Nothing Special   »   [go: up one dir, main page]

CN113528149A - Liquid crystal compound, liquid crystal composition and high-frequency assembly comprising liquid crystal compound - Google Patents

Liquid crystal compound, liquid crystal composition and high-frequency assembly comprising liquid crystal compound Download PDF

Info

Publication number
CN113528149A
CN113528149A CN202010288462.3A CN202010288462A CN113528149A CN 113528149 A CN113528149 A CN 113528149A CN 202010288462 A CN202010288462 A CN 202010288462A CN 113528149 A CN113528149 A CN 113528149A
Authority
CN
China
Prior art keywords
liquid crystal
crystal compound
group
carbon atoms
reaction
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202010288462.3A
Other languages
Chinese (zh)
Other versions
CN113528149B (en
Inventor
李娟利
李建
安忠维
车昭毅
万丹阳
张璐
莫玲超
杨晓哲
胡明刚
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xian Modern Chemistry Research Institute
Original Assignee
Xian Modern Chemistry Research Institute
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xian Modern Chemistry Research Institute filed Critical Xian Modern Chemistry Research Institute
Priority to CN202010288462.3A priority Critical patent/CN113528149B/en
Publication of CN113528149A publication Critical patent/CN113528149A/en
Application granted granted Critical
Publication of CN113528149B publication Critical patent/CN113528149B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
    • 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
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3059—Cyclohexane rings in which at least two rings are linked by a carbon chain containing carbon to carbon triple bonds
    • 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
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3098—Unsaturated non-aromatic rings, e.g. cyclohexene rings
    • 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
    • C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
    • C09K19/44—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40 containing compounds with benzene rings directly linked
    • 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
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
    • C09K2019/3009—Cy-Ph
    • 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
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
    • C09K2019/3016—Cy-Ph-Ph
    • 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
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3059—Cyclohexane rings in which at least two rings are linked by a carbon chain containing carbon to carbon triple bonds
    • C09K2019/3063—Cy-Ph-C≡C-Ph
    • 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
    • C09K2219/00—Aspects relating to the form of the liquid crystal [LC] material, or by the technical area in which LC material are used
    • C09K2219/11—Aspects relating to the form of the liquid crystal [LC] material, or by the technical area in which LC material are used used in the High Frequency technical field

Landscapes

  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention provides a liquid crystal compound, a composition containing the compound and a high-frequency component containing the composition. Wherein, the structural general formula of the liquid crystal compound is shown as the formula (I):
Figure DDA0002449458470000011
wherein ring A is cyclohexyl or cyclohexenyl; r1Is one of a C1-9 linear alkyl group, a linear alkoxy group, a linear fluoroalkyl group, or a C2-9 alkenyl group, an alkenyloxy group, or a difluorovinyl group; x1～X6is-H or-Cl, and at least one is-Cl; m is 0 or 1. The liquid crystal compound has the advantages of low melting point, low dielectric loss, high tuning rate and lower rotational viscosity, and a nematic phase liquid crystal composition formed by adding the liquid crystal compound into mixed liquid crystal not only has low dielectric loss and high tuning rate, but also has low dielectric loss and high tuning rateThe high-frequency component has wide nematic phase temperature range, low melting point and lower rotational viscosity, can improve the performance of the high-frequency component when used for the high-frequency component, and is particularly suitable for the fields of intelligent antenna liquid crystal phase shifters and 5G communication networks.

Description

Liquid crystal compound, liquid crystal composition and high-frequency assembly comprising liquid crystal compound
Technical Field
The invention belongs to the technical field of liquid crystal materials, and particularly relates to an alkyne liquid crystal compound, a composition thereof and a high-frequency component comprising the alkyne liquid crystal compound, which are suitable for the fields of filters, adjustable frequency selection surfaces, phase shifters, phased array radars, satellite navigation, 5G communication networks and the like.
Background
In recent years, liquid crystal materials with low dielectric loss and high dielectric tuning rate have attracted attention for application in liquid crystal microwave device technologies such as smart antennas, filters, tunable frequency selective surfaces, phase shifters, phased array radars, 5G communication networks, and the like.
The dielectric loss of the liquid crystal material is an important factor influencing the insertion loss of the microwave device, and in order to obtain a high-quality liquid crystal microwave device, the dielectric loss of the liquid crystal material must be reduced as much as possible. For a liquid crystal material, the loss tangent varies with the liquid crystal molecules according to the electric field direction, i.e., the loss in the long axis direction and the short axis direction of the liquid crystal molecules varies, and the maximum loss value is generally used as the dielectric loss value of the liquid crystal material when calculating the loss of the liquid crystal material. In addition, the dielectric tuning rate of the liquid crystal material determines the max (tan δ) of the microwave device∥,tanδ⊥) The dielectric tuning rate of the liquid crystal material is determined by the dielectric anisotropy (. DELTA.. di-elect cons.) of the liquid crystal material under microwave and the dielectric constant (. di-elect cons.) in the direction parallel to the molecules∥) Is determined by the ratio of:
τ＝Δε/ε∥
in order to comprehensively evaluate the performance of the liquid crystal material under high frequency, a quality factor (eta) is introduced:
η＝τ/max(tanδ∥,tanδ⊥)
that is, the smaller the loss of the liquid crystal material and the larger the tuning rate, the larger the quality factor, indicating the better the performance of the liquid crystal material.
The nematic phase temperature range of the liquid crystal material determines the working temperature range of the liquid crystal microwave device, and the wider nematic phase temperature interval of the liquid crystal material means the wider working temperature range of the microwave device. The rotational viscosity of the liquid crystal material determines the response speed of the microwave device, the smaller the rotational viscosity is, the faster the response speed is, and in order to meet the requirement of fast switching operation of a high-frequency component, the liquid crystal material needs to have lower rotational viscosity.
In order to satisfy the requirement that the high-frequency component works under the driving of an electric field, the liquid crystal material is required to have a proper dielectric constant under a low frequency, such as 1 KHz. Since the dielectric constant of a liquid crystal material at high frequencies is related to the birefringence of the liquid crystal, it is shown by the following formula:
Figure BDA0002449458460000021
in order to obtain a higher dielectric constant, a liquid crystal material having a high birefringence is also required. The isothiocyanic liquid crystal compound has higher birefringence and larger dielectric anisotropy compared with the conventional fluorine-containing liquid crystal, has higher birefringence and lower rotational viscosity compared with cyano-based liquid crystal, and particularly has lower dielectric loss.
Merck discloses in a patent application No. 201510482208.6 entitled "liquid Crystal Medium and high frequency Module comprising the same" composition M-1 of example 1 suitable for microwave Range applications, formed from a liquid crystalline compound containing fluorinated tolanylidene isothiocyanate and fluorinated phenyl tolanylidene isothiocyanate, having a low rotational viscosity at 20 ℃ of 270 mPas, but a high dielectric loss at 19GHz of 0.0143. The patent discloses that the composition M-4 of example 4, applied in the microwave range, formed from a liquid crystal compound of fluorinated tolytene isothiocyanate, fluorinated terphenyl isothiocyanate and fluorinated phenyl tolytene isothiocyanate, has a rotational viscosity of 698mPa s at 20 ℃ and a dielectric loss of 0.0189 at 19 GHz.
Merck corporation, in "proc.ofspie, 2013, 8642: 86420S-1-86420S-6, entitled "liquid crystal systems for microwave applications" reported that liquid crystal molecules with a bis-tolane skeleton have high tuning rate and low dielectric loss, but the liquid crystal molecules with the bis-tolane skeleton have the problems of large rotational viscosity, high melting point and poor compatibility, and the application of the liquid crystal molecules in mixed liquid crystal formulations is limited. For example, in the journal "liquid crystals, 2000, 27 (2): 283-287 ", entitled" synthetic diacetylated biostoral liquid crystals ", reports on liquid crystal compounds of the bis-diphenylacetylene, the typical structural formula being shown below:
Figure BDA0002449458460000031
the thermal performance data is Cr143.2N192.4I, namely the melting point value is as high as 143.2 ℃. The melting point can be further reduced by extending the terminal flexible chain and introducing larger substituents such as ethyl groups laterally, for example "Liquidcrystals, 2000, 27 (2): 283-287 ", entitled" Synthesis of bis-diphenylacetylene liquid crystal compounds PTP (2) TP-6-3, having the structural formula shown below:
Figure BDA0002449458460000032
the thermal data is Cr20.0N107.8I, namely the melting point value is reduced to 20.0 ℃. The rotational viscosity values of the compounds at 20 ℃ of up to 2100 mPas are disclosed in the patent with the title "component and liquid-crystalline medium for high-frequency technology" filed under the name of Merck, Inc. No. 201080041956.6.
In the patent of Merck, Inc. No. 201280063201.5, entitled "liquid Crystal Medium and high frequency Components containing it", a liquid Crystal mixture M-1 for use in the microwave range is disclosed, consisting of the compound PTP (2) TP-6-3 and a fluorine-containing tolane compound, the rotational viscosity at 20 ℃ of which is reduced to 718mPa · s, the tuning ratio at 30GHz of 0.25, and the dielectric loss of which is 0.0128. Although the tuning rate, the dielectric loss and the rotational viscosity are improved to a certain extent, the tuning rate is still low, the dielectric loss is still high, and the comprehensive performance needs to be further improved.
Disclosure of Invention
Technical problem to be solved
In order to overcome the drawbacks or disadvantages of the background art, the present invention proposes a liquid crystal compound having low dielectric loss, high tuning rate, low melting point, wide nematic phase temperature range and low rotational viscosity, a composition comprising the same, and a high frequency device comprising the same.
(II) technical scheme
In order to solve the technical problems, the invention provides a liquid crystal compound, and the structural general formula of the liquid crystal compound is shown as the formula (I):
Figure BDA0002449458460000041
wherein ring A is cyclohexyl or cyclohexenyl; r1Is one of a C1-9 linear alkyl group, a linear alkoxy group, a linear fluoroalkyl group, or a C2-9 alkenyl group, an alkenyloxy group, or a difluorovinyl group; x 1～X6is-H or-Cl, and at least one is-Cl; m is 0 or 1.
Further, the structure of the liquid crystal compound is one of the following formulas:
Figure BDA0002449458460000042
wherein R is1Is a linear alkyl group having 1 to 9 carbon atoms or an alkenyl group having 2 to 7 carbon atoms; x1～X6is-H or-Cl, and at least one is-Cl.
Further, the structure of the liquid crystal compound is one of the following formulas:
Figure BDA0002449458460000043
Figure BDA0002449458460000051
wherein R is1Is a linear alkyl group having 1 to 9 carbon atoms or an alkenyl group having 2 to 7 carbon atoms.
Further, the structure of the liquid crystal compound is one of the following formulas:
Figure BDA0002449458460000052
wherein R is1Is a linear alkyl group having 1 to 9 carbon atoms or an alkenyl group having 2 to 7 carbon atoms; x1～X6is-H or-Cl, and at least one is-Cl.
Further, the structure of the liquid crystal compound is one of the following formulas:
Figure BDA0002449458460000053
Figure BDA0002449458460000061
wherein R is1Is a linear alkyl group having 1 to 9 carbon atoms or an alkenyl group having 2 to 7 carbon atoms.
In addition, the invention also provides a liquid crystal composition, which comprises 1-90% of a liquid crystal compound shown in a general formula (I), 1-60% of a liquid crystal compound shown in a general formula (II), and 0-50% of a liquid crystal compound shown in a general formula (III):
Figure BDA0002449458460000062
wherein ring A is cyclohexyl or cyclohexenyl; r 1Is one of a C1-9 linear alkyl group, a linear alkoxy group, a linear fluoroalkyl group, or a C2-9 alkenyl group, an alkenyloxy group, or a difluorovinyl group; x1～X6is-H or-Cl, and at least one is-Cl; m is 0 or 1;
Figure BDA0002449458460000063
wherein R is2、R3Each of which is a linear alkyl group, a linear alkoxy group, or a fluoroalkyl group having 1 to 9 carbon atoms, or an alkenyl group, an alkenyloxy group, or a difluorovinyl group having 2 to 9 carbon atoms; b is a single bond, an ethane bridge bond or a carbon-carbon triple bond; x7～X13is-H or-Cl, and at least one is-Cl; n and p are 0 or 1.
Further, the liquid crystal compound represented by the general formula (II) is 10 to 50% and the liquid crystal compound represented by the general formula (III) is 5 to 40%.
Further, the present invention also provides a high-frequency component comprising any one or more of the liquid crystal compounds described above, or the liquid crystal composition of any one of the above.
In addition, the invention also provides a method for preparing the liquid crystal compound, which is characterized by adopting the following synthetic route:
Figure BDA0002449458460000071
the method comprises the following steps:
s1, sequentially adding the raw material (1), calcium carbonate and water into a reaction bottle, adding elemental iodine at the temperature of-5 ℃, and reacting for 2 hours under heat preservation for post-treatment; filtering the reaction solution, extracting the filtrate with toluene, washing the filtrate to be neutral, drying the filtrate with anhydrous magnesium sulfate, filtering, performing rotary evaporation on the filtrate to remove the toluene, and adding a mixed solution of toluene and n-heptane for recrystallization to obtain an intermediate (2);
S2, under the protection of nitrogen, adding the intermediate (2), the raw material (3), bis (triphenylphosphine) palladium dichloride, TBAB and K into a reaction bottle2CO3Toluene, ethanol, water; carrying out reflux reaction for 4h, and then cooling to room temperature for post-treatment; standing and layering the reaction solution, adding toluene into the lower layer for extraction, combining organic phases, washing the organic phases to be neutral, drying the organic phases with anhydrous magnesium sulfate, filtering, and performing recrystallization after rotary evaporation of the filtrate to obtain an intermediate 5; or under the protection of nitrogen, adding the intermediate (2), the raw material (4), bis (triphenylphosphine) palladium dichloride, cuprous iodide, triphenylphosphine and triethylamine into a reaction bottle, reacting for 2 hours, and then carrying out aftertreatment; filtering the reaction solution, carrying out rotary evaporation on the filtrate to remove triethylamine, adding toluene to dissolve, washing with water to be neutral, drying with anhydrous magnesium sulfate, filtering, and carrying out recrystallization on the filtrate after rotary evaporation to obtain an intermediate (5);
s3, adding the intermediate (5), acetone and water into a three-necked bottle, dropwise adding thiophosgene at room temperature, reacting at room temperature for 1 hour after the thiophosgene is added, and monitoring by TLC to stop the reaction when no raw material remains; and (3) carrying out rotary evaporation, adding toluene to dissolve the obtained crude product, washing with water to neutrality, drying with anhydrous magnesium sulfate, filtering, carrying out rotary evaporation, dissolving with n-heptane, and carrying out column chromatography purification to obtain the target compound (6).
10. The method of claim 9, wherein in step S1, the molar ratio of the raw material (1), calcium carbonate and iodine is 1:1.3 (1-0.95), and the reaction temperature is-5-50 ℃; in the step S2, the molar ratio of the intermediate (2) to the raw material (3) is 1 (1-1.3), the temperature of the Suzuki coupling reaction is 0-90 ℃, and the intermediate (2) is bis (triphenylphosphine) palladium dichloride, TBAB: K2CO3The molar ratio of (1), (0.1% -3%) (0.1-0.5) to (1-5); or in the step S2, the molar ratio of the intermediate (2) to the raw material (4) is 1 (1-1.1), the Soniganshira coupling reaction temperature is 0-50 ℃, and the molar ratio of the intermediate (2) to bis (triphenylphosphine) dichloride to cuprous iodide to triphenylphosphine is 1 (0.1-3%) (0.3-9%); in step S3, the molar ratio of the intermediate (5) to the thiophosgene is 1 (1-2).
(III) advantageous effects
The invention provides a liquid crystal compound, a composition containing the compound and a high-frequency component containing the composition. The liquid crystal compound has the advantages of low melting point, low dielectric loss, high tuning rate and low rotational viscosity, and a nematic phase liquid crystal composition formed by adding the liquid crystal compound into mixed liquid crystal has low dielectric loss and high tuning rate, also has a wide nematic phase temperature range, low melting point and low rotational viscosity, can improve the performance of a high-frequency component when being used for the high-frequency component, and is particularly suitable for the fields of intelligent antenna liquid crystal phase shifters and 5G communication networks. The preparation method of the liquid crystal compound has the advantages of short synthesis steps, low raw material cost, easy operation of experimental process and simple post-treatment process.
Detailed Description
In order to make the objects, contents and advantages of the present invention clearer, the following detailed description of the embodiments of the present invention will be given in conjunction with examples.
GC in the examples represents gas chromatography purity (%), test instrument: an HP6820 gas chromatograph of Agilent;1HNMR stands for nuclear magnetic resonance hydrogen spectrum, test instrument: advanced500MHz NMR spectrometer from Bruker; GC-MS represents the gas chromatograph-mass spectrometer, test instrument: agilent MS5975C model GC.
The physical property test method of the liquid crystal compound is as follows:
clearing spot (T)ni): the polarizing hot stage method: and coating the liquid crystal sample on a glass slide, placing the glass slide in an orthogonal polarization microscopic hot table, setting the heating rate to be 3 ℃/min, and observing the temperature of the liquid crystal sample when the liquid crystal sample turns black from a bright state, namely the clearing point. Differential scanning calorimetry: under the protection of nitrogen, the heating rate is set to be 3 ℃/min.
The method for testing the physical properties of the liquid crystal compound under high frequency comprises the following steps: adding the mixed liquid crystal into a basic formula (Host) according to the mass ratio of 20%, and testing the dielectric anisotropy delta epsilon, the dielectric tuning rate tau and the dielectric loss (tan delta) of the mixed liquid crystal at 19GHz by adopting a vector network analyzer and a cavity perturbation method ∥,tanδ⊥) And calculating to obtain the quality factor eta.
Example 1
Synthesis of 2-chloro-4 '- (4-propylcyclohexyl) -4-isothiocyanate-1, 1' -biphenyl
The concrete structure is as follows:
Figure BDA0002449458460000091
the preparation process comprises the following steps:
step 1: synthesis of 3-chloro-4-iodoaniline
Figure BDA0002449458460000092
M-chloroaniline (30g,0.235mol), iodine (179g,0.705mol) and 500ml of water were charged into a reaction flask, and the reaction was stirred at 45 ℃ for 4.5 hours. The reaction solution is cooled to room temperature and then extracted with toluene for 3 times, the organic phases are combined, washed to neutrality by water and the solvent is evaporated. Recrystallizing to obtain the solid, namely 47g of the 3-chloro-4-iodoaniline, with the purity of 99 percent and the yield of 79 percent.
Step 2: synthesis of 2-chloro-4 '- (4-propylcyclohexyl) - [1,1' -biphenyl ] -4-amine
The concrete structure is as follows:
Figure BDA0002449458460000093
to a reaction flask under nitrogen protection were added (4- (4-propylcyclohexyl) phenyl) boronic acid (6.35g, 0.0256mol), 3-chloro-4-iodoaniline (4.99g,0.0197mol), potassium carbonate (27.19g, 0.197mol), PdCl2(PPh3)2(0.14g,0.2mmol), tetrabutylammonium bromide (0.64g, 2.0mmol), 100ml of toluene, 100ml of ethanol, and 100ml of water. And carrying out reflux reaction for 8h, and carrying out post-treatment. The reaction solution was extracted with toluene 3 times, the organic phases were combined, washed with water to neutrality, and dried over anhydrous magnesium sulfate. After the solvent is removed by rotary evaporation, the obtained crude product is recrystallized by toluene to obtain 2-chloro-4 '- (4-propylcyclohexyl) - [1,1' -biphenyl ] benzene ]5.04g of (E) -4-amine, purity 99.74% and yield 77%.
And step 3: synthesis of 2-chloro-4-isothiocyanate-4 '- (4-propylcyclohexyl) -1,1' -biphenyl
The concrete structure is as follows:
Figure BDA0002449458460000101
2-chloro-4 '- (4-propylcyclohexyl) - [1,1' -biphenyl ] -4-amine (5.70g, 0.0154mol), thiophosgene (3.53g, 0.0308mol) and 50mL of chloroform were added to a reaction flask, and the reaction was stirred at 50 ℃ for 1 hour. Adding water into the reaction solution, stirring, layering, adding chloroform into the water layer, extracting, combining several layers, washing to neutrality, and drying with anhydrous magnesium sulfate. Filtering, evaporating filtrate to dryness, purifying by column chromatography, and recrystallizing to obtain white solid 4.05g with purity of 99.79% and yield of 71%.
And (3) structural identification:
1HNMR(CDCl3,500MHz)δ(ppm):0.934-0.963(t,3H), 1.066-1.147(m,2H),1.243-1.286(m,2H),1.313-1.436(m,3H), 1.506-1.563(m,2H),1.907-1.989(m,4H),2.524-2.586(m,1H), 7.179-7.199(q,1H),7.299-7.315(d,J＝8Hz,2H),7.338-7.378(m,4H)； IR(KBr,cm-1):3063,2953,2921,2844,2102,1593,1478,1443,1388, 1070,966,866,821,781,767,697,574。
the above structural identification data indicate that the synthesized compound is indeed 2-chloro-4 '- (4-propylcyclohexyl) -4-isothiocyanate-1, 1' -biphenyl.
The liquid crystal phase transition temperature of 2-chloro-4 '- (4-propylcyclohexyl) -4-isothiocyanate-1, 1' -biphenyl was measured by DSC at a temperature rise of 3 ℃/min and found to be: Cr68.33N103.97I, melting point 68.33 deg.C, clearing point 103.97 deg.C, the compound has a lower melting point.
Example 2
Synthesis of 2-chloro-4 '- (4-ethylcyclohexyl) -4-isothiocyanate-1, 1' -biphenyl
The concrete structure is as follows:
Figure BDA0002449458460000111
2-chloro-4 '- (4-ethylcyclohexyl) -4-isothiocyanate-1, 1' -biphenyl was synthesized in the same manner as in example 1, using (4- (4-ethylcyclohexyl) phenyl) boronic acid instead of (4- (4-propylcyclohexyl) phenyl) boronic acid in step (2) of example 1.
Example 3
Synthesis of 2-chloro-4 '- (4-butylcyclohexyl) -4-isothiocyanate-1, 1' -biphenyl
The concrete structure is as follows:
Figure BDA0002449458460000112
2-chloro-4 '- (4-butylcyclohexyl) -4-isothiocyanate-1, 1' -biphenyl was synthesized in the same manner as in example 1, using (4- (4-butylcyclohexyl) phenyl) boronic acid instead of (4- (4-propylcyclohexyl) phenyl) boronic acid in step (2) of example 1. The GC purity was 99.86% and the yield was 72%.
And (3) structural identification:
1HNMR(CDCl3,500MHz)δ(ppm):0.931–0.959(t,3H),1.066– 1.146(m,2H),1.272–1.407(m,7H),1.502–1.554(m,2H),1.915– 1.988(m,4H),2.507–2.583(m,1H),7.178–7.198(q,1H),7.287– 7.336(m,3H),7.353–7.374(m,3H)；IR(KBr,cm-1):2956,2920,2849, 2088,1594,1544,1479,1270,1070,966,867,816,788,771,695,566.
the liquid crystal phase transition temperature of 2-chloro-4 '- (4-propylcyclohexyl) -4-isothiocyanate-1, 1' -biphenyl was measured by DSC at a temperature rise of 3 ℃/min and found to be: Cr43.56S54.80N 106.77I, melting point 43.56 deg.C, clearing point 106.77 deg.C, the compound has a lower melting point.
Example 4
Synthesis of 2-chloro-4 '- (4-pentylcyclohexyl) -4-isothiocyanate-1, 1' -biphenyl
The concrete structure is as follows:
Figure BDA0002449458460000121
2-chloro-4 '- (4-pentylcyclohexyl) -4-isothiocyanate-1, 1' -biphenyl was synthesized in the same manner as in example 1, using (4- (4-pentylcyclohexyl) phenyl) boronic acid instead of (4- (4-propylcyclohexyl) phenyl) boronic acid in step (2) of example 1. The purity was 99.84%, and the yield was 70%.
And (3) structural identification:
1HNMR(CDCl3,500MHz)δ(ppm):0.929-0.957(t,3H), 1.052-1.150(m,2H),1.265-1.385(m,9H),1.482-1.574(m,2H), 1.914-1.991(m,4H),2.526-2.587(m,1H),7.178-7.199(q,4H), 7.287-7.338(m,3H),7.354-7.380(m,3H)；IR(KBr,cm-1):2952,2921, 2847,2087,1594,1480,1385,1270,1070,967,868,816,768,694,566。
the above structural identification data indicate that the synthesized compound is indeed 2-chloro-4 '- (4-pentylcyclohexyl) -4-isothiocyanate-1, 1' -biphenyl.
The liquid crystal phase transition temperature of 2-chloro-4 '- (4-propylcyclohexyl) -4-isothiocyanate-1, 1' -biphenyl was measured by DSC at a temperature rise of 3 ℃/min and found to be: Cr161.28Cr267.02N 122.66I, melting point 67.02 deg.C, clearing point 122.66 deg.C, the compound has a lower melting point.
The monomer liquid crystal is added into the basic formula Host in a mass percent of 20% to form a mixed liquid crystal, and the physical properties of the formula at 19GHz are tested at 20 ℃ and the data are shown in Table 1.
TABLE 1 test data
Mixed crystal code ε⊥ ε∥ △ε tanδ⊥ tanδ∥ τ η
Host 2.599 3.566 0.967 0.0230 0.0101 0.271 12.2
Example 4+ Host 2.504 3.357 0.853 0.0180 0.0087 0.254 14.1
After the compound of example 4 was added, the loss tangent of the mixed liquid crystal in the vertical direction of the liquid crystal molecules at 19GHz was reduced by 22% and the quality factor was increased by 16%. The compound proved to have the advantages of low dielectric loss and high quality factor.
Example 5
Synthesis of 3-chloro-4-isothiocyanate-4 '- (4-pentylcyclohexyl) -1,1' -biphenyl
The concrete structure is as follows:
Figure BDA0002449458460000131
3-chloro-4-isothiocyanate-4 '- (4-pentylcyclohexyl) -1,1' -biphenyl was synthesized in the same manner as in example 1, using (4- (4-pentylcyclohexyl) phenyl) boronic acid instead of (4- (4-propylcyclohexyl) phenyl) boronic acid in step (2) of example 1 and 2-chloro-4-iodoaniline instead of 4-iodo-3-methylaniline in step (2) of example 1.
Example 6
The specific structure of the synthesis of 2' -chlorine-4 ' -isothiocyanate-4-amyl-2, 3,4, 5-tetrahydro-1, 1':4', 1' -terphenyl is as follows:
Figure BDA0002449458460000132
2' -chloro-4 ' -isothiocyanate-4-pentyl-2, 3,4, 5-tetrahydro-1, 1':4', 1' -terphenyl was synthesized in the same manner as in example 1, using (4' -pentyl-2 ',3',4',5' -tetrahydro- [1,1' -biphenyl ]) boronic acid instead of (4- (4-propylcyclohexyl) phenyl) boronic acid in step (2) of example 1 and 3-chloro-4-iodoaniline instead of 4-iodo-3-methylaniline in step (2) of example 1.
The phase transition temperature of 2' -chloro-4 ' -isothiocyanate-4-pentyl-2, 3,4, 5-tetrahydro-1, 1':4', 1' -terphenyl was measured by DSC at a temperature rise of 3 ℃/min and the results were: Cr53.98N100.89I, melting point 53.98 deg.C, clearing point 100.89 deg.C, the compound has a lower melting point.
The monomer liquid crystal is added into the basic formula Host in a mass percent of 20% to form a mixed liquid crystal, and the physical properties of the formula at 19GHz are tested at 20 ℃ and the data are shown in Table 2.
TABLE 2 test data
Mixed crystal code ε⊥ ε∥ △ε tanδ⊥ tanδ∥ τ η
Host 2.599 3.566 0.967 0.0230 0.0101 0.271 12.2
Example 6+ Host 2.532 3.496 0.964 0.0185 0.0088 0.276 14.9
After the compound of example 6 was added, the loss tangent of the mixed liquid crystal in the vertical direction of the liquid crystal molecules at 19GHz was reduced by 20% and the quality factor was increased by 22%. The compound proves to have the advantages of low dielectric loss and high quality factor.
Example 7
Synthesis of 1- ((4- (4-pentylcyclohexyl) phenyl) ethynyl) -2-chloro-4-isothiocyanatobenzene
The specific structural formula is as follows:
Figure BDA0002449458460000141
the preparation process comprises the following steps:
step 1 Synthesis of 3-chloro-4- ((4- (4-pentylcyclohexyl) phenyl) ethynyl) amine
Figure BDA0002449458460000142
Under the protection of nitrogen, 3-chloro-4-iodoaniline (6.82g,0.0269mol) and PdCl were added into a reaction flask2(PPh3)4(0.56g,0.8mmol), cuprous iodide (0.46g,2.4mmol), triphenylphosphine (0.63g,2.4mmol), and triethylamine 60 ml. After stirring and controlling the temperature at 50 ℃, a mixed solution of 1-ethynyl-4- (4-pentylcyclohexyl) benzene (7.12g,0.028mol) and 60ml triethylamine was added dropwise, and after the addition, the reaction was carried out for 2.5 hours for post-treatment. And filtering the reaction solution, selectively evaporating the filtrate to dryness, adding toluene, washing with water to neutrality, drying with anhydrous magnesium sulfate, filtering, and carrying out rotary evaporation on the filtrate to dryness to obtain a crude product, and recrystallizing with toluene to obtain a pale yellow solid 8.48g, wherein the GC purity is 99.19%, and the yield is 83%.
Step 2:
preparation of 1- ((4- (4-pentylcyclohexyl) phenyl) ethynyl) -2-chloro-4-isothiocyanatobenzene
The specific structural formula is as follows:
Figure BDA0002449458460000143
1- ((4- (4-pentylcyclohexyl) phenyl) ethynyl) -2-chloro-4-isothiocyanatobenzene was synthesized in the same manner as in example 6, using 3-chloro-4- ((4- (4-pentylcyclohexyl) phenyl) ethynyl) amine in place of 2-chloro-4 '- (4-propylcyclohexyl) - [1,1' -biphenyl ] -4-amine in step (3) of example 6.
And (3) structural identification:
1HNMR(CDCl3,500MHz)δ(ppm):0.919-0.947(t,3H), 1.039-1.121(m,2H),1.234-1.359(m,9H),1.430-1.482(m,2H), 1.902-1.922(d,J＝10Hz,4H),2.486-2.535(m,1H),7.099-7.120(q,1H), 7.227-7.243(d,J＝8Hz,2H),7.315-7.319(d,J＝2Hz,1H),7.496- 7.536(q,3H)；IR(KBr,cm-1):2954,2919,2848,2062,1546,1477,1445, 1277,1051,965,868,831,553。
the above structural identification data indicates that the synthesized compound is indeed 1- ((4- (4-pentylcyclohexyl) phenyl) ethynyl) -2-chloro-4-isothiocyanatobenzene.
The liquid crystal phase transition temperature of 1- ((4- (4-pentylcyclohexyl) phenyl) ethynyl) -2-chloro-4-isothiocyanatobenzene was measured by DSC at a temperature rise of 3 ℃/min and found to be: Cr52.69N217.88I, the melting point is 52.69 ℃, the clearing point is up to 217.88 ℃, the nematic phase temperature range is 165 ℃, and the compound has a lower melting point, a very high clearing point and a very wide nematic phase temperature range.
The monomer liquid crystal is added into the basic formula Host in a mass percent of 20% to form a mixed liquid crystal, and the physical properties of the formula at 19GHz are tested at 20 ℃ and the data are shown in Table 3.
TABLE 3 test data
Mixed crystal code ε⊥ ε∥ △ε tanδ⊥ tanδ∥ τ η
Host 2.599 3.566 0.967 0.0230 0.0101 0.271 12.2
Example 7+ Host 2.513 3.507 0.994 0.0184 0.0083 0.283 15.4
After the compound of example 7 was added, the dielectric anisotropy value at 19GHz of the mixed liquid crystal was increased by 3%, the loss tangent in the vertical direction of the liquid crystal molecules was decreased by 20%, the tuning rate was increased by 4%, and the quality factor was increased by 26%. The compound proves to have the advantages of high tuning rate, low dielectric loss and high quality factor.
Example 8
Synthesis of 1- ((4- (4-propylcyclohexyl) phenyl) ethynyl) -2-chloro-4-isothiocyanatobenzene
Figure BDA0002449458460000161
1- ((4- (4-propylcyclohexyl) phenyl) ethynyl) -2-chloro-4-isothiocyanatobenzene was synthesized in the same manner as in example 1, using 3-chloro-4- ((4- (4-propylcyclohexyl) phenyl) ethynyl) amine in place of 2-chloro-4 '- (4-propylcyclohexyl) - [1,1' -biphenyl ] -4-amine in step (3) of example 1.
Example 9
Synthesis of 1- ((4- (4-butylcyclohexyl) phenyl) ethynyl) -2-chloro-4-isothiocyanatobenzene
Figure BDA0002449458460000162
1- ((4- (4-butylcyclohexyl) phenyl) ethynyl) -2-chloro-4-isothiocyanatobenzene was synthesized in the same manner as in example 1, using 3-chloro-4- ((4- (4-butylcyclohexyl) phenyl) ethynyl) amine in place of 2-chloro-4 '- (4-propylcyclohexyl) - [1,1' -biphenyl ] -4-amine in step (3) of example 1.
Example 10
Liquid crystal compositions containing the structures of examples 1, 3, 5, 6 (see table 4) comprise the following components: wherein "%" represents "mass percent", the measurement characteristics in examples are as follows: Δ n: anisotropy of birefringence at 20 ℃ and 589 nm; t isni: clearing the bright spots; k11: a splay elastic constant at 20 ℃; k33: a torsional elastic constant at 20 ℃; Δ ε: dielectric anisotropy at 20 ℃; gamma ray1: rotational viscosity at 20 ℃.
The viscosity is 714 mPas, the dielectric loss at 19GHz is lower than 0.009, the tuning rate can reach 0.314, and the quality factor is 35.3. The liquid crystal composition of the embodiment has particularly good low-temperature compatibility and particularly wide nematic phase temperature range, and also has particularly low dielectric loss, high quality factor and lower rotational viscosity, and further proves the advantages of the composition.
TABLE 4 example 9 composition and Properties
Figure BDA0002449458460000171
As can be seen from the data in table 4: example 10 the low temperature nematic phase temperature can reach-40 ℃, comparative example 1 was rotated
Synthesizing a fluorine-containing isothiocyanate liquid crystal compound 5- ((4- (4-butylcyclohexyl) phenyl) ethynyl) -1, 3-difluoro-2-isothiocyanate according to a literature method, wherein the structure is shown as the following formula:
Figure BDA0002449458460000172
the monomeric liquid crystal of comparative example 1 was added to the base formulation Host at a mass percent of 20% to form a mixed liquid crystal, and the physical properties of the formulation at 19GHz were tested at 20 ℃ and the data are shown in Table 5.
TABLE 5 test data
Mixed crystal code ε⊥ ε∥ △ε tanδ⊥ tanδ∥ τ η
Host 2.599 3.566 0.967 0.0232 0.0101 0.271 12.2
Comparative example 1+ Host 2.509 3.501 0.992 0.0188 0.0084 0.283 15.1
After the compound of comparative example 1 was added, the loss tangent of the mixed liquid crystal in the long axis direction of the liquid crystal molecules was reduced to 0.0188 at a high frequency, and the quality factor was increased to 15.1. The compound of example 7 has the following structure:
Figure BDA0002449458460000181
the physical properties of the formulations at 19GHz were measured at 20 ℃ and the data are shown in Table 6.
TABLE 6 test data
Mixed crystal code ε⊥ ε∥ △ε tanδ⊥ tanδ∥ τ η
Host 2.599 3.566 0.967 0.0230 0.0101 0.271 12.2
Example 7+ Host 2.513 3.507 0.994 0.0184 0.0083 0.283 15.4
Comparing the data in tables 5 and 6, it can be seen that the compound of example 7 has the advantages of lower dielectric loss and higher quality factor.
Comparative example 2
The fluorine-containing isothiocyanate liquid crystal compound 3, 5-difluoro-4-isothiocyanate-4 '- (4-pentylcyclohexyl) -1,1' -biphenyl is synthesized according to a literature method, and has the structure shown as the following formula:
Figure BDA0002449458460000182
The comparative example 2 monomer liquid crystal was added to the base formulation Host at a mass percentage of 20% to form a mixed liquid crystal, and the physical properties of the formulation at 19GHz were measured at 20 ℃ and the data are shown in Table 7.
TABLE 7 test data
Mixed crystal code ε⊥ ε∥ △ε tanδ⊥ tanδ∥ τ η
Host 2.599 3.566 0.967 0.0232 0.0101 0.271 12.2
Comparative example 2+ Host 2.563 3.484 0.921 0.0200 0.0093 0.264 13.2
After the compound of comparative example 2 was added, the loss tangent of the mixed liquid crystal in the long axis direction of the liquid crystal molecules was reduced to 0.02 at a high frequency, and the quality factor was increased to 13.2. The compound of example 4 has the following structure:
Figure BDA0002449458460000191
the monomer liquid crystal is added into a basic formula Host by mass percent of 20% to form a mixed liquid crystal, and the physical properties of the formula at 19GHz are tested at 20 ℃, wherein the loss angle of the liquid crystal molecules in the vertical direction is reduced to 0.0180, and the quality factor is increased to 14.1. The compound is proved to have the advantages of lower dielectric loss and higher quality factor.
Comparative example 3
Liquid crystal compositions containing lateral fluorine substituents of the same backbone structure as in the composition of example 9 (see table 8) comprise the following ingredients: wherein "%" represents "mass percent", the measurement characteristics in examples are as follows: Δ n: anisotropy of birefringence at 20 ℃ and 589 nm; t isni: clearing the bright spots; k11: a splay elastic constant at 20 ℃; k 33: a torsional elastic constant at 20 ℃; Δ ε: dielectric anisotropy at 20 ℃; gamma ray1: rotational viscosity at 20 ℃.
TABLE 8 comparative example 3 compositions and Properties
Figure BDA0002449458460000201
Comparing the data in table 4 and table 8 shows that: the composition of example 10 has a lower low temperature nematic temperature, and remains nematic at-40 ℃; compared with the comparative example 3, the dielectric loss of the composition of the example 10 at 19GHz is reduced by 36%, the tuning rate is improved by 8%, and the quality factor is increased by 1.7 times. It can be seen that the composition of example 10 not only has better low temperature compatibility, but also has lower dielectric loss, higher tuning rate and higher quality factor, further proving the advantages of the composition.
Comparative example 4
Example 4, a formulation consisting of fluorine-containing NCS liquid crystal monomers and properties reported in Merck patent 201510482208.6 are shown in table 9.
TABLE 9 comparative example 4 compositions and Properties
Figure BDA0002449458460000211
Comparing the data in table 4 and table 9, it can be seen that: compared with comparative example 4, the dielectric loss of example 10 at 19GHz is reduced by 53%, and the quality factor is increased by 2 times. It can be seen that the composition of example 10 has lower dielectric loss and higher quality factor, further demonstrating the advantages of the composition.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.

Claims (10)

1. A liquid crystal compound is characterized in that the structural general formula of the liquid crystal compound is shown as formula (I):
Figure FDA0002449458450000011
wherein ring A is cyclohexyl or cyclohexenyl; r1Is one of a C1-9 linear alkyl group, a linear alkoxy group, a linear fluoroalkyl group, or a C2-9 alkenyl group, an alkenyloxy group, or a difluorovinyl group; x1～X6is-H or-Cl, and at least one is-Cl; m is 0 or 1.
2. The liquid crystal compound according to claim 1, wherein the structure of the liquid crystal compound is one of the following formulae:
Figure FDA0002449458450000012
wherein R is1Is a linear alkyl group having 1 to 9 carbon atoms or an alkenyl group having 2 to 7 carbon atoms; x1～X6is-H or-Cl, and at least one is-Cl.
3. The liquid crystal compound according to claim 2, wherein the structure of the liquid crystal compound is one of the following formulae:
Figure FDA0002449458450000013
Figure FDA0002449458450000021
wherein R is1Is a linear alkyl group having 1 to 9 carbon atoms or an alkenyl group having 2 to 7 carbon atoms.
4. The liquid crystal compound according to claim 1, wherein the structure of the liquid crystal compound is one of the following formulae:
Figure FDA0002449458450000022
wherein R is1Is a linear alkyl group having 1 to 9 carbon atoms or an alkenyl group having 2 to 7 carbon atoms; x1～X6is-H or-Cl, and at least one is-Cl.
5. The liquid crystal compound according to claim 4, wherein the structure of the liquid crystal compound is one of the following formulae:
Figure FDA0002449458450000023
Figure FDA0002449458450000031
wherein R is1Is a linear alkyl group having 1 to 9 carbon atoms or an alkenyl group having 2 to 7 carbon atoms.
6. A liquid crystal composition comprising 1 to 90% of a liquid crystal compound represented by the general formula (I), 1 to 60% of a liquid crystal compound represented by the general formula (II), and 0 to 50% of a liquid crystal compound represented by the general formula (III):
Figure FDA0002449458450000032
wherein ring A is cyclohexyl or cyclohexenyl; r1Is one of a C1-9 linear alkyl group, a linear alkoxy group, a linear fluoroalkyl group, or a C2-9 alkenyl group, an alkenyloxy group, or a difluorovinyl group; x1～X6is-H or-Cl and at leastOne is-Cl; m is 0 or 1;
Figure FDA0002449458450000033
wherein R is2、R3Each of which is a linear alkyl group, a linear alkoxy group, or a fluoroalkyl group having 1 to 9 carbon atoms, or an alkenyl group, an alkenyloxy group, or a difluorovinyl group having 2 to 9 carbon atoms; b is a single bond, an ethane bridge bond or a carbon-carbon triple bond; x 7～X13is-H or-Cl, and at least one is-Cl; n and p are 0 or 1.
7. The liquid crystal composition according to claim 6, wherein the liquid crystal compound represented by the general formula (II) is 10 to 50% and the liquid crystal compound represented by the general formula (III) is 5 to 40%.
8. A high-frequency component, characterized in that it comprises a liquid crystal compound according to any one or more of claims 1 to 5, or a liquid crystal composition according to any one of claims 6 to 7.
9. A process for the preparation of a liquid-crystalline compound as claimed in any of claims 1 to 5, characterized in that it employs the following synthetic route:
Figure FDA0002449458450000041
the method comprises the following steps:
s1, sequentially adding the raw material (1), calcium carbonate and water into a reaction bottle, adding elemental iodine at the temperature of-5 ℃, and reacting for 2 hours under heat preservation for post-treatment; filtering the reaction solution, extracting the filtrate with toluene, washing the filtrate to be neutral, drying the filtrate with anhydrous magnesium sulfate, filtering, performing rotary evaporation on the filtrate to remove the toluene, and adding a mixed solution of toluene and n-heptane for recrystallization to obtain an intermediate (2);
s2, under the protection of nitrogen, introducing into a reaction flaskAdding the intermediate (2), the raw material (3), bis (triphenylphosphine) palladium dichloride, TBAB and K2CO3Toluene, ethanol, water; carrying out reflux reaction for 4h, and then cooling to room temperature for post-treatment; standing and layering the reaction solution, adding toluene into the lower layer for extraction, combining organic phases, washing the organic phases to be neutral, drying the organic phases with anhydrous magnesium sulfate, filtering, and performing recrystallization after rotary evaporation of the filtrate to obtain an intermediate 5; or under the protection of nitrogen, adding the intermediate (2), the raw material (4), bis (triphenylphosphine) palladium dichloride, cuprous iodide, triphenylphosphine and triethylamine into a reaction bottle, reacting for 2 hours, and then carrying out aftertreatment; filtering the reaction solution, carrying out rotary evaporation on the filtrate to remove triethylamine, adding toluene to dissolve, washing with water to be neutral, drying with anhydrous magnesium sulfate, filtering, and carrying out recrystallization on the filtrate after rotary evaporation to obtain an intermediate (5);
S3, adding the intermediate (5), acetone and water into a three-necked bottle, dropwise adding thiophosgene at room temperature, reacting at room temperature for 1 hour after the thiophosgene is added, and monitoring by TLC to stop the reaction when no raw material remains; and (3) carrying out rotary evaporation, adding toluene to dissolve the obtained crude product, washing with water to neutrality, drying with anhydrous magnesium sulfate, filtering, carrying out rotary evaporation, dissolving with n-heptane, and carrying out column chromatography purification to obtain the target compound (6).
10. The method according to claim 9, wherein in step S1, the molar ratio of the raw material (1), the calcium carbonate and the iodine is 1:1.3 (1-0.95), and the reaction temperature is-5-50 ℃; in the step S2, the molar ratio of the intermediate (2) to the raw material (3) is 1 (1-1.3), the temperature of the Suzuki coupling reaction is 0-90 ℃, and the intermediate (2) is bis (triphenylphosphine) palladium dichloride, TBAB: K2CO3The molar ratio of (1), (0.1% -3%) (0.1-0.5) to (1-5); or in the step S2, the molar ratio of the intermediate (2) to the raw material (4) is 1 (1-1.1), the Soniganshira coupling reaction temperature is 0-50 ℃, and the molar ratio of the intermediate (2) to bis (triphenylphosphine) dichloride to cuprous iodide to triphenylphosphine is 1 (0.1-3%) (0.3-9%); in step S3, the molar ratio of the intermediate (5) to the thiophosgene is 1 (1-2).
CN202010288462.3A 2020-04-14 2020-04-14 Liquid crystal compound, composition thereof and high-frequency component comprising liquid crystal compound Active CN113528149B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010288462.3A CN113528149B (en) 2020-04-14 2020-04-14 Liquid crystal compound, composition thereof and high-frequency component comprising liquid crystal compound

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010288462.3A CN113528149B (en) 2020-04-14 2020-04-14 Liquid crystal compound, composition thereof and high-frequency component comprising liquid crystal compound

Publications (2)

Publication Number Publication Date
CN113528149A true CN113528149A (en) 2021-10-22
CN113528149B CN113528149B (en) 2023-08-11

Family

ID=78087680

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010288462.3A Active CN113528149B (en) 2020-04-14 2020-04-14 Liquid crystal compound, composition thereof and high-frequency component comprising liquid crystal compound

Country Status (1)

Country Link
CN (1) CN113528149B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116333755A (en) * 2021-12-24 2023-06-27 西安近代化学研究所 Liquid crystal compound and composition with high clearing point and low dielectric loss
CN117004405A (en) * 2022-04-27 2023-11-07 西安近代化学研究所 Liquid crystal composition having a refractive index of wide Wen Gaoshuang, optical communication element, and high-frequency module

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104263380A (en) * 2014-10-09 2015-01-07 西安近代化学研究所 Liquid crystal compound with high birefringence and wide nematic phase temperature interval and composition comprising liquid crystal compound
CN108865180A (en) * 2018-08-17 2018-11-23 西安近代化学研究所 A kind of liquid-crystal composition and the high frequency assembly comprising it
US10224620B2 (en) * 2017-05-19 2019-03-05 Kymeta Corporation Antenna having radio frequency liquid crystal (RFLC) mixtures with high RF tuning, broad thermal operating ranges, and low viscosity
CN110295047A (en) * 2018-03-23 2019-10-01 默克专利股份有限公司 Liquid crystal media
CN110746983A (en) * 2019-10-31 2020-02-04 武汉轻工大学 Achiral side methyl alkyl terphenyl liquid crystal compound, preparation method, liquid crystal composition and application
CN114829543A (en) * 2019-12-10 2022-07-29 默克专利股份有限公司 Aromatic isothiocyanates

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104263380A (en) * 2014-10-09 2015-01-07 西安近代化学研究所 Liquid crystal compound with high birefringence and wide nematic phase temperature interval and composition comprising liquid crystal compound
US10224620B2 (en) * 2017-05-19 2019-03-05 Kymeta Corporation Antenna having radio frequency liquid crystal (RFLC) mixtures with high RF tuning, broad thermal operating ranges, and low viscosity
CN110295047A (en) * 2018-03-23 2019-10-01 默克专利股份有限公司 Liquid crystal media
CN108865180A (en) * 2018-08-17 2018-11-23 西安近代化学研究所 A kind of liquid-crystal composition and the high frequency assembly comprising it
CN110746983A (en) * 2019-10-31 2020-02-04 武汉轻工大学 Achiral side methyl alkyl terphenyl liquid crystal compound, preparation method, liquid crystal composition and application
CN114829543A (en) * 2019-12-10 2022-07-29 默克专利股份有限公司 Aromatic isothiocyanates

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116333755A (en) * 2021-12-24 2023-06-27 西安近代化学研究所 Liquid crystal compound and composition with high clearing point and low dielectric loss
CN117004405A (en) * 2022-04-27 2023-11-07 西安近代化学研究所 Liquid crystal composition having a refractive index of wide Wen Gaoshuang, optical communication element, and high-frequency module
CN117004405B (en) * 2022-04-27 2024-12-13 西安近代化学研究所 Liquid crystal composition with wide temperature and high birefringence, optical communication component and high-frequency component

Also Published As

Publication number Publication date
CN113528149B (en) 2023-08-11

Similar Documents

Publication Publication Date Title
CN113528148A (en) Liquid crystal medium for high-frequency technology and assembly thereof
CN109134423B (en) Compound, liquid crystal composition thereof and photoelectric display device
CN110938438B (en) A kind of side ethyl fluorine-containing triphenyldiyne liquid crystal compound and preparation method, liquid crystal composition and application
CN107207965B (en) Nematic liquid crystal composition and liquid crystal display element using same
TW201620892A (en) 4,6-difluorodibenzothiophene derivatives
KR20150108325A (en) 4,6-difluorodibenzofuran derivatives
CN108517217B (en) Acetylene liquid crystal compound, preparation method thereof, composition containing acetylene liquid crystal compound and high-frequency component containing acetylene liquid crystal medium
WO2022090098A1 (en) Aromatic isothiocyanates
CN114149811A (en) Alkynyl-containing dinaphthalene liquid crystal monomer compound, and preparation method and application thereof
CN113528149B (en) Liquid crystal compound, composition thereof and high-frequency component comprising liquid crystal compound
CN110831931A (en) Thioether derivatives of dibenzothiophenes and dibenzofurans
CN113929701A (en) Dithieno [2, 3-b; 3',2' -d ] thiophene derivative and application thereof
CN114213296A (en) Naphthalene series liquid crystal monomer compound containing isothiocyanato, and preparation method and application thereof
KR100937290B1 (en) Negative Δε fluoride and 1,7-dihydroindacene
CN108753312B (en) Liquid crystal compound, preparation method thereof, composition containing liquid crystal compound and high-frequency component containing liquid crystal medium
WO2022090109A1 (en) Aromatic isothiocyanates
CN112480048B (en) Compound, liquid crystal medium, liquid crystal display element and liquid crystal display
CN116333755B (en) Liquid crystal compound and composition with high-definition bright spots and low dielectric loss
CN115611833B (en) Benzofuran series liquid crystal monomer compound and preparation method and application thereof
JP5704601B2 (en) Diacetylene derivatives
CN115448861A (en) A kind of ethyl naphthalene series liquid crystal monomer compound and its preparation method and application
KR101724588B1 (en) Bent-core dimesogenic compound and method for preparing thereof
CN114350378B (en) Thiophene-containing alkyne liquid crystal compound and preparation method and application thereof
CN102898413B (en) Novel liquid crystal compound with dioxa saturated indene ring and composition thereof
CN114015460A (en) Liquid crystal monomer compound containing single naphthalene series and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant