CN111574405A - Diene negative liquid crystal compound and preparation method and application thereof - Google Patents
Diene negative liquid crystal compound and preparation method and application thereof Download PDFInfo
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- CN111574405A CN111574405A CN202010529903.4A CN202010529903A CN111574405A CN 111574405 A CN111574405 A CN 111574405A CN 202010529903 A CN202010529903 A CN 202010529903A CN 111574405 A CN111574405 A CN 111574405A
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- liquid crystal
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- crystal compound
- negative liquid
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 123
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 76
- 150000001993 dienes Chemical class 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title abstract description 44
- 239000000203 mixture Substances 0.000 claims abstract description 35
- RGOVYLWUIBMPGK-UHFFFAOYSA-N nonivamide Chemical compound CCCCCCCCC(=O)NCC1=CC=C(O)C(OC)=C1 RGOVYLWUIBMPGK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 48
- 238000000034 method Methods 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 6
- 125000001424 substituent group Chemical group 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 4
- 238000007239 Wittig reaction Methods 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 230000031709 bromination Effects 0.000 claims description 2
- 238000005893 bromination reaction Methods 0.000 claims description 2
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000006171 hexacyclic group Chemical group 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 238000006138 lithiation reaction Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 238000007344 nucleophilic reaction Methods 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 150000001299 aldehydes Chemical class 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- 238000000354 decomposition reaction Methods 0.000 claims 1
- 230000004044 response Effects 0.000 abstract description 8
- 230000006750 UV protection Effects 0.000 abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 114
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 74
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 56
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 47
- 239000000243 solution Substances 0.000 description 38
- 229910052757 nitrogen Inorganic materials 0.000 description 28
- 230000004224 protection Effects 0.000 description 28
- 239000000543 intermediate Substances 0.000 description 27
- 238000003756 stirring Methods 0.000 description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 25
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 25
- 238000005406 washing Methods 0.000 description 23
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 21
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 18
- 239000007788 liquid Substances 0.000 description 18
- 239000002904 solvent Substances 0.000 description 18
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- 238000001035 drying Methods 0.000 description 15
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 14
- 238000001816 cooling Methods 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 13
- 238000010992 reflux Methods 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 13
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 12
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 12
- 239000012044 organic layer Substances 0.000 description 11
- 239000003513 alkali Substances 0.000 description 10
- 239000012074 organic phase Substances 0.000 description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 239000005708 Sodium hypochlorite Substances 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- 239000000741 silica gel Substances 0.000 description 9
- 229910002027 silica gel Inorganic materials 0.000 description 9
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 9
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 8
- 239000008346 aqueous phase Substances 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- 150000004714 phosphonium salts Chemical class 0.000 description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 description 6
- 238000000605 extraction Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 230000003301 hydrolyzing effect Effects 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 238000010898 silica gel chromatography Methods 0.000 description 4
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 4
- 239000008399 tap water Substances 0.000 description 4
- 235000020679 tap water Nutrition 0.000 description 4
- 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 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 4
- PKIYFPSPIFCDDB-UHFFFAOYSA-N 4-ethoxy-2,3-difluorophenol Chemical compound CCOC1=CC=C(O)C(F)=C1F PKIYFPSPIFCDDB-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WNJSZOGOYJDJMP-UHFFFAOYSA-N ClCOCCl.C1=CC=C(C=C1)P(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound ClCOCCl.C1=CC=C(C=C1)P(C1=CC=CC=C1)C1=CC=CC=C1 WNJSZOGOYJDJMP-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 description 3
- 239000012279 sodium borohydride Substances 0.000 description 3
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 3
- CHLCPTJLUJHDBO-UHFFFAOYSA-M sodium;benzenesulfinate Chemical compound [Na+].[O-]S(=O)C1=CC=CC=C1 CHLCPTJLUJHDBO-UHFFFAOYSA-M 0.000 description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- BUDQDWGNQVEFAC-UHFFFAOYSA-N Dihydropyran Chemical compound C1COC=CC1 BUDQDWGNQVEFAC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000005903 acid hydrolysis reaction Methods 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 229940043279 diisopropylamine Drugs 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical group O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- -1 polyoxymethylene Polymers 0.000 description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 description 2
- 235000011009 potassium phosphates Nutrition 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- NTKVWOTYTNWGRK-UHFFFAOYSA-N P.Br.Br.Br Chemical compound P.Br.Br.Br NTKVWOTYTNWGRK-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical class [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- YIKMRTHKLRXOBU-UHFFFAOYSA-N bromomethane;triphenylphosphane Chemical compound BrC.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 YIKMRTHKLRXOBU-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 210000002858 crystal cell Anatomy 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/45—Carboxylic acid nitriles having cyano groups bound to carbon atoms of rings other than six-membered aromatic rings
- C07C255/46—Carboxylic acid nitriles having cyano groups bound to carbon atoms of rings other than six-membered aromatic rings to carbon atoms of non-condensed rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/257—Ethers having an ether-oxygen atom bound to carbon atoms both belonging to six-membered aromatic rings
- C07C43/29—Ethers having an ether-oxygen atom bound to carbon atoms both belonging to six-membered aromatic rings containing halogen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
- C09K19/3001—Cyclohexane rings
- C09K19/3066—Cyclohexane rings in which the rings are linked by a chain containing carbon and oxygen atoms, e.g. esters or ethers
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nonlinear Science (AREA)
- Mathematical Physics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a diene negative liquid crystal compound and a preparation method and application thereof. The negative liquid crystal compound has a structure shown as a general formula I. The structure of the negative liquid crystal compound shown as the general formula I has a diene structure and great negative dielectric anisotropy, and can improve the gradient of a liquid crystal composition, reduce the viscosity and shorten the response time. The liquid crystal composition containing the liquid crystal compound has good low-temperature stability and intersolubility, strong UV resistance andhigh VHR and resistivity, and is suitable for display modes such as VA, MVA, PVA, FFS, PSVA, IPS, TFT, etc.
Description
Technical Field
The invention relates to a diene negative liquid crystal compound and a preparation method and application thereof, belonging to the technical field of liquid crystal materials.
Background
In order to make the performance of display devices closer to ideal, research into new liquid crystal compounds has been continuously conducted, which makes the performance of liquid crystal compounds and display devices continuously progress. In recent years, many negative materials containing fluorine or cyanogen at lateral positions are applied to liquid crystal mixtures, but research and development in the field of liquid crystal materials are still far from being completed. In order to improve the performance of liquid crystal display elements, attempts are constantly being made to develop new compounds which are capable of optimizing such displays.
The liquid crystal material is a rod-like organic compound which has liquid fluidity and crystal anisotropy at a certain temperature, has the inherent characteristics of optical anisotropy (delta n) and dielectric anisotropy (delta), and is a key photoelectric material for producing display devices. None of the liquid crystalline compounds has so far been able to meet all the requirements. It is generally desirable that a mixture of 2 to 25 monomer compounds, more preferably 3 to 18 compounds, can be used as the liquid crystal phase.
The optical characteristics of the liquid crystal before and after the application of a voltage as a dielectric reversibly change. Liquid crystal displays use a wide variety of electro-optic effects. Special liquid-crystalline media are required for the novel VA displays. For example, liquid crystal media with negative dielectric anisotropy need to have a high VHR after UV exposure. The LC phase used in electro-optic displays needs to meet a number of requirements. Of particular importance are chemical and physical stability to moisture, air, such as thermal stability, resistance to infrared radiation, the visible and ultraviolet regions, and direct or alternating electric fields.
As the display technology advances, the demand for display devices is increasing, and increasing the response speed of liquid crystal display devices is an important way to achieve this demand, and the response speed of liquid crystal displays is mainly limited by the liquid crystal dielectric anisotropy, the thickness of the liquid crystal cell, and the rotational viscosity of the liquid crystal, and therefore, there is a significant demand for liquid crystal media having suitable properties for practical use, such as a wide operating range, suitable optical anisotropy, high dielectric anisotropy and particularly low rotational viscosity according to the display mode.
Although the liquid crystal composition with extremely large negative dielectric anisotropy exists in the prior art, the characteristics of high gradient, low power consumption and fast response cannot be simultaneously considered, such as: the compound proposed in CN108315017 has a very large absolute value of negative dielectric anisotropy, but with the continuous progress of technology, the steepness, response speed, power consumption, etc. cannot fully meet the market demand. The present invention has been made in view of this situation.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a diene negative liquid crystal compound and a preparation method thereof. The compound has a diene structure and great negative dielectric anisotropy, can remarkably improve the gradient of a liquid crystal composition and reduce the viscosity when applied to a negative liquid crystal composition, shortens the response time, and the liquid crystal composition containing the liquid crystal compound has good low-temperature stability and intersolubility, strong UV resistance, high VHR (very high-frequency response) and high resistivity.
The invention provides a diene negative liquid crystal compound, which has the following general formula:
wherein R is1A substituted or unsubstituted linear or branched alkenyl radical selected from C2 to C15， R2Selecting a substituted or unsubstituted straight chain or branched chain alkyl or alkoxy of C1-C15, wherein the substituent is selected from F, Cl, Br, I or CN;
ring A represents cyclohexyl, phenylene, phenyl, an oxygen-containing hexacyclic group or phenylene containing a substituent, wherein the substituent is selected from F, Cl, Br, I or CN;
Z1is selected from-CH2CH2-、-CF2O-or-CH2O-；
L1Selected from H, CN, CH3Or F.
Further, the negative liquid crystal compound is selected from at least one of the following structural formulas:
further, said R1Selected from alkenyl, in particular ethenyl, propenyl or butenyl.
Further, said R2Is selected from methyl or alkoxy of C1-C7.
Further, the negative liquid crystal compound is selected from at least one of the following structural formulas:
the invention also provides a preparation method of the negative liquid crystal compound, and the preparation method of the compound I-2 comprises the following steps:
(1) compound (I)
Reacting to produce the compound
(2) Compound (I)
Reacting to produce the compound
(3) The compounds obtained in the step (1) and the step (2) react to generate
Further with
Reaction to form
Further, the preparation of the compound I-7 comprises the following steps:
with a compound
Preparing a compound by taking the raw material through metal lithiation and nucleophilic reaction
Preparing aldehyde through wittig reaction and hydrolysis reaction
Followed by reduction and bromination to prepare intermediate compounds
And compounds
Reacting to obtain the compound
The invention also provides a negative liquid crystal composition which comprises the liquid crystal compound.
The invention also provides a liquid crystal display comprising the liquid crystal compound.
The invention also provides the application of the liquid crystal display device in VA, MVA, PVA, FFS, PSVA, IPS and TFT display modes.
The liquid crystal compound has the advantages of larger refractive index, equivalent clearing point, larger △, lower rotational viscosity and higher K33/K11It is more suitable for low-voltage and high-gradient VA type liquid crystal display.
Detailed Description
The invention will be illustrated below with reference to specific embodiments. It should be noted that the following examples are illustrative of the present invention, and are not intended to limit the present invention. Other combinations and various modifications within the spirit or scope of the present invention may be made without departing from the spirit or scope of the present invention.
Example 1
A method for preparing a negative liquid crystal compound I-2 comprises the following steps:
with a compound
Preparation of the Compounds as starting materials
Further with
Reaction to form
Preferably, the method for preparing the compound c by using the compound a as a raw material comprises the following steps:
1) dissolving the compound a in one or more of dichloromethane, THF or methanol, cooling to-80-0 ℃ under the protection of nitrogen, dropwise adding organic alkali or inorganic alkali, introducing a formaldehyde aqueous solution, formaldehyde gas or an organic solvent of formaldehyde after complete lithium substitution, reacting completely to obtain a compound b mixed solution, adding acid to adjust the pH value to be neutral, and separating and purifying to obtain a compound b;
2) dissolving the compound b in dichloromethane, adding triethylamine, dropwise adding p-toluenesulfonyl chloride (TsCl) at 0 ℃, stirring for a period of time, heating for refluxing, and separating and purifying after complete reaction to obtain a compound c;
3) adding the compound c, the compound YL-1 and alkali into a polar solvent for dissolving, and after the reaction is finished at the temperature of 60-200 ℃, carrying out post-separation and purification to obtain a negative liquid crystal compound I-2;
more preferably, the base in 1) is potassium tert-butoxide, and the solvent used is dichloromethane or tetrahydrofuran; 3) the alkali used in the step (1) is potassium carbonate, sodium carbonate or potassium phosphate, and the solvent is water or N, N-dimethylformamide;
preferably, the molar ratio of compound c, compound YL-1 and base is 0.8-1.5: 0.8-1.5: 1.0-3.0.
Preferably, the preparation of compound a comprises the following steps:
1) adding compound YL-2 and 47% hydriodic acid solution into a three-neck flask under the protection of nitrogen, refluxing until the reaction is finished, separating and purifying to obtain the compound
2) Dissolving the compound m-1 in dichloromethane, adding Tempo and sodium bromide under stirring, controlling the temperature to be 0-10 ℃, dropwise adding sodium bicarbonate aqueous solution of sodium hypochlorite, and after complete reaction, separating and purifying feed liquid to obtain the compound
3) Mixing phosphonium salt and tetrahydrofuran, cooling to-20-30 deg.C under nitrogen protection, adding alkali, reacting for a certain time, adding mixed solution of compound m-2 and tetrahydrofuran, gradually heating to room temperature, reacting completely, separating and purifying to obtain compound
4) Dissolving a compound m-3 in acetonitrile, adding triphenylphosphine under stirring, carrying out reflux reaction, and carrying out desolventizing and crystallization to obtain the compound
5) Mixing chloromethyl ether triphenylphosphine salt and tetrahydrofuran, cooling to-30-30 ℃ under the protection of nitrogen, adding alkali, reacting for a certain time, and adding a compound
And tetrahydrofuran, gradually raising the temperature to room temperature, and separating and purifying after complete reaction to obtain the compound
6) Dissolving a compound m-5 in tetrahydrofuran, stirring for aldehyde dissolution, controlling the temperature to be-10-20 ℃, dropwise adding 10% dilute hydrochloric acid, after dropwise adding, carrying out heat preservation reaction until the reaction of raw materials is finished, then extracting, washing with water, drying, and desolventizing to obtain the compound
7) Adding the phosphonium salt (m-4) into tetrahydrofuran, controlling the temperature to be-10-20 ℃, and adding potassium tert-butoxide in batches. And after the addition, controlling the temperature to be minus 20-10 ℃, and dropwise adding a solution of m-6 and tetrahydrofuran. After the dropwise addition is finished, preserving the temperature until the m-6 reaction is finished, then quenching, washing with water, extracting, drying, desolventizing and purifying to obtain the compound a.
Example 2
A method for preparing a negative liquid crystal compound I-1 comprises the following steps:
1) dissolving the compound 2-1 in one or more of THF, dimethyl tetrahydrofuran or methanol, cooling to-30- -30 deg.C under nitrogen protection, adding borohydride, quenching, adjusting pH to neutral with acid, separating and purifying to obtain compound 2-2;
2) dissolving the compound 2-2 in dichloromethane, adding triethylamine, dropwise adding p-toluenesulfonyl chloride (TsCl) at 0 ℃, stirring for a period of time, heating for refluxing, and separating and purifying after complete reaction to obtain a compound 2-3;
3) adding the compound 2-3, the compound YL-1 and alkali into a polar solvent for dissolving, carrying out reverse heat preservation at the temperature of 60-150 ℃ until the reaction is finished, and then carrying out separation and purification to obtain a negative liquid crystal compound I-1;
more preferably, the base in 1) is potassium tert-butoxide, and the solvent used is tetrahydrofuran;
3) the alkali is potassium carbonate, sodium carbonate or potassium phosphate, and the solvent is water or N, N-dimethylformamide;
3) under the protection of nitrogen, adding alkali in batches at-30-30 ℃, and reacting completely to obtain a negative liquid crystal compound I-1;
preferably, the molar ratio of compound 2-3, compound YL-1 and base is 1.0: 1.0-2.0: 1.0-2.0.
Preferably, the preparation of compound 2-1 comprises the following steps:
1) dihydropyran (THP), p-toluenesulfonic acid, dichloromethane at 0-40 deg.C, adding compound YL-2, reacting, separating, and purifying to obtain compound
2) Dissolving the compound n-1 in dichloromethane, adding Tempo and sodium bromide under stirring, controlling the temperature to be-10-5 ℃, dropwise adding a sodium bicarbonate aqueous solution of sodium hypochlorite, and after complete reaction, separating and purifying feed liquid to obtain the compound
3) Dissolving the compound n-2 in alkane or dichloromethane, stirring with ethylene glycol and p-toluenesulfonic acid, controlling the temperature at 40-150 ℃, refluxing and separating water, and after complete reaction, separating and purifying feed liquid to obtain the compound
4) Dissolving the compound n-3 in dichloromethane, adding Tempo and sodium bromide under stirring, controlling the temperature to be-5-5 ℃, dropwise adding a sodium bicarbonate aqueous solution of sodium hypochlorite, and after complete reaction, separating and purifying feed liquid to obtain the compound
5) Mixing phosphonium salt and tetrahydrofuran, cooling to-10-10 ℃ under the protection of nitrogen, adding alkali, reacting for a certain time, adding a mixed solution of a compound m-4 and tetrahydrofuran, gradually increasing the temperature to room temperature, and separating and purifying after complete reaction to obtain a compound n-5;
6) the resulting n-5 was added to a three-necked flask, and sodium benzenesulfinate, n-heptane, concentrated hydrochloric acid and water were added. Carrying out reflux reaction for 30 hours, cooling to room temperature, separating liquid, washing with water, carrying out decompression and desolventizing, and purifying to obtain the n-5 trans-configuration;
7) dissolving a compound n-5 in tetrahydrofuran, stirring for aldehyde dissolution, controlling the temperature to be minus 10-20 ℃, dropwise adding 10% dilute hydrochloric acid, after dropwise adding, carrying out heat preservation reaction until the reaction of the raw materials is finished, and then extracting, washing with water, drying and desolventizing to obtain a compound 2-1;
example 3
A process for the preparation of compound TM-1 comprising the steps of:
(1) preparation of m-4a
(2) Preparation of m-6
(3) Preparation of 1-1a
(4) Preparation of TM-1
Step 1.1:
Under the protection of nitrogen, 130gYL-2, 500ml of dichloromethane and 280g of 47% hydroiodic acid were added into a three-necked flask, and the reaction was stopped after 20 hours of reflux reaction. After adding sodium bisulfite and stirring for 30 minutes, the organic layer was separated, the aqueous layer was extracted with dichloromethane, the organic phases were combined, washed to neutrality with water, dried, and the solvent was removed under reduced pressure to give 230g of a viscous pale yellow oil m-1, which was used as it was in the next step.
Step 1.2
Adding 230gm-1 and 2300ml of dichloromethane into a three-neck flask, stirring and dissolving completely, adding 12g of sodium bromide and 6g of Tempo, cooling to-10 ℃, dropwise adding 700g of sodium bicarbonate solution of sodium hypochlorite (500g of sodium hypochlorite solution +200g of water saturated sodium bicarbonate), and controlling the temperature to-10-5 ℃ in the dropwise adding process. After the dropwise addition, the reaction mixture was kept warm for 5 minutes, and a sodium hydrogen sulfite solution was added to the reaction mixture and stirred for 30 minutes. Separating, extracting water layer with dichloromethane, mixing organic layers, washing with water to neutral, rotary evaporating to remove solvent to obtain m-2 pale yellow liquid 225g, and using in next step.
Step 1.3
Under the protection of nitrogen, 358g of bromomethane triphenylphosphine salt and 1000ml of tetrahydrofuran are added into a three-neck flask, after stirring for 10 minutes, the temperature is reduced to-10 ℃, and then 115g of potassium tert-butoxide is added into the reaction liquid in batches, so that the system turns into bright red. Adding a mixed solution of 220g of the compound (m-2) and 500ml of tetrahydrofuran, gradually raising the temperature to room temperature, hydrolyzing, extracting an aqueous phase by toluene, combining organic layers, washing with water, drying, desolventizing a crude product by using an n-heptane solvent, carrying out silica gel column chromatography to obtain 200g of the compound (m-3a), and directly carrying out the next reaction.
Step 1.4
A1000 ml three-necked flask equipped with a thermometer and mechanically stirred was taken up, and 180g of (m-3a) intermediate, 240g of triphenylphosphine and 450ml of acetonitrile were added thereto, and the mixture was refluxed for 30 hours, desolventized, and then crystallized from a mixed solvent of tetrahydrofuran and toluene to obtain 330g of (m-4a) white powder
Step 1.5
Under the protection of nitrogen, 275g of chloromethyl ether triphenylphosphine salt and 1000ml of tetrahydrofuran are added into a three-neck flask, after stirring for 10 minutes, the temperature is reduced to minus 10 ℃, and then 92g of potassium tert-butoxide is added into the reaction liquid in batches, so that the system turns to bright red. Adding a mixed solution of 100g of the compound (YL-3) and 150ml of tetrahydrofuran, gradually raising the temperature to room temperature, hydrolyzing, extracting an aqueous phase by toluene, combining organic layers, washing with water, drying, desolventizing, carrying out silica gel column chromatography on a crude product after desolventizing by using an n-heptane solvent to obtain 118g of the compound (m-5), and directly carrying out the next reaction.
Step 1.6
Dissolving 118g of the compound (m-5) in 300ml of tetrahydrofuran, stirring and dissolving, controlling the temperature to be minus 10-20 ℃, dropwise adding 150ml of 15% dilute hydrochloric acid, keeping the temperature to react after the dropwise adding is finished, then extracting with dichloromethane, washing with water, drying, and performing reduced pressure desolventizing to obtain 100g of the intermediate (m-6) as colorless liquid.
Step 1.7
A mechanically stirred three-necked flask equipped with a thermometer was charged with 300g of (m-4a) intermediate and 1000ml of tetrahydrofuran, and cooled to-10 ℃ to add 68g of potassium tert-butoxide in portions. After the addition is finished, controlling the temperature to be minus 10 ℃ to minus 5 ℃, dropwise adding (m-6)80g and 400ml tetrahydrofuran, gradually increasing the temperature to the room temperature, hydrolyzing, extracting the water phase by toluene, combining the organic layers, washing with water, drying, desolventizing the crude product by using an n-heptane solvent, carrying out silica gel column chromatography to obtain 120g of the compound (1-1a), and directly carrying out the next step of reaction.
Step 1.8
100g of the obtained 1-1a colorless liquid is added into a three-necked bottle, 1000ml of n-heptane, 12g of concentrated hydrochloric acid, 12g of deionized water and 32g of sodium benzene sulfinate are added, reflux reaction is carried out for 45 hours, the temperature is reduced to room temperature, liquid separation is carried out, water washing is carried out until the solution is neutral, decompression and desolventization are carried out, silica gel column is carried out, and recrystallization is carried out, so that 60g of the product with the purity of 98.9 percent is obtained.
Step 1.9
Under the protection of nitrogen, a solution of 30g of diisopropylamine and 60ml of THF is added into a three-neck flask, and 125ml of butyllithium (2.5 mol. L) is added dropwise after the temperature is reduced to-20 DEG C-1) And keeping the temperature at-20 ℃ for 2 hours. The reaction solution was cooled to-80 ℃ and a solution of 60g of 1-1a and 100ml of tetrahydrofuran was added dropwise. Subsequently, the temperature was controlled at-65 ℃ and formaldehyde gas (obtained by thermal decomposition of polyoxymethylene) was introduced. After the reaction was complete, hydrolysis with hydrochloric acid, extraction with dichloromethane and vacuum desolventization gave 52g of intermediate 1-2 a.
Step 1.10
41.2g of p-toluenesulfonyl chloride, 200ml of dichloromethane and 23.6g of triethylamine were charged into a three-necked flask. Cooling to 5-10 deg.C, adding 44g of intermediate 1-2a dissolved in 500ml of dichloromethane, and controlling the temperature below-30 deg.C. After the addition was complete, the mixture was allowed to slowly warm to room temperature and kept stirring at room temperature for 5 hours. The upper aqueous phase was separated, extracted twice with dichloromethane, the organic phases combined, washed three times with 500ml tap water and dried over anhydrous sodium sulfate. After vacuum desolventization, the mixture was passed through a silica gel column to obtain 60g of intermediates 1 to 3 a.
Step 1.11
28.3g of 2, 3-difluoro-4-ethoxyphenol (0.15mol), 41.4g of potassium carbonate (0.3mol), 200ml of DMF and 4.84g of tetrabutylammonium bromide (0.015mol) are added into a three-neck flask under the protection of nitrogen, stirred and heated to 120 ℃, 42g of solution of 1-3a (0.15mol) dissolved in 60ml of DMF is added dropwise, and after the dropwise addition is finished, the temperature is heated to reflux for 8 hours. Stopping the reaction, and naturally cooling to room temperature. Toluene and water were added, and the layers were stirred. Extracting water phase with toluene once, washing organic phase with water, drying, passing through silica gel column, and vacuum concentrating. Crystallization from ethanol gave 34g of the product TM-1 as a white powder.
The TM-1 series of compounds was prepared analogously:
example 4
A process for the preparation of compound TM-2 comprising the steps of:
(1) preparation of n-4
(2) Preparation of 2-1a
(3) Preparation of TM-2
Step 2.1
Under the protection of nitrogen, 288gYL-2, 768ml of dichloromethane and 185g of 2, 3-dihydropyran are added into a three-mouth bottle, the temperature is reduced to 0 ℃, 5g of p-toluenesulfonic acid is added, the temperature is gradually increased to the room temperature, the reaction is kept for 24 hours, and the reaction is stopped. The reaction mixture was slowly poured into an aqueous saturated sodium bicarbonate solution with stirring, after stirring for 30 minutes, the organic layer was separated, the aqueous layer was extracted with dichloromethane, the organic phases were combined, washed with water to neutrality, dried, and the solvent was removed under reduced pressure to give 400g of a viscous pale yellow oil n-1, which was used as it was.
Step 2.2
380g of intermediate n-1 and 2800ml of dichloromethane are added to a three-necked flask, and after stirring to dissolve completely, 17g of sodium bromide and 6g of Tempo are added. Cooling to-10 ℃, dropwise adding sodium bicarbonate solution of sodium hypochlorite (850g of sodium hypochlorite solution and 350g of saturated sodium bicarbonate solution), and controlling the temperature to-10-5 ℃ in the dropwise adding process. After the dropwise addition, the reaction mixture was kept warm for 5 minutes, and a sodium hydrogen sulfite solution was added to the reaction mixture and stirred for 30 minutes. Separating, extracting the water layer with dichloromethane, combining the organic layers, washing to neutrality, rotary evaporating to remove the solvent to obtain n-2 pale yellow liquid 300g, and using in the next step.
Step 2.3
Adding 300g of intermediate n-2 and 1350ml of toluene into a three-necked bottle under the protection of nitrogen, stirring for 10 minutes, adding 95g of ethylene glycol and 10g of p-toluenesulfonic acid, heating to reflux and divide water into a water separator, dripping without water drops, cooling to room temperature, adding 50ml of water, stirring for 30 minutes, extracting an aqueous phase from toluene, combining organic layers, carrying out hydrochloric acid washing, washing with water, drying, desolventizing to obtain 220g of compound n-3, and directly carrying out the next reaction.
Step 2.4
200g of intermediate n-3 and 2000ml of dichloromethane are added into a three-necked flask, after stirring and full dissolution, 14g of sodium bromide and 5g of catalyst Tempo are added, the temperature is reduced to-10 ℃, 740g of sodium bicarbonate solution of sodium hypochlorite (prepared by mixing 520g of sodium hypochlorite solution and 220g of saturated sodium bicarbonate solution) is dropwise added, and the temperature in the dropwise adding process is controlled to-10-5 ℃. After the dropwise addition, the reaction mixture was kept warm for 5 minutes, and a sodium hydrogen sulfite solution was added to the reaction mixture and stirred for 30 minutes. The liquid separation, aqueous layer with dichloromethane extraction, after the organic layer, combined, washed neutral, rotary evaporation to remove the solution, n-4 pale yellow liquid 195g, direct next use.
Step 2.5
Under the protection of nitrogen, 520g of phosphonium salt m-4a (see the preparation method for reference)
Example 1.4) and 2300ml of tetrahydrofuran, stirring for 10 minutes, cooling to-10 ℃, and then adding 118g of potassium tert-butoxide to the reaction solution in batches to turn the system into bright red. Adding 190g of a mixed solution of the intermediate n-4 prepared in the previous step and 250ml of tetrahydrofuran, gradually raising the temperature to room temperature, hydrolyzing, extracting a water phase with toluene, combining organic layers, washing with water, drying, desolventizing, carrying out silica gel column chromatography on a crude product obtained after the desolventizing with an n-heptane solvent to obtain 287g of the intermediate n-5a, and carrying out the next step of reaction.
Step 2.6
Under the protection of nitrogen, 285g of the obtained n-5 colorless liquid of the cis-trans mixture is added into a three-necked bottle, 1250ml of toluene, 25g of concentrated hydrochloric acid, 25g of deionized water and 50g of sodium benzene sulfinate are added, reflux reaction is carried out for 60 hours, the temperature is reduced to room temperature, liquid separation is carried out, water washing is carried out until the mixture is neutral, decompression and desolventization are carried out, and recrystallization is carried out, so that 103g of the product with the purity of 97.9 percent is obtained.
Step 2.7
Dissolving 100g of compound n-5 in 300ml of toluene, stirring and dissolving, controlling the temperature to be minus 10-20 ℃, dropwise adding 80ml of 85% formic acid, heating to 50 ℃ after dropwise adding is finished until the raw materials react, adding 100ml of water, removing a water layer, washing an organic layer with saturated sodium bicarbonate, washing with water, drying, and removing solvent under reduced pressure to obtain 75g of an intermediate 2-1 a.
Step 2.8
Under the protection of nitrogen, 75g of intermediate 2-1a and 100ml of THF solution are added into a three-mouth bottle, the temperature is reduced to-10 ℃, and 13.5g of sodium borohydride is added in batches. After the reaction was completed, the reaction was incubated, hydrolyzed with hydrochloric acid, extracted with dichloromethane, and desolventized under vacuum to obtain 75g of intermediate 2-2 a.
Step 2.9
Into a three-necked flask, 75g of the obtained 2-2a, 300ml of methylene chloride and 23.6g of triethylamine were added. The temperature is reduced to 5 to 10 ℃, 58g of p-toluenesulfonyl chloride is dropped and dissolved in 100ml of dichloromethane solution, and the temperature is controlled to be below minus 30 ℃. After the addition was complete, the mixture was allowed to slowly warm to room temperature and kept stirring at room temperature for 5 hours. The upper aqueous phase was separated, extracted twice with dichloromethane, the organic phases combined, washed three times with 500ml tap water and dried over anhydrous sodium sulfate. After vacuum desolventization, the mixture was passed through a silica gel column to obtain 120g of intermediate 2-3 a.
Step 2.10
Under the protection of nitrogen, 56.6g of 2, 3-difluoro-4-ethoxyphenol, 84g of anhydrous potassium carbonate, 400ml of DMF and 9.6g of tetrabutylammonium bromide are added into a three-necked bottle, the mixture is stirred and heated to 120 ℃, 84g of a solution of the intermediate 2-3a dissolved in 120ml of DMF is added dropwise, and the mixture is heated to reflux for 8 hours after the dropwise addition is finished. Stopping the reaction, and naturally cooling to room temperature. Toluene and water were added, and the layers were stirred. Extracting water phase with toluene once, washing organic phase with water, drying, passing through silica gel column, and vacuum concentrating. Crystallization from ethanol gave 100g of TM-2 as a white powder.
The TM-2 series compounds are prepared similarly
Example 5
A process for the preparation of compound TM-3 comprising the steps of:
(1) preparation of 3-3a
(2) Preparation of TM-3
Step 3.1
Under the protection of nitrogen, a solution of 130g of diisopropylamine and 250ml of THF is added into a three-neck flask, the temperature is reduced to-20 ℃, and 530ml of butyllithium (2.5 mol. L) is added dropwise-1) And keeping the temperature at-20 ℃ for 2 hours. The reaction solution was cooled to-80 ℃ and a solution of 250g of intermediate 2-1a (preparation scheme is shown in examples 2.1 to 2.7) and 200ml of tetrahydrofuran was added dropwise. Subsequently, the temperature was controlled between-45 ℃ and-40 ℃, and 142g of methyl iodide and 200ml of THF solution were added dropwise. After the reaction was completed, hydrolysis with hydrochloric acid, extraction with dichloromethane, and vacuum desolventization gave 125g of intermediate 3-1 a.
Step 3.2
Under the protection of nitrogen, 120g of solution prepared by the intermediate 3-1a and 100ml of THF is added into a three-mouth bottle, the temperature is reduced to-10 ℃, and sodium borohydride is added in batches. After the reaction is finished, the mixture is hydrolyzed by hydrochloric acid, extracted by dichloromethane and desolventized in vacuum to obtain 120g of the intermediate 3-2 a.
Step 3.3
52g of intermediate 3-2a, 200ml of dichloromethane and 23.6g of triethylamine were added to a three-necked flask under nitrogen protection. The temperature is reduced to 5 to 10 ℃, 41.2g of p-toluenesulfonyl chloride is dripped and dissolved in 100ml of dichloromethane solution, and the temperature is controlled to be below-30 ℃. After the addition was complete, the mixture was allowed to slowly warm to room temperature and kept stirring at room temperature for 5 hours. The upper aqueous phase was separated, extracted twice with dichloromethane, the organic phases combined, washed three times with 500ml tap water and dried over anhydrous sodium sulfate. After vacuum desolventization, the mixture was passed through a silica gel column to obtain 82g of intermediate 3-3 a.
Step 3.4
Under the protection of nitrogen, 28.3g of 2, 3-difluoro-4-ethoxyphenol, 41.4g of potassium carbonate, 200ml of DMF and 4.84g of tetrabutylammonium bromide are added into a three-necked bottle, the mixture is stirred and heated to 120 ℃, 62g of 3-3a solution dissolved in 60ml of DMF is added dropwise, the temperature is raised to reflux for 8 hours after the dropwise addition is finished, the reaction is stopped, and the temperature is naturally reduced to room temperature. Toluene and water were added, and the layers were stirred. Extracting water phase with toluene once, washing organic phase with water, drying, passing through silica gel column, and vacuum concentrating. Crystallization with ethanol gave 50g of the product TM-3 as a white powder.
The TM-3 series compounds are prepared similarly
Example 6
A process for the preparation of compound TM-4 comprising the steps of:
(1) preparation of 4-1a
(2) Preparation of TM-4
Step 4.1
Under the protection of nitrogen, a solution of 158gYL-4a and 350ml THF was added into a three-necked flask, the reaction solution was cooled to-80 deg.C, and 435ml butyl lithium solution (2.5 mol. L) was added dropwise-1). Then controlling the temperature between minus 85 ℃ and minus 75 ℃, and dropwise adding 120g of N, N-dimethylformamide. After the reaction, hydrochloric acid hydrolysis, dichloromethane extraction and vacuum desolventizing are carried out to obtain 162g of intermediate Y-1a, the GC purity is 96.4%, and the intermediate Y-1a is directly used in the next step.
Step 4.2
Under the protection of nitrogen, 400ml of THF and 282g of chloromethyl ether triphenylphosphine salt are added into a three-neck flask, the temperature is reduced to O ℃, and 93.3gt-BuOK is added in batches. After the addition, the reaction was kept for 1.5 hours. Cooling to-10 deg.C, adding dropwise solution prepared from 140gY-1a and 150mL THF, reacting at 5 deg.C for 1 hr, adding solution prepared from 10g NH4Cl and 200mL water, extracting with 500mL toluene, washing organic phase with water to neutrality, adding anhydrous Na2S04Drying, and removing solvent under reduced pressure to obtain liquid-solid mixture. 500ml of n-hexane are added, suction filtration is carried out and the filter cake is rinsed with 100ml of n-hexane. The filtrate and elution were combined, and the solvent was removed under reduced pressure to obtain 152.5g of a pale yellow liquid having a GC purity of 94.3% (cis + trans).
Step 4.3
A three-necked flask equipped with a thermometer and a stirrer and protected by N2 was charged with 145 g of Y-2a and 330ml of THF, the temperature was controlled to 30 ℃ or lower, 110ml of 15% hydrochloric acid was added dropwise thereto, and the mixture was kept warm for 4 hours after completion of the addition. Adding 400ml water, extracting with 300ml dichloromethane, washing with water to neutrality, adding anhydrous Na2S04Drying, decompressing and removing the solvent to obtain 130g of light yellow liquid with the GC purity of 88.2 percent.
Step 4.4
Under the protection of nitrogen, 100g of Y-4a and 200ml of THF solution are added into a three-mouth bottle, the temperature is reduced to-10 ℃, and 20g of sodium borohydride is added in batches. After the reaction is finished, the solution is hydrolyzed by hydrochloric acid, extracted by dichloromethane and exsolution in vacuum to obtain 100g of Y-4a, the GC purity is 87.5 percent
Step 4.5
50g of Y-4a are dissolved in 200ml of dichloromethane under the protection of nitrogen, the temperature is controlled at 10 ℃, 75g of phosphine tribromide is added dropwise, the temperature is slowly raised to the room temperature after the dropwise addition is finished, and the room temperature is kept and the stirring is carried out for 5 hours. The upper aqueous phase was separated, extracted twice with dichloromethane, the organic phases were combined, washed three times with tap water and dried over anhydrous sodium sulfate. After vacuum desolventizing, the mixture was passed through a silica gel column and distilled under reduced pressure to obtain 45g of 4-1a product, GC: 97.3 percent.
Step 4.6
Under the protection of nitrogen, 19g of tetramethylethylenediamine and 80ml of tetrahydrofuran are added into a reaction bottle, the temperature is reduced to-78 ℃ under the protection of nitrogen, and 45ml of butyl lithium (2.5 mol. L) is added dropwise-1) After the addition, the temperature was kept at-70 ℃ to-80 ℃ for 1 hour, 36.6g of the intermediate 1-1a prepared in example 1.7 was added dropwise, and after the addition, the temperature was gradually raised to-45 ℃ and 39g of the intermediate 4-1a was added dropwise. After the addition, the temperature was gradually raised to room temperature and the mixture was stirred for 5 hours. After acidic hydrolysis, ethyl acetate is added for extraction, water washing is carried out, and the solvent is removed to obtain light yellow solid. Passing through silica gel column, crystallizing to obtain 32g of white powder TM-4, GC content 99.93%
The TM-4 series of compounds was prepared similarly:
the present invention will be explained and explained below by giving descriptions of various parameters of the single crystals described in examples 3 to 6, each of which was obtained by testing by a conventional method, and a liquid crystal display material comprising upper and lower glass substrates supporting transparent electrodes and a liquid crystal medium sandwiched therebetween.
Cp (. degree. C.) represents the clearing point.
DELTA.n represents the optical anisotropy at 20 ℃ of 589 nm.
Δ represents the dielectric anisotropy at 25 ℃.
γ1(mPas) represents the rotational viscosity at 20 ℃.
K11、K33Representing the elastic constant.
The liquid-crystalline compound of the invention has a higher refractive index, comparable clearing point, higher △, lower rotational viscosity, higher K than comparative example M-133/K11It is more suitable for low-voltage and high-gradient VA type liquid crystal display.
Further, the same liquid crystal system (mother) was added with the same amount of 10% by weight of each of example TM1-4 of the present invention and comparative example M-1 to prepare liquid crystal compositions, and the parameters were measured.
The rotational viscosity of the liquid crystal composition provided by the invention at 20 ℃ is tested by using an INSTEC physical property tester of American INSTEC (China constant quotient), the model of ALCT-PP1 is that gamma 1 is less than or equal to 300 mPa.s.
The liquid crystal composition provided by the invention is prepared by adopting a traditional method, and is prepared by mixing two or more compounds at a proper temperature; or dissolving the components in an organic solvent such as acetone, chloroform, methanol, etc., and removing the solvent by distillation.
The liquid crystal composition provided by the invention also needs to be added with proper additives, such as an anti-ultraviolet agent, an antistatic agent, an antioxidant, an antifoaming agent and the like.
Vo (V) represents the threshold voltage at 20 ℃.
a (%) represents (V)1-V0)/V0*100％，V1(V) represents the saturation voltage at 20 ℃ and a smaller value of a indicates a higher steepness.
The parent formulation is shown in the following table:
table 1: composition of parent formula
TABLE 2 Performance parameters of example TM1-4 and comparative example M-1 in the matrix
As can be seen from the above table, the example TM has more excellent performance parameters in the liquid crystal composition than the comparative example M-1, has larger absolute value of negative dielectric anisotropy, lower rotational viscosity and higher gradient under the condition of similar clearing point and refractive index, and TM-1 and TM-4 have lower voltage than TM-2 and TM-3, so the inventive example is more suitable for VA type liquid crystal display with low voltage and high gradient.
The liquid crystal compound has a diene structure and great negative dielectric anisotropy, can improve the gradient of a liquid crystal composition, reduce the viscosity and shorten the response time, and the liquid crystal composition containing the liquid crystal compound has good low-temperature stability and intersolubility, stronger UV resistance and high VHR and resistivity, and is suitable for display modes such as VA, MVA, PVA, FFS, PSVA, IPS, TFT and the like.
The present invention may be embodied in other specific forms without departing from its spirit or essential characteristics. The above-described embodiments of the invention are therefore to be considered in all respects as illustrative and not restrictive, and all changes which come within the meaning and range of equivalency of the claims are to be embraced within their scope.
Claims (10)
1. A diene negative liquid crystal compound characterized in that the general formula has the following structure:
wherein R is1C2-C15 substituted or unsubstituted straight chain or branched chain alkene is selectedRadical, R2Selecting a substituted or unsubstituted straight chain or branched chain alkyl or alkoxy of C1-C15, wherein the substituent is selected from F, Cl, Br, I or CN;
ring A represents cyclohexyl, phenylene, phenyl, an oxygen-containing hexacyclic group or phenylene containing a substituent, wherein the substituent is selected from F, Cl, Br, I or CN;
Z1is selected from-CH2CH2-、-CF2O-or-CH2O-；
L1Selected from H, CN, CH3Or F.
2. The negative liquid crystal compound according to claim 1, wherein the negative liquid crystal compound is selected from at least one of the following structural formulae:
3. the negative liquid crystal compound according to claim 1 or 2, wherein R is1Selected from alkenyl, in particular ethenyl, propenyl or butenyl.
4. The negative liquid crystal compound according to claim 1 or 2, wherein R is2Is selected from methyl or alkoxy of C1-C7.
5. The negative liquid crystal compound according to claim 1 or 2, wherein the negative liquid crystal compound is selected from at least one of the following structural formulae:
6. a method for preparing a negative liquid crystal compound according to claim 2, wherein said compound i-2 is prepared by the steps of:
(1) compound (I)
Reacting to produce the compound
(2) Compound (I)
Reacting to produce the compound
(3) The compounds obtained in the step (1) and the step (2) react to generate
Further with
Reaction to form
7. A method for preparing a negative liquid crystal compound according to claim 2, wherein said compound i-7 is prepared by the steps of:
with a compound
Preparing a compound by taking the raw material through metal lithiation and nucleophilic reaction
Then undergoing a wittig reaction and waterPreparation of aldehydes by decomposition reactions
Followed by reduction and bromination to prepare intermediate compounds
And compounds
Reacting to obtain the compound
8. A negative liquid crystal composition comprising the liquid crystal compound according to claim 1 or 2.
9. A liquid crystal display comprising the liquid crystal compound according to claim 1 or 2.
10. Use of a liquid crystal display device as claimed in claim 9 in VA, MVA, PVA, FFS, PSVA, IPS and TFT display modes.
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| WO2022073400A1 (en) * | 2020-10-09 | 2022-04-14 | 烟台显华化工科技有限公司 | Liquid crystal compound having negative dielectric anisotropy, liquid crystal composition, and liquid crystal display device |
| CN115216307A (en) * | 2021-04-15 | 2022-10-21 | 河北迈尔斯通电子材料有限公司 | Low-threshold low-power-consumption low-viscosity liquid crystal composition |
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