CN115611833B - Benzofuran series liquid crystal monomer compound and preparation method and application thereof - Google Patents
Benzofuran series liquid crystal monomer compound and preparation method and application thereof Download PDFInfo
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- CN115611833B CN115611833B CN202211416718.XA CN202211416718A CN115611833B CN 115611833 B CN115611833 B CN 115611833B CN 202211416718 A CN202211416718 A CN 202211416718A CN 115611833 B CN115611833 B CN 115611833B
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 81
- 150000001875 compounds Chemical class 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 239000000178 monomer Substances 0.000 title claims abstract description 33
- 150000001907 coumarones Chemical class 0.000 title claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims description 62
- 239000007787 solid Substances 0.000 claims description 58
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 42
- 239000002904 solvent Substances 0.000 claims description 42
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 34
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 32
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 30
- 239000012074 organic phase Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 238000001914 filtration Methods 0.000 claims description 20
- 238000004537 pulping Methods 0.000 claims description 18
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 12
- 239000012065 filter cake Substances 0.000 claims description 12
- 239000012071 phase Substances 0.000 claims description 12
- 238000003786 synthesis reaction Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 239000000741 silica gel Substances 0.000 claims description 11
- 229910002027 silica gel Inorganic materials 0.000 claims description 11
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 10
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 10
- -1 isothiocyanato compound Chemical class 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 10
- AQRLNPVMDITEJU-UHFFFAOYSA-N triethylsilane Chemical compound CC[SiH](CC)CC AQRLNPVMDITEJU-UHFFFAOYSA-N 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000010791 quenching Methods 0.000 claims description 7
- 230000000171 quenching effect Effects 0.000 claims description 7
- HXTWKHXDFATMSP-UHFFFAOYSA-N 4-bromo-2-hydroxybenzaldehyde Chemical compound OC1=CC(Br)=CC=C1C=O HXTWKHXDFATMSP-UHFFFAOYSA-N 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 229960000549 4-dimethylaminophenol Drugs 0.000 claims description 5
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- PQJJJMRNHATNKG-UHFFFAOYSA-N ethyl bromoacetate Chemical compound CCOC(=O)CBr PQJJJMRNHATNKG-UHFFFAOYSA-N 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 239000001632 sodium acetate Substances 0.000 claims description 5
- 235000017281 sodium acetate Nutrition 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 125000001810 isothiocyanato group Chemical group *N=C=S 0.000 claims description 4
- ZBSZCHDBZRCUES-UHFFFAOYSA-N 1-ethynyl-4-(4-propylphenyl)benzene Chemical group C1=CC(CCC)=CC=C1C1=CC=C(C#C)C=C1 ZBSZCHDBZRCUES-UHFFFAOYSA-N 0.000 claims description 3
- 238000004440 column chromatography Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 125000003944 tolyl group Chemical group 0.000 claims description 3
- VCAFHMCSPWVSJS-UHFFFAOYSA-N 1-butyl-4-(4-ethynylphenyl)benzene Chemical group C1=CC(CCCC)=CC=C1C1=CC=C(C#C)C=C1 VCAFHMCSPWVSJS-UHFFFAOYSA-N 0.000 claims description 2
- XWKFPIODWVPXLX-UHFFFAOYSA-N 2-methyl-5-methylpyridine Natural products CC1=CC=C(C)N=C1 XWKFPIODWVPXLX-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000013078 crystal Substances 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 abstract description 4
- 125000003545 alkoxy group Chemical group 0.000 abstract description 2
- 125000000217 alkyl group Chemical group 0.000 abstract description 2
- 239000004305 biphenyl Substances 0.000 abstract description 2
- 235000010290 biphenyl Nutrition 0.000 abstract description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 9
- 238000004128 high performance liquid chromatography Methods 0.000 description 8
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000011261 inert gas Substances 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- YNHIGQDRGKUECZ-UHFFFAOYSA-N dichloropalladium;triphenylphosphanium Chemical compound Cl[Pd]Cl.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-N 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 238000004809 thin layer chromatography Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000010933 acylation Effects 0.000 description 2
- 238000005917 acylation reaction Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 238000000589 high-performance liquid chromatography-mass spectrometry Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000000386 microscopy Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 230000003044 adaptive effect Effects 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 239000013022 formulation composition Substances 0.000 description 1
- 150000002540 isothiocyanates Chemical class 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 230000036314 physical performance Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/78—Benzo [b] furans; Hydrogenated benzo [b] furans
- C07D307/82—Benzo [b] furans; Hydrogenated benzo [b] furans with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the hetero 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
- C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
- C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
- C09K19/3405—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom the heterocyclic ring being a five-membered 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
- C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
- C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
- C09K19/3405—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom the heterocyclic ring being a five-membered ring
- C09K2019/3408—Five-membered ring with oxygen(s) in fused, bridged or spiro ring systems
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Liquid Crystal Substances (AREA)
Abstract
The invention relates to the technical field of liquid crystal, in particular to a benzofuran series liquid crystal monomer compound and a preparation method thereofThe liquid crystal monomer compound has the structural formula as follows:
Description
Technical Field
The invention relates to a benzofuran series liquid crystal monomer compound, a preparation method and application thereof, belonging to the technical field of liquid crystal.
Background
With the continuous development of liquid crystal display technology and the continuous improvement of liquid crystal display requirements of people, the liquid crystal material has to show better performance matching between physical performance and photoelectric performance in the display technology and the application of optical devices. In recent years, liquid crystal materials with high birefringence are more and more important because the thickness of a liquid crystal box can be effectively reduced, which means that the response speed of a device can be greatly improved, and the performance parameter is particularly important in the application fields of high-speed display systems such as 3D display, field sequential display and the like, liquid crystal light valves, spatial light modulators in adaptive optics and the like. From the perspective of a mixed liquid crystal formula, a proper single crystal component is selected, a liquid crystal monomer with high birefringence is added, and the liquid crystal with high birefringence required by a liquid crystal display panel capable of meeting fast response is designed through mixing.
For a liquid crystal laser device, the device generates high heat during use, and the liquid crystal material used is required to have a wide nematic phase temperature range, and particularly, a high clearing point is required to prevent the device from losing liquid crystal property due to reaching the clearing point during use, so that the device cannot normally operate. From the perspective of the mixed liquid crystal formula, the proper single crystal component is selected, the liquid crystal monomer with higher clearing point is added, and the liquid crystal which can meet the requirement of the laser device on high clearing point is designed through mixing.
In addition, with the continuous development of liquid crystal technology, since liquid crystal compounds have suitable optical anisotropy (Δ n), dielectric anisotropy (Δ ∈), viscosity (γ), and other characteristics, there have been many reports in recent literature that liquid crystal compounds can satisfy some characteristics required for microwave technology components. The use of liquid-crystalline media in microwave technology, in particular phase shifters, is described in the patent application with the application number DE102004029429A, in which liquid-crystalline media based on mixtures of nitriles, mostly aromatic, and isothiocyanates are discussed. In the patent application EP2982730A, the use of liquid-crystalline media consisting entirely of mixtures of isothiocyanate compounds in the field of microwave devices is described. However, these compositions still suffer from several drawbacks, and there is a need to improve some of the physical properties of these media, such as clearing point, phase range, stability of storage especially at low temperatures, and viscosity thereof. 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 proper dielectric constant under low frequency, and in order to obtain higher dielectric constant, the liquid crystal material is also required to have high birefringence.
In view of the numerous different parameters that must be considered and improved for developing liquid crystal media for microwave applications, it is desirable to have a wider range of possible mixture compositions for developing such liquid crystal media.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a benzofuran liquid crystal monomer compound, a preparation method and application thereof, and liquid crystal molecules with high birefringence are designed by changing the chemical structure of the liquid crystal molecules, so that the birefringence and clearing point of a liquid crystal component are improved, and the performance of the liquid crystal component can be improved.
The technical scheme for solving the technical problems is as follows: the structural formula of the benzofuran series liquid crystal monomer compound is shown as follows:
Wherein R is any one of alkyl and alkoxy;
x is any one of phenyl, biphenyl, phenylalkynyl and biphenylalkynyl.
Further, the molecular formula of R is-C n H 2n+1 、-O-C n H 2n+1 N is an integer of 1 to 10; wherein in said R groups there are zero, one or more-CH groups 2 -the group is replaced by any of
、
。
Further, the structural formula of X is any one of the following structural formulas:
、
said Y is 1 Is H or F, said Y 2 Is H or F, wherein the number of F in X is 0, 1 or 2.
Further, the liquid crystal monomer compound is any one of the following structures:
the invention also discloses a preparation method of the benzofuran series liquid crystal monomer compound, when the structure of X in the general formula I contains alkynyl, namely when the structure of X is
Said Y is 1 Is H or F, said Y 2 Is H or F, wherein the number of F in X is 0, 1 or 2. The preparation method comprises the following steps:
the first step is as follows: preparation of intermediate m1
m1
Dissolving 4-bromo-2-hydroxybenzaldehyde in DMF, adding potassium carbonate, dropwise adding ethyl bromoacetate into the system at 10 to 20 ℃, heating to raise the temperature, keeping the temperature for reaction, filtering after the reaction is finished, acidifying a filter cake, and filtering to obtain a pink target compound m1;
the second step is that: preparation of intermediate m2
m2
Mixing the intermediate m1 and dichloroethane, heating, dripping an acylating reagent, keeping the temperature for reaction until the system is completely dissolved after dripping, and removing the solvent after the reaction is finished to obtain a white-like solid target compound m2;
the third step: preparation of intermediate m3
m3
Dissolving the intermediate m2 in dichloroethane, adding bis (triphenylphosphine) palladium dichloride and triphenylphosphine under the protection of inert gas, heating, slowly dropwise adding triethylsilane, keeping the temperature for reaction after the dropwise adding is finished, cooling the system, slowly adding ice water and 2, 6-dimethylpyridine, quenching the reaction, separating out a lower organic phase, washing with water to be neutral, passing through a column, removing the solvent from the column liquid, pulping by adopting the solvent, and filtering to obtain a yellow solid target compound m3;
the fourth step: preparation of intermediate m4
m4
Dissolving the intermediate m3 and a terminal alkyne compound in triethylamine, adding bis (triphenylphosphine) palladium dichloride, cuI, triphenylphosphine and DMAP under the protection of inert gas, heating, carrying out heat preservation reaction, removing a solvent after the reaction is finished to obtain a black solid, passing the obtained solid through a silica gel column, and removing the solvent from the column liquid to obtain a yellow solid target compound m4;
the fifth step: preparation of intermediate m5
m5
Dissolving the intermediate m4 in tetrahydrofuran, adding hydroxylamine hydrochloride, sodium acetate and water, heating, carrying out heat preservation reaction, separating an upper organic phase after the reaction is finished, removing the solvent to obtain a yellow solid, pulping the yellow solid by using the solvent, and carrying out suction filtration to obtain a yellow solid target compound intermediate m5;
and a sixth step: preparation of intermediate m6
m6
Dissolving the intermediate m5 in THF, adding NCS and DMF, reacting at 20 to 30 ℃ for 1 to 2 hours under heat preservation, and filtering to remove insoluble substances to obtain orange red filtrate, namely THF solution of the target compound intermediate m 6;
the seventh step: synthesis of isothiocyanato compounds
Dissolving thiourea and triethylamine in THF, cooling, dropwise adding a THF solution of an intermediate m6 into the system, keeping the temperature and stirring, after the reaction is finished, adding water into the system, quenching the reaction, extracting a water phase with toluene, combining organic phases, washing with water to be neutral, removing the solvent to obtain a black viscous liquid, and carrying out column chromatography and recrystallization on the obtained solid to obtain the target compound.
Further, the preparation method of the liquid crystal monomer compound comprises the following steps:
the first step is as follows: preparation of intermediate m1
m1
Dissolving 1 equivalent of 4-bromo-2-hydroxybenzaldehyde in DMF, adding 3 to 4 equivalents of potassium carbonate, dropwise adding 1 to 2 equivalents of ethyl bromoacetate into the system at 10 to 20 ℃, heating to 130 to 140 ℃, keeping the temperature and reacting for 5 to 6 hours, filtering after the reaction is finished, acidifying a filter cake, and filtering to obtain a pink target compound m1;
the second step: preparation of intermediate m2
m2
Mixing 1 equivalent of the intermediate m1 and dichloroethane, heating to 50 to 60 ℃, dropwise adding 1 to 2 equivalents of an acylation reagent, carrying out heat preservation reaction at 50 to 60 ℃ for 1 to 2 hours after dropwise adding until the system is completely dissolved, and removing the solvent after the reaction is finished to obtain a white solid target compound m2;
the third step: preparation of intermediate m3
m3
Dissolving 1 equivalent of the intermediate m2 in dichloroethane, adding 0.001 to 0.003 equivalent of bis (triphenylphosphine) palladium dichloride and 0.002 to 0.006 equivalent of triphenylphosphine under the protection of inert gas, heating to 80 to 90 ℃, slowly dropwise adding 1 to 2 equivalents of triethylsilane, keeping the temperature at 80 to 90 ℃ for reaction for 4 to 6 hours, cooling the system to 15 to 25 ℃ at the inner temperature after the reaction is finished, slowly adding the mixture into ice water and 2, 6-dimethylpyridine, quenching the reaction, separating a lower organic phase, washing the lower organic phase with water to be neutral, passing through a column, draining the solvent from the column liquid, pulping by using the solvent, and filtering to obtain a yellow solid target compound m3;
the fourth step: preparation of intermediate m4
m4
Dissolving 1 equivalent of the intermediate m3 and 1.0 to 1.5 equivalents of the terminal alkyne compound in triethylamine, adding 0.001 to 0.01 equivalent of bis (triphenylphosphine) palladium dichloride, 0.002 to 0.02 equivalent of CuI, 0.003 to 0.03 equivalent of triphenylphosphine and 0.001 to 0.01 equivalent of DMAP under the protection of inert gas, heating to 80 to 90 ℃, keeping the temperature, reacting for 1 to 2 hours, finishing the reaction, removing a dry solvent to obtain a black solid, passing the obtained solid through a silica gel column, and removing the dry solvent from a column liquid to obtain a yellow solid target compound m4;
the fifth step: preparation of intermediate m5
m5
Dissolving 1 equivalent of the intermediate m4 in tetrahydrofuran, adding 1 to 2 equivalents of hydroxylamine hydrochloride, 1 to 2 equivalents of sodium acetate and water, heating to 50 to 55 ℃, and keeping the temperature for reaction for 1 to 2 hours to finish the reaction. Separating out an upper organic phase, drying the solvent to obtain a yellow solid, pulping the yellow solid by adopting the solvent, and performing suction filtration to obtain a yellow solid target compound intermediate m5;
and a sixth step: preparation of intermediate m6
m6
Dissolving 1 equivalent of the intermediate m5 in THF, adding 1 to 2 equivalents of NCS and DMF, carrying out heat preservation reaction at 20 to 30 ℃ for 1 to 2 hours, filtering to remove insoluble substances after the reaction is finished, and obtaining orange red filtrate, namely THF solution of the target compound intermediate m 6;
the seventh step: synthesis of isothiocyanato compounds
Dissolving 1-2 equivalents of thiourea and 1-2 equivalents of triethylamine in THF, cooling to 10-20 ℃, dropwise adding 1 equivalent of THF solution of an intermediate m6 into the system, after dropwise adding, stirring for 10-30 minutes under a heat preservation condition, finishing the reaction, adding water into the system, quenching the reaction, extracting a water phase with toluene, combining organic phases, washing to be neutral, removing the solvent to obtain a black viscous liquid, and carrying out column chromatography and recrystallization on the obtained solid to obtain the target compound.
Furthermore, the dosage of DMF in the first step is 3-10g/g, and preferably 5g/g.
In the first step, the TLC detection means can be adopted according to actual conditions when the reaction is judged to be finished, and the raw material 4-bromo-2-hydroxybenzaldehyde is detected to be reacted completely.
In the first step, the filter cake is acidified by using hydrochloric acid or sulfuric acid, preferably hydrochloric acid.
In the second step the acylating agent is acylated with oxalyl chloride or thionyl chloride, preferably oxalyl chloride.
In the second step, the reaction is carried out until the system is completely dissolved, and if the system is not completely dissolved, 0.1 to 0.5eq acylation reagent needs to be added.
In the second step, the solvent is removed by evaporation preferably using a rotary evaporator at 50 to 60 ℃.
The inert gas in the third step is any one of nitrogen and argon, preferably nitrogen.
The reaction time in the third step is 5 to 6 hours, and the reaction can be tracked by adopting a GC detection means according to actual conditions until the reaction of the raw material intermediate m2 is completely detected.
In the third step, the solvent is removed by evaporation at 50 to 60 ℃ preferably using a rotary evaporator.
The solvent adopted by pulping in the third step is any one of n-hexane, n-heptane and petroleum ether, and n-hexane is preferred.
Further, the acetylene-terminated compound in the fourth step has the following general formula:
wherein R has a molecular formula of-C n H 2n+1 、-O-C n H 2n+1 Any one of the above, wherein n is an integer of 1 to 10; wherein in said R groups there are zero, one or more-CH groups 2 -the group is replaced by any of
、
；
Said Y 1 Is H or F, said Y 2 Is H or F, wherein the number of F in the terminal alkyne compound is 0, 1 or 2.
The inert gas in the fourth step is any one of nitrogen and argon, preferably nitrogen.
The reaction time in the fourth step is 6 to 8 hours, and the reaction of the raw material intermediate m3 can be detected to be complete by adopting an HPLC detection means according to actual conditions.
In the fourth step, the solvent is removed by evaporation at 50 to 60 ℃ preferably using a rotary evaporator.
The eluent used in the fourth step is any one of toluene, dichloroethane and dichloromethane, preferably toluene.
And (5) the reaction time in the fifth step is 1 to 2h, and the reaction can be tracked by adopting an HPLC (high performance liquid chromatography) or TLC (thin-layer chromatography) detection method according to actual conditions until the reaction of the raw material intermediate m4 is completed.
In the fifth step, the solvent is removed by evaporation at 50 to 60 ℃ preferably using a rotary evaporator.
The solvent used for pulping in the fifth step is any one of toluene, dichloroethane and dichloromethane, and toluene is preferred.
And the reaction time in the sixth step is 1 to 2h, and the reaction can be tracked by HPLC or TLC detection means according to actual conditions until the reaction of the raw material intermediate m5 is completed.
The column solvent in the seventh step is any one of petroleum ether, n-hexane and n-heptane, preferably n-hexane.
The recrystallization solvent in the seventh step is any one of petroleum ether, n-hexane, and n-heptane, and n-hexane is preferred.
The invention also discloses application of the benzofuran series liquid crystal monomer compound, and the liquid crystal monomer compound is applied to a liquid crystal composition.
Further, the liquid crystal monomer compound is applied to a liquid crystal display or a high-frequency technology component.
Furthermore, the high-frequency technical component is a liquid crystal-based antenna element, a phase shifter, a tunable filter or a tunable metamaterial structure.
The invention has the beneficial effects that:
the benzofuran series liquid crystal monomer compound containing the isothiocyanato prepared by the invention has higher birefringence and clearing point, can improve the birefringence and the clearing point of a liquid crystal component when used in a mixed crystal formula, can improve the performance of the liquid crystal component, and can be applied to the field of liquid crystal display and microwave devices.
In the structure of the benzofuran series liquid crystal monomer compound containing the isothiocyanato, the birefringence and clearing point of the liquid crystal monomer can be improved by introducing the benzofuran group. Compared with CN114213296A, the liquid crystal monomer compound prepared by the invention has higher clearing point. The liquid crystal monomer compound of the invention cannot be synthesized by adopting the embodiment method of CN114213296A, and the synthesis method is changed, so that the synthesis of the liquid crystal monomer compound of the invention is completed. The liquid crystal monomer compound prepared by the synthesis method has higher yield.
Detailed Description
The following is a detailed description of specific embodiments of the invention. This invention can be embodied in many different forms than those herein described and many modifications may be made by those skilled in the art without departing from the spirit of the invention and the scope of the invention is therefore not limited to the specific embodiments disclosed.
Unless defined otherwise, 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 belongs. The terminology used is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Example 1
In that
In
With the structure of R as-C 3 H 7 ，Y 1 、Y 2 For example, = H (abbreviated as 3 BTBfNCS), the synthesis method of the benzofuran-series liquid crystal monomer compound is as follows.
Step 1: synthesis of intermediate m1
40.2g (0.2 mol) of 4-bromo-2-hydroxybenzaldehyde, 82.9g (0.6 mol) of potassium carbonate and 201.0g of DMF were charged into a 500mL three-necked flask. 50.1g (0.3 mol) of ethyl bromoacetate is dripped into the system at 10 to 20 ℃, and after dripping, the temperature is raised to 130 to 140 ℃, and the reaction is kept for 6 hours, thus finishing the reaction. Cooling the system to the internal temperature of 15-25 ℃, filtering to obtain 90.0g (wet weight) of a white filter cake, adding 100.0g of 10% diluted hydrochloric acid into the filter cake, heating to 55-60 ℃, keeping the temperature, stirring and pulping for 2 hours, and finishing pulping. And cooling the system to 15-25 ℃, filtering to obtain a pink solid, and drying to obtain 35.4g of a pink solid intermediate m1, wherein the GC purity is more than 99.0%, and the yield is 73.44%.
Step 2: synthesis of intermediate m2
35.4g (0.147 mol) of intermediate m1 and 177.0g of dichloroethane were charged in a 500mL three-necked flask. Heating to 50-60 ℃, slowly dripping 28.1g (0.221 mol) of oxalyl chloride into the system, keeping the temperature at 50-60 ℃ for 1 hour until the system is completely dissolved after dripping, and finishing the reaction. The solvent was removed to give 36.9g of off-white solid intermediate m2, GC purity greater than 98.0%, yield 96.85%. The next step was carried out without purification.
And 3, step 3: synthesis of intermediate m3
22.1g (0.085 mol) of intermediate m2, 0.119g (1.7X 10 mol) -4 mol）Pd(PPh 3 )Cl 2 、0.089g（3.4×10 -4 mol）PPh 3 And 200.4g of dichloroethane were charged into a 500mL three-necked flask. Heating to 80-90 ℃, slowly dripping 10.9g (0.094 mol) of triethylsilane, keeping the temperature at 80-90 ℃ for 5 hours after dripping, and finishing the reaction. The temperature of the system is reduced to 15 to 25 ℃, and the system is slowly added into 200.0g of ice water and 10.7g of 2, 6-lutidine, and the mixture is continuously stirred for 5min at 15 to 25 ℃. Standing, separating lower organic phase, washing with water for 2 times to neutrality (200 g water each time) to obtain yellow clear organic phase 150.0g. 150.0g of equal amount of normal hexane is added into the prepared organic phase, the mixture is uniformly mixed, the mixture passes through a silica gel column, after the column passing is finished, the solution is dried, 32.0g of brown yellow oily liquid is obtained, and the yield is more than 100 percent. Adding 128.0g of n-hexane (4 g/g of crude product dosage) into the obtained brown yellow oily liquid, separating out a yellow solid from the system, pulping for 1 hour at 15 to 25 ℃, filtering, and drying a filter cake to obtain 6.2g of a yellow solid intermediate m3, wherein the GC purity is more than 98.0%, and the yield is as follows: 32.46 percent.
And 4, step 4: synthesis of intermediate m4
5.2g (0.023 mol) of intermediate m3, 5.1g (0.023 mol) of 4-ethynyl-4 '-propyl-1, 1' -biphenyl, 0.087g (1.15X 10 mol) were added -4 mol）Pd(PPh 3 )Cl 2 、0.044g（2.30×10 -4 mol）CuI、0.090g（3.45×10 -4 mol）PPh 3 、0.014g（1.15×10 -4 mol) DMAP and 104.0g triethylamine were added to a 250mL three-necked flask, and the flask was purged with nitrogen for 30 minutes. Heating to 80 to 90 ℃, and keeping the temperature for 1 hour to finish the reaction. Removing the solvent to obtain a black solid, passing the obtained solid through a silica gel column (the column-passing solvent is toluene), removing the solvent from the column-passing liquid to obtain 7.7g of a yellow solid intermediate m4, wherein the HPLC purity is more than 92.0 percent, and the yield is as follows: 91.67 percent.
And 5, step 5: synthesis of intermediate m5
14.6g (0.04 mol) of intermediate m4 and 87.6g of THF were charged into a 250mL three-necked flask, and 3.3g (0.048 mol) of hydroxylamine hydrochloride, 3.9g (0.048 mol) of sodium acetate and 87.6g of water were charged into a 250mL Erlenmeyer flask, shaken to be completely dissolved, and added dropwise to the system. Keeping the temperature at 50 to 55 ℃ for 1 hour, and finishing the reaction. The heating was turned off, the upper organic phase was separated off and the solvent was drained off to give 11.8g of a yellow solid. Adding 236.0g of toluene into the obtained yellow solid, heating to 80-90 ℃, pulping for 1 hour, cooling to 15-25 ℃, and performing suction filtration to obtain 10.2g of yellow solid intermediate m5, wherein the HPLC purity is more than 95.0%, and the yield is as follows: 67.11 percent.
And 6, a step of: synthesis of intermediate m6
9.1g (0.024 mol) of intermediate m5 and 54.6g of THF are placed in a 250mL three-necked flask under nitrogen. 3.2g (0.024 mol) of NCS and 16.0g of DMF are put into a conical flask, shaken to be completely dissolved, slowly dripped into the system, and after dripping, the reaction is carried out for 1 hour at the temperature of 20 to 30 ℃ and the reaction is finished. Insoluble matter was removed by filtration, and the filtrate was used directly in the next reaction in a yield of 100%.
And 7, step 7: synthesis of isothiocyanato compounds
2.0g (0.0264 mol) of thiourea, 2.7g (0.0264 mol) of triethylamine and 4.0g of THF are added to a 250mL three-necked flask and the temperature is reduced to 10 to 20 ℃. And (3) dropwise adding the prepared intermediate m6 solution into the system, keeping the temperature and stirring for 10 minutes after dropwise adding is finished, and finishing the reaction. Adding water into the system, quenching the reaction, extracting the water phase with toluene, combining the organic phases, washing with water to neutrality, and removing the solvent to obtain 7.2g of black viscous liquid. The obtained solid is dissolved in n-hexane at 50 to 60 ℃ and passed through a silica gel column at 50 to 60 ℃. And (3) drying the column passing liquid to obtain 5.3g of light yellow solid, recrystallizing the light yellow solid by using normal hexane to obtain 4.8g of light yellow powder, wherein the HPLC purity is more than 99.0 percent, and the yield is as follows: 51.06 percent.
3BTBfNCS: phase transition point was measured by Differential Scanning Calorimetry (DSC) and microscopy: melting point: 151 ℃, clearing point: 213 ℃. Testing characteristic ion M/Z by liquid phase mass spectrometer (HPLC-MS) + Comprises the following steps: 393, 435. 1 H-NMR(400MHz,CDCl 3 ):δ=7.576~7.616（m,5H）,δ=7.527~7.547（d,J=8.0Hz,2H）,δ=7.418~7.470（m,2H）,δ=7.258~7.280（d,J=8.8Hz,2H）,δ=6.420（s,1H）,δ=2.621~2.659(t,2H），δ=1.643~1.736（m,2H）,δ=0.964~1.000（t,3H）ppm。
Example 2
In the general formula
In
With the structure of R as-C 4 H 9 ，Y 1 、Y 2 For example, the synthesis method of the benzofuran-series liquid crystal monomer compound is as follows.
4BTBfNCS was prepared by the same method as in example 1 except that: the 4-ethynyl-4 '-propyl-1, 1' -biphenyl is replaced by the starting material 4-ethynyl-4 '-butyl-1, 1' -biphenyl in step 4.
4BTBfNCS: HPLC purity greater than 99.0%, phase transition point by Differential Scanning Calorimeter (DSC) and microscopy: melting point 143 ℃ and clearing point 196 ℃. Testing characteristic ion M/Z by liquid phase mass spectrum combined instrument (HPLC-MS) + Comprises the following steps: 405, 447. 1 H-NMR(400MHz,CDCl 3 ):δ=7.567~7.610（m,5H）,δ=7.515~7.536（d,J=8.4Hz,2H）,δ=7.410~7.461（m,2H）,δ=7.251~7.272（d,J=8.4Hz,2H）,δ=6.412（s,1H）,δ=2.635~2.673(t,2H），δ=1.575~1.674（m,2H）,δ=1.342~1.435（m,2H）,δ=0.891~0.984（t,3H）ppm。
Examples of the applications
M is a mother mixed crystal, and the formula is shown in the following table 1:
TABLE 1 formulation composition of parent mixed crystal M
M-1 to M-2 are obtained by mixing 90 percent of mother liquid crystal and 10 percent of single crystal, and the parameters are as follows in the following table 2:
TABLE 2 parameter data table of each mixed crystal
Compared with other liquid crystals, the isothiocyanic monocrystal containing the benzofuran ring has better miscibility, higher clearing point and birefringence, is beneficial to widening the working temperature range of mixed crystals, improving the birefringence of the mixed crystals, reducing the thickness of devices and shortening the response time.
And (4) conclusion: from the above data, it can be seen that the mixed liquid crystal to which the novel liquid crystal monomer is added has excellent physical properties.
The structure according to the present example is as follows 3:
TABLE 3 Structure of the compound according to this example
The technical features of the embodiments described above may be arbitrarily combined, and for brevity of description, all possible combinations of the technical features in the embodiments described above are not exhaustive, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
It will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention as defined in the following claims.
Claims (6)
1. The benzofuran series liquid crystal monomer compound is characterized in that the liquid crystal monomer compound has any one of the following structures:
2. a process for preparing the liquid crystal monomer compound of benzofuran series according to claim 1, wherein
In the case that R has the structure of-C 3 H 7 ，Y 1 、Y 2 = H, its preparation method steps are as follows:
the first step is as follows: preparation of intermediate m1
m1
Adding 40.2g of 4-bromo-2-hydroxybenzaldehyde, 82.9g of potassium carbonate and 201.0g of DMF (dimethyl formamide) into a 500mL three-necked bottle, dropwise adding 50.1g of ethyl bromoacetate into the system at 10-20 ℃, after dropwise adding, heating to 130-140 ℃, keeping the temperature and reacting for 6 hours, after the reaction is finished, cooling the system to the internal temperature of 15-25 ℃, filtering to obtain 90.0g of a white filter cake with wet weight, adding 100.0g of 10% diluted hydrochloric acid into the filter cake, heating to 55-60 ℃, keeping the temperature, stirring and pulping for 2 hours, after pulping, cooling the system to 15-25 ℃, filtering to obtain a pink solid, and drying to obtain a pink solid intermediate m1;
the second step: preparation of intermediate m2
m2
Adding 35.4g of intermediate m1 and 177.0g of dichloroethane into a 500mL three-necked bottle, heating to 50-60 ℃, slowly dripping 28.1g of oxalyl chloride into the system, keeping the temperature at 50-60 ℃ for reaction for 1 hour after dripping is finished until the system is completely dissolved, and removing the solvent after the reaction is finished to obtain a white-like solid intermediate m2;
the third step: preparation of intermediate m3
m3
22.1g of intermediate m2, 0.119g of Pd (PPh) 3 )Cl 2 、0.089g PPh 3 And 200.4g of dichloroethane plusPutting the mixture into a 500mL three-necked flask, heating to 80-90 ℃, slowly dropwise adding 10.9g of triethylsilane, after dropwise adding, keeping the temperature at 80-90 ℃ for 5 hours, after the reaction is finished, reducing the system to the inner temperature of 15-25 ℃, slowly adding the mixture into 200.0g of ice water and 10.7g of 2, 6-dimethylpyridine, continuously stirring for 5 minutes at 15-25 ℃, standing, separating out a lower organic phase, washing with water for 2 times to neutrality, washing with water for 200g each time to obtain 150.0g of a yellow clear organic phase, adding 150.0g of n-hexane into the prepared organic phase, uniformly mixing, passing through a silica gel column, draining the solution to obtain 32.0g of brown-yellow oily liquid, adding 128.0g of n-hexane into the obtained brown-yellow oily liquid, separating out a yellow solid of the system, pulping at 15-25 ℃ for 1 hour, filtering, and drying a filter cake to obtain a yellow solid intermediate m3;
the fourth step: preparation of intermediate m4
m4
5.2g of intermediate m3, 0.023mol of 4-ethynyl-4 '-propyl-1, 1' -biphenyl, 0.087g of Pd (PPh) 3 )Cl 2 、0.044g CuI、0.090g PPh 3 Adding 0.014g of DMAP and 104.0g of triethylamine into a 250mL three-necked flask, replacing with nitrogen for 30 minutes, heating to 80-90 ℃, keeping the temperature and reacting for 1 hour, removing the solvent after the reaction is finished to obtain a black solid, passing the obtained solid through a silica gel column, wherein the column solvent is toluene, and removing the solvent from the column liquid to obtain a yellow solid intermediate m4;
the fifth step: preparation of intermediate m5
m5
Adding 14.6g of intermediate m4 and 87.6g of THF into a 250mL three-necked bottle, adding 3.3g of hydroxylamine hydrochloride, 3.9g of sodium acetate and 87.6g of water into a 250mL conical bottle, shaking to be completely dissolved, dropwise adding the mixture into the system, carrying out heat preservation reaction at 50-55 ℃ for 1 hour, closing and heating after the reaction is finished, separating an upper organic phase, drying the solvent to obtain 11.8g of yellow solid, adding 236.0g of toluene into the obtained yellow solid, heating to 80-90 ℃, pulping for 1 hour, cooling to 15-25 ℃, and carrying out suction filtration to obtain 10.2g of yellow solid intermediate m5;
and a sixth step: preparation of intermediate m6
m6
Adding 9.1g of intermediate m5 and 54.6g of THF into a 250mL three-necked flask, shaking to be completely dissolved in a conical flask under the protection of nitrogen, slowly dripping into the system, reacting for 1 hour at the temperature of 20-30 ℃ after dripping is finished, and filtering to remove insoluble substances to obtain a filtrate which is a solution of intermediate m 6;
the seventh step: synthesis of isothiocyanato compounds
Adding 2.0g of thiourea, 2.7g of triethylamine and 4.0g of THF into a 250mL three-necked bottle, cooling to 10 to 20 ℃, dropwise adding the prepared solution of the intermediate m6 into the system, keeping the temperature and stirring for 10 minutes after the dropwise adding is completed, adding water into the system, quenching the reaction, extracting a water phase by toluene, combining organic phases, washing the organic phases to be neutral, drying the solvent to obtain 7.2g of black viscous liquid, dissolving the black viscous liquid in n-hexane at 50 to 60 ℃, passing through a silica gel column at 50 to 60 ℃, drying the column liquid to obtain 5.3g of light yellow solid, and recrystallizing the light yellow solid by n-hexane to obtain light yellow powder, namely the isothiocyanato compound.
3. A process for preparing the benzofuran series liquid crystal monomer compound according to claim 1, wherein
In the case that R has the structure of-C 4 H 9 ，Y 1 、Y 2 = H, its preparation method steps are as follows:
the first step is as follows: preparation of intermediate m1
m1
Adding 40.2g of 4-bromo-2-hydroxybenzaldehyde, 82.9g of potassium carbonate and 201.0g of DMF (dimethyl formamide) into a 500mL three-necked bottle, dropwise adding 50.1g of ethyl bromoacetate into the system at 10-20 ℃, after dropwise adding, heating to 130-140 ℃, keeping the temperature and reacting for 6 hours, after the reaction is finished, cooling the system to the internal temperature of 15-25 ℃, filtering to obtain 90.0g of a white filter cake with wet weight, adding 100.0g of 10% diluted hydrochloric acid into the filter cake, heating to 55-60 ℃, keeping the temperature, stirring and pulping for 2 hours, after pulping, cooling the system to 15-25 ℃, filtering to obtain a pink solid, and drying to obtain a pink solid intermediate m1;
the second step: preparation of intermediate m2
m2
Adding 35.4g of intermediate m1 and 177.0g of dichloroethane into a 500mL three-necked bottle, heating to 50-60 ℃, slowly dripping 28.1g of oxalyl chloride into the system, keeping the temperature at 50-60 ℃ for reaction for 1 hour until the system is completely dissolved, and draining the solvent after the reaction is finished to obtain a white-like solid intermediate m2;
the third step: preparation of intermediate m3
m3
22.1g of intermediate m2, 0.119g of Pd (PPh) 3 )Cl 2 、0.089g PPh 3 Adding 200.4g of dichloroethane into a 500mL three-necked flask, heating to 80-90 ℃, slowly dripping 10.9g of triethylsilane, after dripping, keeping the temperature at 80-90 ℃ for 5 hours, after the reaction is finished, reducing the system temperature to 15-25 ℃, slowly adding 200.0g of ice water and 10.7g of 2, 6-lutidine, continuously stirring for 5 minutes at 15-25 ℃, standing, separating out a lower organic phase, washing for 2 times to neutrality, washing with 200g of water each time to obtain 150.0g of a yellow clear organic phase, adding 150.0g of n-hexane with the same amount into the prepared organic phase, uniformly mixing, passing through a silica gel column,after the column chromatography is finished, removing the solution to obtain 32.0g of brown yellow oily liquid, adding 128.0g of n-hexane into the brown yellow oily liquid to separate out a yellow solid, pulping at 15 to 25 ℃ for 1 hour, filtering, and drying a filter cake to obtain a yellow solid intermediate m3;
the fourth step: preparation of intermediate m4
m4
5.2g of intermediate m3, 0.023mol of 4-ethynyl-4 '-butyl-1, 1' -biphenyl, 0.087g of Pd (PPh) 3 )Cl 2 、0.044g CuI、0.090g PPh 3 Adding 0.014g of DMAP and 104.0g of triethylamine into a 250mL three-necked flask, replacing with nitrogen for 30 minutes, heating to 80-90 ℃, keeping the temperature and reacting for 1 hour, removing the solvent after the reaction is finished to obtain a black solid, passing the obtained solid through a silica gel column, wherein the column solvent is toluene, and removing the solvent from the column liquid to obtain a yellow solid intermediate m4;
the fifth step: preparation of intermediate m5
m5
Adding 14.6g of intermediate m4 and 87.6g of THF into a 250mL three-necked bottle, adding 3.3g of hydroxylamine hydrochloride, 3.9g of sodium acetate and 87.6g of water into a 250mL conical bottle, shaking to be completely dissolved, dropwise adding the mixture into the system, carrying out heat preservation reaction at 50-55 ℃ for 1 hour, closing and heating after the reaction is finished, separating an upper organic phase, drying the solvent to obtain 11.8g of yellow solid, adding 236.0g of toluene into the obtained yellow solid, heating to 80-90 ℃, pulping for 1 hour, cooling to 15-25 ℃, and carrying out suction filtration to obtain 10.2g of yellow solid intermediate m5;
and a sixth step: preparation of intermediate m6
m6
Adding 9.1g of intermediate m5 and 54.6g of THF into a 250mL three-necked bottle, shaking the mixture into a conical flask under the protection of nitrogen, slowly adding the mixture into the system in a dropwise manner, keeping the temperature at 20-30 ℃ for 1 hour after the completion of dropwise adding, finishing the reaction, filtering to remove insoluble substances, and obtaining a filtrate which is a solution of an intermediate m 6;
the seventh step: synthesis of isothiocyanato compounds
Adding 2.0g of thiourea, 2.7g of triethylamine and 4.0g of THF into a 250mL three-necked bottle, cooling to 10 to 20 ℃, dropwise adding the prepared solution of the intermediate m6 into the system, keeping the temperature and stirring for 10 minutes after the dropwise adding is completed, adding water into the system, quenching the reaction, extracting a water phase by toluene, combining organic phases, washing the organic phases to be neutral, drying the solvent to obtain 7.2g of black viscous liquid, dissolving the black viscous liquid in n-hexane at 50 to 60 ℃, passing through a silica gel column at 50 to 60 ℃, drying the column liquid to obtain 5.3g of light yellow solid, and recrystallizing the light yellow solid by n-hexane to obtain light yellow powder, namely the isothiocyanato compound.
4. Use of the benzofuran-series liquid crystal monomer compound according to claim 1 in a liquid crystal composition.
5. Use of the benzofuran-series liquid crystal monomer compound according to claim 1 in a liquid crystal display or high frequency technology component.
6. Use of the monomeric compounds of the benzofuran series of liquid crystals as claimed in claim 5, wherein said high frequency technology component is a liquid crystal based antenna element, a phase shifter, a tunable filter or a tunable metamaterial structure.
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