CN110551076A - benzoxazole liquid crystal compound containing acetylene bonds and preparation method thereof - Google Patents
benzoxazole liquid crystal compound containing acetylene bonds and preparation method thereof Download PDFInfo
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- CN110551076A CN110551076A CN201910813705.8A CN201910813705A CN110551076A CN 110551076 A CN110551076 A CN 110551076A CN 201910813705 A CN201910813705 A CN 201910813705A CN 110551076 A CN110551076 A CN 110551076A
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- ethynyl
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 60
- 150000001875 compounds Chemical class 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 title claims abstract description 18
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 title claims description 31
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 32
- 125000003545 alkoxy group Chemical group 0.000 claims description 28
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 23
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 20
- -1 4- (1, 3-dioxolane-2-yl) phenyl Chemical group 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 12
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 10
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 10
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 10
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 claims description 8
- ZRYZBQLXDKPBDU-UHFFFAOYSA-N 4-bromobenzaldehyde Chemical compound BrC1=CC=C(C=O)C=C1 ZRYZBQLXDKPBDU-UHFFFAOYSA-N 0.000 claims description 8
- 125000000649 benzylidene group Chemical group [H]C(=[*])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 8
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 claims description 7
- XIRIIWVACGWQSX-UHFFFAOYSA-N C1=CC(C#CC(C)(O)C)=CC=C1C1OCCO1 Chemical compound C1=CC(C#CC(C)(O)C)=CC=C1C1OCCO1 XIRIIWVACGWQSX-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 229960001701 chloroform Drugs 0.000 claims description 6
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 5
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 5
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 5
- 235000019253 formic acid Nutrition 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- CEBKHWWANWSNTI-UHFFFAOYSA-N 2-methylbut-3-yn-2-ol Chemical compound CC(C)(O)C#C CEBKHWWANWSNTI-UHFFFAOYSA-N 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- 239000012071 phase Substances 0.000 description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 239000012074 organic phase Substances 0.000 description 9
- 230000004044 response Effects 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 230000007704 transition Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- ZMXYNJXDULEQCK-UHFFFAOYSA-N 2-amino-p-cresol Chemical compound CC1=CC=C(O)C(N)=C1 ZMXYNJXDULEQCK-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- LGBIFIGDFFVXIW-UHFFFAOYSA-N 1-hexoxy-4-iodobenzene Chemical compound CCCCCCOC1=CC=C(I)C=C1 LGBIFIGDFFVXIW-UHFFFAOYSA-N 0.000 description 1
- VLZVIIYRNMWPSN-UHFFFAOYSA-N 2-Amino-4-nitrophenol Chemical compound NC1=CC([N+]([O-])=O)=CC=C1O VLZVIIYRNMWPSN-UHFFFAOYSA-N 0.000 description 1
- 239000004988 Nematic liquid crystal Substances 0.000 description 1
- 238000003477 Sonogashira cross-coupling reaction Methods 0.000 description 1
- 230000003044 adaptive effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000001810 isothiocyanato group Chemical group *N=C=S 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000005935 nucleophilic addition reaction Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/52—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings condensed with carbocyclic rings or ring systems
- C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
- C07D263/56—Benzoxazoles; Hydrogenated benzoxazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached in position 2
- C07D263/57—Aryl or substituted aryl radicals
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
The invention discloses a benzoxazole liquid crystal compound containing an alkyne bond and a preparation method thereof, belonging to the technical field of materials.A structural formula of the compound is , wherein R represents a linear alkyl group of C 5 -C 12, and X represents hydrogen, methyl or nitro.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a benzoxazole liquid crystal compound containing an acetylene bond and a preparation method thereof.
Background
The liquid crystal material is widely applied to the display fields of tablet personal computers, mobile phones, notebook computers, high-definition televisions and the like, and the non-display fields of optical modulators, laser beam deflection, adaptive optics and the like. The liquid crystal photoelectric device has the advantages of low driving voltage, large phase modulation amount, light weight, low power consumption and the like.
The liquid crystal material is a key core material of the liquid crystal photoelectric device, and the performance optimization of the liquid crystal photoelectric device is mainly realized by regulating and controlling the structure and components of the liquid crystal material. In recent years, fast response is an important development direction in which liquid crystal electro-optical devices have been pursued. In order to improve the response speed of the liquid crystal photoelectric device, on one hand, a liquid crystal compound with low viscosity can be adopted, and the viscosity of the liquid crystal compound has a direct relation with the response time of the liquid crystal device, namely, the lower the viscosity of the liquid crystal material is, the smaller the response time of the liquid crystal device is, and the faster the response speed is; on the other hand, the cell thickness of the liquid crystal device can be reduced, the lower the cell thickness of the liquid crystal device is, the faster the response speed is, and the use of the liquid crystal material with large optical anisotropy (delta n) can effectively reduce the cell thickness of the liquid crystal device in practical application. Therefore, the large delta n liquid crystal is a key material for realizing quick response of the liquid crystal photoelectric device.
The structure of the liquid crystal compound is generally constructed by taking a benzene ring, a cyclohexyl group, an aromatic heterocyclic ring and the like as rigid skeletons, and the conjugation length of liquid crystal molecules can be increased by introducing acetylene bonds, increasing the benzene ring, introducing a cyano group or an isothiocyanato group and the like, so that the delta n of the liquid crystal compound is further improved. At present, although there are many optical anisotropic liquid crystal materials, the Δ n is not large enough and the variety is not large enough, which limits the application of the materials in liquid crystal photoelectric devices. In particular, there are very few large Δ n aromatic heterocyclic liquid crystal compounds that can be used as liquid crystal electro-optical devices.
Disclosure of Invention
The invention aims to provide a benzoxazole liquid crystal compound with a large birefringence and containing an alkyne bond, and a preparation method with simple process steps and high yield for the compound.
In view of the above purpose, the structural formula of the benzoxazole liquid crystal compound containing an acetylene bond adopted by the invention is as follows:
Wherein R represents C5~C12And X represents H, CH3、NO2Any one of them.
The preparation method of the benzoxazole liquid crystal compound containing the acetylene bond comprises the following steps:
1. preparation of 4- (4- (1, 3-dioxolan-2-yl) phenyl) -2-methylbut-3-yn-2-ol
Adding p-bromobenzaldehyde, p-toluenesulfonic acid and ethylene glycol into trichloromethane, reacting for 6-8 h at 50-70 ℃, removing the solvent by reduced pressure evaporation, then adding 2-methyl-3-butine-2-ol, cuprous iodide, triphenylphosphine, tetrakis (triphenylphosphine) palladium and triethylamine under the protection of nitrogen, reacting for 8-10 h at 80-90 ℃, separating and purifying to obtain 4- (4- (1, 3-dioxolane-2-yl) phenyl) -2-methylbut-3-alkyne-2-ol, wherein the reaction equation is as follows:
2. preparation of 2- (4- ((4- (alkoxy) phenyl) ethynyl) phenyl) -1, 3-dioxolane
Adding 4- (4- (1, 3-dioxolane-2-yl) phenyl) -2-methylbut-3-alkyne-2-alcohol, 1-iodine-4- (alkoxy) benzene shown in formula I, ethylene glycol ethyl ether, sodium hydroxide and tetrakis (triphenylphosphine) palladium into toluene, reacting for 8-10 h at 60-80 ℃ under the protection of nitrogen, separating and purifying after the reaction is finished, and obtaining 2- (4- ((4- (alkoxy) phenyl) ethynyl) phenyl) -1, 3-dioxolane, wherein the reaction equation is as follows:
in the formula I, R represents C5~C12linear alkyl group of (1).
3. Preparation of 4- ((4- (alkoxy) phenyl) ethynyl) benzaldehyde
Adding 4- ((4- (alkoxy) phenyl) ethynyl) phenyl) -1, 3-dioxolane and formic acid into tetrahydrofuran, reacting for 5-6 h at 50-70 ℃, separating and purifying after the reaction is finished to obtain 4- ((4- (alkoxy) phenyl) ethynyl) benzaldehyde, wherein the reaction equation is as follows:
4. Preparation of 2- ((4- ((4- (alkoxy) phenyl) ethynyl) benzylidene) amino) phenol
Adding 4- ((4- (alkoxy) phenyl) ethynyl) benzaldehyde and aminophenol shown in a formula II into ethanol, stirring and refluxing for 4-6 h, distilling under reduced pressure to remove a solvent, and recrystallizing to obtain 2- ((4- ((4- (alkoxy) phenyl) ethynyl) benzylidene) amino) phenol, wherein the reaction equation is as follows:
In formula II, X represents H, CH3、NO2Any one of them.
5. Preparation of benzoxazole liquid crystal compounds containing acetylenic bond
Adding 2- ((4- ((4- (alkoxy) phenyl) ethynyl) benzylidene) amino) phenol and dichlorodicyanoquinone (DDQ) into trichloromethane, performing reflux reaction for 4-6 h, stopping the reaction, separating and purifying to obtain a target compound, namely a benzoxazole liquid crystal compound containing an acetylene bond, wherein the reaction equation is as follows:
in the step 1, the molar ratio of p-bromobenzaldehyde to p-toluenesulfonic acid and ethylene glycol is preferably 4: 0.9-1.2: 80-90, and the molar ratio of p-bromobenzaldehyde to 2-methyl-3-butyn-2-ol, cuprous iodide, triphenylphosphine and tetrakis (triphenylphosphine) palladium is preferably 1: 0.4-1: 0.01-0.03: 0.04-0.08: 0.007-0.01.
in the step 2, the molar ratio of 4- (4- (1, 3-dioxolan-2-yl) phenyl) -2-methylbut-3-yn-2-ol to 1-iodo-4- (alkoxy) benzene, ethylene glycol ethyl ether, sodium hydroxide and tetrakis (triphenylphosphine) palladium is preferably 1:1 to 1.2:10 to 15:5 to 8:0.02 to 0.05.
In the step 3, the molar ratio of the 2- (4- ((4- (hexyloxy) phenyl) ethynyl) phenyl) -1, 3-dioxolane to the formic acid is preferably 1: 180-185.
In the step 4, the molar ratio of 4- ((4- (alkoxy) phenyl) ethynyl) benzaldehyde to aminophenol is preferably 1: 1.1-1.5.
in the step 5, the molar ratio of 2- ((4- ((4- (alkoxy) phenyl) ethynyl) benzylidene) amino) phenol to dichlorodicyanobenzoquinone is preferably 1:1.1 to 1.5.
the invention has the following beneficial effects:
The liquid crystal compound is prepared by taking p-bromobenzaldehyde, 2-methyl-3-butine-2-alcohol, 1-iodine-4- (alkoxy) benzene and aminophenol as raw materials through reactions such as Sonogashira coupling, nucleophilic addition, ring closing and the like, has a heterocyclic liquid crystal mesomorphic phase type, has a large birefringence and a wide nematic phase interval, is simple in preparation steps and high in yield, and can be applied to liquid crystal photoelectric devices to improve the response speed of the liquid crystal photoelectric devices.
Drawings
FIG. 1 is a DSC curve (rise/fall rate of 5 ℃ C./min) of the liquid crystal compound obtained in example 1.
FIG. 2 is a photograph (200X) of a POM in which the temperature of the liquid crystal compound obtained in example 1 was raised to 179.2 ℃.
FIG. 3 is a photograph (200X) of a POM in which the temperature of the liquid crystal compound obtained in example 1 was lowered to 201.8 ℃.
Detailed Description
The invention will be further described in detail with reference to the following figures and examples, but the scope of the invention is not limited to these examples.
example 1
1. Preparation of 4- (4- (1, 3-dioxolan-2-yl) phenyl) -2-methylbut-3-yn-2-ol
10g (54mmol) of p-bromobenzaldehyde, 2.3g (13.4mmol) of p-toluenesulfonic acid and 75g (1203.6mmol) of ethylene glycol are added into a 250mL three-neck flask provided with a condenser and a stirrer, 100mL of chloroform dried by a molecular sieve is added into the flask, the reaction is stopped after stirring for 6h in a constant-temperature oil bath kettle at 60 ℃, the solvent is evaporated under reduced pressure, 2.01g (23.8mmol) of 2-methyl-3-butyn-2-ol, 0.2g (1.0mmol) of cuprous iodide and 0.6g (2.2mmol) of triphenylphosphine are added into the flask, 80mL of triethylamine is added into the flask as a reaction solvent, the flask is heated and aerated with nitrogen protection at 80 ℃, after 1h of reaction, 0.5g (0.43mmol) of tetrakis (triphenylphosphine) palladium is rapidly added under the nitrogen protection, and the reaction is stopped after 8h of reaction. After the reaction is finished, diluting the reaction system with water, extracting with dichloromethane, separating out an organic phase, repeatedly extracting an aqueous phase with dichloromethane, combining the organic phases, washing the obtained organic phase with a saturated ammonium chloride aqueous solution for three times, drying the organic phase with anhydrous magnesium sulfate, distilling the solvent under reduced pressure, adding 7g of silica gel to prepare a sample, and performing column chromatography (eluent is a mixed solution of petroleum ether and ethyl acetate in a volume ratio of 30: 1) to obtain a yellow oily liquid 4- (4- (1, 3-dioxolan-2-yl) phenyl) -2-methylbut-3-yn-2-ol, wherein the yield is 44%, and the reaction equation is as follows:
2. preparation of 2- (4- ((4- (hexyloxy) phenyl) ethynyl) phenyl) -1, 3-dioxolane
a250 mL three-neck flask provided with a stirrer and a condenser is sequentially added with 2.8g (12mmol) of 4- (4- (1, 3-dioxolan-2-yl) phenyl) -2-methylbut-3-yn-2-ol, 3.8 g (12.6mmol) of 1-iodo-4- (hexyloxy) benzene, 10.8g (120.5mmol) of ethylene glycol ethyl ether, 2.9g (72.2mmol) of sodium hydroxide and 80mL of toluene, heated in a constant temperature oil bath at 70 ℃ and protected by nitrogen, after reacting for 1h, 0.28g (0.24mmol) of tetrakis (triphenylphosphine) palladium is rapidly added under the protection of nitrogen, and the reaction is stopped after continuing to react for 8 h. After the reaction is finished, diluting the reaction system with water, extracting with dichloromethane, separating out an organic phase, repeatedly extracting an aqueous phase with dichloromethane, combining the organic phases, washing the obtained organic phase with a saturated ammonium chloride solution for three times, drying the organic phase with anhydrous magnesium sulfate, distilling the solvent under reduced pressure to remove the solvent, adding 7g of silica gel to prepare a sample, and performing column chromatography (eluent is a mixed solution of petroleum ether and ethyl acetate in a volume ratio of 30: 1) to obtain a light yellow solid 2- (4- ((4- (hexyloxy) phenyl) ethynyl) phenyl) -1, 3-dioxolane with the yield of 59%, wherein the reaction equation is as follows:
3. Preparation of 4- ((4- (hexyloxy) phenyl) ethynyl) benzaldehyde
2.5g (7.4mmol) of 2- (4- ((4- (hexyloxy) phenyl) ethynyl) phenyl) -1, 3-dioxolane, 62g (1339mmol) of formic acid, and 80mL of tetrahydrofuran were sequentially added to a 250mL single-neck flask equipped with a stirrer and a condenser, and the mixture was heated in a constant temperature oil bath at 60 ℃ for reaction for 6 hours. After the reaction is finished, extracting a reaction solution by using dichloromethane and water, carrying out rotary evaporation and concentration to obtain a white solid, adding absolute ethyl alcohol for recrystallization to obtain a white solid, namely 4- ((4- (hexyloxy) phenyl) ethynyl) benzaldehyde, wherein the yield is 83%, and the reaction equation is as follows:
4. Preparation of 2- ((4- ((4- (hexyloxy) phenyl) ethynyl) benzylidene) amino) -4-methylphenol
In a 100mL single-neck flask equipped with a stirrer and a condenser were charged 0.4g (1.4mmol) of 4- ((4- (hexyloxy) phenyl) ethynyl) benzaldehyde, 0.20g (1.6mmol) of 2-amino-4-methylphenol, and 40mL of absolute ethanol, and the mixture was refluxed at 80 ℃ for 6 hours until the reaction was complete. After cooling to room temperature, yellow needle crystals precipitated and were filtered off with a buchner funnel, a yellow solid, 2- ((4- ((4- (hexyloxy) phenyl) ethynyl) benzylidene) amino) -4-methylphenol, was obtained in 83% yield, according to the following reaction equation:
5. Preparation of 2- (4- ((4- (hexyloxy) phenyl) ethynyl) phenyl) -5-methylbenzoxazole liquid crystal
In a 100mL single-neck flask equipped with a stirrer and a condenser were charged 0.2g (0.50mmol) of 2- ((4- ((4- (hexyloxy) phenyl) ethynyl) benzylidene) amino) -4-methylphenol, 0.14g (0.62mmol) of DDQ, and 80mL of chloroform, which was heated to reflux using a constant temperature oil bath and reacted for 5h to completion. When the reaction liquid is cooled to room temperature, extracting the reaction liquid by using dichloromethane and water, combining organic phases, removing the solvent by rotation, adding 4g of silica gel for sample preparation, and performing column chromatography (eluent is a mixed liquid with petroleum ether and ethyl acetate in a volume ratio of 30: 1) to obtain a white solid 2- (4- ((4- (hexyloxy) phenyl) ethynyl) phenyl) -5-methylbenzoxazole liquid crystal compound, wherein the yield is 89%, and the reaction equation is as follows:
spectral data for the product are as follows:
IR(KBr)v(cm-1):2923,2852,2208,1598,1510,1469,1406,1242,1045,833,794.
1H-NMR(400MHz,CDCl3,TMS)δ(ppm)=8.23-8.16(m,2H),7.66-7.60(m 2H),7.57-7.52(m,1H),7.51-7.45(m,2H),7.45-7.40(d,3JH-H=8.45Hz,1H),7.19-7.12(dd,3JH-H=8.24Hz,4JH-H=1.59Hz 1H),6.93-6.83(m,2H),4.00-3.88(q,3JH-H=6.55Hz,2H),2.48(s,3H),1.89-1.72(m,2H),1.51-1.32(m,6H),1.01-0.88(t,3JH-H=6.68Hz,3H).
MS (MALDI-TOF) m/z: theoretical 409.53, found 409.22.
Example 2
in step 4 of this example, 2-amino-4-methylphenol in step 4 of example 1 was replaced with an equimolar amount of o-aminophenol, and the other steps were the same as in example 1 to obtain 2- (4- ((4- (hexyloxy) phenyl) ethynyl) phenyl) benzoxazole having the following structural formula in a yield of 89%.
Spectral data for the product are as follows:
IR(KBr)v(cm-1):2927,2852,2208,1598,1510,1458,1280,1240,1174,1049,838.1H-NMR(400MHz,CDCl3,TMS)δ(ppm)=7.99-7.93(m,1H),7.86-7.83(m 1H),7.64-7.60(m,1H),7.53-7.48(m,2H),7.43-7.35(m,3H),6.97-6.83(m,2H),4.07-3.91(q,3JH-H=6.57Hz,2H),1.86-1.72(m,2H),1.51-1.31(m,6H),0.99-0.84(t,3JH-H=6.88Hz,3H).
MS (MALDI-TOF) m/z: theoretical 395.5, found 395.21.
Example 3
in step 4 of this example, 2-amino-4-methylphenol in step 4 of example 1 was replaced with an equimolar amount of 2-amino-4-nitrophenol, and the other steps were the same as in example 1 to obtain 2- (4- ((4- (hexyloxy) phenyl) ethynyl) phenyl) -5-nitrobenzoxazole having the following structural formula in a yield of 67%.
Spectral data for the product are as follows:
IR(KBr)v(cm-1):2933,2862,2204,1596,1512,1344,1249,1016,823,738,6.
1H-NMR(400MHz,CDCl3,TMS)δ(ppm)=8.65-8.62(d,J4 H-H=2.44Hz,1H),8.35-8.29(dd,J3 H-H=8.9Hz,J4 H-H=2.26Hz,1H),8.25-8.20(m,2H),7.73-7.63(m,3H),7.50-7.44(m,2H),6.94-6.84(m,2H),4.07-3.94(q,3JH-H=6.83Hz,2H),1.86-1.73(m,2H),1.51-1.32(m,6H),0.99-0.84(t,3JH-H=6.88Hz,3H).
MS (MALDI-TOF) m/z: theoretical value 440.5, found 440.23.
The optical anisotropy and thermal properties of the liquid crystal compounds prepared in the above examples 1 to 3 were tested to obtain the birefringence, phase transition temperature and phase transition enthalpy. The birefringence was obtained as a theoretical value by Gaussian09 software; the experimental value can also be obtained through Abbe refractometer test; the phase transition temperature and enthalpy of phase change are determined by differential scanning calorimeter measurements. The results are shown in tables 1 and 2.
TABLE 1 Birefringence
TABLE 2 phase transition temperature and enthalpy of phase transition
Note: cr in the table represents a crystalline phase; n represents a nematic phase; i represents isotropy.
As can be seen from tables 1 and 2, the Liquid crystal compounds of the present invention (experimental value. DELTA.n.gtoreq.0.623) and the large birefringence Liquid crystal compounds in the literature (Liquid Crystals,2017, 44:14-15,2184-2191) are described(test value Δ n is 0.305), Δ n is significantly increased, further proving that the liquid crystal compound of the present invention has excellent optical anisotropy.
As can be seen from Table 2, the liquid crystal compounds of the present invention each have a wide nematic phase interval.
As can be seen from the DSC curve (temperature rise and fall rate of 5 ℃/min) in FIG. 1 and the POM photographs (200X) in FIGS. 2 and 3, the compound of the present invention has a nematic liquid crystal texture and a liquid crystal phase at both temperature rise and fall.
Claims (7)
1. An alkyne bond-containing benzoxazole liquid crystal compound, which is characterized in that the structural formula of the compound is as follows:
Wherein R represents C5~C12And X represents H, CH3、NO2any one of them.
2. A method for preparing a benzoxazole liquid crystal compound containing an acetylene bond according to claim 1, characterized in that it comprises the following steps:
(1) Preparation of 4- (4- (1, 3-dioxolan-2-yl) phenyl) -2-methylbut-3-yn-2-ol
Adding p-bromobenzaldehyde, p-toluenesulfonic acid and ethylene glycol into trichloromethane, reacting for 6-8 h at 50-70 ℃, removing the solvent by reduced pressure evaporation, then adding 2-methyl-3-butine-2-ol, cuprous iodide, triphenylphosphine, tetrakis (triphenylphosphine) palladium and triethylamine under the protection of nitrogen, reacting for 8-10 h at 80-90 ℃, separating and purifying to obtain 4- (4- (1, 3-dioxolane-2-yl) phenyl) -2-methylbut-3-alkyne-2-ol, wherein the reaction equation is as follows:
(2) Preparation of 2- (4- ((4- (alkoxy) phenyl) ethynyl) phenyl) -1, 3-dioxolane
Adding 4- (4- (1, 3-dioxolane-2-yl) phenyl) -2-methylbut-3-alkyne-2-alcohol, 1-iodine-4- (alkoxy) benzene shown in formula I, ethylene glycol ethyl ether, sodium hydroxide and tetrakis (triphenylphosphine) palladium into toluene, reacting for 8-10 h at 60-80 ℃ under the protection of nitrogen, separating and purifying after the reaction is finished, and obtaining 2- (4- ((4- (alkoxy) phenyl) ethynyl) phenyl) -1, 3-dioxolane, wherein the reaction equation is as follows:
in the formula I, R represents C5~C12The linear alkyl group of (1);
(3) preparation of 4- ((4- (alkoxy) phenyl) ethynyl) benzaldehyde
adding 2- (4- ((4- (alkoxy) phenyl) ethynyl) phenyl) -1, 3-dioxolane and formic acid into tetrahydrofuran, reacting for 5-6 h at 50-70 ℃, separating and purifying after the reaction is finished to obtain 4- ((4- (alkoxy) phenyl) ethynyl) benzaldehyde, wherein the reaction equation is as follows:
(4) Preparation of 2- ((4- ((4- (alkoxy) phenyl) ethynyl) benzylidene) amino) phenol
Adding 4- ((4- (alkoxy) phenyl) ethynyl) benzaldehyde and aminophenol shown in a formula II into ethanol, stirring and refluxing for 4-6 h, distilling under reduced pressure to remove a solvent, and recrystallizing to obtain 2- ((4- ((4- (alkoxy) phenyl) ethynyl) benzylidene) amino) phenol, wherein the reaction equation is as follows:
in formula II, X represents H, CH3、NO2Any one of them;
(5) Preparation of benzoxazole liquid crystal compounds containing acetylenic bond
Adding 2- ((4- ((4- (alkoxy) phenyl) ethynyl) benzylidene) amino) phenol and dichlorodicyanoquinone into chloroform, carrying out reflux reaction for 4-6 h, stopping the reaction, and separating and purifying to obtain the benzoxazole liquid crystal compound containing the acetylenic bond.
3. The method for preparing benzoxazole liquid crystal compound containing an alkyne bond according to claim 2, characterized in that: in the step (1), the molar ratio of the p-bromobenzaldehyde to the p-toluenesulfonic acid and the ethylene glycol is 4: 0.9-1.2: 80-90, and the molar ratio of the p-bromobenzaldehyde to the 2-methyl-3-butyn-2-ol, the cuprous iodide, the triphenylphosphine and the tetrakis (triphenylphosphine) palladium is 1: 0.4-1: 0.01-0.03: 0.04-0.08: 0.007-0.01.
4. the method for preparing benzoxazole liquid crystal compound containing an alkyne bond according to claim 2, characterized in that: in the step (2), the molar ratio of the 4- (4- (1, 3-dioxolan-2-yl) phenyl) -2-methylbut-3-yn-2-ol to the 1-iodo-4- (alkoxy) benzene, the ethylene glycol ethyl ether, the sodium hydroxide and the tetrakis (triphenylphosphine) palladium is 1: 1-1.2: 10-15: 5-8: 0.02-0.05.
5. The method for preparing benzoxazole liquid crystal compound containing an alkyne bond according to claim 2, characterized in that: in the step (3), the molar ratio of the 2- (4- ((4- (alkoxy) phenyl) ethynyl) phenyl) -1, 3-dioxolane to formic acid is 1: 180-185.
6. The method for preparing benzoxazole liquid crystal compound containing an alkyne bond according to claim 2, characterized in that: in the step (4), the molar ratio of the 4- ((4- (alkoxy) phenyl) ethynyl) benzaldehyde to aminophenol is 1: 1.1-1.5.
7. The method for preparing benzoxazole liquid crystal compound containing an alkyne bond according to claim 2, characterized in that: in the step (5), the molar ratio of the 2- ((4- ((4- (alkoxy) phenyl) ethynyl) benzylidene) amino) phenol to the dichlorodicyanobenzoquinone is 1: 1.1-1.5.
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