CN115448862B - Binaphthyl series liquid crystal monomer compound and preparation method and application thereof - Google Patents
Binaphthyl series liquid crystal monomer compound and preparation method and application thereof Download PDFInfo
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 78
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 78
- 239000000178 monomer Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- ZDZHCHYQNPQSGG-UHFFFAOYSA-N binaphthyl group Chemical group C1(=CC=CC2=CC=CC=C12)C1=CC=CC2=CC=CC=C12 ZDZHCHYQNPQSGG-UHFFFAOYSA-N 0.000 title description 2
- 125000000304 alkynyl group Chemical group 0.000 claims abstract description 9
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 8
- 230000003287 optical effect Effects 0.000 claims abstract description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 239000011737 fluorine Substances 0.000 claims abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 108
- 238000006243 chemical reaction Methods 0.000 claims description 54
- 239000002904 solvent Substances 0.000 claims description 34
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 20
- 238000004321 preservation Methods 0.000 claims description 19
- 230000007935 neutral effect Effects 0.000 claims description 18
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 17
- 239000011261 inert gas Substances 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 15
- 239000012074 organic phase Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 13
- 238000004440 column chromatography Methods 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 11
- -1 arylamine compound Chemical class 0.000 claims description 10
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-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
- WJKHJLXJJJATHN-UHFFFAOYSA-N triflic anhydride Chemical compound FC(F)(F)S(=O)(=O)OS(=O)(=O)C(F)(F)F WJKHJLXJJJATHN-UHFFFAOYSA-N 0.000 claims description 10
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- NXQGGXCHGDYOHB-UHFFFAOYSA-L cyclopenta-1,4-dien-1-yl(diphenyl)phosphane;dichloropalladium;iron(2+) Chemical compound [Fe+2].Cl[Pd]Cl.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 NXQGGXCHGDYOHB-UHFFFAOYSA-L 0.000 claims description 9
- 235000011056 potassium acetate Nutrition 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 238000003786 synthesis reaction Methods 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 7
- 239000012071 phase Substances 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 238000010791 quenching Methods 0.000 claims description 6
- 230000000171 quenching effect Effects 0.000 claims description 6
- UCCUXODGPMAHRL-UHFFFAOYSA-N 1-bromo-4-iodobenzene Chemical compound BrC1=CC=C(I)C=C1 UCCUXODGPMAHRL-UHFFFAOYSA-N 0.000 claims description 5
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 5
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 5
- 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 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- JVVRCYWZTJLJSG-UHFFFAOYSA-N 4-dimethylaminophenol Chemical compound CN(C)C1=CC=C(O)C=C1 JVVRCYWZTJLJSG-UHFFFAOYSA-N 0.000 claims description 4
- 229960000549 4-dimethylaminophenol Drugs 0.000 claims description 4
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-dimethylaminopyridine Substances CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 4
- 229950011260 betanaphthol Drugs 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- RAFNCPHFRHZCPS-UHFFFAOYSA-N di(imidazol-1-yl)methanethione Chemical compound C1=CN=CN1C(=S)N1C=CN=C1 RAFNCPHFRHZCPS-UHFFFAOYSA-N 0.000 claims description 4
- 238000005516 engineering process Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- BMIBJCFFZPYJHF-UHFFFAOYSA-N 2-methoxy-5-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine Chemical compound COC1=NC=C(C)C=C1B1OC(C)(C)C(C)(C)O1 BMIBJCFFZPYJHF-UHFFFAOYSA-N 0.000 claims 1
- 239000013078 crystal Substances 0.000 abstract description 13
- 238000009776 industrial production Methods 0.000 abstract description 2
- 150000002540 isothiocyanates Chemical class 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 34
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 28
- 229910052757 nitrogen Inorganic materials 0.000 description 17
- 239000003208 petroleum Substances 0.000 description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000010586 diagram Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 239000003480 eluent Substances 0.000 description 6
- 238000001953 recrystallisation Methods 0.000 description 6
- 125000003944 tolyl group Chemical group 0.000 description 6
- 125000001624 naphthyl group Chemical group 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000001819 mass spectrum Methods 0.000 description 4
- AWQKULXTGASLSW-UHFFFAOYSA-N 6-propylnaphthalen-2-ol Chemical compound C1=C(O)C=CC2=CC(CCC)=CC=C21 AWQKULXTGASLSW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- XRMZKCQCINEBEI-UHFFFAOYSA-N 4-bromo-2-fluoro-1-iodobenzene Chemical compound FC1=CC(Br)=CC=C1I XRMZKCQCINEBEI-UHFFFAOYSA-N 0.000 description 2
- DNJUDXYIQGTFLF-UHFFFAOYSA-N CCC(C(C(C=C1)=C2)=CC=C2C#C)=C1N Chemical compound CCC(C(C(C=C1)=C2)=CC=C2C#C)=C1N DNJUDXYIQGTFLF-UHFFFAOYSA-N 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- OAMZXMDZZWGPMH-UHFFFAOYSA-N ethyl acetate;toluene Chemical compound CCOC(C)=O.CC1=CC=CC=C1 OAMZXMDZZWGPMH-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 125000001810 isothiocyanato group Chemical group *N=C=S 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000002790 naphthalenes Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- CEBKHWWANWSNTI-UHFFFAOYSA-N 2-methylbut-3-yn-2-ol Chemical compound CC(C)(O)C#C CEBKHWWANWSNTI-UHFFFAOYSA-N 0.000 description 1
- GIOJJCLCMBZSQZ-UHFFFAOYSA-N 6-butylnaphthalen-2-ol Chemical group C1=C(O)C=CC2=CC(CCCC)=CC=C21 GIOJJCLCMBZSQZ-UHFFFAOYSA-N 0.000 description 1
- RZHYFKAUCHBXAH-UHFFFAOYSA-N 6-propoxynaphthalen-2-ol Chemical group C1=C(O)C=CC2=CC(OCCC)=CC=C21 RZHYFKAUCHBXAH-UHFFFAOYSA-N 0.000 description 1
- YNHIGQDRGKUECZ-UHFFFAOYSA-L PdCl2(PPh3)2 Substances [Cl-].[Cl-].[Pd+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000013022 formulation composition Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000010363 phase shift Effects 0.000 description 1
- 238000007867 post-reaction treatment Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C331/00—Derivatives of thiocyanic acid or of isothiocyanic acid
- C07C331/16—Isothiocyanates
- C07C331/28—Isothiocyanates having isothiocyanate groups bound to carbon atoms of six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/26—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids
- C07C303/28—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids by reaction of hydroxy compounds with sulfonic acids or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/025—Boronic and borinic acid compounds
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/32—Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems
- C09K19/322—Compounds containing a naphthalene ring or a completely or partially hydrogenated naphthalene ring
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
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Abstract
The invention relates to the technical field of liquid crystal compounds, in particular to a dinaphthyl series liquid crystal monomer compound, a preparation method and application thereof, wherein the structural formula of the liquid crystal monomer compound is shown as the following formula (I):
(I) Wherein R is 1 Is any one of alkyl and alkoxy, R 2 Is any one of alkyl and alkoxy; x is any one of a single bond, alkynyl, phenyl, fluorine-containing phenyl, phenyl alkynyl and fluorine-containing phenyl alkynyl. The isothiocyanate-containing dinaphthyl liquid crystal monomer compound has higher resistivity, larger optical anisotropy, lower viscosity and higher birefringence index, and can be used in a mixed crystal formulaThe birefringence and clearing point of the liquid crystal component are improved, and the performance of the liquid crystal component can be improved. And the preparation method is simple, has high yield and is suitable for industrial production.
Description
Technical Field
The invention relates to a dinaphthyl series liquid crystal monomer compound and a preparation method and application thereof, belonging to the technical field of liquid crystal compounds.
Background
At present, liquid crystal has been widely applied in the display field, with the development of science and technology, the application range of liquid crystal is gradually increased, the research on the application of liquid crystal in microwave devices starts from the end of the 20 th century, develops rapidly in the beginning of the century, especially has gained wide attention all over the world in recent years, develops rapidly, and is found to be applicable to important fields such as tunable filters, reconfigurable antennas, adjustable frequency selectors, adjustable phase shifters and the like. However, there are fundamental problems to be solved in many aspects of some key technologies, such as liquid crystal materials, orientation, packaging, wiring, device design and functional characterization.
In order to meet the development requirements of liquid crystal display panels, various liquid crystal compounds are synthesized, and in practical applications, a plurality of liquid crystal compounds are usually mixed into a liquid crystal composition. Therefore, it is a research focus of researchers to synthesize a liquid crystal compound having specific properties to improve optical anisotropy and clearing point of a liquid crystal composition, reduce viscosity of the liquid crystal composition, and improve response speed of the liquid crystal composition.
However, it is known that liquid crystal monomers with high birefringence tend to have high viscosity, which are contradictory, so we need to consider two aspects, namely, from the viewpoint of molecular design, by connecting large conjugated rigid centers in series by suitable connecting bridges and connecting flexible chain segment groups with proper lengths at the ends, a liquid crystal monomer with relatively high birefringence and relatively low viscosity is obtained. Secondly, from the perspective of the mixed liquid crystal formula, a proper single crystal component is selected, a liquid crystal monomer with higher birefringence is added, and mixed liquid crystal with high birefringence and low viscosity required by a liquid crystal display panel capable of meeting fast response is designed.
Patent application CN114213296A discloses a naphthalene series liquid crystal monomer compound containing an isothiocyanato and a preparation method thereof, and describes that a mixture liquid crystal medium formed by the liquid crystal monomer compound is applied to the field of microwave devices. Patent application CN103555343A also discloses a naphthalene series liquid crystal monomer compound containing an isothiocyanato and a preparation method thereof, wherein the liquid crystal molecules have larger dielectric anisotropy. However, the liquid crystal dielectric materials reported in these patent applications have the disadvantages of high dielectric loss, insufficient phase shift, and still have to be improved in some physical properties, such as clearing point, phase range, etc.
Disclosure of Invention
The invention provides a dinaphthyl series liquid crystal monomer compound and a preparation method and application thereof aiming at the defects in the prior art, wherein the dinaphthyl series liquid crystal monomer compound has higher resistivity, larger optical anisotropy, lower viscosity and higher birefringence, and the preparation method is simple and has high yield.
The technical scheme for solving the technical problems is as follows: a double naphthyl series liquid crystal monomer compound, the structural formula of which is shown as the following formula (I):
（I）
wherein R is 1 Is any one of alkyl and alkoxy, R 2 Is any one of alkyl and alkoxy; x is a single bond, alkynyl, phenyl, fluorine-containing phenyl, phenylalkynyl, fluorine-containing benzeneAny one of alkynyl groups.
Further, said R 1 、R 2 Are all selected from-C n H 2n+1 、-O-C n H 2n+1 Wherein n is an integer of 1 to 10.
Further, the structural formula of X is any one of the following structural formulas:
wherein, Y 1 、Y 2 The group is H or F, and the number of F groups in X is 0, 1 or 2.
Further, the liquid crystal monomer compound is selected from any one of the following structures:
the invention also discloses a preparation method of the dinaphthyl series liquid crystal monomer compound, which comprises the following steps:
the first step is as follows: preparation of intermediate m1
m1
Dissolving 6-substituent-2-naphthol in dichloroethane and triethylamine, cooling to-5 to 0 ℃, dropwise adding trifluoromethanesulfonic anhydride, heating after dropwise adding, carrying out heat preservation reaction, carrying out quenching reaction after reaction is finished, separating a lower organic phase, washing with water to be neutral, passing through a column, removing a solvent from a column liquid, and obtaining a light yellow oily substance m1;
the second step is that: preparation of intermediate m2
m2
Dissolving the intermediate m1, pinacol bisboronate and potassium acetate in toluene, adding 1,1' -bis (diphenylphosphino) ferrocene palladium dichloride (II) under the protection of inert gas, heating, carrying out heat preservation reaction, cooling to room temperature after the reaction is finished, carrying out suction filtration, washing the filtrate to be neutral, passing through a column, removing the solvent from the solution passing through the column, and recrystallizing to obtain a white solid target compound m2;
the third step: preparation of intermediate m3
m3
Mixing the intermediate m2, p-bromoiodobenzene, potassium carbonate, toluene and water together, adding tetrakis (triphenylphosphine) palladium under the protection of inert gas, heating and carrying out heat preservation reaction, cooling the system to room temperature after the reaction is finished, separating an upper organic phase, washing with water to be neutral, passing through a column, removing a solvent through a column liquid, and recrystallizing to obtain a yellow powdery solid target compound m3;
the fourth step: preparation of intermediate m4
m4
Dissolving m3 in triethylamine, adding an arylamine compound, adding bis (triphenylphosphine) palladium dichloride, triphenylphosphine, DMAP and cuprous iodide as catalysts under the protection of inert gas, heating, carrying out heat preservation reaction, and after the reaction is finished, purifying by column chromatography to obtain a target compound m4;
the fifth step: synthesis of dinaphthyl series liquid crystal monomer compound
Dissolving m4 in an organic solvent, dropwise adding a tetrahydrofuran solution of N, N' -thiocarbonyldiimidazole at the temperature of 30-35 ℃ under the protection of inert gas, carrying out heat preservation reaction, washing the reaction solution to be neutral, removing the solvent from an organic phase, and purifying by column chromatography to obtain the target compound.
Further, when the X structure in the formula (I) contains alkynyl, the preparation method of the double-naphthyl liquid crystal monomer compound comprises the following steps:
the first step is as follows: preparation of intermediate m1
Dissolving 1 equivalent of 6-substituent-2-naphthol in dichloroethane and triethylamine, cooling to-5 to 0 ℃, dropwise adding 1.1 to 1.5 equivalents of trifluoromethanesulfonic anhydride, heating to 15 to 20 ℃ after dropwise adding, and reacting for 2 to 3 hours under the condition of heat preservation, wherein the reaction is finished. Adding water for quenching, separating a lower organic phase, washing with water to neutrality, passing through a column, and removing the solvent from the column passing liquid to obtain a pale yellow oily substance m1 (which is solidified at room temperature);
the second step is that: preparation of intermediate m2
Dissolving 1 equivalent of the intermediate m1, 1.1 to 1.5 equivalents of pinacol bisboronate and 1.5 to 2.0 equivalents of potassium acetate in toluene, adding 0.005 to 0.01 equivalent of 1,1' -bis (diphenylphosphino) ferrocene palladium dichloride (II) under the protection of inert gas, heating to 105 to 110 ℃, carrying out heat preservation reaction for 6 to 8 hours, cooling to room temperature after the reaction is finished, carrying out suction filtration, washing the filtrate to be neutral, passing through a column, removing a dry solvent from the column liquid, and recrystallizing to obtain a white solid target compound m2;
the third step: preparation of intermediate m3
1 equivalent of the intermediate m2, 1.05 to 1.2 equivalents of p-bromoiodobenzene, 1.5 to 2.0 equivalents of potassium carbonate, toluene and water are mixed together, 0.005 to 0.01 equivalent of tetrakis (triphenylphosphine) palladium is added under the protection of inert gas, the temperature is raised to 75 to 80 ℃, the reaction is kept for 5 to 6 hours, and the reaction is finished. Cooling the system to room temperature, separating an upper organic phase, washing with water to be neutral, passing through a column, removing the solvent from the column passing liquid, and recrystallizing to obtain a yellow powdery solid target compound m3;
the fourth step: preparation of intermediate m4
Dissolving 1 equivalent of m3 in triethylamine, adding 1.1 to 1.5 equivalents of an end alkynyl arylamine compound, adding 0.01 to 0.05 equivalent of bis (triphenylphosphine) palladium dichloride, 0.02 to 0.1 equivalent of triphenylphosphine, 0.05 to 0.1 equivalent of DMAP and 0.01 to 0.02 equivalent of cuprous iodide as catalysts under the protection of inert gas, heating to 85 to 90 ℃, carrying out heat preservation reaction for 6 to 8 hours, finishing the reaction, and carrying out column chromatography purification to obtain a target compound m4;
the fifth step: synthesis of dinaphthyl series liquid crystal monomer compound
Dissolving 1 equivalent of m4 in an organic solvent, dropwise adding 1 to 1.5 equivalents of N, N' -thiocarbonyldiimidazole tetrahydrofuran solution at the temperature of 30 to 35 ℃ under the protection of inert gas, carrying out heat preservation reaction for 8 to 12h, washing the reaction solution to be neutral, removing the organic phase from the dry solvent, and purifying by column chromatography to obtain the target compound.
Further, in the first step, the dosage of the trifluoromethanesulfonic anhydride is 1.1 to 1.5g/g; preferably 1.2g/g.
In the first step, the reaction time is generally 2 to 3 hours, and a gas phase detection method can be adopted according to actual conditions until the raw material 6-substituent-2-naphthol completely reacts.
In the second step, the inert gas is one of nitrogen and argon; preferably with nitrogen.
In the second step, the eluent adopted by the column chromatography is any one or the mixture of any two of toluene, dichloroethane and ethyl acetate; toluene is preferred.
In the second step, the solvent is removed by evaporation, preferably by a rotary evaporator at 80 to 90 ℃.
In the second step, the recrystallization solvent is any one or any two of toluene, petroleum ether, dichloroethane and ethyl acetate; preferably the mass ratio of toluene: petroleum ether = 2.
In the third step, the inert gas is one of nitrogen and argon, preferably nitrogen.
In the third step, the eluent adopted by the column chromatography is any one or the mixture of any two of toluene, dichloroethane and ethyl acetate; toluene is preferred.
In the third step, the solvent is removed by evaporation preferably using a rotary evaporator at 80 to 90 ℃.
In the third step, the medium recrystallization solvent is any one or any two of toluene, petroleum ether, dichloroethane and ethyl acetate; preferably the mass ratio of toluene: petroleum ether = 2.
In the fourth step, the inert gas is one of nitrogen and argon, preferably nitrogen.
In the fourth step, when the structure of X in the formula (I) contains alkynyl, the arylamine compound is any one of the following structural formulas:
when the structure of X in the formula (I) does not contain alkynyl, the arylamine compound is any one of the following structural formulas:
Y 1 、Y 2 the substituent isH or F, wherein the number of F substituents is 0, 1 or 2 2 The group being-C n H 2n+1 、-O-C n H 2n+1 Wherein n is an integer of 1 to 10.
In the fourth step, the eluent used for column chromatography is any one or a mixture of any two of toluene, petroleum ether, dichloroethane and ethyl acetate, and the mass ratio of toluene: petroleum ether = 2.
In the fifth step, the inert gas is one of nitrogen and argon; preferably nitrogen.
In the fifth step, the solvent for dissolving the intermediate m4 is any one of dichloromethane, dichloroethane and toluene; preferably dichloromethane.
In the fifth step, the eluent for column chromatography is any one or mixture of toluene, petroleum ether, dichloroethane and ethyl acetate; preferably dichloroethane: petroleum ether = 10.
The invention also discloses application of the dinaphthyl series liquid crystal monomer compound, and the liquid crystal monomer compound is applied to a liquid crystal composition.
The application of the double-naphthyl liquid crystal monomer compound is to apply the liquid crystal monomer compound to a liquid crystal display or a high-frequency technical component.
The high-frequency technical component is any one of a liquid crystal-based antenna element, a phase shifter, a tunable optical filter and a tunable metamaterial structure.
The invention has the beneficial effects that:
the double-naphthyl liquid crystal compound has higher resistivity, larger optical anisotropy, lower viscosity and higher birefringence, can improve the birefringence and clearing point of a liquid crystal component when being used in a mixed crystal formula, and can improve the performance of the liquid crystal component.
The preparation method of the dinaphthyl series liquid crystal compound is simple, high in yield and suitable for industrial production.
Compared with the prior patents CN114213296A and CN103555343A, the present invention provides a liquid crystal monomer compound with a double naphthalene ring structure, which has better thermal stability and optical stability due to the molecular plane structure of the double naphthalene ring, and has higher phase transition temperature and optical anisotropy constant in the application process due to the existence of the double naphthalene structure, thereby improving the display effect of liquid crystal.
Drawings
FIG. 1 is a mass spectrum of the target compound 3NPTNENCS in example 1;
FIG. 2 is a hydrogen nuclear magnetic diagram of the target compound 3NPTNENCS in example 1;
FIG. 3 is an enlarged partial view of FIG. 2 showing chemical shifts 0.7-3.5;
FIG. 4 is an enlarged view of a portion of FIG. 2 showing chemical shift 7.2-8.2;
FIG. 5 is a carbon nuclear magnetic diagram of the target compound 3NPTNENCS in example 1;
FIG. 6 is an enlarged partial view of chemical shifts 118.0-144.0 of FIG. 5;
FIG. 7 is a mass spectrum of the target compound 4NPTNENCS in example 2;
FIG. 8 is a hydrogen nuclear magnetic diagram of the target compound 4NPTNENCS in example 2;
FIG. 9 is an enlarged partial view of FIG. 8 at chemical shift 0.7-3.4;
FIG. 10 is an enlarged partial view of chemical shifts 7.1-8.1 of FIG. 8;
FIG. 11 is a carbon nuclear magnetic diagram of the target compound 4NPTNENCS in example 2;
FIG. 12 is an enlarged view of a portion of FIG. 11 showing chemical shifts 121.0-142.0.
Detailed Description
The following is a detailed description of specific embodiments of the invention. The present invention may be embodied in many different forms than those specifically described herein and those skilled in the art will be able to make similar modifications without departing from the spirit of the invention and it is therefore not intended to be 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 the general formula
In
With R 1 Has the structure of-C 3 H 7 ，R 2 Has a structure of-C 2 H 5 And X has the structure
(3 NPTNENCS for short) as an example, a synthetic method of the dinaphthyl series liquid crystal monomer compound is introduced.
The structural formula of the target compound 3NPTNENCS is as follows:
the specific synthetic route is shown as follows:
the method comprises the following specific steps:
(1) Preparation of m 1:
49.7g (0.267 mol) of 6-propyl-2-naphthol is dissolved in 200g of dichloroethane and 30g of triethylamine, the temperature is reduced to minus 5 to 0 ℃, 90.4g (0.320 mol) of trifluoromethanesulfonic anhydride is dripped in, after dripping, the temperature is raised to 15 to 20 ℃, the reaction is kept for 2 to 3 hours, and the reaction is finished. Water is added for quenching, a lower organic phase is separated out, water is washed to be neutral, the mixture passes through a column, the column passing liquid is subjected to solvent removal, and 82.1g of light yellow oily matter m1 (solidified at room temperature) is obtained, the GC purity is 99.2%, and the yield is 80.6%.
(2) And m2 is prepared:
62.0g (0.195 mol) of m1, 74.2g (0.292 mol) of pinacol bisboronate and 38.3g (0.390 mol) of potassium acetate are dissolved in 300g of toluene and 1.4268g (1.95X 10 mol) of potassium acetate are added under nitrogen protection -3 mol）1,1' -bis (diphenylphosphino) ferrocene palladium dichloride (II), heating to 105-110 ℃, and keeping the temperature for reaction for 6-8 hours to finish the reaction. Cooling to room temperature, performing suction filtration, washing the filtrate to be neutral, passing through a column (the column-passing solvent is toluene), removing the solvent from the column-passing liquid, and performing vacuum distillation on the column-passing liquid by using a mass ratio of toluene: recrystallization from petroleum ether = 2.
(3) And m3 is prepared:
32.6g (0.110 mol) of intermediate m2, 34.2g (0.121 mol) of p-bromoiodobenzene, 22.8g (0.165 mol) of potassium carbonate, 326.0g of toluene and 91.2g of water are mixed together, and 1.2711g (1.1X 10 g) of water are added under nitrogen protection -3 And (3) mol) of tetrakis (triphenylphosphine) palladium, heating to 75-80 ℃, and keeping the temperature for reaction for 5-6 hours to finish the reaction. Cooling the system to room temperature, separating an upper organic phase, washing with water to be neutral, passing through a column (the column-passing solvent is toluene), removing the solvent from column-passing liquid, and removing the solvent by using a solvent prepared from the following components in mass ratio of toluene: recrystallization from petroleum ether = 2.
(4) And m4 is prepared:
14.3g (0.044 mol) of m3 are dissolved in 120.0g of triethylamine, 9.0g (0.046 mol) of 1-ethyl-6-ethynylnaphthalen-2-amine are added, and 0.3084g (4.4X 10) are added under nitrogen protection -4 mol) bis (triphenylphosphine) palladium dichloride, 0.2308g (8.8X 10) -4 mol) triphenylphosphine, 0.2688g (2.2X 10) -3 mol）DMAP，0.0838g（4.4×10 -4 mol) cuprous iodide is used as a catalyst, the temperature is raised to 85 to 90 ℃, the reaction is carried out for 6 to 8 hours under the condition of heat preservation, and the reaction is finished. Purification by column chromatography (eluent toluene: petroleum ether =2, mass ratio) gave 10.4g of target compound m4 as a tan solid, with HPLC purity 96.5% and yield 53.8%.
(5) Preparation of 3 NPTNENCS:
10.4g (0.024 mol) of m4 is dissolved in 63g of dichloromethane, and under the protection of nitrogen, 85g of tetrahydrofuran solution of 6.3g (0.036 mol) of N, N' -thiocarbonyldiimidazole is dripped at the temperature of 30 to 35 ℃, and the reaction is carried out for 8 to 12h under the condition of heat preservation. Adding water into the system, quenching reaction, extracting water phase with toluene, mixing organic phases, washing with water to neutrality, and removing solvent to obtain 20.0g of brown yellow solidA body. Purifying by column chromatography (eluent is dichloroethane: petroleum ether =10:1, mass ratio) to obtain 6.0g of white solid 3NPTNENCS, wherein the HPLC purity is more than 99.0%, and the yield is 51.7%. The spectral data were determined as follows: 1 H-NMR（400 MHz，CDCl 3 ）：δ=0.99（t，3H），1.32（t，3H），1.70~1.80（m，2H），2.77（t，2H），3.12~3.18（m，2H），7.31~7.33（d，1H），7.35~7.37（dd，1H），7.63~7.74（m，8H），7.80~7.82（d，1H），7.84~7.86（d，1H），7.96~7.98（d，1H），8.02（s，1H）。
the mass spectrum of 3NPTNENCS is shown in figure 1, the hydrogen nuclear magnetic diagram is shown in figures 2-4, and the carbon nuclear magnetic diagram is shown in figures 5-6.
Example 2:
the structural formula of the target compound 4NPTNENCS is as follows:
the synthesis is as in example 1, except that R 1 Has the structure of n-butyl (-C) 4 H 9 ) The 6-propyl-2-naphthol in example 1 was replaced with 6-n-butyl-2-naphthol.
The mass spectrum of 4NPTNENCS is shown in FIG. 7, the hydrogen nuclear magnetic diagram is shown in FIGS. 8-10, and the carbon nuclear magnetic diagram is shown in FIGS. 11-12.
The spectral data were determined as follows: 1 H-NMR（400 MHz，CDCl 3 ）：δ=0.95（t，3H），1.30（t，3H），1.37~1.43（m，2H），1.66~1.74（m，2H），2.78（t，2H），3.10~3.15（m，2H），7.28~7.30（d，1H），7.34~7.36（dd，1H），7.60~7.72（m，8H），7.78~7.80（d，1H），7.81~7.84（d，1H），7.93~7.96（d，1H），8.00（s，1H）。
example 3:
the structural formula of the target compound 3NPTPNENCS is as follows:
Example 4:
the structural formula of the target compound 3NPNENCS is as follows:
the synthesis was as described in example 1, except that the starting materials were used
Substitute raw material
。
Example 5:
the structural formula of the target compound 3NPGNENCS is as follows:
the synthesis was as described in example 1, except that the starting materials were used
Substitute raw material
。
Example 6:
the structural formula of the target compound 3ONPTNENCS is as follows:
the synthesis is as in example 1, except that R 1 Has the structure of n-propyloxy (-OC) 3 H 7 ). 6-propyl-2-naphthol from example 1 was replaced with 6-n-propyloxy-2-naphthol.
The raw material arylamine compound can be
The preparation method is characterized by comprising the following steps of:
example 7:
the structural formula of the raw material arylamine compound 6-ethynyl-1-ethylnaphthalene-2-amine is as follows:
the specific synthetic route is as follows:
the method comprises the following specific steps:
(1) Preparation of n 2:
50.0g (0.200 mol) of n1 and 25.2g (0.300 mol) of 2-methyl-3-butyn-2-ol are dissolved in 400.0g of triethylamine and 0.7019g (1.0X 10) are added under nitrogen protection -3 mol) bis (triphenylphosphine) palladium (II) dichloride, 0.3810g (2.0X 10) -3 mol) cuprous iodide and 0.5246g (2.0X 10) -3 mol) triphenylphosphine, heating to 80-90 ℃, keeping the temperature and reacting for 2-4 hours, and finishing the reaction. Cooling to room temperature, carrying out suction filtration, carrying out acid washing on the filtrate to neutrality, passing through a column (the column-passing solvent is toluene), removing the solvent from the column-passing liquid, and carrying out mass ratio of toluene: ethanol =1, and 2 was recrystallized to obtain 45.1g of the target compound n2 as a yellow solid with a GC purity of 95.3% and a yield of 89.0%.
(2) Preparation of n 3:
dissolving 38.0g (0.150 mol) of n2 and 0.8417g (0.015 mol) of potassium hydroxide in a mixed solution of 228.0g of toluene and 38.0g of ethanol, heating to 80 to 90 ℃ under the protection of nitrogen, preserving heat and distilling for 2 to 4 hours, and ending the reaction. Adding water for quenching, separating an upper organic phase, washing with water to be neutral, passing through a column, removing a dry solvent from a column passing solution, and adding toluene: recrystallization from petroleum ether = 1.
Example 8:
starting arylamine Compound 6- (2-fluoro-4- (4, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) phenyl) -1-ethylnaphthalen-2-amine of the formula:
the specific synthetic route is shown as follows:
the method comprises the following specific steps:
(1) Preparation of n 4:
25.0g (0.100 mol) of n1, 38.1g (0.150 mol) of pinacol bisboronate and 19.6g (0.200 mol) of potassium acetate are dissolved in 200g of toluene, and 0.3659g (0.5X 10 mol) of potassium acetate are added under nitrogen protection -3 mol) 1,1' -bis (diphenylphosphino) ferrocene palladium dichloride (II), heating to 105-110 ℃, and keeping the temperature for reaction for 6-8 hours to finish the reaction. Cooling to room temperature, performing suction filtration, washing the filtrate to be neutral, passing through a column (the column-passing solvent is toluene), removing the solvent from the column-passing liquid, and performing vacuum distillation on the column-passing liquid by using a mass ratio of toluene: ethanol =1, and 5, to give 22.3g of the target compound n4 as a brown solid with a GC purity of 99.0% and a yield of 75.0%.
(2) Preparation of n 5:
18.0g (0.061 mol) of n4, 19.1g (0.064 mol) of 2-fluoro-4-bromoiodobenzene, 12.6g (0.092 mol) of potassium carbonate, 144g of toluene and 50.4g of water are mixed together, and 0.7049g (6.1X 10 g) of toluene is added under nitrogen protection -4 And (3) mol) of tetrakis (triphenylphosphine) palladium, heating to 75-80 ℃, and keeping the temperature for reaction for 5-6 hours to finish the reaction. Cooling the system to room temperature, separating an upper organic phase, washing with water to be neutral, passing through a column (the column-passing solvent is toluene), removing the dry solvent from column-passing liquid, and adding toluene in a mass ratio of: ethanol =1, and 2, 14.9g of the target compound n5 was obtained as a yellow powdery solid, with a GC purity of 97.8% and a yield of 71.0%.
(3) Preparation of n 6:
45.0g (0.131 mol) of n5, 49.8g (0.196 mol) of pinacol bisborate and 38.5g (0.392 mol) of potassium acetate were dissolved in 360g of toluene, and 0.4783g (6.5X 10 mol) of potassium acetate were added under nitrogen protection -4 mol) 1,1' -bis (diphenylphosphino) ferrocene palladium (II) dichloride and heatingAnd keeping the temperature of the mixture at 105 to 110 ℃ for reaction for 6 to 8 hours, and finishing the reaction. Cooling to room temperature, carrying out suction filtration, washing the filtrate to be neutral, passing through a column (the column-passing solvent is toluene), removing the dry solvent from the column-passing liquid, and reacting the mixture with toluene: recrystallization from petroleum ether = 1.
Example 9
Starting arylamine compounds
The specific preparation method comprises the following steps:
preparation was carried out in the same manner as in example 7 except that
Is replaced by
To do so
The preparation was carried out by the same procedures as in example 8 except for replacing 2-fluoro-4-bromoiodobenzene with p-bromoiodobenzene.
Examples of the applications
The parameters of the prepared single crystal are shown in the following table 1:
TABLE 1 Single Crystal parameter Table
M is a mother mixed crystal, and the formula is shown in the following table 2:
TABLE 2 formulation composition of the parent mixed crystals
M-1 to M-9 are obtained by mixing 90% of mother mixed crystals and 10% of single crystals, and the parameters are as follows in Table 3:
TABLE 3 table of parameter data of each mixed crystal
Compared with other liquid crystals, the isothiocyanic monocrystal containing the naphthalene 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.
In prior published patents CN114213296A, CN103555343A and WO2022043376A1, liquid crystal monomer compounds having similar structures were selected
（3PTNENCS）、
（5BTNNCS）、
The (4 ONTPNCS) compound is better than the compound in the aspect of birefringence of the liquid crystal monomer. However, they were prepared into mixed crystals (M-7, M-8 and M-9) under the same conditions as those in the present application, and they were not as excellent in birefringence and clearing point as the compounds of the present application.
In addition, in terms of the process method and the raw material cost, the synthesis of raw materials which are not environment-friendly or are key to national management and control, such as acyl chloride, aluminum trichloride, hydrazine hydrate and the like, is avoided, the overall process route is more environment-friendly, the involved post-reaction treatment is easy to operate, reaction byproducts are controllable and can be simply and harmlessly treated, the raw material cost and the process production cost can be effectively saved, and the harmfulness and the danger in the process production process are greatly reduced.
And (4) conclusion: therefore, the mixed liquid crystal added with the novel liquid crystal monomer has excellent physical properties, and the process method used by the invention is green, environment-friendly, economical and feasible.
The structure according to the embodiment of the present invention is as follows:
table 4 structures of compounds referred to in examples of the present invention
Any combination of the technical features of the above embodiments may be performed, and for the sake of brevity, all possible combinations of the technical features in the above embodiments are not exhaustive, but should be considered as being within the scope of the present disclosure as long as no contradiction exists 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 (10)
1. A dinaphthyl series liquid crystal monomer compound is characterized in that the structural formula of the liquid crystal monomer compound is shown as the following formula (I):
（I）
wherein R is 1 Is any one of alkyl and alkoxy, R 2 Is any one of alkyl and alkoxy; x is any one of a single bond, alkynyl, phenyl, fluorine-containing phenyl, phenyl alkynyl and fluorine-containing phenyl alkynyl.
2. The bis-naphthyl liquid crystal monomer compound according to claim 1, wherein R is 1 、R 2 Are all selected from-C n H 2n+1 、-O-C n H 2n+1 Wherein n is an integer of 1 to 10.
3. The bis-naphthyl liquid crystal monomer compound according to claim 1, wherein X has a structural formula selected from the group consisting of:
wherein, Y 1 、Y 2 The group is H or F, and the number of F groups in X is 0, 1 or 2.
4. The dinaphthyl series liquid crystal monomer compound as claimed in claim 1, wherein the liquid crystal monomer compound is selected from any one of the following structures:
5. a method for preparing the dinaphthyl series liquid crystal monomer compound according to any one of claims 1 to 4, comprising the steps of:
the first step is as follows: preparation of intermediate m1
m1
Dissolving 6-substituent-2-naphthol in dichloroethane and triethylamine, cooling to-5 to 0 ℃, dropwise adding trifluoromethanesulfonic anhydride, heating after dropwise adding, carrying out heat preservation reaction, carrying out quenching reaction after the reaction is finished, separating a lower organic phase, washing with water to be neutral, passing through a column, and removing a solvent from a column liquid to obtain a light yellow oily substance m1;
the second step is that: preparation of intermediate m2
m2
Dissolving the intermediate m1, the pinacol ester bisboronate and potassium acetate in toluene, adding 1,1' -bis (diphenylphosphino) ferrocene palladium dichloride (II) under the protection of inert gas, heating, carrying out heat preservation reaction, cooling to room temperature after the reaction is finished, carrying out suction filtration, washing the filtrate to be neutral, passing through a column, removing a solvent from the column solution, and recrystallizing to obtain a white solid target compound m2;
the third step: preparation of intermediate m3
m3
Mixing the intermediate m2, p-bromoiodobenzene, potassium carbonate, toluene and water together, adding tetrakis (triphenylphosphine) palladium under the protection of inert gas, heating and carrying out heat preservation reaction, cooling the system to room temperature after the reaction is finished, separating an upper organic phase, washing the upper organic phase to be neutral by water, passing through a column, removing a dry solvent from a column liquid, and recrystallizing to obtain a yellow powdery solid target compound m3;
the fourth step: preparation of intermediate m4
m4
Dissolving m3 in triethylamine, adding an arylamine compound, adding bis (triphenylphosphine) palladium dichloride, triphenylphosphine, DMAP and cuprous iodide as catalysts under the protection of inert gas, heating, carrying out heat preservation reaction, and after the reaction is finished, purifying by column chromatography to obtain a target compound m4;
the fifth step: synthesis of dinaphthyl series liquid crystal monomer compound
Dissolving m4 in an organic solvent, dropwise adding a tetrahydrofuran solution of N, N' -thiocarbonyldiimidazole at the temperature of 30-35 ℃ under the protection of inert gas, carrying out heat preservation reaction, washing the reaction solution to be neutral, removing the solvent from an organic phase, and purifying by column chromatography to obtain the target compound.
6. The method for producing a dinaphthyl series liquid crystal monomer compound according to claim 5, wherein when the X structure in formula (I) contains an alkynyl group, in the fourth step, the arylamine compound is any one of the following structural formulae:
when the structure of X in the formula (I) does not contain alkynyl, in the fourth step, the arylamine compound is any one of the following structural formulas:
Y 1 、Y 2 the substituent is H or FWherein the number of F substituents is 0, 1 or 2 2 The group being-C n H 2n+1 、-O-C n H 2n+1 Wherein n is an integer of 1 to 10.
7. The method for preparing the dinaphthyl series liquid crystal monomer compound as claimed in claim 5, wherein in the first step, the temperature for the heat preservation reaction is 15-20 ℃;
in the second step, the temperature of the heat preservation reaction is 105 to 110 ℃;
in the third step, the temperature of the heat preservation reaction is 75 to 80 ℃;
in the fourth step, the reaction temperature is kept at 85 to 90 ℃.
8. Use of the dinaphthyl liquid crystal monomer compound according to any one of claims 1 to 4 in a liquid crystal composition.
9. Use of a bis-naphthyl liquid crystal monomer compound according to any one of claims 1 to 4, characterized in that the liquid crystal monomer compound is used in liquid crystal displays or high frequency technology components.
10. Use of the bis-naphthyl series liquid crystal monomer compound according to claim 9, wherein the high frequency technology component is any one of a liquid crystal-based antenna element, a phase shifter, a tunable optical filter, and a tunable metamaterial structure.
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| CN114213296B (en) * | 2021-12-23 | 2024-01-26 | 中节能万润股份有限公司 | Naphthalene series liquid crystal monomer compound containing isothiocyanato and preparation method and application thereof |
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