CN117510315A - dl- (±) -beta-methyl amyl terphenyl liquid crystal compound, preparation method and application thereof - Google Patents
dl- (±) -beta-methyl amyl terphenyl liquid crystal compound, preparation method and application thereof Download PDFInfo
- Publication number
- CN117510315A CN117510315A CN202311475770.7A CN202311475770A CN117510315A CN 117510315 A CN117510315 A CN 117510315A CN 202311475770 A CN202311475770 A CN 202311475770A CN 117510315 A CN117510315 A CN 117510315A
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- China
- Prior art keywords
- liquid crystal
- crystal compound
- reaction
- beta
- reactant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 176
- 150000001875 compounds Chemical class 0.000 title claims abstract description 138
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- -1 isothiocyano Chemical group 0.000 claims abstract description 27
- 125000001309 chloro group Chemical group Cl* 0.000 claims abstract description 23
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 15
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 125000001424 substituent group Chemical group 0.000 claims abstract description 8
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 91
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 88
- 238000003756 stirring Methods 0.000 claims description 50
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 49
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 47
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 45
- 239000000543 intermediate Substances 0.000 claims description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 39
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 37
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 36
- 239000000463 material Substances 0.000 claims description 36
- 239000002904 solvent Substances 0.000 claims description 35
- 239000000376 reactant Substances 0.000 claims description 34
- 239000000203 mixture Substances 0.000 claims description 33
- 238000010438 heat treatment Methods 0.000 claims description 30
- 229910052757 nitrogen Inorganic materials 0.000 claims description 27
- 238000005406 washing Methods 0.000 claims description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 20
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 18
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 18
- 229910052740 iodine Inorganic materials 0.000 claims description 18
- 239000011630 iodine Substances 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 18
- 239000003208 petroleum Substances 0.000 claims description 18
- 238000010992 reflux Methods 0.000 claims description 18
- 239000000126 substance Substances 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 17
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical compound ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 claims description 15
- 238000000967 suction filtration Methods 0.000 claims description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 14
- 238000000746 purification Methods 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 13
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 238000011282 treatment Methods 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- 238000004440 column chromatography Methods 0.000 claims description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 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
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 9
- 229910052763 palladium Inorganic materials 0.000 claims description 9
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 230000005684 electric field Effects 0.000 claims description 7
- 238000000605 extraction Methods 0.000 claims description 7
- 238000001179 sorption measurement Methods 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 238000001953 recrystallisation Methods 0.000 claims description 6
- NHDIQVFFNDKAQU-UHFFFAOYSA-N tripropan-2-yl borate Chemical compound CC(C)OB(OC(C)C)OC(C)C NHDIQVFFNDKAQU-UHFFFAOYSA-N 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 5
- 238000004891 communication Methods 0.000 claims description 5
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 5
- QFWPJPIVLCBXFJ-UHFFFAOYSA-N glymidine Chemical compound N1=CC(OCCOC)=CN=C1NS(=O)(=O)C1=CC=CC=C1 QFWPJPIVLCBXFJ-UHFFFAOYSA-N 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 4
- 230000005540 biological transmission Effects 0.000 claims description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 4
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 3
- 239000004289 sodium hydrogen sulphite Substances 0.000 claims description 3
- 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 claims description 2
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 claims description 2
- 238000003747 Grignard reaction Methods 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 230000004913 activation Effects 0.000 claims description 2
- 239000003463 adsorbent Substances 0.000 claims description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 2
- IPWKHHSGDUIRAH-UHFFFAOYSA-N bis(pinacolato)diboron Chemical compound O1C(C)(C)C(C)(C)OB1B1OC(C)(C)C(C)(C)O1 IPWKHHSGDUIRAH-UHFFFAOYSA-N 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- 230000000977 initiatory effect Effects 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 235000011056 potassium acetate Nutrition 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 1
- 238000002844 melting Methods 0.000 abstract description 24
- 230000008018 melting Effects 0.000 abstract description 23
- 238000003786 synthesis reaction Methods 0.000 abstract description 22
- 230000015572 biosynthetic process Effects 0.000 abstract description 20
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 abstract description 17
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 5
- 230000021615 conjugation Effects 0.000 abstract description 3
- 238000013461 design Methods 0.000 abstract description 2
- 238000009826 distribution Methods 0.000 abstract description 2
- 239000012071 phase Substances 0.000 description 37
- 239000012044 organic layer Substances 0.000 description 23
- 239000000243 solution Substances 0.000 description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 18
- 235000019441 ethanol Nutrition 0.000 description 13
- 239000004988 Nematic liquid crystal Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 238000001914 filtration Methods 0.000 description 11
- 239000000706 filtrate Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 9
- 230000007704 transition Effects 0.000 description 9
- 238000002390 rotary evaporation Methods 0.000 description 8
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 8
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- 230000009286 beneficial effect Effects 0.000 description 7
- 229940125898 compound 5 Drugs 0.000 description 7
- 230000003287 optical effect Effects 0.000 description 7
- 238000006467 substitution reaction Methods 0.000 description 7
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 239000003480 eluent Substances 0.000 description 6
- 230000005496 eutectics Effects 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 238000003760 magnetic stirring Methods 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 238000001308 synthesis method Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 5
- 239000007818 Grignard reagent Substances 0.000 description 4
- 229960000583 acetic acid Drugs 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 150000004795 grignard reagents Chemical class 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 239000012265 solid product Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 150000002540 isothiocyanates Chemical class 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 description 3
- XDJWZONZDVNKDU-UHFFFAOYSA-N 1314-24-5 Chemical compound O=POP=O XDJWZONZDVNKDU-UHFFFAOYSA-N 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 238000003810 ethyl acetate extraction Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 125000001810 isothiocyanato group Chemical group *N=C=S 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 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 description 2
- 230000010363 phase shift Effects 0.000 description 2
- VSAISIQCTGDGPU-UHFFFAOYSA-N phosphorus trioxide Inorganic materials O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- XPEIJWZLPWNNOK-UHFFFAOYSA-N (4-phenylphenyl)boronic acid Chemical compound C1=CC(B(O)O)=CC=C1C1=CC=CC=C1 XPEIJWZLPWNNOK-UHFFFAOYSA-N 0.000 description 1
- PBMVYDNBOIVHBO-DOFZRALJSA-N (5z,8z,11z,14z)-n-(4-nitrophenyl)icosa-5,8,11,14-tetraenamide Chemical compound CCCCC\C=C/C\C=C/C\C=C/C\C=C/CCCC(=O)NC1=CC=C([N+]([O-])=O)C=C1 PBMVYDNBOIVHBO-DOFZRALJSA-N 0.000 description 1
- RLJXJUHMVYLIBW-UHFFFAOYSA-N 1,2,3-trifluoro-5-iodobenzene Chemical compound FC1=CC(I)=CC(F)=C1F RLJXJUHMVYLIBW-UHFFFAOYSA-N 0.000 description 1
- IQXYRXOYBYUMLV-UHFFFAOYSA-N 1-fluoro-2-(2-phenylphenyl)benzene Chemical group FC1=CC=CC=C1C1=CC=CC=C1C1=CC=CC=C1 IQXYRXOYBYUMLV-UHFFFAOYSA-N 0.000 description 1
- DQTJNHXTFILGGG-UHFFFAOYSA-N 2,5-difluoro-4-iodoaniline Chemical compound NC1=CC(F)=C(I)C=C1F DQTJNHXTFILGGG-UHFFFAOYSA-N 0.000 description 1
- HCUZNQLIMDDCHF-UHFFFAOYSA-N 2,6-difluoro-4-iodoaniline Chemical compound NC1=C(F)C=C(I)C=C1F HCUZNQLIMDDCHF-UHFFFAOYSA-N 0.000 description 1
- AJUHJMMNWVKCER-UHFFFAOYSA-N 2-(2-phenylphenyl)aniline Chemical compound NC1=CC=CC=C1C1=CC=CC=C1C1=CC=CC=C1 AJUHJMMNWVKCER-UHFFFAOYSA-N 0.000 description 1
- PFNHSEQQEPMLNI-UHFFFAOYSA-N 2-methyl-1-pentanol Substances CCCC(C)CO PFNHSEQQEPMLNI-UHFFFAOYSA-N 0.000 description 1
- CHXXMQJPYOKYSB-UHFFFAOYSA-N 3,5-difluoro-4-iodoaniline Chemical compound NC1=CC(F)=C(I)C(F)=C1 CHXXMQJPYOKYSB-UHFFFAOYSA-N 0.000 description 1
- UISBOJCPTKUBIC-UHFFFAOYSA-N 4-iodo-3-methylaniline Chemical compound CC1=CC(N)=CC=C1I UISBOJCPTKUBIC-UHFFFAOYSA-N 0.000 description 1
- 238000006677 Appel reaction Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004990 Smectic liquid crystal Substances 0.000 description 1
- 239000005626 Tribenuron Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000003098 cholesteric effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000005672 electromagnetic field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 230000005251 gamma ray Effects 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 125000002346 iodo group Chemical group I* 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- UQPUONNXJVWHRM-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 UQPUONNXJVWHRM-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- ZWZVWGITAAIFPS-UHFFFAOYSA-N thiophosgene Chemical compound ClC(Cl)=S ZWZVWGITAAIFPS-UHFFFAOYSA-N 0.000 description 1
- BQZXUHDXIARLEO-UHFFFAOYSA-N tribenuron Chemical compound COC1=NC(C)=NC(N(C)C(=O)NS(=O)(=O)C=2C(=CC=CC=2)C(O)=O)=N1 BQZXUHDXIARLEO-UHFFFAOYSA-N 0.000 description 1
- GQHWSLKNULCZGI-UHFFFAOYSA-N trifluoromethoxybenzene Chemical compound FC(F)(F)OC1=CC=CC=C1 GQHWSLKNULCZGI-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01P—WAVEGUIDES; RESONATORS, LINES, OR OTHER DEVICES OF THE WAVEGUIDE TYPE
- H01P1/00—Auxiliary devices
- H01P1/18—Phase-shifters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
- C07C25/18—Polycyclic aromatic halogenated hydrocarbons
-
- 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
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
- C07C43/225—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring 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
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Abstract
The invention discloses a dl- (±) -beta-methyl amyl terphenyl liquid crystal compound, a preparation method and application thereof, wherein the liquid crystal compound has a structure shown as a structural formula (I):wherein X is 1 ‑X 6 Each independently selected from-H, -F, -Cl or-CH 3 Y is independently selected from-F, -NCS or-OCF 3 Dl- (±) -beta-methylpentyl is an achiral alkyl group. The invention introduces achiral dl- (. + -.) -beta-methylpentyl into the design synthesis of terphenyl liquid crystal compound, and uses isothiocyano (-NCS), F atom and trifluoromethoxy (-OCF) 3 ) Is polar end group, F atom, cl atom or-CH is introduced at different benzene ring side positions 3 And the substituent groups are used for improving the distribution density of benzene ring electron cloud, increasing the molecular polarity and pi-electron conjugation degree and reducing the intermolecular acting force and order degree, so that the novel terphenyl liquid crystal compound with larger double refractive index, larger dielectric constant, low melting point and wider nematic phase temperature range is obtained.
Description
Technical Field
The invention belongs to the technical field of liquid crystal materials, and particularly relates to a dl- (±) -beta-methylpentyltribiphenyl liquid crystal compound, a preparation method and application thereof.
Background
The liquid crystal material is used as a transmission medium of communication devices such as a microwave phase shifter and the like, and the performance of the liquid crystal material directly influences the performance and the use of the microwave phase shifter. The molecular structure of the liquid crystal material for microwaves must be as follows:
(1) large dielectric anisotropy, high birefringence, wide nematic phase temperature range, low melting point and good low-temperature intersolubility;
(2) the molecular structure is stable, the polarizability is small, the microwave absorption is small or no absorption is realized, and the dielectric loss is low;
(3) low intermolecular force, low viscosity, and good gamma 1 /K ii Values (viscoelastic coefficients);
(4) the dielectric properties are stable and the dependence on temperature is small, in particular to be suitable for low temperature operation.
However, according to the current research report, the existing liquid crystal material for microwaves has the following general problems: (1) or insufficient phasor due to insufficient birefringence and permittivity; (2) or the dielectric loss is larger due to the wave absorption and polarization effects of the molecular structural groups; (3) or the low-temperature performance of the mixed liquid crystal material and the outdoor working temperature are limited due to the lack of a nematic liquid crystal compound with low melting point and high delta n value; (4) or the response time of the microwave device is longer due to the larger viscosity of the liquid crystal compound, and the information transmission speed and the application development of the device are affected. Especially, the high-birefringence nematic liquid crystal compound has the problems of high viscosity, low response speed and high melting point, and is difficult to satisfy the outdoor-use-temperature-below-50 ℃ nematic liquid crystal state of a liquid crystal microwave device; research and development of novel low-melting-point low-viscosity liquid crystal compounds and liquid crystal materials meeting the performance requirements of microwave devices, with high dielectric constant and low consumption, high response speed and suitability for low-temperature operation are urgently needed, and become key and application development bottlenecks.
The terphenyl liquid crystal molecules are liquid crystal compounds with higher double refractive index and certain polarity, have small absorption (or polarizability) to microwaves due to stable molecular structure and larger pi-electron conjugation degree, have double refractive index and dielectric constant which meet the use of microwave devices, and have low high-frequency dielectric loss, and are usually used as main components of liquid crystal compositions for microwaves. However, the reported terphenyl liquid crystal compound has a higher melting point, which is not beneficial to lowering the eutectic point of the liquid crystal composition and is also not beneficial to the low-temperature environment work of a microwave device. For example, 4' -butyl-2, 6-difluoro-terphenyl isothiocyanate (abbreviated as 4 PPUS) has a mesogenic phase of Cr 101 ℃ N200 ℃ Iso. In order to reduce the eutectic point of the liquid crystal composition, the Chinese patent invention is an achiral side methyl alkyl terphenyl liquid crystal compound, a preparation method, the liquid crystal composition and application thereof (CN 201911057697.5A, 2019.10.31.) adopts dl- (+ -) -2-methyl-butyl as a terphenyl isothiocyanate liquid crystal compound (abbreviated as 4 (1) PPUS) with a terminal alkyl, the melting point is 89 ℃, the clearing point is 161 ℃, the mesogenic phase state is Cr 89 ℃ N161 ℃ Iso, and the nematic phase state temperature range is 72 ℃; it has a melting point 12.5℃lower than that of the relevant n-butyl compound (abbreviated to 4 PPUS). This also shows that the terminal flexible branched chain-beta-methyl can lower the melting point of the liquid crystal compound, which is beneficial to developing the low-melting-point terphenyl liquid crystal compound and the low-freezing-point liquid crystal material for microwaves.
As the branched-beta-methyl alkyl chain is used as a flexible end group, the rigidity of the molecule can be reduced, the steric hindrance between the molecules can be increased, and the intermolecular acting force can be reduced, so that the melting point of the compound can be reduced. In order to further reduce the melting point of the terphenyl liquid crystal compound, the group of researchers tries to further increase the carbon number of an alkyl chain, dl- (±) -beta-methyl-pentyl is introduced into terphenyl molecules, and a novel low-melting point liquid crystal compound 4' - [ dl- (±) -beta-methyl-pentyl ] -2, 6-difluoro terphenyl isothiocyanate (abbreviated as 5 (1) PPUS) is designed and synthesized, and the mesogenic phase state of the compound is tested to be Cr 66 ℃ N159 ℃ Iso. Compared with N-amyl terphenyl isothiocyanate compound (abbreviated as 5PPUS, liquid crystal phase state is Cr 88 ℃ and N188 ℃ Iso), the melting point is reduced by 22 ℃.
Disclosure of Invention
The invention aims to provide a dl- (±) -beta-methyl amyl terphenyl liquid crystal compound, a preparation method and application thereof. The invention introduces achiral dl- (. + -.) -beta-methylpentyl into the design synthesis of terphenyl liquid crystal compound, and uses isothiocyano (-NCS), F atom and trifluoromethoxy (-OCF) 3 ) Is polar end group, F atom, cl atom or-CH is introduced at different benzene ring side positions 3 And the substituent groups are used for improving the distribution density of benzene ring electron cloud, increasing the molecular polarity and pi-electron conjugation degree and reducing the intermolecular acting force and order degree, so that the novel terphenyl liquid crystal compound with larger double refractive index, larger dielectric constant, low melting point and wider nematic phase temperature range is obtained.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the invention provides a dl- (±) -beta-methyl amyl terphenyl liquid crystal compound, which has the structure shown in (i):
wherein the side substituent X 1 -X 6 Each independently selected from H atom, F atom,Or Cl atom or-CH 3 A group; y is independently selected from F atom, -NCS or-OCF 3 。
In the technical scheme of the invention, the isothiocyanato dl- (±) -beta-methylpentyltrimethylene liquid crystal compound (I) has the following advantages: the liquid crystal compound ensures that liquid crystal molecules have enough birefringence and molecular polarity due to a pi-electron conjugated system containing terphenyl; and dl- (±) -beta-methylpentyl is taken as a terminal group, the beta-methyl can increase the flexibility of a molecular alkyl chain, and simultaneously fluorine atoms, chlorine atoms or methyl are introduced at the side position of a benzene ring, so that the length-diameter ratio of molecules is reduced, the melting point of the compound is effectively reduced, the temperature range of a nematic phase is widened, and the mesogen and dielectric properties of the high-birefringence liquid crystal molecules are improved.
In the technical scheme of the invention, optionally, when the polar end group (Y) in the dl- (. + -.) -beta-methylpentyltrimethylene liquid crystal compound (I) is a-NCS group, the compound is shown as the following structural formula (Ia-i):
wherein the substituent X 1 -X 6 Each independently selected from-H, -F, -Cl or-CH 3 。
Preferably, a part of the compound structural formula (Ia-i) of the isothiocyanato- (±) - β -methylpentyltrimethylene liquid crystal compound (Ia-i) is as follows, but is not limited thereto:
the dielectric constant (delta epsilon) of the liquid crystal compound (Ia-i) in the microwave 4-40GHz band r ) Not less than 0.96, maximum dielectric loss (tan. Delta. Epsilon.) r max) is less than 6.7X10 -3 The method comprises the steps of carrying out a first treatment on the surface of the The microwave phase modulation quantity (tau) is more than or equal to 0.253, high frequencyThe quality factor (eta) of the liquid crystal compound as a microwave medium is more than 42. It has the following advantages: the pi-electron conjugated system of the terphenyl is added in the molecular structure due to the fact that the terphenyl contains the-NCS group, so that the liquid crystal molecules are ensured to have enough birefringence and dipole moment, and dielectric loss is reduced.
In the technical scheme of the invention, optionally, the polar end group (Y) in the liquid crystal compound (I) is-OCF 3 (trifluoromethoxy) having the structural formula (Ib-i) as follows:
wherein X is 1 -X 4 Each independently selected from-H, -F, -Cl or-CH 3 ；X 5 、X 6 Each independently selected from-H, -F or-Cl.
Preferably, a part of the compound structural formula (Ib-i) of the liquid crystal compound (Ib-i) is as follows, but is not limited thereto:
the liquid crystal compound (Ib-i) has the following advantages: the liquid crystal compound contains-OCF 3 The group increases the pi-electron conjugated system of the terphenyl, has small polarizability, high thermal stability, low viscosity and melting point of the molecule, and has larger double refractive index and dielectric constant; is beneficial to improving the mesogenic and dielectric properties of the high-birefringence liquid crystal molecules.
In the technical scheme of the invention, when the polar end group (Y) of the liquid crystal compound (I) is fluorine atom, the structural formula (Ic-I) is as follows:
wherein X is 1 -X 4 Each independently selected from-H, -F or-Cl, X 5 、X 6 Each independently selected from-H, -F, -Cl or-CH 3 。
Preferably, a part of the compound structural formula (Ic-i) of the liquid crystal compound (Ic-i) is as follows, but is not limited thereto:
the liquid crystal compound (Ic-i) has the following advantages: the molecular structure is stable, the molecules have certain polarity, the melting point and the viscosity are lower, the eutectic point, the rotational viscosity and the microwave dielectric loss of the liquid crystal composition are reduced, and the low-temperature dielectric performance of the liquid crystal microwave device is improved.
The invention also provides a preparation method of the dl- (±) -beta-methyl amyl terphenyl liquid crystal compound, which comprises the following steps: taking dl- (±) -2-methyl-amyl alcohol-1 as a raw material, carrying out an Appel substitution reaction, and then respectively carrying out a grignard reagent coupling reaction with bromobenzene with different substituents to obtain an achiral dl- (±) -beta-methylpentyl substituted (bi) benzene intermediate (i); then carrying out periodate and boric acid preparation, and carrying out Suzuki coupling reaction to obtain intermediates (ii), (iii) and (iv) and target compounds (Ib-i) and (Ic-i) respectively; finally, the low-melting-point isothiocyanation dl- (. + -.) -beta-methyl-amyl terphenyl liquid crystal compound (Ia-i) is synthesized by using thiophosgene to carry out an isothiocyanation reaction method.
In the technical scheme of the invention, the preparation of the isothiocyanato dl- (±) -beta-methylpentyltrimethylene liquid crystal compound shown in the structural formula (Ia-i) is preferably exemplified, and the synthesis steps of the compound (Ia-i) are as follows:
step S10: with an appropriate amount of CH 2 Cl 2 Dissolving triphenylphosphine, adding iodine simple substance below 10deg.C, and stirring until iodine simple substance is completely dissolved. Mixing dl- (±) -beta-methyl-1-pentanol with triethylamine, then dripping, reacting for two hours after dripping, precipitating and separating generated phosphorus trioxide by using a proper amount of petroleum ether (60-90), and extracting a reaction solution; and then washing, drying and decompressing distillation are carried out to distill the product dl- (±) -1-iodo-beta-methyl-pentane.
Step S20: adding magnesium scraps, dried anhydrous THF and a plurality of iodine simple substances into a three-neck flask; after the activation and the initiation of the Grignard reaction, the first reactant (1) is dissolved in a solvent and added into a constant pressure dropping funnel, the mixture is dropped at a constant speed, the temperature is raised for reflux reaction, and finally the reaction liquid is gray liquid and is rapidly put into the next step. Anhydrous copper chloride, dl- (±) -1-iodo-beta-methyl-pentane and dried anhydrous THF are added into a three-neck flask, a small amount of diluted hydrochloric acid is added after the reaction is finished, and the mixture is continuously stirred to fully hydrolyze the mixture, and the mixture is subjected to suction filtration, washing, extraction and purification treatment to obtain a first intermediate (i).
Step S30: mixing the obtained first intermediate (i), iodic acid, iodine simple substance, acetic acid, water and concentrated sulfuric acid for reaction, heating to 80-100 ℃, carrying out reflux reaction, cooling to below 60 ℃ after the reaction is finished, adding sodium bisulphite solution, carrying out suction filtration, washing, extracting and purifying treatment to obtain a second intermediate (ii).
Step S40: under the protection of nitrogen, adding the second intermediate (ii) into dried THF at the temperature of-80 to 75 ℃, dropwise adding n-butyllithium, stirring and reacting for 0.5 hour, adding triisopropyl borate, fully mixing, naturally heating to 20 to 25 ℃ and reacting for 2 hours, finally adding hydrochloric acid, and separating, washing and purifying to obtain a white solid third intermediate (iii).
Step S50: mixing the third intermediate (iii), the second reactant (2), a palladium (0-valent) catalyst, potassium carbonate, ethanol, toluene and anaerobic water under the protection of nitrogen, and carrying out Suzuki coupling reaction at the temperature of 75 ℃ under the stirring condition for 8-10 hours; after completion of the reaction, the fourth intermediate (iv) is then obtained by washing, separation, drying and purification.
Step S60: uniformly mixing the fourth intermediate (iv), calcium carbonate, water and methylene dichloride, cooling to 0-5 ℃, adding the mixture of methylene dichloride and carbon dichloride after reaction, heating to 20-25 ℃, fully stirring and reacting for 8-10 hours, heating to 45-50 ℃, adding ethanol to remove unreacted carbon dichloride, and carrying out suction filtration, washing and purification to obtain the dl- (+ -) -beta-methylpentyl terphenyl target molecular structure (Ia-i) compound.
The preparation method and steps of the target compounds (Ib-i) and (Ic-i) are basically the same as those of the synthesis steps S10-S50, except that in the step S50, the target compounds are obtained by separating, purifying and refining after the reaction of the third reactant (3) or the fourth reactant (4) respectively.
In the synthesis step, the first reactant in step S20 is a compound represented by the following structural formula (1); in step S50, the second reactant is a structural compound shown in the following structural formula (2), the third reactant is a structural compound shown in the following structural formula (3), and the fourth reactant is a structural compound shown in the following structural formula (4):
Wherein X of the reactants (1), (2) 1 -X 6 Each independently selected from H atom, F atom, cl atom or-CH 3 A group; and X of reactants (3) and (4) 1 -X 4 Each independently selected from H atoms, F atoms, or Cl atoms.
In the technical scheme of the invention, the first intermediate in the synthesis step S20 is a compound with a structure shown in the following structural formula (i), the second intermediate in the synthesis step S30 is a compound with a structure shown in the following structural formula (ii), the third intermediate in the synthesis step S40 is a compound with a structure shown in the following structural formula (iii), and the fourth intermediate in the synthesis step S50 is a compound with a structure shown in the following structural formula (iv). Their molecular structural formula is shown below:
wherein X is 1 -X 6 Independently selected from H atom, F atom, cl atom or-CH 3 。
In the technical scheme of the invention, the synthetic method for preparing the liquid crystal compound (I) has the following advantages:
(1) In the synthesis step, the molecular conformation of the terminal alkyl dl- (±) -beta-methylpentylbiphenyl compound is not changed, and the terminal alkyl dl- (±) -beta-methylpentylbiphenyl compound always maintains an achiral conformational state, thereby being beneficial to forming a nematic liquid crystal state, avoiding forming a cholesteric phase and being beneficial to the work of a microwave device.
(2) The synthesis operation is simple, the reaction yield is high, and the method is favorable for the research of the amplified production process.
In the technical scheme of the invention, after recrystallization and column chromatography purification, the liquid phase purity of the liquid crystal compound (I) reaches more than 99.5%, and then the electric field adsorption method is utilized to refine each component compound to remove ions through an ion adsorbent so as to improve the resistivity and the charge retention rate of the liquid crystal compound and enable the resistivity to reach 1.0x10 12 The conductive dielectric loss caused by accidental factors in the manufacturing process is reduced by more than omega cm; thereby obtaining the nematic liquid crystal compound with high dielectric constant and low consumption which can meet the use of microwave K wave band.
The liquid crystal compound (I) prepared by the invention introduces polar end isothiocyano or fluorine atom or trifluoromethoxy into the molecular structure to obtain nematic liquid crystal compound with large dielectric constant (delta epsilon), high delta n value, stable structure, small absorption coefficient to microwave and low dielectric loss. The liquid crystal compound (I) is mixed with other liquid crystal compounds with a plurality of wide Wen Xianglie phases to prepare a Wen Xianglie-phase liquid crystal composition material with a low co-solidifying point, high dielectric constant and low consumption, which can meet the use of microwave K wave bands, so that the microwave dielectric loss is reduced, and the microwave phase modulation quantity and the device quality factor are improved.
The liquid crystal compound (I) provided by the invention increases the microwave phase modulation quantity, reduces the microwave dielectric loss quantity (namely microwave insertion loss), and improves the quality factor of a microwave device. It can be applied to liquid crystal material medium of microwave high-frequency devices including but not limited to microwave phase shifters, wave guides, etc.
The present invention also provides a microwave communication device using the liquid crystal compound (I) as a main component of a microwave information transmission medium.
The invention has the beneficial effects that:
(1) Compared with the straight-chain terphenyl compound with similar structure, the liquid crystal compound prepared by the invention has the advantages that the flexibility of molecules is increased, the length-diameter ratio is reduced, the steric hindrance is increased, the smectic phase range is compressed, the nematic phase temperature range is widened, the melting point of the terphenyl liquid crystal compound is reduced, the melting point of the terphenyl liquid crystal compound is lower than that of the straight-chain amyl terphenyl compound with equivalent structure by more than 20 ℃, and the low-temperature performance and the viscosity of the liquid crystal material are improved.
(2) The liquid crystal compound can be added into the existing liquid crystal composition for microwaves, so that the low-temperature eutectic point of the liquid crystal composition or the low-temperature solidifying point of the liquid crystal material can be reduced, and the outdoor low-temperature use problem of the liquid crystal material for microwaves can be solved.
(3) The novel liquid crystal compound synthesized by the invention has low dielectric loss at high frequency (4-40 GHz), is only below 0.0065, and can improve the quality factor of a liquid crystal microwave device.
Detailed Description
The invention will be further described with reference to specific examples for better illustrating the objects, technical solutions and advantages of the invention. This invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the concept of the invention to those skilled in the art, and the present invention will only be defined by the appended claims.
The invention relates to the relevant professional knowledge in the field of liquid crystal materials, and for the convenience of understanding, the relevant performance parameter terms of the liquid crystal materials are introduced as follows:
delta epsilon represents the dielectric constant, or dielectric anisotropy; they have a parallel dielectric constant @ epsilon ∥ "and vertical dielectric constant" ε ⊥ The dielectric constant is usually given by delta epsilon=epsilon ∥ -ε ⊥ ；
Δn represents optical anisotropy, i.e., birefringence (589 nm,25 ℃): the liquid crystal compound and the method for expressing optical anisotropy of the mixed liquid crystal material are characterized in that the liquid crystal has birefringence with refractive index anisotropy, which is the same as that of the optical uniaxial crystal. Uniaxial crystals having two different refractive indices n ∥ And n ⊥ 。
n ⊥ The electric vector vibration direction of the light source is perpendicular to the optical axis of the liquid crystal molecules corresponding to the ordinary light; n is n ∥ The electric vector vibration direction thereof is parallel to the optical axis of the liquid crystal molecules corresponding to the extraordinary rays. Therefore, the birefringence is denoted by "Δn", Δn=n ∥ -n ⊥ The requirement of the microwave high-frequency device is that the delta n value is more than or equal to 0.35, and the higher the delta n value is, the more favorable the improvement of the microwave phase shift quantity.
Cr. the melting point or solid-to-liquid state transition temperature of the liquid crystal compound; n. represents the liquid crystal nematic phase transition temperature; iso. is the temperature at which the phase state of a liquid crystal compound or composition changes to a liquid state (isotropic state), i.e., clear point temperature (°c);
ρ represents the resistivity (unit: Ω·cm) of the liquid crystal material; gamma ray 1 The rotational viscosity of the liquid crystal (unit: mPa.s,25 ℃ C.).
Dielectric anisotropy in the microwave range (Δε) r ) The definition is as follows: delta epsilon r ≡ε r∥ -ε r⊥ . Wherein the component epsilon of the long axis of the liquid crystal is parallel r (I) perpendicular to the liquid crystal long axis component ε r,⊥ ；
Tunability (τ) is defined as: τ≡Δε r /ε r|| ；
The term maximum dielectric loss (tan delta epsilon) r ) ": liquid crystal materials are used as dielectric materials for microwaves, and the dielectric loss of the dielectric materials is generally defined by the loss tangent tan delta epsilon r Expressed, and defined as:
in general, under a direct current field, only the conduction loss generated by leakage current in the dielectric medium; however, in the microwave electromagnetic field, there are various types of loss due to polarization, i.e., relaxation polarization loss, in addition to the conduction loss. At this time, complex dielectric constant ε r ≡ε r ′-iε r "the ratio of the imaginary part to the real part is the dielectric loss value, also known as the dielectric loss factor; delta is a phase angle of the electric field E behind the electric displacement D of the liquid crystal medium due to polarization relaxation; namely: tan delta epsilon r ≡ε r "/ε r ′。
The dielectric loss of microwaves is divided into the tangent value (tan delta epsilon) r⊥ ) And a parallel dielectric loss tangent (tan delta epsilon) r,∥ ). In general, the parallel dielectric loss value is relatively small (tan. Delta. Epsilon.) r,∥ Less than or equal to about 0.006); the maximum dielectric loss of the liquid crystal material in the microwave band corresponds to the tangent (tan delta epsilon) r⊥ ) The main performance index parameters of the liquid crystal material in a microwave field are reflected, and the maximum dielectric loss is generally required to be smaller than 0.01, namely:
tanδε rmax ＝max.{tanδε r∥ ,tanδε r⊥ }＝tanδε r⊥ ≤0.01
the term "high dielectric low-loss" liquid crystal material refers to a liquid crystal material with high dielectric anisotropy, high optical anisotropy and low dielectric loss; after the microwave is irradiated by the liquid crystal material, the dielectric loss is very small, and tan delta epsilon r⊥ (or tan delta epsilon) r max) is less than about 0.008, tan delta epsilon r|| The value is lower than 0.004.
The term "phase modulation factor of a microwave liquid crystal phase shifter", denoted "τ", refers to a parameter reflecting the phase modulation capability of a liquid crystal material for microwave frequencies; the general requirements are: τ is more than or equal to 0.25, or τ is more than or equal to 0.15 and less than or equal to 0.5;
The term "quality factor" (eta, or FOM) of liquid crystal refers to the comprehensive evaluation result of dielectric properties of liquid crystal as a microwave medium material, and reflects the performance quality of the liquid crystal material, wherein eta is generally more than or equal to 25.
The material quality (η) is defined as:
for ease of expression, in the following examples, the structures of the liquid crystal compounds are represented by the codes listed in Table 1:
table 1: group structure code of liquid crystal compound
The earliest liquid crystal materials used were Merck company products K15, E7, germany, with Δn values below 0.2, small Δεr values at high frequencies, large dielectric losses, and excessively thick LC cells (d=254 μm), with response times exceeding 350ms; reuterM.2013 et al reported the effect of high frequency on different end groups such as-F, -CN, -NCS. In recent years, german Merck reports that the mixed liquid crystal material with high delta n value of isothiocyanato-polycyclic aromatic ethynyl has delta n value of about 0.25-0.30, and improves the dielectric property of microwave devices, but the dielectric loss is still larger. In 2013 and 2015, herman J et al report that isothiocyanato-lateral ethyl tetraphenyldiacetylene liquid crystal compounds (delta n is more than or equal to 0.6) have obviously increased microwave phase shift, but have larger dielectric loss and high melting point of materials, and can not meet the use requirement of extreme low-temperature environment. However, research on the influence of the low-temperature photoelectric property of the liquid crystal for microwaves has not been reported yet. Therefore, according to the findings in the prior large amount of research processes, the development of a liquid crystal material for microwaves with high dielectric constant, low consumption and low melting point is still needed in practical application.
The invention provides a dl- (±) -beta-methyl amyl terphenyl liquid crystal compound which has a structure shown as a structural formula (I):
wherein X is 1 -X 6 Each independently selected from-H, -F, -Cl or-CH 3 Y is independently selected from-F, -NCS or-OCF 3 Dl- (±) -beta-methylpentyl is an achiral alkyl group.
The invention also provides a preparation method of the dl- (±) -beta-methyl amyl terphenyl liquid crystal compound (I), and the synthetic route is as follows:
in the following synthesis steps, the separation, washing and purification treatment are carried out according to a conventional post-treatment method in the field of organic synthesis, for example, the separation may be carried out by extraction and filtration, the washing may be carried out by water washing or a corresponding acid-base solution until the product is neutral, the purification may be carried out by column chromatography, recrystallization and the like. The following separation, washing and purification treatments are the same as those described herein and will not be described again.
In the technical scheme of the invention, the preparation method specifically comprises the following steps:
step S10: adding a small amount of CH 2 Cl 2 As solvent to dissolve triphenyl phosphate, adding iodine simple substance at the temperature below 10 deg.c, stirring for 1 hr until the iodine simple substance is completely dissolved. And mixing dl- (. + -.) -2-methyl-1-pentanol with triethylamine, dripping, reacting for 2h at low temperature, and heating to 25deg.C for 6h. After the reaction is finished, the phosphorus trioxide is extracted by petroleum ether. Distilling the filtrate under reduced pressure to obtain dl- (±) -1-iodo-2-methyl-pentane; testing its optical rotation [ alpha ] ] D ＝0°(20℃)。
Step S20: magnesium turnings, dried THF and several elemental iodides were added to a three-necked flask. And (3) dissolving the first reactant (1) in a solvent, adding the solvent into a constant-pressure dropping funnel, protecting the solvent by nitrogen, dropping the solvent at a constant speed, heating and refluxing the solution after the reaction is initiated, and rapidly adding the solution into the next step when the final reaction solution is gray liquid. Anhydrous copper chloride, dl- (±) -1-iodo-beta-methyl-pentane and THF are added into a three-necked flask, a small amount of dilute hydrochloric acid is added after the reaction is finished, and the mixture is continuously stirred to fully hydrolyze the mixture, and the mixture is subjected to suction filtration, washing, extraction and purification treatment to obtain a first intermediate (i).
The invention provides a concrete implementation mode, which comprises the following steps: under the protection of nitrogen, adding magnesium powder, tetrahydrofuran and a plurality of iodine simple substances into a reaction bottle, uniformly mixing, then dropwise adding a tetrahydrofuran solution of a first reactant into the reaction bottle, and fully reacting under the heating condition to obtain the Grignard reagent. Then adding copper chloride, dl- (±) -1-iodo-beta-methyl-pentane and tetrahydrofuran into another reaction bottle under the protection of nitrogen, fully mixing to form a mixed solution, dripping the prepared grignard reagent into the mixed solution, heating and refluxing for reaction for 5-7 hours, adding hydrochloric acid, stirring, suction filtering, separating liquid, extracting a water layer with toluene, washing with water to be neutral, drying an organic layer with anhydrous sodium sulfate, and distilling under reduced pressure to remove the solvent to obtain a first intermediate (i). Wherein, the reaction bottle can be a three-neck flask or an organic synthesis reaction kettle and other containers, and is determined according to the consumption of reaction raw materials or the yield requirement of reaction products during specific operation. The following reaction flask is similar to this case, and will not be described again.
Step S30: mixing the obtained first intermediate (i), iodic acid, iodine simple substance, acetic acid, water and concentrated sulfuric acid for reaction, heating to 80-100 ℃, carrying out reflux reaction, cooling to below 60 ℃, adding sodium bisulphite solution, carrying out suction filtration, washing, extracting and purifying treatment to obtain a second intermediate (ii).
The invention provides a concrete implementation mode, which comprises the following steps: sequentially adding the first intermediate (i), iodic acid, iodine simple substance, acetic acid, water and concentrated sulfuric acid into a reaction bottle, fully mixing, heating to 80-100 ℃, refluxing for 6-8 hours, stopping heating and cooling, then adding a saturated sodium bisulphite solution to remove excessive iodine, stopping stirring, carrying out suction filtration, washing a filter cake twice by using dichloromethane, washing filtrate by using water, extracting by using dichloromethane to obtain a lower organic layer, and carrying out reduced pressure distillation to remove a solvent to obtain a second intermediate (ii).
Step S40: and (3) adding the second intermediate (ii) into dried THF at the temperature of-80 to 75 ℃ under the protection of nitrogen, dropwise adding n-butyllithium, stirring and reacting for 1.5 hours, adding the composition of triisopropyl borate and tetrahydrofuran, fully mixing, heating to 20 to 25 ℃ for reacting for 2 hours, finally adding dilute hydrochloric acid, and separating, washing and purifying to obtain a third intermediate (iii) of white solid.
The invention provides a concrete implementation mode, which comprises the following steps: under the protection of nitrogen, tetrahydrofuran and a second intermediate (ii) are sequentially added into a reaction bottle at the temperature of minus 80-75 ℃, then n-butyllithium solution is slowly added dropwise into the reaction bottle, after stirring for 1.5 hours, the composition of triisopropyl borate and tetrahydrofuran is slowly injected, stirring is continued for 2 hours, then the reaction can be finished after slowly heating to the room temperature of 20-25 ℃, finally, dilute hydrochloric acid is added, stirring is carried out for 0.5 hour, liquid separation and ethyl acetate extraction are carried out, the organic phase is washed to be neutral by water, and the solvent is rotationally distilled off after drying by anhydrous sodium sulfate. The petroleum ether recrystallization gave the third intermediate (iii).
Step S50: under the protection of nitrogen, carrying out Suzuki coupling reaction on the third intermediate (iii), the second reactant (2), the third reactant (3) or the fourth reactant (4), a palladium catalyst, calcium carbonate, ethanol, toluene and water under the stirring condition of 75 ℃ in temperature, and then separating, washing, drying and purifying to obtain a fourth intermediate (iv), or dl- (+ -.) -beta-methylpentyltribiphenyl liquid crystal compound (Ib-i) or (Ic-i).
The invention provides a concrete implementation mode, which comprises the following steps: under the protection of nitrogen, adding a third intermediate (iii), a second reactant (2), a third reactant (3) or a fourth reactant (4), a palladium catalyst and K into a reaction bottle 2 CO 3 Reflux-reacting ethanol, toluene and water for 5-7h under heating and stirring, stopping stirring, naturally cooling the reaction solution to room temperature, adding hydrochloric acid for neutralization, filtering to remove insoluble substances, adding toluene for extraction and separation, washing with water to be neutral, drying with anhydrous sodium sulfate, filtering, loading into a chromatographic column, preparing a dry sample, using petroleum ether as a eluting agent, and removing solvent by rotary evaporation to obtain a fourth intermediate dl- (+ -) -beta-methylpentyl fluorine-containing terphenyl amine (iv), or dl- (+ -) -beta-methylpentyl trifluoro-terphenyl liquid crystal compound (Ib-i) or dl- (+ -) -beta-methylpentyl fluorine-containingA fluoroterphenyl liquid crystal compound (Ic-i).
Step S60: and (3) uniformly mixing the fourth intermediate (iv), calcium carbonate, water and methylene dichloride, cooling to 0-5 ℃, adding a mixed solution of methylene dichloride and carbon dichloride for reaction, heating to 20-25 ℃ for reaction for 4 hours, heating to about 40 ℃ after the complete reaction, adding ethanol, and carrying out suction filtration, washing and purification to obtain the dl- (+ -) -beta-methylpentyl terphenyl isothiocyanate target compound (Ia-i).
The invention provides a concrete implementation mode, which comprises the following steps: sequentially adding the fourth intermediate (iv), calcium carbonate, water and methylene dichloride into a reaction bottle, stirring and mixing uniformly, cooling to 0-5 ℃, slowly dropwise adding a mixed solution of methylene dichloride and carbon dichloride for full reaction, removing an ice bath after 1 hour, heating the reaction bottle to room temperature of 20-25 ℃, continuing to react for 2 hours, heating to about 40 ℃, adding a proper amount of ethanol to destroy incompletely reacted carbon dichloride, stirring and refluxing for 30 minutes. And then carrying out suction filtration, washing with water, separating liquid, extracting a water layer by using dichloromethane, combining organic layers, and carrying out reduced pressure distillation to remove the dichloromethane to obtain the dl- (+ -) -beta-methylpentyltribiphenyl isothiocyanate liquid crystal compound (Ia-i).
In the preparation step S10 of the liquid crystal compound (I), the molar ratio of dl- (. + -.) -beta-methyl-1-amyl alcohol, triphenylphosphine and the second reactant (iii) is 1.1: (1.1-1.15): 1.0; in step S20, the molar ratio of the first intermediate (1), thionyl chloride and anhydrous aluminum trichloride is 1:5: (1.3-1.8); in the step S30, the molar ratio of the second intermediate (2), hydrazine hydrate, KOH, DMSO is 1: (1.2-1.8): (2-2.5): (0.1-0.8); in its step S40, the third intermediate (3), dipinacol diboron, potassium acetate, pd (dppf) Cl 2 The molar ratio of (2) is 1:2:3:0.01; in the step S50, the feeding molar ratio of the fourth intermediate (4), the third reactant (iv), the tetrakis triphenylphosphine palladium and the potassium carbonate is 1: (1-1.05): (0.001-0.003): (2-4), wherein the reaction temperature of the Suzuki coupling reaction is 40-80 ℃.
The invention provides a preparation method of dl- (±) -beta-methyl amyl terphenyl liquid crystal compound, which is characterized in that the dl- (±) -beta-methyl amyl terphenyl liquid crystal compound (I) is prepared by synthesis methods such as halogen substitution, iodo, grignard coupling, suzuki coupling reaction and the like; the synthesis yield is high, the operation is simple, the process is easy, and the mass production can be realized. The dl- (±) -beta-methyl amyl terphenyl liquid crystal compound (I) has the advantages of relatively low melting point and dielectric loss, can meet the use requirement of liquid crystal media of high-frequency devices such as microwave phase shifters and the like, can be used for improving the low-temperature eutectic point and low-temperature dielectric property of microwave high-frequency liquid crystal compositions, and provides a liquid crystal material with better performance for developing microwave communication devices.
In the technical scheme of the invention, optionally, the code, molecular structure, phase and dielectric properties of the synthesized part dl- (±) -beta-methylpentyltribiphenyl isothiocyanate liquid crystal compound (I) are shown in table 2:
table 2: code, molecular structure, phase and dielectric properties of liquid crystal compounds (I)
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In the technical scheme provided by the invention, in order to further improve the purity and resistivity of the prepared dl- (±) -beta-methylpentyltrimethylene liquid crystal compound (I), a column chromatography and an electric field adsorption method (Chinese patent application CN 101760203B, 2009) are adopted, and by utilizing a high-activity adsorption material, the adsorption method and an external electric field adsorption method are combined together, the dl- (±) -beta-methylpentyltrimethylene liquid crystal compound (I) obtained by purification is further refined, so that the content of trace impurity ions in the liquid crystal compound is reduced, and the resistivity or charge retention rate of a liquid crystal material is improved; refined liquid crystal is fed by ZC36 type high resistance instrumentLine test, resulting in a high resistivity (ρ) higher than 1.0X10 12 Ω.cm 3 The liquid crystal compound sample achieves the purpose of reducing dielectric loss caused by medium conduction.
Specifically, an electric field adsorption method is adopted: dissolving the crude product in toluene to prepare a solution to be treated; toluene, a solution to be treated and nano silicon dioxide are respectively and correspondingly added into a cathode solvent chamber, a sample chamber and an anode solvent chamber of the three-tank ionic membrane purifier, an oxide film electrode is adopted, the electrode spacing is set to be 6-15mm, the electric field strength is set to be 1.0-4kV/cm, and the purification is carried out for 30min, so that the liquid crystal compound refined product is obtained.
According to the embodiment of the invention, the microwave dielectric property of the dl- (±) -beta-methylpentyl fluorine-containing terphenyl liquid crystal compound (I) is tested. The preparation method comprises the steps of (1) mixing a refined dl- (±) -beta-methylpentyl fluorine-containing terphenyl liquid crystal compound (I) with a liquid crystal solvent (Mt) according to a certain mass ratio by using a lateral ethyl triphenyldiyne liquid crystal composition as the liquid crystal solvent (Mt) to obtain a room-temperature nematic liquid crystal composition, and testing the dielectric property of the room-temperature nematic liquid crystal composition in a microwave 4-40GHz band; the dielectric constant (delta epsilon) of the obtained microwave frequency band r ) Not less than 0.86, maximum dielectric loss (tan. Delta. Epsilon.) r max) is less than 6.7X10 -3 The method comprises the steps of carrying out a first treatment on the surface of the The microwave phase modulation quantity (tau) is more than or equal to 0.24, and the quality factor (eta) of the high-frequency liquid crystal compound serving as a microwave medium is more than 42.
The microwave dielectric properties of the liquid crystal composition were tested by the Chengdu Enchi microwave technology Co., ltd. Using the rectangular cavity perturbation method. The testing method is that liquid crystal is introduced into Polytetrafluoroethylene (PTFE) or quartz glass capillary; the capillary has an inner diameter of 1.5mm and an outer diameter of 2.78mm, and the effective length of the sample is 2.0cm; introducing the filled capillary into the center of the cylindrical resonant cavity, wherein the resonant frequency is 10GHz-35GHz; the magnetic field strength is 0.3T-1.0T by using a vector network analyzer (N5227 APNA microwave network analyzer, keysight Technologies Inc. USA).
Example 1: DL- (+ -) -4' - (beta-methylpentyl) -2, 6-difluoro terphenyl isothiocyanate compound 5 (1) PPUS, the molecular structural formula of which is:
the synthesis method comprises the following steps:
the first step: into a 1000mL three-necked flask equipped with magnetic stirring, 300mL of CH was added 2 Cl 2 As a solvent, 131.15g (0.5 mol) of triphenylphosphine was added and dissolved by stirring, the temperature was lowered to 10℃or below in a low-temperature tank, 126.9g (0.5 mol) of elemental iodine was added and stirred until the elemental iodine was completely dissolved. 51g (0.5 mol) dl- (. + -.) -beta-methyl-1-pentanol and 50ml triethylamine were mixed and put into a constant pressure low liquid funnel to be added dropwise into a three-neck flask, and reacted for two hours after the dropwise addition was completed. After the temperature is raised to room temperature of 20-30 ℃, the reaction is continued for two hours, after the solid of the phosphorus tribenuron is extracted by petroleum ether, 68.9g of colorless transparent liquid is distilled under reduced pressure when the vacuum degree is minus 0.09MPa and the temperature is 120 ℃, and the product dl- (+ -.) -1-iodo-2-methyl-pentane is an intermediate product, and the yield is 65%.
And a second step of: into a 500ml three-necked flask, 8.26g (0.34 mol) of magnesium turnings, 20ml of dried THF and 3 elemental iodine were charged, 75.4g (0.325 mol) of bromodiphenyl was dissolved in 300ml of THF and then added to a constant pressure dropping funnel under nitrogen protection. Firstly, slowly dripping a bromodiphenyl solution at room temperature of 20 ℃ until the reaction is initiated, dripping the bromodiphenyl solution into a three-mouth bottle at a constant speed, heating to 60 ℃ after all dripping is completed, carrying out reflux reaction for 30min, and rapidly adding the reaction liquid which is black liquid after the reaction is completed into the next part of reaction.
Into a 1000mL three-necked flask equipped with a spherical condenser, a constant pressure dropping funnel (nitrogen protection) and magnetic stirring were charged 2.0g (0.0148 mol) of anhydrous copper chloride, 68.9g (0.325 mol) of dl- (+ -.) -1-iodo-. Beta. -methyl-pentane and 100mL of anhydrous tetrahydrofuran. N (N) 2 And (3) protecting, dripping the Grignard reagent, and after finishing, starting to heat to 70 ℃, and refluxing for 6 hours. Adding a small amount of diluted hydrochloric acid after the reaction is finished, continuously stirring to fully hydrolyze, filtering, extracting the separated liquid with ethyl acetate, and using the organic layer withoutDrying over sodium sulfate water for 24h, and distilling off the solvent under reduced pressure gave 54.90g of pale yellow liquid as intermediate dl- (±) -1- (. Beta. -methylpentyl) biphenyl in 71% yield.
And a third step of: 13.53g (0.077 mol) iodic acid, 19.53g (0.077 mol) iodine simple substance, 54.9g (0.23 mol) intermediate dl- (±) -1- (. Beta. -methylpentyl) biphenyl, 300mL glacial acetic acid, 50mL water and 10mL concentrated sulfuric acid are sequentially added into a 1000mL double-neck flask provided with a reflux condenser and a stirrer, stirring is started, the color of the reaction solution is dark purple, the temperature is slowly increased to 100 ℃, the reflux stirring is continued for 7h, then heating is stopped, natural cooling is performed to room temperature 20 ℃, then saturated sodium bisulfite solution is added to remove excessive iodine until the reaction solution is yellow, stirring is stopped, suction filtration is performed, then dichloromethane and water are used for extraction, a lower organic layer is obtained, the organic layer is dried for 24h with anhydrous sodium sulfate, the solvent is removed by reduced pressure distillation, and 62.97g white solid intermediate dl- (±) -4' - (beta-methylpentyl) -1-iodobiphenyl is obtained, and the yield is 75%.
Fourth step: a1000 ml three-necked flask was equipped with a stirrer and a 250ml constant pressure dropping funnel. 62.97g (0.173 mol) dl- (+ -.) -4' - (β -methylpentyl) -1-iodobiphenyl, 500ml dry tetrahydrofuran, was added to the flask. Nitrogen protection is carried out in a low-temperature tank, the system temperature reaches minus 78 ℃, 90ml (0.225 mol) of n-butyllithium is injected, after slow dropwise addition is finished, after stirring for 1.5h, 59.8ml (0.259 mol) of triisopropyl borate is injected, after slow dropwise addition is finished, stirring is continued for 2h, after slowly rising to room temperature of 20 ℃, the reaction can be finished, 150ml of 10% hydrochloric acid is added, stirring and standing are carried out, ethyl acetate is extracted and separated, an organic layer is dried for 24h by anhydrous sodium sulfate, and the solvent is removed. Recrystallization from petroleum ether gave 35.1g of the intermediate dl- (±) -4' - (β -methylpentyl) biphenylboronic acid as a white solid in 72% yield.
Fifth step: 9.17g (0.0325 mol) dl- (. + -.) -4' - (beta-methylpentyl) biphenylboronic acid, 8.16g (0.032 mol) 2, 6-difluoro-4-iodoaniline, 16.58g (0.12 mol) K are sequentially added to a 250mL three-necked flask 2 CO 3 After 4 times of nitrogen substitution of 75mL of ethanol, 75mL of toluene and 10mL of water, 0.43g (0.1 mol% of catalyst) of tetraphenylphosphine palladium is added under the protection of nitrogen; heating and stirring at 75deg.C Reflux reaction is carried out for 7h, TCL is used for tracking and detection, and stirring is stopped after the reaction is completed; cooling to room temperature, adding dichloromethane, extracting, separating, drying an organic layer by using anhydrous sodium sulfate for 24 hours, removing a solvent, recrystallizing twice by using ethyl acetate and petroleum ether, and carrying out suction filtration to obtain 11.19g of yellow solid of an intermediate dl- (±) -4' - (beta-methylpentyl) -2, 6-difluoro terphenyl amine, wherein the yield is 86.5%.
Sixth step: 9.31g (0.093 mol) of CaCO 3 10ml of water, 100ml of methylene chloride and 11.19g (0.0306 mol) of dl- (. + -.) -4"- (beta-methylpentyl) -2, 6-difluoroterphenylamine were charged into a 250ml three-necked flask equipped with a magnetic stirring, a low temperature thermometer and a 100ml constant pressure dropping funnel, stirring was started, and when the temperature was lowered to 0℃with an ice bath, a mixture of 20ml of methylene chloride and 10.7g (0.093 mol,7 ml) of carbon dichloride was slowly dropped, and the dropping speed was controlled so as to ensure that no drastic rise in the reaction temperature occurred. After the dripping is finished, the reaction temperature is kept at 0 ℃ for continuous reaction for 1h, the ice bath is removed, the temperature is naturally raised to 20 ℃ and the reaction is continued for 1h. After the reaction is completed, 100ml of absolute ethyl alcohol is added, the temperature is raised to 45 ℃ for continuous reaction for 30min, so as to destroy the carbon dichloride which is not completely reacted. Extracting and separating liquid by using dichloromethane and water, combining organic layers, drying the organic layers by using anhydrous sodium sulfate for 24 hours, purifying the filtrate by using a column chromatography method after spin-drying, taking petroleum ether as a eluent, and spin-evaporating to remove solvent to obtain 10.92g of a white solid product target product 5 (1) PPUS, wherein the yield is 87.5%. The phase transition temperature is Cr 66 ℃ N159 ℃ Iso. Molecular structure spectrum identification data are as follows:
1 H-NMR(400MHz,CDCl 3 )δ(ppm):7.65(s,2H),7.59–7.53(m,4H),7.24(dq,J＝7.1,1.1Hz,4H),2.84(ddt,J＝13.4,7.7,0.9Hz,1H),2.63(ddt,J＝13.5,7.9,1.1Hz,1H),1.97–1.86(m,1H),1.50–1.23(m,4H),1.01(d,J＝7.0Hz,3H),0.90(t,J＝7.4Hz,3H)。
13 C-NMR(100MHz,CDCl 3 )δ(ppm):160.28,160.21,158.26,158.20,140.76,139.93,138.80,138.57,138.54,138.52,138.42,138.36,138.29,131.50,131.47,131.44,129.67,128.14,127.72,127.40,118.90,118.74,118.58,113.20,113.18,113.04,113.02,43.68,38.22,34.47,21.06,20.30,14.24。
19 F-NMR(376MHz,CDCl 3 )δ(ppm):-129.29。
The molecular structure of the prepared target compound is consistent with the structure shown in the structural formula.
Example 2: DL- (+ -) -4' - (beta-methylpentyl) -3, 5-difluoro terphenyl isothiocyanate liquid crystal compound 5 (1) PPUIS, the structural formula of which is:
the synthesis method comprises the following steps:
the first to fourth steps of this example were carried out in the same manner as in example 1, and dl- (±) -4' - (β -methylpentyl) biphenylboronic acid in the fourth step of the synthesis in example 1 was used as it is in this example.
Fifth step: 9.17g (0.0325 mol) dl- (. + -.) -4' - (beta-methylpentyl) biphenylboronic acid, 8.16g (0.032 mol) 3, 5-difluoro-4-iodoaniline, 16.58g (0.12 mol) K are sequentially added to a 250mL three-necked flask 2 CO 3 After 4 times of nitrogen substitution of 75mL of ethanol, 75mL of toluene and 10mL of water, 0.43g (0.1 mol% of catalyst) of tetraphenylphosphine palladium is added under the protection of nitrogen; heating and stirring, controlling the temperature at 75 ℃, carrying out reflux reaction for 7h, tracking and detecting by using TCL, and stopping stirring after the reaction is complete; cooling to room temperature, adding dichloromethane, extracting, separating, drying an organic layer by using anhydrous sodium sulfate for 24 hours, removing a solvent, recrystallizing twice by using ethyl acetate and petroleum ether, and carrying out suction filtration to obtain 11.19g of yellow solid intermediate dl- (±) -4' - (beta-methylpentyl) -3, 5-difluoro terphenyl amine, wherein the yield is 86.5 percent.
Sixth step: 9.31g (0.093 mol) of CaCO 3 10ml of water, 100ml of methylene chloride and 11.19g (0.031 mol) of dl- (+ -) -4' - (beta-methylpentyl) -3, 5-difluoroterphenylamine were charged into a 250ml three-necked flask equipped with a magnetic stirring, a low temperature thermometer and a 100ml constant pressure dropping funnel, stirring was started, and when the temperature was lowered to 0℃with an ice bath, a mixture of 20ml of methylene chloride and 10.7g (0.093 mol,7 ml) of carbon dichloride was slowly dropped, and the dropping speed was controlled so as to ensure that no drastic rise in the reaction temperature occurred. After the dripping is finished, the reaction temperature is kept at 0 ℃ for a timeAnd (3) continuing the reaction for 1h, removing the ice bath, naturally heating to 20 ℃, and continuing the reaction for 1h. After the reaction is completed, 100ml of absolute ethyl alcohol is added, the temperature is raised to 45 ℃ for continuous reaction for 30min, so as to destroy the carbon dichloride which is not completely reacted. Extracting with dichloromethane and water, separating, mixing organic layers, drying the organic layers with anhydrous sodium sulfate for 24h, evaporating filtrate to dryness, purifying with column chromatography, and removing solvent by rotary evaporation to obtain 11.04g of white solid product target product 5 (1) PPUIS with yield of 87.5%; the phase transition temperature is Cr 89 ℃ N161 ℃ Iso. Molecular structure spectrum identification data are as follows:
1 H-NMR(400MHz,CDCl 3 )δ(ppm):7.67(s,2H),7.53-7.43(m,4H),7.29-7.20(m,4H),2.82(ddt,J＝13.4,7.7,0.9Hz,1H),2.66(ddt,J＝13.5,7.9,1.0Hz,1H),1.92(dtt,J＝8.0,7.1,6.1Hz,1H),1.52-1.24(m,5H),1.00(d,J＝7.0Hz,3H),0.91(t,J＝7.4Hz,3H)。
13 C-NMR(100MHz,CDCl 3 )δ(ppm):162.21,162.15,160.20,160.13,140.93,139.93,138.80,135.93,132.02,131.95,131.89,130.70,130.68,130.65,130.53,130.46,130.40,129.67,127.94,127.40,119.21,119.05,118.89,110.14,110.12,109.98,109.96,43.68,38.22,34.47,21.06,20.30,14.24。
19 F-NMR(376MHz,CDCl 3 )δ(ppm):-109.13。
the molecular structure of the prepared target compound is consistent with the structure shown in the structural formula.
Example 3: DL- (+ -) -4' - (beta-methylpentyl) -2, 5-difluoro terphenyl isothiocyanate liquid crystal compound 5 (1) PPGfS has the structural formula:
the synthesis method comprises the following steps:
the first to fourth steps of this example were carried out in the same manner as in example 1, and dl- (±) -4' - (β -methylpentyl) biphenylboronic acid in the fourth step of the synthesis in example 1 was used as it is in this example.
Fifth step: at 250mL three9.17g (0.0325 mol) dl- (+ -.) -4' - (beta-methylpentyl) biphenylboronic acid, 8.16g (0.032 mol) 2, 5-difluoro-4-iodoaniline, 16.6g (0.12 mol) K are sequentially added to a flask 2 CO 3 After 4 times of nitrogen substitution, 75mL of ethanol, 75mL of toluene and 10mL of water, 0.43g (0.1 mol% of catalyst tetrakis triphenylphosphine palladium (0) was added under nitrogen protection; heating and stirring, controlling the temperature at 75 ℃, carrying out reflux reaction for 7h, tracking and detecting by using TCL, and stopping stirring after the reaction is complete; cooling to room temperature, adding dichloromethane, extracting and separating, drying an organic layer with anhydrous sodium sulfate for 24 hours, removing a solvent, recrystallizing with ethyl acetate and petroleum ether twice, and carrying out suction filtration to obtain 11.3g of yellow solid intermediate dl- (±) -4' - (beta-methylpentyl) -2, 5-difluoro terphenyl amine, wherein the yield is 89.5%.
Sixth step: 9.31g (0.093 mol) of CaCO 3 10ml of water, 100ml of methylene chloride and 11.3g (0.031 mol) of dl- (+ -) -4' - (beta-methylpentyl) -2, 6-difluoro-terphenylamine were added to a 250ml three-necked flask equipped with a magnetic stirring, a low temperature thermometer and a 100ml constant pressure dropping funnel, stirring was started, and when the temperature was lowered to 0℃with an ice bath, a mixture of 20ml of methylene chloride and 10.7g (0.093 mol,7 ml) of carbon dichloride was slowly dropped, and the dropping speed was controlled so as to ensure that no drastic rise in the reaction temperature occurred. After the dripping is finished, the reaction temperature is kept at 0 ℃ for continuous reaction for 1h, the ice bath is removed, the temperature is naturally raised to 20 ℃ and the reaction is continued for 1h. After the reaction is completed, 100ml of absolute ethyl alcohol is added, the temperature is raised to 45 ℃ for continuous reaction for 30min, so as to destroy the carbon dichloride which is not completely reacted. Suction filtering, extracting with dichloromethane and water, separating liquid, mixing organic layers, drying the organic layers with anhydrous sodium sulfate for 24h, rotary evaporating filtrate, purifying by column chromatography, and rotary evaporating petroleum ether as eluent to remove solvent to obtain 11.1g of white solid target product 5 (1) PPGfS with yield of 87.96%. The phase transition temperature is: cr 50 ℃, sm 76 ℃, N136 ℃, iso130 ℃, N20 ℃ Cr. Molecular structure spectrum identification data are as follows:
1 H-NMR(400MHz,CDCl 3 )δ(ppm):7.70–7.61(m,4H),7.59–7.53(m,2H),7.45(ddd,J＝11.8,8.0,5.0Hz,2H),7.24(dt,J＝8.4,1.1Hz,2H),2.81(ddt,J＝13.5,7.9,1.0Hz,1H),2.63(ddt,J＝13.5,7.9,1.0Hz,1H),1.92(ttd,J＝7.8,6.8,5.9Hz,1H),1.53–1.24(m,4H),1.00(d,J＝7.0Hz,2H),0.91(t,J＝7.4Hz,3H)。
13 C-NMR(100MHz,CDCl 3 )δ(ppm):159.46,159.44,157.45,157.43,156.49,156.46,154.47,154.45,140.72,139.93,138.80,135.71,135.68,135.64,135.62,129.67,128.81,128.79,128.74,128.64,128.58,127.52,127.40,124.70,124.66,119.24,119.18,119.08,119.02,117.47,117.41,117.31,117.25,113.85,113.78,113.69,113.62,43.68,38.22,34.47,21.06,20.30,14.24。
19 F-NMR(376MHz,CDCl 3 )δ(ppm):-111.71,-123.03。
The molecular structure of the prepared target compound is consistent with the structure shown in the structural formula.
Example 4: DL- (+ -) -4' - (beta-methylpentyl) -3-methyltribiphenyl isothiocyanate liquid crystal compound 5 (1) PPPi (1) S, which has the structural formula:
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the synthesis method comprises the following steps:
this example the first to fourth steps are the same as in example 1, and dl- (±) -4' - (β -methylpentyl) biphenylboronic acid synthesized in the fourth step of example 1 is used directly in this example.
Fifth step: into a 250mL three-necked flask, 10g (0.0354 mol) of dl- (. + -.) -4' - (β -methylpentyl) biphenylboronic acid, 7.85g (0.034 mol) of 4-iodo-3-methylaniline and 16.6g (0.12 mol) of K were successively introduced 2 CO 3 After 4 times of nitrogen substitution of 75mL of ethanol, 75mL of toluene and 10mL of water, 0.45g (0.11 mol% of catalyst) of tetraphenylphosphine palladium is added under the protection of nitrogen; heating and stirring, controlling the temperature at 75 ℃, carrying out reflux reaction for 7h, tracking and detecting by using TCL, and stopping stirring after the reaction is complete; cooling to room temperature, adding dichloromethane, extracting, separating, drying the organic layer with anhydrous sodium sulfate for 24h, removing solvent, recrystallizing with ethyl acetate and petroleum ether twice, and suction filtering to obtain 9.77g yellow solid of intermediate dl- (±) -4' - (beta-methylpentyl) -3-methyl terphenyl amine with yield 84.3％。
Sixth step: 7.6g (0.0759 mol) of CaCO 3 10ml of water, 100ml of methylene chloride and 9.77g (0.0287 mol) of dl- (+ -) -4' - (beta-methylpentyl) -3-methyltrianiline are added into a 250ml three-necked flask equipped with magnetic stirring, a low temperature thermometer and a 100ml constant pressure dropping funnel, stirring is started, and when the temperature is lowered to 0 ℃ by using an ice bath, a mixture of 20ml of methylene chloride and 8.72g (0.0759 mol,6 ml) of carbon dichloride is slowly dropped, and the dropping speed is controlled so as to ensure that no drastic rise of the reaction temperature occurs. After the dripping is finished, the reaction temperature is kept at 0 ℃ for continuous reaction for 1h, the ice bath is removed, the temperature is naturally raised to 20 ℃ and the reaction is continued for 1h. After the reaction is completed, 100ml of absolute ethyl alcohol is added, the temperature is raised to 45 ℃ for continuous reaction for 30min, so as to destroy the carbon dichloride which is not completely reacted. Suction filtering, extracting with dichloromethane and water, separating liquid, mixing organic layers, drying the organic layers with anhydrous sodium sulfate for 24h, rotary evaporating filtrate, purifying by column chromatography, and rotary evaporating petroleum ether as eluent to remove solvent to obtain 9.35g white solid target product 5 (1) PPPi (1) S with yield of 85.1%. The phase transition temperature is Cr 60 ℃ and N105 ℃ Iso, and the molecular structure spectrum identification data are as follows:
1 H-NMR(400MHz,CDCl 3 )δ(ppm):7.68–7.57(m,4H),7.58–7.52(m,2H),7.47–7.34(m,3H),7.23(dt,J＝8.4,1.0Hz,2H),2.83(ddt,J＝13.3,7.8,0.9Hz,1H),2.62(ddt,J＝13.5,7.8,1.0Hz,1H),2.48(s,2H),1.92(tdt,J＝7.9,6.9,6.0Hz,1H),1.53–1.25(m,5H),0.98(d,J＝7.1Hz,3H),0.91(t,J＝7.4Hz,3H)。
13 C-NMR(100MHz,CDCl 3 )δ(ppm):140.72,140.01,139.93,139.13,138.80,137.16,135.34,133.45,129.67,128.27,127.47,127.37,127.33,124.31,43.70,38.22,34.49,21.22,20.91,20.30,14.24。
the molecular structure of the prepared target compound is consistent with the structure shown in the structural formula.
Example 5: DL- (+ -) -4' - (beta-methylpentyl) -1,2, 6-trifluoro-terphenyl liquid crystal compound 5 (1) PPUF is synthesized, and the molecular structural formula is as follows:
the synthesis method comprises the following steps:
the first to fourth steps of this example were carried out in the same manner as in example 1, and dl- (±) -4' - (β -methylpentyl) biphenylboronic acid synthesized in the fourth step of example 1 was directly used in this example.
Fifth step: 10g (0.0354 mol) dl- (. + -.) -4' - (beta-methylpentyl) biphenylboronic acid, 9.77g (0.034 mol) 4-iodo-1, 2, 6-trifluorobenzene, 0.43g (0.1 mol) palladium catalyst, 16.6g (0.12 mol) K under a nitrogen blanket 2 CO 3 Carrying out Suzuki coupling reaction on 75mL of ethanol, 75mL of toluene and 10mL of water under the stirring condition of 75 ℃ for 7 hours, tracking and detecting by using TCL, and stopping stirring after the reaction is completed; cooling to room temperature, neutralizing with hydrochloric acid, filtering to remove insoluble substances, adding dichloromethane to extract, drying the organic layer with anhydrous sodium sulfate for 24 hr, and removing solvent. The filtrate is purified by a column chromatography method after being dried by rotary evaporation, petroleum ether is used as eluent, and 9.86g of white solid product target product 5 (1) PPUF is obtained after the solvent is removed by rotary evaporation, and the yield is 78.75%. The phase transition temperature is Cr 62.7 ℃ N110.4 ℃ Iso, and the molecular structure spectrum identification data are as follows:
1 H-NMR(400MHz,CDCl 3 )δ(ppm):7.64(s,3H),7.64–7.55(m,2H),7.32–7.25(m,2H),7.23(dt,J＝8.4,1.0Hz,2H),2.79(ddt,J＝13.5,7.9,0.9Hz,1H),2.66(ddt,J＝13.5,7.9,1.0Hz,1H),1.99–1.88(m,1H),1.53–1.25(m,4H),1.00(d,J＝7.1Hz,3H),0.94–0.84(m,3H)。
13 C-NMR(100MHz,CDCl 3 )δ(ppm):151.83,151.77,151.68,151.61,149.82,149.76,149.66,149.60,142.64,142.48,142.32,140.76,140.62,140.46,140.39,140.30,138.99,138.24,138.21,138.19,137.01,136.99,136.95,136.92,136.88,136.86,129.56,128.07,127.66,127.45,111.80,111.77,111.73,111.71,111.64,111.61,111.57,111.55,43.51,38.15,34.36,20.87,20.48,14.24。
19 F-NMR(376MHz,CDCl 3 )δ(ppm):-133.20,-154.30。
The molecular structure of the prepared target compound is consistent with the structure shown in the structural formula.
Example 6 synthesis of DL- (±) -4"- (β -methylpentyl) -2, 6-difluoro-1-trifluoromethoxy terphenyl liquid crystalline compound 5 (1) PPUOT having the structural formula:
the synthesis of this example includes the following steps:
this example the first to fourth steps are the same as in example 1, and dl- (±) -1- (. Beta. -methylpentyl) -4' -biphenylboronic acid synthesized in step 4 of example 1 is used directly in this example.
Fifth step: under the protection of nitrogen, 10g (0.0354 mol) dl- (. + -.) -4' - (beta-methylpentyl) biphenyl boric acid, 11.47g (0.0354 mol) 4-iodo-2, 6-trifluoromethoxybenzene, 0.43g (0.1 mol) palladium catalyst, 16.58g (0.12 mol) K 2 CO 3 Carrying out Suzuki coupling reaction on 75mL of ethanol, 75mL of toluene and 10mL of water under the stirring condition of 75 ℃ for 7 hours, tracking and detecting by using TCL, and stopping stirring after the reaction is completed; cooling to room temperature, neutralizing with hydrochloric acid, filtering to remove insoluble substances, adding dichloromethane to extract, drying the organic layer with anhydrous sodium sulfate for 24 hr, and removing solvent. The filtrate is purified by a column chromatography method after being dried by rotary evaporation, petroleum ether is used as eluent, and 11.41g of white solid product target product 5 (1) PPUOT is obtained after the solvent is removed by rotary evaporation, and the yield is 74.2 percent. The phase transition temperature is Cr 71 ℃ N128 ℃ Iso, and the molecular structure spectrum identification data are as follows:
1 H-NMR(400MHz,CDCl 3 )δ(ppm):7.67–7.59(m,4H),7.62–7.55(m,2H),7.27–7.19(m,4H),2.81(ddt,J＝13.5,7.9,1.0Hz,1H),2.63(ddt,J＝13.5,7.9,1.0Hz,1H),1.97–1.83(m,1H),1.50–1.24(m,4H),1.00(d,J＝7.0Hz,3H),0.93–0.84(m,3H).
13 C-NMR(100MHz,CDCl 3 )δ(ppm):155.81,155.80,155.75,155.74,153.80,153.79,153.73,153.73,140.71,140.39,138.82,137.99,137.97,137.94,137.26,137.20,137.13,130.70,130.61,129.54,128.09,127.62,127.48,122.07,119.93,111.97,111.94,111.81,111.78,43.65,38.17,34.36,20.91,20.40,14.22.
19 F-NMR(376MHz,CDCl 3 )δ(ppm):-60.00,-128.15.
The molecular structure of the prepared target compound is consistent with the structure shown in the structural formula.
Example 7: DL- (+ -) -4'- (beta-methylpentyl) -2',2, 6-trifluoro-1-trifluoromethoxy terphenyl liquid crystal compound 5 (1) PGUOT synthesis. The molecular structural formula is as follows:
the synthesis of this example includes the following steps:
the first to second steps of this embodiment are the same as those of embodiment 1. However, the starting material in the second synthesis step was changed from bromodiphenyl in the previous examples to 3' -fluorobromodiphenyl.
And a third step of: a1000 ml three-necked flask was equipped with a stirrer and a 100ml constant pressure dropping funnel. Into the flask was added 38.2g (0.1 mol) dl- (. + -.) -4' - (β -methylpentyl) -2-fluoroiodobiphenyl, 400ml dry tetrahydrofuran. Nitrogen protection is carried out in a low-temperature tank, the system temperature reaches minus 78 ℃, 52ml (0.13 mol) of n-butyllithium is injected, after slow dropwise addition is finished, 34.6ml (0.15 mol) of triisopropyl borate is injected after stirring for 1.5h, after slow dropwise addition is finished, stirring is continued for 2h, the reaction can be finished after slowly rising to room temperature of 20 ℃, 150ml of 10% hydrochloric acid is added, stirring and standing are carried out, ethyl acetate extraction and liquid separation are carried out, and an organic layer is dried for 24h by anhydrous sodium sulfate, and the solvent is removed. Recrystallization from petroleum ether gave 23.4g of the intermediate dl- (±) -4' - (β -methylpentyl) biphenylboronic acid as a white solid in 78% yield.
Fourth step: into a 250mL three-necked flask, 10.5g (0.035 mol) of DL- (. + -.) -4' - (β -methylpentyl) -2-fluorobiphenyl boronic acid, 11g (0.034 mol) of 2, 6-difluoro-4-iodotrifluoroethoxy benzene and 16.6g (0.12 mol) of K were successively introduced 2 CO 3 After 4 times of nitrogen substitution of 75mL of ethanol, 75mL of toluene and 10mL of water, 0.43g (0.1% mol ratio) of catalyst tetra triphenylphosphine palladium is added under the protection of nitrogen; heating and stirring, controlling the temperature at 75 ℃,reflux reaction for 7h, tracking and detecting by TCL, stopping stirring after the reaction is complete; cooling to room temperature, neutralizing with hydrochloric acid, filtering to remove insoluble substances, adding dichloromethane to extract, drying the organic layer with anhydrous sodium sulfate for 24 hr, and removing solvent. The filtrate is purified by a column chromatography method after being dried by rotary evaporation, petroleum ether is used as eluent, and 11.54g of white crystal product 5 (1) PGUOT is obtained after the solvent is removed by rotary evaporation, and the yield is 75.1%; the phase transition temperature is Cr 52.1 ℃ N121.4 ℃ Iso. The molecular structure identification data are as follows:
1 H-NMR(400MHz,CDCl 3 )δ(ppm):7.72(dd,J＝8.5,4.9Hz,1H),7.62–7.56(m,2H),7.48(ddd,J＝13.9,8.2,1.9Hz,2H),7.29(ddd,J＝7.4,2.1,1.1Hz,2H),7.22(dt,J＝8.4,1.1Hz,2H),2.79(ddt,J＝13.5,7.9,1.1Hz,1H),2.63(ddt,J＝13.5,7.9,1.0Hz,1H),1.95–1.84(m,1H),1.51–1.24(m,4H),0.98(d,J＝7.1Hz,3H),0.94–0.84(m,3H)。
13 C-NMR(100MHz,CDCl 3 )δ(ppm):161.03,159.02,156.33,156.32,156.27,156.26,154.32,154.31,154.25,154.24,140.47,140.40,137.34,137.31,130.48,130.40,129.89,129.83,129.77,129.74,129.70,129.67,129.62,128.72,128.70,128.67,128.56,128.54,128.51,128.04,124.91,124.89,122.07,119.93,113.71,113.55,113.51,113.49,113.46,113.35,113.33,113.30,43.63,38.19,34.36,20.95,20.40,14.22。
19 F-NMR(376MHz,CDCl 3 )δ(ppm):-60.00,-118.74,-128.15.
the molecular structure of the prepared target compound is consistent with the structure shown in the structural formula.
Example 8, microwave frequency range performance test examples of achiral dl- (±) - β -methylpentyltrimethylene based liquid crystal compounds (I):
firstly, a triphenyldiyne liquid crystal compound with a lower melting point and a higher birefringence (delta n=0.394, 589.2nm and 20 ℃) is mixed according to a certain ratio to prepare a mother liquid crystal Mt (or called solvent liquid crystal), then the synthesized part of dl- (±) -beta-methylpentyltribiphenyl liquid crystal compound (I) is used as a liquid crystal compound (or called solute liquid crystal) to be tested, the mass ratio of the mother liquid crystal to the liquid crystal to be tested=80 wt% to 20wt% is used as the liquid crystal compound to be tested, and then the mixture is mixed to prepare a room temperature nematic liquid crystal composition, and then the microwave dielectric property of the room temperature nematic liquid crystal composition is tested. The microwave dielectric properties were tested by the Chengdu Enchi microwave technology Co., ltd, using the rectangular cavity perturbation method. Test conditions: the test frequency band is 10-35GHz, the test temperature is 20 ℃ and the ambient humidity is 30%; and testing the dielectric property of the liquid crystal material by using a microwave dielectric property tester through a rectangular cavity resonance perturbation method. The test results are shown in table 3 below:
TABLE 3 dielectric Properties of dl- (. + -.) -beta-methylpentyltribiphenyl liquid Crystal Compound (I) at 19.6GHz
| Sample of | ε r∥ | ε r⊥ | Δε r | tanδε r⊥ | tanδε r∥ | τ | η |
| Mt | 3.251 | 2.460 | 0.791 | 0.00912 | 0.00371 | 0.243 | 26.68 |
| 5(1)PPUS | 3.648 | 2.621 | 1.027 | 0.00593 | 0.00307 | 0.282 | 47.47 |
| 5(1)PPUiS | 3.606 | 2.656 | 0.950 | 0.00245 | 0.00143 | 0.263 | 107.53 |
| 5(1)PPGfS | 3.635 | 2.637 | 0.998 | 0.00287 | 0.00183 | 0.275 | 95.66 |
| 5(1)PPPi(1)S | 3.575 | 2.643 | 0.932 | 0.00411 | 0.00231 | 0.261 | 63.43 |
| 5(1)PGUS | 3.769 | 2.656 | 1.113 | 0.00651 | 0.00371 | 0.295 | 45.36 |
| 5(1)PGGfS | 3.743 | 2.707 | 1.036 | 0.00545 | 0.00274 | 0.277 | 50.79 |
| 5(1)PPUOT | 3.550 | 2.638 | 0.912 | 0.00567 | 0.00278 | 0.257 | 45.31 |
| 5(1)PGUOT | 3.516 | 2.632 | 0.884 | 0.00607 | 0.00335 | 0.251 | 41.56 |
| 5(1)PPUF | 3.479 | 2.624 | 0.855 | 0.00583 | 0.00351 | 0.246 | 42.16 |
As can be seen from the results of the microwave dielectric properties of the liquid crystal compounds in the examples, the liquid crystal compounds provided by the invention have dielectric properties satisfying the microwave conditions, and more importantly, have lower melting points. The (Ia-i) series of compounds can be used as the main component of nematic liquid crystal materials for microwave phase shifters, and are nematic liquid crystal compounds with double refractive indexes and dielectric constants meeting the microwave liquid crystal conditions and lower low-temperature eutectic points.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (9)
- Dl- (±) -beta-methylpentyltribiphenyl liquid crystal compound characterized in that: the liquid crystal compound has a structure shown in a structural formula (I):Wherein X is 1 -X 6 Each independently selected from-H, -F, -Cl or-CH 3 Y is independently selected from-F, -NCS or-OCF 3 Dl- (±) -beta-methylpentyl is an achiral alkyl group.
- 2. The liquid crystal compound according to claim 1, wherein: the polar end group Y of the liquid crystal compound is an isothiocyano group, which is a compound having a structure represented by the following structural formula (Ia-i):wherein X is 1 -X 6 Each independently selected from-H, -F, -Cl or-CH 3 。
- 3. The liquid crystal compound according to claim 1, wherein: the polar end group Y of the liquid crystal compound is trifluoromethoxy, and is a compound having a structure shown in the following structural formula (Ib-i):wherein X is 1 -X 4 Each independently selected from-H, -F, -Cl or-CH 3 ；X 5 、X 6 Each independently selected from-H, -F or-Cl.
- 4. The liquid crystal compound according to claim 1, wherein: when the polar terminal group Y of the liquid crystal compound is F atom, it is a compound having a structure represented by the following structural formula (Ic-i):wherein X is 1 -X 4 Each independently selected from-H, -F, or-Cl; x is X 5 、X 6 Each independently selected from-H, -F, -Cl or-CH 3 。
- 5. The liquid crystal compound according to claim 1 to 4, wherein: the liquid crystal compound is purified by column chromatography, recrystallization and electric field adsorption or treated by specific adsorbent, and has resistivity up to 1.0X10 12 The above.
- The preparation method of dl- (±) -beta-methyl amyl terphenyl liquid crystal compound is characterized by comprising the following steps: the method comprises the following steps:step S10: with an appropriate amount of CH 2 Cl 2 Dissolving triphenylphosphine, adding iodine simple substance below 10deg.C, and stirring until iodine simple substance is completely dissolved. Mixing dl- (±) -beta-methyl-1-pentanol with triethylamine, then dripping, reacting for two hours after dripping, and precipitating and separating generated phosphorus tribenzoxide and an extraction reaction liquid by using a proper amount of petroleum ether (60-90); washing with water, drying and distilling under reduced pressure to obtain dl- (+ -) -1-iodo-beta-methyl-pentane;step S20: adding magnesium scraps, dried anhydrous THF and a plurality of iodine simple substances into a three-neck flask; after the activation and the initiation of the Grignard reaction, the first reactant (1) is dissolved in a solvent and added into a constant pressure dropping funnel, the mixture is dropped at a constant speed, the temperature is raised for reflux reaction, and finally the reaction liquid is gray liquid and is rapidly put into the next step. Adding anhydrous copper chloride, dl- (±) -1-iodo-beta-methyl-pentane and dried anhydrous THF into a three-neck flask, adding a small amount of dilute hydrochloric acid after the reaction is finished, continuously stirring to fully hydrolyze the mixture, and carrying out suction filtration, washing, extraction and purification treatment to obtain a first intermediate (i);Step S30: mixing the obtained first intermediate (i), iodic acid, iodine simple substance, acetic acid, water and concentrated sulfuric acid for reaction, heating to 80-100 ℃, carrying out reflux reaction, cooling to below 60 ℃ after the reaction is finished, adding sodium bisulphite solution, carrying out suction filtration, washing, extracting and purifying treatment to obtain a second intermediate (ii);step S40: under the protection of nitrogen, adding the second intermediate (ii) into dried THF at the temperature of-80 to 75 ℃, dropwise adding n-butyllithium, stirring and reacting for 0.5 hour, adding triisopropyl borate, fully mixing, naturally heating to 20 to 25 ℃ and reacting for 2 hours, finally adding hydrochloric acid, and separating, washing and purifying to obtain a white solid third intermediate (iii); step S50: mixing the third intermediate (iii), a palladium (0-valent) catalyst, potassium carbonate, ethanol, toluene and anaerobic water under the protection of nitrogen, adding the second reactant (2) or the third reactant (3) or the fourth reactant (4), and carrying out Suzuki coupling reaction at the temperature of 75 ℃ under the stirring condition, wherein the reaction time is 8-10 hours; after the completion of the reaction, the fourth intermediate (iv), or the target compound (Ib-i), or the target compound (Ic-i) is obtained by washing, separation, drying and purification treatment;Step S60: uniformly mixing the fourth intermediate (iv), calcium carbonate, water and methylene dichloride, cooling to 0-5 ℃, adding the mixture of methylene dichloride and carbon dichloride after reaction, heating to 20-25 ℃, fully stirring and reacting for 8-10 hours, heating to 45-50 ℃, adding ethanol to remove unreacted carbon dichloride, and carrying out suction filtration, washing and purification to obtain the dl- (+ -) -beta-methylpentyl terphenyl target molecular structure (Ia-i) compound;the structural formulas of the first reactant (1), the second reactant (2), the third reactant (3) and the fourth reactant (4) are respectively shown as follows:wherein the substituent X of the first reactant (1) 5 -X 6 Each independently selected from H atom, or F atom, or Cl atom, or-CH 3 A group; substituent X of the second reactant (2), the third reactant (3) and the fourth reactant (4) 1 -X 4 Each independently selected from H atoms, or F atoms, or Cl atoms;the structural formulas of the first intermediate (i), the second intermediate (ii), the third intermediate (iii) and the fourth intermediate (iv) are respectively shown as follows:wherein the substituent X 1 -X 6 Independently selected from-H, -F, -Cl or-CH 3 。
- 7. The method of manufacturing according to claim 6, wherein:in step S10, the molar ratio of dl- (±) - β -methyl-1-pentanol, triphenylphosphine, second reactant is 1.1: (1.1-1.15): 1.0; and/or the number of the groups of groups,In step S20, the molar ratio of the first intermediate, thionyl chloride, and anhydrous aluminum trichloride is 1:5: (1.3-1.8); and/or the number of the groups of groups,in step S30, the molar ratio of the second intermediate, hydrazine hydrate, KOH, DMSO is 1: (1.2-1.8): (2-2.5): (0.1-0.8); and/or the number of the groups of groups,in step S40, the third intermediate, dipinacol diboron, potassium acetate, pd (dppf) Cl 2 The molar ratio of (2) is 1:2:3:0.01; and/or the number of the groups of groups,in S50, the feeding mole ratio of the fourth intermediate, the third reactant, the tetra-triphenylphosphine palladium and the potassium carbonate is 1: (1-1.05): (0.001-0.003): (2-4);the reaction temperature of the Suzuki coupling reaction is 40-80 ℃.
- 8. Use of a liquid crystal compound according to claims 1-5 in a liquid crystal material medium for microwave high frequency devices.
- 9. A microwave communication device, characterized by: the microwave communication device uses the liquid crystal compound according to any one of claims 1 to 5 as a main component of a microwave information transmission medium.
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