eluted eluted eluted eluted eluted eluted elution elution elution elution elution .
  • the compound of formula 5 (15 g, 90.27 mmol), 1-bromoindole (24.3 g, 117.4 mmol) and potassium carbonate (18.7 g, 135.5 mmol) were refluxed in dry anhydrous ethanol (90 1 ). After cooling to room temperature, suction filtration was carried out, the filter cake was washed with ethanol, and the solvent was removed from the filtrate. Water (36 ml) and sodium hydroxide (30.7 g) were added and refluxed for 1.5 h. The mixture was cooled to room temperature, acidified by the addition of 40% sulfuric acid, and the resulting precipitate was filtered, and the crude product was recrystallized from ethanol to give the compound of formula 6 as colorless powder (20 g), yield 84%.
  • Example 2 The compound was tested by a polarizing microscope and the compound had a melting point of 90 ° C and a clearing point of 107 ° C. When the temperature is lowered, a discotic liquid crystal nematic phase is formed, and its texture is shown in Fig. 1.
  • Example 2 The compound was tested by a polarizing microscope and the compound had a melting point of 90 ° C and a clearing point of 107 ° C. When the temperature is lowered, a discotic liquid crystal nematic phase is formed, and its texture is shown in Fig. 1.
  • Example 2 Example 2
  • reaction step 2.2 Same as reaction step 1.1.
  • reaction step 2.2 Same as reaction step 1.1.
  • reaction step 2.2
  • the compound of the formula 10 (10 g, 42 mmol) was added to triethylamine (5 ml) and tetrahydrofuran (30 ml), and acryloyl chloride (6.6 g, 63 mmol) was added dropwise. The reaction was carried out at room temperature overnight. It was poured into water (150 ml), and the resulting precipitate was filtered, and the crude product was recrystallized from ethanol to give the compound of formula 11 as colorless powder ( 8.2 g).
  • the compound of the formula 9 (0.12 g, 0.208 mmol), the compound of the formula 11 (0.49 g, 1.67 mmol) and DCC (0.34 g, 1.67 mmol) were added to dichloromethane (5 ml), and DMAP (catalytic amount) was added, The reaction was carried out at room temperature overnight. After filtration, the filter cake was washed with dichloromethane and the filtrate was dried.
  • the compound has a melting point of 92°) C, the clearing point is 134'C.
  • the discotic liquid crystal nematic phase is formed at the time of temperature rise, and its texture is shown in Fig. 2.
  • the compound of formula 17 (0.1 g, 0.36 mmol) was added to dry tetrahydrofuran (10 ml), then the compound of formula 18 (0.5 g, 1.62 mmol), DCC (0.33 g, 1.62 mmol) and DMAP ( Catalytic amount), the reaction was carried out at room temperature overnight. Filtration, the filtrate was dried to give a crude product, which was purified on silica gel column (dichloromethane/ethyl acetate, volume ratio 60:1) to give the compound of formula 19 as colorless powder (0.26). g), yield 65%.
  • reaction step 4.2 is similar to the reaction step 3.3, and the compound of the formula 4 is obtained as a colorless powder, yield 45%.
  • Reaction step 4.2 is similar to the reaction step 3.3, and the compound of the formula 4 is obtained as a colorless powder, yield 45%.
  • reaction step 4.3 The reaction step is similar to reaction step 3.4.
  • the compound of the formula 20 was obtained as a colorless powder in a yield of 45%.
  • Reaction step 4.3 The reaction step 4.3
  • reaction step is similar to the reaction step 3.5, and the compound of the formula 21 is obtained as a colorless powder in a yield of 100%.

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Abstract

本发明提供可以作为液晶介质的组分的具有通式（I）或通式（II）的结构的苯并菲衍生物和应用。该化合物可形成负性盘状液晶组合物，具有合适的液晶相温度，较低的清亮点，能够应用在TFT液晶显示器中，作为光学补偿膜（盒）材料使用。

Description

苯并菲衍生物及其应用
技术领域 本发明涉及作为液晶介质的组分的化合物及其应用。 背景技术 在目前的 TFT液晶显示器中， 使用具有正双折射率 （Δη Χ^ Διι ι ηο) 的棒状液晶 材料。 棒状液晶材料的各向异性会造成显示器的漏光， 并导致其视角变窄。 为了改善显示 器的视角， 使用具有负双折射率 （Δη < 0) 的光学补偿膜， 对线偏光通过液晶盒后的光程 差进行补偿， 是一种有效的方法。 目前己经报导的光学补偿膜材料有经过单轴或双轴拉伸 的聚合物薄膜、 主链型液晶高分子、 具有刚性链节的高分子、 光聚合的棒状液晶高分子、 盘状液晶化合物。 具有单光轴向列相的苯并菲类盘状液晶， 双折射率为负值， 且其绝对值大小与通常用 于液晶显示器的棒状液晶相近， 因此， 可作为光学补偿膜 （盒）材料使用， 用来对线偏光 通过液晶盒后的光程差进行补偿。 在 US 7495730， US 7443474和 US 5518783中， 报导了具有向相的六芳酯苯并菲化合 物作为光学补膜材料使用。 己经报导的这类材料， 熔点多数较高 (在 100'C以上)， 清亮点 在 20(TC左右。 在制备光学补偿膜时， 必须加热到材料的清亮点以上， 再缓慢降温， 以控 制盘状分子的取向。 因此， 在保证液晶相温度范围在合适的范围内， 降低材料的清亮点可 以节省能源， 减化制备工艺。 在作为光学补偿盒材料时， 材料的熔点必须低于室温。 因此， 存在提供具有合适的液晶相温度、 较低的清亮点的液晶材料的需要。 发明内容 本发明的目的是克服向列相苯并菲类盘状液晶熔点高的难题，如通过引入三个烷氧基 侧链，在保持足够宽的液晶温度范围的同时，降低材料的熔点，甚至使熔点达到室温以下。 本发明提供一种具有通式 (I)或通式 (Π)的盘状分子化合物， 以及包含所述盘状分子化 合物组成的向列相盘状液晶介质。
Figure imgf000003_0001
其中各基团具有以下含义-
R1选自 H、 F、 Cl、 Br、 -CN、 -SCN、 OR2或 SR2， 其中 R2为可被一个或多个 F、 CI 或 Br取代的具有 1到 20个 C原子的直链或支链烷基， 其中所述具有 1到 20个 C原子的 直链或支链垸基中的一个或多个不相邻的 CH2基团可以被 -0-、-CO-0-、-0-CO-或 -0-CO-0- 代替， 前提是 0原子不直接相连；
L为符合下式连接基团：
-A1-A2-A3 -A4-(A5-A4)a-(A5)b-( A6)c-，
其中 A1端与苯并菲核连接， A1为 -0-CO-, A2为亚苯基， A3为 -0-、 -0-CO-、 -CO-0-、
-NH-CO-或- 0-CO-0-, A4为 1到 12个碳原子的亚烷基， A5为 -0-, A6为 -CO-， a=0、 1或
2, b=0或 1， c=0或 1 ;
Q 为 H 或可聚合的官能团， 所述可聚合的官能团选自由一 eH= c:H2、
— CH=CH2
—— CH=CH—— CH3 、 —— CH=CH—— C2H5 —— CH=CH-n-C3H7 、 CH3 、
― CH=C― CH3 /°\
I C一 CH
CH3 — C≡CH、 H 2、一 OH、一 CHO、一 COOH、一 N=C=0、
_ NH2、 一 SH和一]p= C= s组成的组。
L选自由下列通式组成的组。 其中， 通式左端连接在苯并菲核上。
-O-CO-Ph-O-R- (L1 )
-0-CO-Ph-O-R-O- (L2 )
-0-CO-Ph-O-R-CO- ( L3 )
-0-CO-Ph-O-R-O-CO- (L4) -O-CO-Ph-O-R-O-R-O-CO- (L5);
-O-CO-Ph-O-R-O-R-O-R-O-CO- (L6);
-O-CO-Ph-O-CO-R- (L7);
-O-CO-Ph-O-CO-R-O- (L8);
-O-CO-Ph-O-CO- R-O-CO- (L9);
-O-CO-Ph-O-CO-R-O-Al-O-CO- (L10);
-O-CO-Ph-NH-CO-R- (Lll);
-O-CO-Ph-NH-CO-R-O- (L12);
-O-CO-Ph-NH-CO-R-O-CO- (L13);
-O-CO-Ph-NH-CO-R-O-R-O-CO- (L14);
-O-CO-Ph-CO-O-R- (L15);
-O-CO-Ph-CO-O-R-O- (L16);
-O-CO-PhCOO-R-O-CO- (L17);
-O-CO-Ph-CO-O-R-O-R-O-CO- (L18);
-O-CO-Ph-O-CO-O- - (L19);
-O-CO-Ph-O-CO-O-R-O- (L20);
-O-CO-Ph-O-CO-O-R-O-CO- (L21)； 以及
-O-CO-Ph-O-CO-O-R-O-R-O-CO- (L22)； 其中， R为 1到 12个 C原子的亚烷基； 并且 Ph为亚苯基。 本发明的另一方面还提供包含一种或更多种本发明的盘状分子化合物的液晶介质。 本发明的另一方面还提供包含上述液晶介质的液晶显示器的光学补偿膜以及包含上 述液晶介质的液晶显示器的光学补偿盒。 合成路线一：
首先用愈创木酚、 溴代垸和碳酸钾在乙醇（或丙酮） 中回流反应 24 8小时， 制备邻 二垸氧基苯。邻二垸氧基苯在二氯甲垸溶液中用三氯化铁氧化， 反应 1~2小时得到六垸氧 基苯并菲 1和 2的混合物， 分离提纯得到 1和 2的纯物质。 化合物 1中加入苯硫酚、 碳酸 钾， 在 N， N，-二甲基甲酰胺中回流 1〜2小时， 得到三垸氧基三羟基苯并菲 3, 进一步与苯 甲酸衍生物， 室温时在 Ν,Ν'-二环己基碳二亚胺 (DCC)和 4'-Ν，Ν-二甲基氨基吡啶 (DMAP) 作用下反应 6~8小时， 可得到目标产物 4。 化合物 2的反应参照化合物 1。
Figure imgf000004_0001
Figure imgf000005_0001
合成路线二： 首先用邻苯二酚、 溴代烷和碳酸钾在乙醇中回流反应 24~48小时， 制备 邻二烷氧基苯； 邻二烷氧基苯在二氯甲烷溶液中用三氯化铁氧化， 反应约 1~2小时得到六 烷氧基苯并菲 5， 再和 B-溴 -9-硼杂双环 [3.3.1]壬烷室温反应 30〜48h， 得到三烷氧基三羟基 苯并菲 3和 6, 3进一步与 5-氯 -1-苯基 -1H-四唑和碳酸钾在丙酮中回流 12~18h; 再用钯碳 (0.35g)做催化剂， 40°C时通入氢气进行还原反应 24~48h, 生成三垸氧基苯并菲 7; 再与三 溴化硼在室温反应 4~8h, 脱去 个烷基， 生成二羟基苯并菲 8; 最后再酯化（方法同合成
Figure imgf000005_0002
本发明的优点为用简短的路线， 合成含三个酯基侧链和三个垸氧基（或氢）侧链的苯 并菲。 三个烷氧基侧链有助于调节液晶相的温度范围。 附图说明 图 1是式 7的化合物在降温过程中拍摄的织构图。
图 2是式 12的化合物在升温过程中拍摄的织构图, 具体实施方式 以下将结合具体实施方案来说明本发明。 需要说明的是， 下面的实施例仅用来说明本 发明， 而不用来限制本发明。 在不偏离本发明主旨或范围的情况下， 可进行本发明构思内 的其他各种组合和改良。 在下述的实施例中， 所有百分比表示重量百分比。 下述的温度是摄氏度。 Mp表示熔 点， Cp表示清亮点， h表示小时， min表示分钟， Κτ表示晶体相， Ne表示向列相和 Is表 示各向同性相。 这些符号间的数字表示所述相间的转变发生的温度。 除非另有提及， 烷基 表示正垸基。 1H NMR所用仪器为 Varian 300MHz, 或 Bruker 300MHz, 测试内标为三甲 基硅垸 (TMS)， 溶剂为氘代氯仿 （CDC13)， 有说明的除外。 由一般已知的方法确定物理、 物化和电光参数， 如同在 "Merck Liquid Crystals —Physical Properties of Liquid Crystals—Description of the Measurement Methods ( Merck液晶
——液晶的物理性能——测量方法的说明） "中所描述的那样。 实施例 1
合成式 7的化合物
Figure imgf000006_0001
式 1 的化合物 (6.4g, 0.05mol)， 1-溴己垸 (12.4g， 0.075mol)和碳酸钾 (13.8g， O.lmol)在干 燥的丙酮 (60 1^)中回流4811。 降温到室温抽滤， 滤饼用丙酮冲洗， 滤液除去溶剂， 减压蒸 馏， 收集到 105-110°C之间的组份 （真空度约为 8mm汞柱）， 得到式 2的化合物为无色油 状物 (9.9g), 产率为 95%. Ή NMR, δ: 6.90 (s， 4H)， 4.01 (t， 2H, J= 6.6 Hz), 3.87 (s， 3H), 1.85 (m, 2H), 1.47-1.32 (m, 6H)， 0.91 (t, 3H，J= 6.9 Hz)。 反应步骤 1.2
Figure imgf000007_0001
室温下，式 2的化合物 (1.04g，5mmol) 和三氯化铁 (1.95g， 12mmol) 在二氯甲垸 (DCM ) (22ml)中搅拌 1.5h。 再转入甲醇 (90ml), 过滤出生成的沉淀， 粗产物用硅胶柱提纯 (二氯甲 焼 /石油醚， 体积比 1 : 1〜3:2)， 得到式 3的化合物为无色固体 (0.46g)， 产率 45%。 1H NMR, 0: 7.85 (s, IH), 7.83(s, 4H)， 7.82(s， IH), 4.26 (t, 6H, J= 6.9 Hz), 4.11 (s, 9H)， 2.03-1.93 (m, 6H); 1.62-1.54(m, 6H), 1.43-1.37 (m, 12H), 0.94 (t, 9H, J= 6.9Hz)。
Figure imgf000007_0002
在 N2保护下， 式 3 的化合物 （0.83g, 1.34mmol), 苯硫酚 （0.88g, 8mmol)和碳酸钾 (1.66g, 12mmol) 在二甲基甲酰胺 （DMF ) (6ml) 中回流 1.5 h。 冷却到室温， 加入稀盐酸 (30 ml) 酸化。 过滤出生成的沉淀物， 粗产物用硅胶柱提纯 (淋洗液二氯甲烧 /石油醚， 体积 比 2: 1), 得到式 4的化合物为无色固体 (0.34g)， 产率 44%。 1H NMR, δ: 7.91 (s， IH), 7.90 (s, IH), 7.88 (s, 1H)， 7.72 (s， IH), 7.60 (s， IH), 7.59 (s,lH), 5.88 (s, 1H)， 5.87 (s, IH), 5.85 (s， IH), 4.22-4.14 (m, 6H), 1.96-1.82 (m, 6H)， 1.61-1.39 (m， 18H), 0.94 (t， 9H，J= 6.6Hz)。 反
Figure imgf000007_0003
式 5的化合物 （15g, 90.27mmol), 1-溴壬垸 (24.3g， 117.4mmol)和碳酸钾 (18.7g， 135.5 mmol )在干燥的无水乙醇 (90 1^)中回流4811。 降温到室温， 再抽滤， 滤饼用乙醇洗漆， 滤 液除去部分溶剂， 加入水 (36 ml)和氢氧化钠 (30.7 g)， 回流 1.5h。 降温到室温， 加入 40% 的硫酸酸化，过滤生成的沉淀，粗产物用乙醇重结晶，得到式 6的化合物为无色粉末 (20g)， 产率 84%。 1H NMR, 0: 8.09 (d, 2H, J= 8.7Hz), 6.97 (d， 2H, J= 8.7Hz), 4.07 (t, 2H, J= 6.3 Hz), 1.85 (m, 2H), 1.49-1.30 (m, 12H), 0.91 (t， 3H，J= 6.9 Hz)。 反应步骤 1
Figure imgf000008_0001
式 4的化合物 (0.2g， 0.347mmol), 式 6的化合物 （0.734g， 2.78mmol)和 Ν,Ν'-二环己基 碳二亚胺 (DCC) (0.57g， 2.88mmol)加入到四氢呋喃 (5ml)中， 再加入二甲基氨基吡啶 (DMAP) (催化量)， 室温反应过夜。 过滤， 用二氯甲烷 (20ml)洗涤滤饼， 滤液旋干， 粗 产物用硅胶柱提纯 (淋洗液石油醚 /乙酸乙酯， 体积比 4:1)， 得到式 7的化合物为无色固体 (0.36g),产率 80% 0 Ή NM , <5; 8,21 (s, 1H)， 8.19-8.13 (m, 6H)， 7.98 (s， IH), 7.94 (s, IH), 7.89 (s, 1H)， 7.85 (s, IH), 7.75 (s, IH), 6.96-6.90 (m, 6H), 4.22-4.12 (m, 6H), 4.06-4.02 (m, 6H)， 1.85-1.80 (m, 6H), 1.72-1.67 (m, 6H), 1.54-1.19 (m, 60H)， 0.99-0.78 (m, 18H)。 用偏光显微镜测试， 该化合物的熔点为 90°C， 清亮点为 107°C。 在降温时形成盘状液 晶向列相， 其织构图见图 1。 实施例 2
合成式 12的化合物
Figure imgf000008_0003
Figure imgf000008_0002
反应歩骤 2.1，
同反应步骤 1.1。 反应步骤 2.2:
Figure imgf000009_0001
与反应步骤 1.2相似，得到式 8的化合物。式 8的化合物为无色固体,产率 5%。1H NMR, δ 7.74 (s, 3H)， 7.71(s, 3H), 4.2 l(t, 6H, J- 6.8Hz), 4.07 (s, 9H), 1.98-1.91 (m, 6H)， 1.56-1.51(m: 6H), 1.38- 1.37 (m， 12H), 0.91 (t， 9H, J= 6.8Hz)。 反应步骤 2.3
Figure imgf000009_0004
Figure imgf000009_0002
与反应步骤 L3相似， 得到式 9的化合物。 式 9的化合物为无色固体， 产率 42%。 1H NMR, δ: 7.91 (s, 3H), 7.77 (s, 3H)， 5.92 (s, 311)， 4.24 (t， 6H, J = 6.4 Hz), 1.95-1.90 (m, 6H), 1.56-1.53 (m， 6H), 1.43-1.39 (m， 12H), 0.95 (t, 9H，J= 6.8 Hz)。 反应步骤 2.4
H2SQ4 (40%) ηο。6Η120
Figure imgf000009_0003
与反应步骤 1.4相似， 得到式 10的化合物为无色粉末， 产率 83%。 反应步骤 2.5
HOC6H120-<^^ -COOH + CH2=CHCOCI CH2=CHCO OCeH^O— <^^>-COOH
10 11
式 10的化合物 (10g， 42mmol)加入到三乙胺 (5ml)和四氢呋喃 (30ml)中， 滴加丙烯酰氯 (6.6g, 63mmol), 0.5h滴加完毕。 室温反应过夜。 倒入水 (150ml)中， 过滤生成的沉淀， 粗 产物用乙醇重结晶， 得到式 11的化合物为无色粉末（ 8.2g)，产率 64%。 'Η ΝΜΙ , & δ.Οό ^, 2Η, J= 8·7Ηζ)， 6.93 (d， 2H， J = 8.7Hz), 6.48 (dd, 1H， J = 1.5， 17.4Hz), 6.21 (dd, 1H, J= 10.2， 17.4Hz), 5.86 (dd, 1H, J = 1.5, 10.2Hz), 4.17 (t, 2H, J = 6.6Hz)， 4.05 (t, 2H， J = 6.6Hz), 1.85-1.81 (m, 2H), 1.75-1.70 (m, 2H), 1.53-1.46 (m, 4H)。
Figure imgf000010_0001
式 9的化合物 (0.12g， 0.208mmol), 式 11的化合物 (0.49g， 1.67mmol) 和 DCC (0.34g, 1.67mmol)加入到二氯甲垸 (5ml)中， 加入 DMAP (催化量)， 室温反应过夜。 过滤， 用二氯 甲烷洗涤滤饼，滤液旋干。粗产物用硅胶柱提纯 (淋洗液二氯甲焼 /乙酸乙酯，体积比 100:1)， 得到式 12的化合物为无色固体 (0.24g)， 产率 84%。 1H NMR, 8.15 (s, 3H), 8.11 (d, 6H, J= 7.2Hz), 7.72 (s， 3H), 6.88 (d, 6H, J = 7.2Hz), 6.45 (dd, 3H， J = 1.5, 17.4Hz), 6.19 (dd， 3H, J = 10.2, 17.4Hz), 5.85 (dd, 3H， J = 1.5, 10.2Hz), 4.22 (m, 12H), 4.03(t, 6H, J = 6.3Hz), 1.88-1.68 (m, 18H), 1.60-1.53(m, 12H), 1.49-1.12 (m, 18H)， 0.78 (t, 9H, J= 6.8 Hz 用偏光显微镜测试， 该化合物熔点为 92°C， 清亮点为 134'C。 在升温时形成盘状液晶 向列相， 其织构图见图 2。 实施例
Figure imgf000010_0002
反应歩骤 3.1
Figure imgf000010_0003
式 13的化合物 (20g，0.1816mol)， 1-溴代正己烷 (89.9g， 0.5448mol)， 无水碳酸钾 (75.3g， 0.5448mol)及碘化钾 (6.0g)在无水乙醇 (250ml)中回流 48小时。 冷却到室温， 抽滤。 滤饼用 丙酮 (150ml)洗涤两次。 滤液浓缩， 再减压蒸馏， 收集 149-157'C (0.7mmHg) 的馏分， 得 式 14的化合物为无色油状液体 (48g)， 产率 96%。 1H NMR, δ: 6.89 (s, 4H), 3.99 (t, 4H， J= 6.9 Hz), 1.83-1.76 (m, 4H, J= 6.9 Hz), 1.49-1.31 (m, 12H), 0.9 (t, 6H, J= 6.9 Hz)。 反应步骤 3.2
Figure imgf000011_0001
室温下， 式 14的化合物 （21.3g， 76.6mmol) 和三氯化铁 (41.0g， 252.84mmol) 在 DCM (510 ml) 中搅拌 1.5h。 再转入甲醇 (100ml)和冰 (200g)的混合物中， 过滤出生成的沉淀， 粗 产物用硅胶柱提纯 (乙酸乙酯 /石油醚， 体积比 1 :50)， 得到式 15的化合物为无色固体 (13.3 g), 产率 63% Ή NMR, S: 7.84 (s， 6H)， 4.23 (t， 12H, J = 6.9 Hz), 1.94 (t, 12H, J = 6.9 Hz), 1.58-1.38 (m, 36H)， 0.94 (t, 18H， J= 6.9 Hz)。
Figure imgf000011_0002
氩气保护下，式 15的化合物 （3g，3.4mmol) 和 溴 -9-硼杂双环 [3.3.1]壬垸（ 16.3mmol， 1 mol dm"3 的二氯甲烷溶液 16.3ml) 室温反应 30h， 然后缓慢加入 2-氨基乙醇 (1 ml)。 再加 入水 (20ml)， 用二氯甲烷 (50ml)萃取三次。 有机层用无水 MgS04干燥后除去溶剂， 粗产物 用硅胶柱提纯 (二氯甲烷 /石油醚， 体积比 3:2)， 得到式 9的化合物为无色粉末 (0.94g)， 产 率 38%。
Figure imgf000011_0003
氮气保护下，式 9的化合物 (5.8g, lOmmol), 5-氯小苯基 -1H-四唑 (1.81g， lOmmol), 碳酸 钾 (2.76,20mmol)在丙酮（40ml )中回流 18h。冷却到室温， 过滤， 用丙酮 (30ml)冼涤滤饼。 把滤液倒入 140ml水中，滤出生成的沉淀，减压干燥，得粗产品 7g。溶于四氢呋喃（20ml ) 和苯 (20ml)中， 加入钯碳 (0.35g)， 通入氢气， 40°C时反应 24h. 降温到室温， 过滤， 旋去溶 剂， 粗产物用硅胶柱提纯 (二氯甲烧 /石油醚， 体积比 1 :3)， 得到式 16的化合物为无色粉末 (4.3g)，产率 81%。 1H NMR, S: 8.43 (d, 3H, J= 9.0 Hz), 7.92 (d, 3H, J= 2.4 Hz), 7.19 (dd， 3H, J = 9.0, 2.4 Hz),4.16 (t， 6H, J = 6.6Hz), 1.93 (m, 6H), 1.55-1.51 (m, 6H), 1.39-1.37 (m, 12H), 0.93 (t, 9H, J= 6.6 Hz)。
Figure imgf000012_0001
氮气保护下， 式 16的化合物 （0.53g, lmmol)加入到干燥的二氯甲烷 （15ml) 中， 降 温到 O'C, 滴加三溴化硼 (1.5g, 6mmol), 自然升温到室温， 倒入冰水中， 过滤生成的沉淀， 减压干燥，得式 17的化合物为浅灰色粉末 0.28g (产率 100%)。 Ή NMR (CD3OD) δ: 8.36 (d, 3H, J= 9.0 Hz), 7.86 (d, 3H, J= 2.4 Hz), 7.07 (dd, 3H， J= 9.0, 2.4 Hz)。 反应步骤 3.6
HOC6H120
Figure imgf000012_0002
与反应步骤 2.5相似，得到式 18的化合物为无色粉末，产率 90%。 Ή NMR, δ: 8.06 (d， 2H, J = 9.0 Hz), 6.94 (d， 2H, J = 9.0 Hz), 6.09(s, 1 H), 5.55 (s， 1H), 4.19 (t, 2H, J = 6.6Hz), 4.05(t, 2H， J= 6.6Hz), 1.94 (s, 3H), 1.85-1.70 (m, 4H)， 1.53-1.46 (m, 4H)。
Figure imgf000012_0003
氮气保护下， 式 17的化合物 (0.1g， 0.36mmol)加入到干燥的四氢呋喃 （10ml ) 中， 再 加入式 18的化合物 (0.5g， 1.62mmol), DCC(0.33g, 1.62mmol)和 DMAP (催化量）， 室温反 应过夜. 过滤， 把滤液旋干得粗产物， 用硅胶柱提纯 (二氯甲焼 /乙酸乙酯， 体积比 60:1), 得到式 19的化合物为无色粉末（0.26g)，产率 65%。 1H NMR, δ: 8.60 (d, 3H, J= 9.0 Hz), 8.42 (s, 3H)， 8.24 (d， 6H, J= 9.0 Hz), 7.54 (d, 3H, J= 9.0 Hz), 7.16 (d， 6H, J= 9.0， 2.4 Hz), 6.11 (s, 3H), 5.56 (s, 3H), 4.20 (t， 6H, J = 6.6Hz), 4.10 (t， 6H, J = 6.6Hz), 2.17 (s, 9H)， 1.95-1.70 (m， 12H), 1.61-1.50 (m, 12H)。 用偏光显微镜测试， 该化合物室温下为蜡状固体， 熔点为 134°C。 实施例 4
合成式 23的化合物
Figure imgf000013_0001
反应步骤与反应步骤 3.3相似， 得到式 4的化合物为无色粉末， 产率 45%。 反应步骤 4.2
Figure imgf000013_0002
反应步骤与反应步骤 3.4相似。得到式 20的化合物为无色粉末， 产率 45%。 1H NMR, δ: 8.50 (d, 2H, J = 9.0 Hz), 8.44 (d, 1H, J= 9.0 Hz), 7.96 (s， 1H)， 7.95 (s, 2H), 7.28 (d, 2H, J = 9.0 Hz), 7.22 (d, 1H, J= 9.0 Hz), 4.23 (m, 6H), 1.95-1.91 (m, 6H), 1.58-1.55 (m, 6H), 1.43-1.4 (m, 12H), 0.98-0.96 (m, 9H)。 反应步骤 4.3
Figure imgf000014_0001
反应步骤与反应步骤 3.5相似， 得到式 21的化合物为无色粉末， 产率 100%。 反应步骤 4.4
Figure imgf000014_0002
与反应步骤 1.4相似， 得到式 22的化合物为无色粉末，产率 82%。 1H NMR, δ 8.07 (d, 2H， J = 9.0 Hz), 6.95 (d, 2H, J = 9.0 Hz), 4.04 (t， 2H, J = 6.6Hz)， 1.85-1.76 (m, 2H)， 1.49-1.31 (m, 8H)， 0.92 (t， 3H, J= 6.6Hz)。
Figure imgf000014_0003
步骤与反应步骤 1.5相似， 得到式 23的化合物为无色粉末，产率 81%。 'H NMR, <5: 8.1 (d, 2H, J= 9.0 Hz), 8.61 (d, 1H, J= 9.0 Hz), 8.41 (s, 1H), 8.36 (s， 2H)， 8.25-8.19 (m, 6H), 7.55 (s, 2H), 7.53 (s, 1H), 7.03-6.98 (m, 6H), 4.10-4.04 (m, 6H)， 1.85-1.82 (m, 6H)， 1.49-1.25 (m, 24H), 0.91 (m, 9H)。 用偏光显微镜测试， 该化合物室温下为蜡状固体， 熔点为 183T：。 s/u/ O ioosld ϊ/-ϊ68ϊεϊοίAV
Figure imgf000015_0001
Figure imgf000016_0001
由上表可知， 本发明提供的苯并菲的衍生物的清亮点远低于现有材料的清亮点， 可以 达到节省能源， 减化制备工艺的目的。

Claims

权利要求
-种盘状分子化合物， 具有通式 (I)或通式 (Π)的结构,
Figure imgf000017_0001
(II)
其中：
R1选自 H、 F、 Cl、 Br、 -CN、 -SCN、 OR2或 SR2， 其中 R2为可被一个或多个 F、 CI 或 Br取代的具有 1到 20个 C原子的直链或支链垸基， 其中所述具有 1到 20个 C原子的 直链或支链垸基中的一个或多个不相邻的 CH2基团可以被 -0-、-CO-0-、-0-CO-或 -0-CO-0- 代替， 前提是 0原子不直接相连：
L为符合下式的连接基团：
-A1-A2-A3 -A4-(A5-A4)a-(A5)b-( A6)c -，
其中 A1端与苯并菲核连接， A1为 -0-CO-, A2为亚苯基， A3为 -0-、 -0-CO-、 -CO-0-、 -NH-CO-或 -0-CO-0-, A4为 1到 12个碳原子的亚烷基， A5为 -0-， A6为 -CO-, a=0、 1或 2, b=0或 1， c=0或 1 ;
Q 为 H 或可聚合的官能团 所述可聚合的官能团选自由 -CH=CH2
CH=CH,
—— CH=CH CH, C7H, 一 CH=CH-n-C,H_ CH 3
CH C O
CH,
C— CH.
CH， 、—— C≡ CH H OH、一 CHO、—— COOH N==C— O
NH, SH和一 N= C= S组成的组。
2. 如权利要求 1所述的盘状分子化合物， 其特征在于， 所述 L选自下列通式组成的 组： -O-CO-Ph-O-R- (Ll);
-O-CO-Ph-O-R-O- (L2);
-O-CO-Ph-O-R-CO- (L3);
-O-CO-Ph-O-R-O-CO- (L4);
-O-CO-Ph-O-R-O-R-O-CO- (L5);
-O-CO-Ph-O-R-O-R-O-R-O-CO- (L6);
-O-CO-Ph-O-CO-R- (L7);
-O-CO-Ph-O-CO-R-O- (L8);
-O-CO-Ph-O-CO-R-O-CO- (L9);
-O-CO-Ph-O-CO-R-O-Al-O-CO- (L10);
-O-CO-Ph-NH-CO-R- (LID;
- O-CO-Ph-NH-CO-R-O- (L12);
-O-CO-Ph-NH-CO-R-O-CO- (L13);
-O-CO-Ph-NH-CO-R-O-R-O-CO- (L14);
-O-CO-Ph-CO-O-R- (L15)；
-O-CO-Ph-CO-O-R-O- (L16);
-O-CO-Ph-CO-O-R-O-CO- (L17);
-O-CO-Ph-CO-O-R-O-R-O-CO- (L18);
-O-CO-Ph-O-CO-O-R- (L19);
-O-CO-Ph-O-CO-O-R-O- (L20);
-O-CO-Ph-O-CO-O-R-O-CO- (L21)； 以及
-O-CO-Ph-O-CO-O-R-O-R-O-CO- (L22)； 其中，
R为 1到 12个 C原子的亚垸基； 并且
Ph为亚苯基。
3. 如权利要求 2 所述的盘状分子化合物， 其特征在于， 所述盘状分子化合物选自下 列化合物组成的组
Figure imgf000018_0001
( 12)；
( 19)； 以及
Figure imgf000019_0001
(23 )。
4. 一种液晶介质， 其特征在于， 包含一种或更多种如权利要求 1-3所述的盘状分子化 合物。
5. 一种液晶显示器的光学补偿膜， 其特征在于， 所述光学补偿膜包含权利要求 4所 述的液晶介质。
6 一种液晶显示器的光学补偿盒， 其特征在于， 所述光学补偿盒包含权利要求 4所述 的液晶介质。
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CN105461628B (zh) * 2014-07-07 2020-05-15 江苏和成新材料有限公司 苯并菲-苝单酰亚胺二甲酸酯二元化合物及其制备方法及应用
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