Isorhodanine liquid crystal monomer compound and application thereof
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- VALIANT CO LTD
- Filing Date
- 2022-01-20
- Publication Date
- 2026-06-19
Smart Images
Figure CN116515498B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to a naphthalene-based liquid crystal monomer compound containing isothiocyanate and its applications, belonging to the field of liquid crystal material technology. Background Technology
[0002] In recent years, liquid crystal materials with low dielectric loss and high dielectric tunability have attracted much attention for their application in liquid crystal microwave devices such as filters, tunable frequency selective surfaces, phase shifters, phased-array radar, and 5G communication networks. Liquid crystal materials with fast response, low viscosity, and high birefringence have become a hot topic. CN110499163A describes a liquid crystal monomer with relatively high birefringence and relatively low viscosity designed by connecting a series-connected, highly conjugated rigid center and attaching appropriately long flexible chain segments to the ends.
[0003] Due to the suitable optical anisotropy (Δn), dielectric anisotropy (Δε), and viscosity (γ) properties of liquid crystal compounds, with the continuous development of liquid crystal technology, many recent publications have reported that liquid crystal compounds can meet some of the properties required for microwave technology components. Some common specific applications include: Proc. of SPIE, 2013, 8642:86420S-1-86420S-6, entitled "Liquid Crystal for Microwave Applications," which reports liquid crystal molecules with a bisphenylacetylene backbone. These molecules have high optical anisotropy (Δn) and dielectric anisotropy (Δε), but their high melting point and poor compatibility limit their applications. The paper “Novel highbirefringent isothiocyanates based on quaterphenyl and phenylethynyltolanemolecular cores” in “Liquid Crystals, 2013.40(9):1174-1182” reports isothiocyanate liquid crystal compounds with diphenylethynyl tolanemolecular cores. Although these compounds also have high optical anisotropy (Δn) and dielectric anisotropy (Δε), their high melting point and poor solubility greatly limit their applications.
[0004] Currently, liquid crystal materials used in microwave technology devices need to possess the following characteristics: high birefringence, fast response speed, good solubility, and low viscosity. However, to date, there are few liquid crystal materials that simultaneously meet all of these conditions. Therefore, there is an urgent need to develop liquid crystal dielectric materials with performance suitable for corresponding practical applications. Summary of the Invention
[0005] To address the shortcomings of existing technologies, this invention provides a naphthalene-based liquid crystal monomer compound containing isothiocyanate and its applications. The naphthalene-based liquid crystal monomer compound containing isothiocyanate has high birefringence, good solubility, large optical anisotropy, and fast response speed.
[0006] The technical solution of this invention to solve the above-mentioned technical problems is as follows: a naphthalene-based liquid crystal monomer compound containing an isothiocyanate group, the general structural formula of which is shown below:
[0007]
[0008] Y is an alkyl or alkoxy group;
[0009] Z is selected from single bond, alkyl group, Any one of phenyl or benzoynyl;
[0010] R1, R2, R3, and R4 are each selected from H, F, alkyl, or alkoxy groups.
[0011] Furthermore, the molecular formula of Y is -OC. m H 2m -、-C m H 2m O- or -C m H 2m - any one of the following, where m is an integer from 0 to 5.
[0012] Furthermore, when R1, R2, R3, and R4 are alkyl or alkoxy groups, their general formula is -C n H 2n+1 -OC n H 2n+1 , where n is an integer from 1 to 25.
[0013] Furthermore, the structural formula of Z is any one of the following: single bond, alkyl group, ... The substituents Z1 to Z4 are H or F, and the number of F substituents is 0 to 4.
[0014] Furthermore, the liquid crystal monomer compound is any one of the following structural formulas:
[0015]
[0016]
[0017] Most preferably, the liquid crystal monomer compound is any one of the following structural formulas:
[0018]
[0019] This invention also discloses the applications of the naphthalene series liquid crystal monomer compounds containing isothiocyanates:
[0020] The liquid crystal monomer compound is used in liquid crystal compositions.
[0021] The aforementioned liquid crystal monomer compound can also be applied to microwave components of high-frequency devices. These microwave components are phase-shifting devices, tunable filters, or electronic beam-controlled antennas. The electronic beam-controlled antenna is a phased array antenna.
[0022] The beneficial effects of the present invention are as follows: the naphthalene ring-containing isothiocyanate series liquid crystal monomer compounds are not only easy to prepare, but also have a high birefringence, which is beneficial to reduce the thickness of the device and shorten the response time. In addition, the liquid crystal monomer compounds have a wide nematic phase temperature, which can improve the clearing point of the liquid crystal component, have good solubility, and have large anisotropy and dielectric constant, which can improve the performance of the liquid crystal component. Attached Figure Description
[0023] Figure 1 The image shows the 1H-NMR spectrum of the 3F4ONTPNCS described in the embodiment;
[0024] Figure 2 The image shows the 1H-NMR spectrum of F4ONGTUNCS described in the embodiment;
[0025] Figure 3 The image shows the 1H-NMR spectrum of F4ONTPUNCS described in the embodiment;
[0026] Figure 4 The image shows the 1H-NMR spectrum of F4ONUTUNCS described in the embodiment. Detailed Implementation
[0027] To make the above-mentioned objects, features, and advantages of the present invention more apparent and understandable, specific embodiments of the present invention are described in detail below. Many specific details are set forth in the following description to provide a thorough understanding of the present invention. However, the present invention can be practiced in many other ways different from those described herein, and those skilled in the art can make similar modifications without departing from the spirit of the present invention. Therefore, the present invention is not limited to the specific embodiments disclosed below.
[0028] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
[0029] All raw materials used in this invention are known compounds and can be obtained by purchasing.
[0030] Example 1:
[0031] In the general formula Taking Y as -C3H6O- and R1, R2, R3, and R4 as H (abbreviated as 3F4ONTPNCS), this paper introduces the synthesis method of this naphthalene-containing isothiocyanate series liquid crystal monomer compound:
[0032] Step 1: Synthesis of intermediate A1
[0033]
[0034] 84.5 g (0.66 mol) of 4,4,4-trifluoro-1-butanol, 147.2 g (0.66 mol) of 6-bromo-2-naphthol and 736.0 g of THF were added to a three-necked flask, and 159.7 g (0.79 mol) of diisopropyl azodicarbonate was added dropwise. After incubation at 35–40 °C for 3 h, the solvent was removed and 660 g of anhydrous ethanol was added. Recrystallization yielded 175.9 g of white solid, with a yield of 80.0% and a purity >95%.
[0035] Step 2: Synthesis of intermediate A2
[0036]
[0037] 20.0 g (0.116 mol) of p-bromoaniline, 1.37 g (0.00522 mol) of triphenylphosphine, 1.42 g (0.01160 mol) of DMAP, 60.0 g of triethylamine, and 22.8 g (0.232 mol) of trimethylsilylacetylene were added sequentially to a three-necked flask. After purging with nitrogen, 1.22 g (0.00174 mol) of Pd(PPh3)2Cl2 and 0.66 g (0.00348 mol) of CuI were added to the system, and the mixture was kept at 70–75 °C for 15 h. After the incubation period, the reaction solution was dried, 82 g of toluene was added, and the mixture was stirred and filtered. The filtrate was dried to remove the solvent, and then recrystallized with 61 g of petroleum ether to give 7.0 g of a grayish-white solid, with a yield of 34.5% and a purity >96%.
[0038] Step 3: Synthesis of intermediate A3
[0039]
[0040] 7.0 g (0.037 mol) A2, 21.0 g methanol, 21.0 g dichloromethane and 15.3 g (0.111 mol) potassium carbonate were added to a reaction flask and reacted at room temperature for 2 h. After filtration, the filtrate was dried, dissolved in 22.5 g dichloromethane, washed with water until neutral, and the solvent was removed to give 3.7 g of gray solid. The yield was 83.7% and the purity was >95%.
[0041] Step 4: Synthesis of intermediate A4
[0042]
[0043] 40.0 g (0.12 mol) Al, 14.1 g (0.12 mol) A3, 0.094 g (0.00036 mol) triphenylphosphine and 119.7 g triethylamine were added to a reaction flask, followed by 0.253 g (0.00036 mol) Pd(PPh3)2Cl2 and 0.137 g (0.00072 mol) CuI. The mixture was kept at 65–75 °C for 4 h. The reaction solution was desolventized, and 221 g toluene was added to the desolventized residue for slurrying. The mixture was filtered, and the filtrate was desolventized. Then, 132 g anhydrous ethanol and 22 g toluene were added for recrystallization to obtain 15.5 g of yellow solid, with a yield of 35.0% and a purity >90%.
[0044] Step 5: Synthesis of isothiocyanate compounds
[0045]
[0046] 5.0 g (0.013 mol) of A4 and 20 g of THF were added to a reaction flask. 3.6 g (0.0203 mol) of thiocarbonyl diimidazole dissolved in 21.6 g of dichloromethane was added dropwise. After the addition was complete, the reaction was maintained at 30–35 °C for 2 h. 100 g of water was added to quench the reaction mixture. The organic phase was washed with water until neutral, and the organic phase was dried. The residue was dissolved in n-heptane and passed through a silica gel column. The residue was dried after column chromatography to obtain 3.2 g of white solid, with a yield of 58.2% and a purity >99.9%.
[0047] The phase transition point was determined by differential scanning calorimetry (DSC) and microscopy: melting point 132.04℃. The characteristic ion M / Z ratio was determined by gas chromatography-mass spectrometry (GC-MS). + The answer is: 411. 1 H-NMR (400MHz, CDCl3): δ=7.959 (s, 1H), δ=7.661~7.684 (d, J=8.8Hz, 1H), δ=7.697~7.720 (d, J=8.8Hz, 1H), δ=7.488~7.529 (m, 3H), δ=7.156~7.189(m,3H), δ=7.069~7.075(d,J=2.4Hz,1H), δ=4.095~4.125(t,2H), δ=2.319~2.387(m,2H), δ=2.071~2.141(m,2H)ppm.
[0048] Example 2:
[0049] In the general formula Taking Y as -C3H6O-, Z1, Z2, Z3, and Z4 as H, R1 and R3 as H, and R2 and R4 as F as an example (abbreviated as F4ONTPUNCS), this paper introduces the synthesis method of this naphthalene ring-containing isothiocyanate series liquid crystal monomer compound:
[0050] Step 1: Synthesis of intermediate B1
[0051]
[0052] 219.8 g (0.66 mol) Al, 5.19 g (0.0198 mol) triphenylphosphine, 8.06 g (0.0660 mol) DMAP, 129.7 g (1.32 mol) trimethylsilylacetylene, and 659.4 g triethylamine were added to a reaction flask, followed by 4.63 g (0.0066 mol) Pd(PPh3)2Cl2 and 2.51 g (0.0132 mol) CuI. The mixture was kept at 80–85 °C for 4 h. After acidification with dilute hydrochloric acid and dilution with toluene, the mixture was washed with water until neutral. The solvent was removed, and 631 g of anhydrous ethanol was added. The mixture was stirred for 30 min and filtered to obtain 131.2 g of a yellow solid, with a yield of 56.7% and a purity >99%.
[0053] Step 2: Synthesis of intermediate B2
[0054]
[0055] 139.7 g (0.37 mol) B1, 153.4 g (1.11 mol) potassium carbonate, 393.0 g methanol and 393.0 g dichloromethane were added to a reaction flask and reacted at 25-30 °C for 2 h. After the reaction was completed, the mixture was filtered, and the filtrate was washed with water until neutral. The filtrate was then dried to obtain 101.9 g of a yellow solid, with a yield of 99.0% and a purity of >99%.
[0056] Step 3: Synthesis of intermediate B3
[0057]
[0058] 30.0 g (0.108 mol) B2, 30.6 g (0.108 mol) p-bromoiodobenzene and 180.0 g triethylamine were added to a reaction flask, followed by 0.08 g (0.0003 mol) PPh3, 0.21 g (0.0003 mol) Pd(PPh3)2Cl2 and 0.11 g (0.0006 mol) CuI. The mixture was kept at 60–65 °C for 5 h. After the reaction was complete, the mixture was acidified with dilute hydrochloric acid, diluted with toluene, and washed with water until neutral. The solution was dried to obtain 62.9 g of a yellow solid with a purity of 99% and a yield >100%.
[0059] Step 4: Synthesis of intermediate B4
[0060]
[0061] 22.8 g (0.110 mol) of 4-bromo-2,6-difluoroaniline, 27.9 g (0.110 mol) of pinacol diborate, 32.4 g (0.330 mol) of potassium acetate, and 68.4 g of toluene were added to a reaction flask, purged with nitrogen, and 0.21 g (0.0003 mol) of Pd(PPh3)2Cl2 was added. The mixture was kept at 65–70 °C for 4 h. After the reaction was complete, the mixture was filtered, and the filtrate was washed with water until neutral. The solvent was removed, and the solution was recrystallized with 56 g of petroleum ether to give 23.7 g of a grayish-white solid, with a yield of 84.3% and a purity >97%.
[0062] Step 5: Synthesis of intermediate B5
[0063]
[0064] 10 g (0.023 mol) B3, 7.1 g (0.028 mol) B4, and 100 g toluene were added to a reaction flask, followed by 0.016 g Pd(PPh3)2Cl2. A potassium carbonate aqueous solution (3.2 g potassium carbonate + 9.6 g tap water) was added dropwise. The mixture was kept at 65–70 °C for 4 h, allowed to stand and separate into layers, washed with water until neutral, and the organic phase was dried. 44 g anhydrous ethanol was added and the mixture was slurried to obtain 10.1 g of off-white solid, with a yield of 91.0% and a purity >99.5%.
[0065] Step 5: Synthesis of isothiocyanate compounds
[0066]
[0067] 5.0 g (0.010 mol) F4ONTPUNCS-C1, 3.6 g (0.020 mol) thiocarbonyl diimidazole and 20.0 g DMF were added to a reaction flask and kept at 45-50 °C for 8 h. 100 g toluene was added, and the mixture was filtered. The filtrate was dried, and the residue was dissolved in 123 g petroleum ether and 6 g acetone. The solution was passed through a silica gel column and dried to obtain 1.6 g of white solid. The yield was 30%, and the purity was greater than 99.5%.
[0068] The phase transition point was determined by differential scanning calorimetry (DSC) and microscopy: melting point 152.84℃. The characteristic ion M / Z ratio was determined by high-performance liquid chromatography-mass spectrometry (HPLC-MS). + The value is: 523. 1H-NMR (400MHz, CDCl3): δ = 7.956 (s, 1H), δ = 7.653~7.711 (m, 2H), δ = 7.614 (s, 1H), δ = 7.593~7.598 (d, J = 2Hz, 2H), δ = 7.510~7.536 (dd, 1H), δ = 7.464~ 7.486(dd,2H), δ=7.133~7.172(m,3H), δ=7.085~7.091(d,J=2.4Hz,1H), δ =4.114~4.145(t,2H), δ=2.287~2.407(m,2H), δ=2.074~2.143(m,2H)ppm.
[0069] Example 3
[0070] In the general formula Taking Y as -C3H6O-, Z1 and Z3 as H, Z2 and Z4 as F, R1 and R3 as H, and R2 and R4 as F as an example (abbreviated as F4ONUTUNCS), this paper introduces the synthesis method of this series of isothiocyanate-containing naphthalene ring liquid crystal monomer compounds:
[0071] Step 1: Synthesis of intermediate C1
[0072]
[0073] 20.0 g (0.060 mol) Al, 10.4 g (0.066 mol) 3,5-difluorophenylboronic acid, 8.3 g (0.060 mol) potassium carbonate, 60.0 g toluene, and 24.9 g water were added to a reaction flask, followed by the addition of 0.04 g Pd(PPh3)2Cl2. The mixture was kept at 65–70 °C for 4 h, cooled to room temperature, and allowed to stand to separate into layers. The organic phase was washed with water until neutral, and the solvent was removed to give 18.1 g of a pale yellow solid, with a yield of 82.3% and a purity >99%.
[0074] Step 2: Synthesis of intermediate C2
[0075]
[0076] 30.0 g (0.082 mol) Cl and 150.0 g THF were added to a reaction flask, and the temperature was lowered to -60 to -50 °C. 32.8 mL of n-butyllithium solution was added dropwise. After the addition was complete, the temperature was maintained at -60 to -50 °C for 2 h. Then, 20.8 g (0.082 mol) of iodine dissolved in 104 g of THF was added dropwise. After the addition was complete, the temperature was maintained at -50 to -40 °C for 2 h. After the temperature was complete, 100 g of 5% sodium sulfite aqueous solution was added to quench the reaction, removing the aqueous phase. The organic phase was desolvated to obtain 48.2 g of a yellow solid. Recrystallization with toluene and anhydrous ethanol yielded 33.0 g of a white solid, with a yield of 81% and a purity >97%.
[0077] Step 3: Synthesis of intermediate C3
[0078]
[0079] 28.9 g (0.059 mol) C2 and 115.6 g triethylamine were added to a reaction flask. After purging with nitrogen, 0.309 g PPh3, 0.414 g Pd(PPh3)2Cl2, and 0.112 g CuI were added. The temperature was raised to 55–60 °C, and a solution of 13.6 g 4-ethynyl-2,6-difluoroaniline dissolved in 40 g triethylamine was added dropwise. After the addition was complete, the mixture was kept at 55–60 °C for 10 h. After the incubation period, 300 g toluene was added for dilution, and the mixture was washed with water until neutral. The organic phase was dried to obtain a brownish-yellow solid. 120 g anhydrous ethanol was added, and the mixture was stirred at 50 °C for 0.5 h. After filtration, 26.7 g of a yellow solid was obtained, with a yield of 87.5% and a purity >99%.
[0080] Step 4: Synthesis of isothiocyanate compounds
[0081]
[0082] 5.0 g of C3, 3.5 g of thiocarbonyl diimidazole, 0.119 g of DMAP, and 20 g of DMF were added to a reaction flask and incubated at 45–50 °C for 10 h. The mixture was then filtered, and the filtrate was poured into 100 g of water and filtered again to obtain 5 g of a yellow solid. This solid was dissolved in petroleum ether and subjected to column chromatography to give 2.0 g of a white solid. Yield: 37%, purity >99%.
[0083] The phase transition point was determined by differential scanning calorimetry (DSC) and microscopy: melting point 206.59℃. The characteristic ion M / Z ratio was determined by high-performance liquid chromatography-mass spectrometry (HPLC-MS). + The answer is: 559. 1 H-NMR (400MHz, CDCl3): δ=7.944~7.948 (d, J=1.6Hz, 1H), δ=7.802~7.806 (d, J=1.6Hz, 1H), δ=7.782 (s, 1H), δ=7.612~7.638 (dd, 1H), δ=7 .262~7.309(dt,1H), δ=7.244(s,1H), δ=7.137~7.206(m,4H), δ=4.148~4.178(t,2H), δ=2.304~2.425(m,2H), δ=2.095~2.165(m,2H)ppm.
[0084] Application Examples
[0085] M is the parent mixed crystal, and its formula and structure are as follows:
[0086]
[0087] M-1 to M-4 are obtained by mixing 90% parent liquid crystal with 10% single crystal. The single crystals used are 3F4ONTPNCS, F4ONGTUNCS, F4ONTPUNCS, and F4ONUTUNCS prepared in Examples 1-4, respectively, with the following parameters:
[0088] mixed crystal Birefringence Δn M 0.050 M-1(3F4ONTPNCS) 0.091 M-2 (F4ONGTUNCS) 0.087 M-3(F4ONTPUNCS) 0.121 M-4 (F4ONUTUNCS) 0.110
[0089] As can be seen from the table above, the naphthalene-based liquid crystal monomer compounds containing isothiocyanate groups described in this invention have high birefringence, which is beneficial for reducing device thickness and shortening response time.
[0090] Conclusion: The data above show that the mixed liquid crystals with added naphthalene-based liquid crystal monomer compounds containing isothiocyanates have excellent physical properties.
[0091] The structure involved in this embodiment:
[0092]
[0093] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.
[0094] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the protection scope of the present invention. Therefore, the protection scope of this invention patent should be determined by the appended claims.
Claims
1. A naphthalene-based liquid crystal monomer compound containing an isothiocyanate group, characterized in that, The liquid crystal monomer compound is any one of the following structural formulas: ； ； ； 。 2. The naphthalene-series liquid crystal monomer compound containing isothiocyanate group according to claim 1, characterized in that, The liquid crystal monomer compound is any one of the following structural formulas: ； 。 3. The application of a naphthalene-based liquid crystal monomer compound containing an isothiocyanate group according to any one of claims 1-2, characterized in that, The liquid crystal monomer compound is used in liquid crystal compositions.
4. Use of a naphthalene series liquid crystal monomer compound containing isothiocyanic group according to any one of claims 1 to 2, characterized in that, The liquid crystal monomer compound is used in microwave components of high-frequency devices.
5. The application of the naphthalene-series liquid crystal monomer compound containing isothiocyanate according to claim 4, characterized in that, The microwave component is a phase-shifting device, a tunable filter, or an electronic beam control antenna.
6. The use of a naphthalene series liquid crystal monomer compound containing isothiocyanide according to claim 5, characterized by, The electronic beam control antenna is a phased array antenna.