CN113897202A - Difluoromethyleneoxy liquid crystal compound and synthesis method thereof - Google Patents
Difluoromethyleneoxy liquid crystal compound and synthesis method thereof Download PDFInfo
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 40
- 150000001875 compounds Chemical class 0.000 title claims abstract description 28
- 125000005701 difluoromethyleneoxy group Chemical group FC(F)([*:1])O[*:2] 0.000 title claims abstract description 15
- 238000001308 synthesis method Methods 0.000 title abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 35
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 9
- YNHIGQDRGKUECZ-UHFFFAOYSA-N dichloropalladium;triphenylphosphanium Chemical compound Cl[Pd]Cl.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000010992 reflux Methods 0.000 claims abstract description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 28
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- -1 difluoromethylenedioxy Chemical group 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 19
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 18
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 238000001704 evaporation Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- IRHPJGPQWZEZRX-UHFFFAOYSA-N 4-bromo-2,6-difluorobenzoic acid Chemical compound OC(=O)C1=C(F)C=C(Br)C=C1F IRHPJGPQWZEZRX-UHFFFAOYSA-N 0.000 claims description 13
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 239000003480 eluent Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 10
- HFHFGHLXUCOHLN-UHFFFAOYSA-N 2-fluorophenol Chemical compound OC1=CC=CC=C1F HFHFGHLXUCOHLN-UHFFFAOYSA-N 0.000 claims description 9
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 9
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 8
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 8
- 229910052794 bromium Inorganic materials 0.000 claims description 8
- 238000004440 column chromatography Methods 0.000 claims description 8
- IKGLACJFEHSFNN-UHFFFAOYSA-N hydron;triethylazanium;trifluoride Chemical compound F.F.F.CCN(CC)CC IKGLACJFEHSFNN-UHFFFAOYSA-N 0.000 claims description 8
- 239000012044 organic layer Substances 0.000 claims description 8
- 239000003208 petroleum Substances 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000012295 chemical reaction liquid Substances 0.000 claims description 7
- ZJLMKPKYJBQJNH-UHFFFAOYSA-N propane-1,3-dithiol Chemical compound SCCCS ZJLMKPKYJBQJNH-UHFFFAOYSA-N 0.000 claims description 7
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 239000002585 base Substances 0.000 claims 1
- 238000002844 melting Methods 0.000 abstract description 9
- 230000008018 melting Effects 0.000 abstract description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 4
- 239000011737 fluorine Substances 0.000 abstract description 4
- 230000003287 optical effect Effects 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 18
- 239000000463 material Substances 0.000 description 10
- 238000005160 1H NMR spectroscopy Methods 0.000 description 9
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- SHRYZLBRADLPQN-UHFFFAOYSA-N 5-bromo-2-[difluoro-(3,4,5-trifluorophenoxy)methyl]-1,3-difluorobenzene Chemical compound FC1=C(F)C(F)=CC(OC(F)(F)C=2C(=CC(Br)=CC=2F)F)=C1 SHRYZLBRADLPQN-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- JNJQMYIUBAJAOL-UHFFFAOYSA-N 5-bromo-2-[(3,5-difluorophenoxy)-difluoromethyl]-1,3-difluorobenzene Chemical compound C1=C(F)C=C(C=C1OC(C1=C(C=C(Br)C=C1F)F)(F)F)F JNJQMYIUBAJAOL-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- BZXQRXJJJUZZAJ-UHFFFAOYSA-N (2,4,6-trimethylphenyl)boronic acid Chemical compound CC1=CC(C)=C(B(O)O)C(C)=C1 BZXQRXJJJUZZAJ-UHFFFAOYSA-N 0.000 description 3
- TYONHSPZXLFWKI-UHFFFAOYSA-N (2,4-dimethylphenyl)boronic acid Chemical compound CC1=CC=C(B(O)O)C(C)=C1 TYONHSPZXLFWKI-UHFFFAOYSA-N 0.000 description 3
- ZRTWIJKGTUGZJY-UHFFFAOYSA-N 3,4,5-trifluorophenol Chemical compound OC1=CC(F)=C(F)C(F)=C1 ZRTWIJKGTUGZJY-UHFFFAOYSA-N 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- HJSSBIMVTMYKPD-UHFFFAOYSA-N 3,5-difluorophenol Chemical compound OC1=CC(F)=CC(F)=C1 HJSSBIMVTMYKPD-UHFFFAOYSA-N 0.000 description 1
- RHMPLDJJXGPMEX-UHFFFAOYSA-N 4-fluorophenol Chemical compound OC1=CC=C(F)C=C1 RHMPLDJJXGPMEX-UHFFFAOYSA-N 0.000 description 1
- VLGSRJCUNKGJCE-UHFFFAOYSA-N boric acid 1,3,5-trimethylbenzene Chemical compound B(O)(O)O.CC1=CC(=CC(=C1)C)C VLGSRJCUNKGJCE-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005672 electromagnetic field Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
- C09K19/20—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a chain containing carbon and oxygen atoms as chain links, e.g. esters or ethers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a difluoromethyleneoxy liquid crystal compound and a synthesis method thereof, wherein a fluorine-containing intermediate and phenylboronic acid are used as raw materials, bis (triphenylphosphine) palladium dichloride is used as a catalyst, and the compound is obtained by fully reacting in toluene at a reflux temperature and carrying out post-treatment. The difluoro methyleneoxy liquid crystal compound has higher optical anisotropy and dielectric anisotropy, higher clearing point, low melting point and low viscosity, can be used for preparing liquid crystal mixtures, and has wide application prospect.
Description
Technical Field
The invention relates to the field of liquid crystal materials, in particular to a difluorometheneoxy liquid crystal compound and a synthesis method thereof.
Background
Liquid crystals are a class of materials that is intermediate between the properties of a conventional liquid and the properties of a solid crystal, both in terms of flowability and continuity of the liquid, and in terms of ordered arrangement and anisotropy of the crystal. At present, the application of liquid crystal in the field of photoelectric display is rapidly developed, and the liquid crystal display technology has become the mainstream of the flat panel display industry, and basically replaces the cathode ray display. The liquid crystal material is one of key special photoelectric materials for liquid crystal display, and can endow various excellent performances of liquid crystal display devices. In addition, the liquid crystal material is also widely applied to the high and new technical fields of electronic sensors, aerospace and the like.
The existing liquid crystal material is required to have the performances of good chemical, physical and thermal stability, low viscosity, stability to electric field and electromagnetic field radiation, wider nematic phase temperature range, proper refractive index, proper dielectric anisotropy, faster response speed, higher voltage holding ratio and the like. Since the atomic radius of fluorine atoms is small and the introduction of fluorine atoms can affect the dipole moment of molecules, the liquid crystal material containing fluorine at the terminal has smaller dielectric anisotropy than that of the liquid crystal material substituted with other groups. In addition, fluorine atoms are introduced into the central bridge bond, so that the widening effect of molecules can be effectively reduced, the dielectric constant of the molecules can be increased, the melting point of the molecules can be reduced, and the liquid crystal molecular material with low melting point can be prepared. Chinese patents 201510065153.9 and 201310250122.1 both report some liquid crystal molecular structures containing fluorine at the terminal and at the central bridge bond, and show better performance. As the demand of high-end liquid crystal materials in the market is increasing, more novel fluorine-containing liquid crystal compounds are required to be developed.
Disclosure of Invention
The invention aims to solve the technical problem of providing a difluoromethyleneoxy liquid crystal compound and a synthetic method thereof.
The structure of the difluoromethylenedioxy liquid crystal compound is shown as the formula (I):
r in the formula (I)1Is CH3Or H; r2、R3And R4Is F or H, and at least one of them is F.
Further, the structural formula is one selected from the following formulas (I-1) to (I-6):
in the formulae (I-1) to (I-6), R1Is CH3Or H; r2、R3And R4Is F or H, and at least one of them is F.
The difluoro methyleneoxy liquid crystal compound is prepared according to the following method: in the presence of alkali in nitrogen atmosphere, under the catalysis of bis (triphenylphosphine) palladium dichloride, an intermediate shown in a formula (II) and phenylboronic acid shown in a formula (III) fully react in toluene at a reflux temperature, and a difluoromethylenedioxy liquid crystal compound shown in a formula (I) is obtained through aftertreatment:
in the formula (II), R2、R3And R4Is F or H, and at least one of them is F; in the formula (III), R1Is CH3Or H.
In the above reaction, the alkali can be sodium carbonate, sodium acetate, sodium bicarbonate, cesium carbonate, potassium carbonate and the like, preferably potassium carbonate; the amount ratio of the intermediate (II) to phenylboronic acid (III) to bis (triphenylphosphine) palladium dichloride to potassium carbonate is 1: 1.5-2.5: 0.01-0.05: 1.5-3.5; the dosage of the solvent toluene is 5-20 times of the mass of the intermediate (II); the reaction time is recommended to be 4-16 hours.
The post-treatment can adopt the following steps: and (3) after the reaction is finished, adding water into the reaction liquid, stirring, extracting by using dichloromethane, separating an organic layer, evaporating the solvent under reduced pressure, performing column chromatography separation, collecting eluent containing the target compound by using petroleum ether as an eluent, and evaporating the solvent to obtain the difluoromethylenedioxy liquid crystal compound shown in the formula (I).
The intermediate (II) of the present invention can be prepared as follows: adding 4-bromo-2, 6-difluorobenzoic acid and 1, 3-propanedithiol into a mixed solvent of toluene and n-heptane under the atmosphere of nitrogen, heating to 40-60 ℃, dropwise adding trifluoromethanesulfonic acid, heating for azeotropic entrainment of water after dropwise addition is finished to remove water generated in the reaction, cooling the reaction system to room temperature after finishing the addition, dropwise adding methyl tert-butyl ether, continuously cooling to-5 ℃ after dropwise addition is finished, stirring for 0.5-1 hour, and separating out solids precipitated in the reaction system. Dissolving the precipitated solid in dichloromethane, cooling to-80 to-60 ℃ in a nitrogen atmosphere, dropwise adding a mixture of triethylamine and the fluorophenol shown in the formula (IV), reacting for 1-3 hours after dropwise adding, then dropwise adding triethylamine trihydrofluoride and bromine, reacting for 0.5-1.5 hours, heating to room temperature, and performing aftertreatment to obtain an intermediate shown in the formula (II);
in the formula (IV), R2、R3And R4Is F or H, and at least one of them is F.
In the reaction for preparing the intermediate (II), the amount ratio of the 4-bromo-2, 6-difluorobenzoic acid to 1, 3-propanedithiol to trifluoromethanesulfonic acid to triethylamine to fluorophenol (IV) to triethylamine trihydrofluoride salt to bromine is 1: 1-1.5: 0.8-1.3: 1-1.5: 4-6; the using amounts of the toluene solvent and the n-heptane solvent are respectively 4-6 times of the mass of the 4-bromo-2, 6-difluorobenzoic acid; the azeotropic water carrying time is 3-7 hours; the using amount of the methyl tert-butyl ether is 5-7 times of the mass of the 4-bromo-2, 6-difluorobenzoic acid; the using amount of the dichloromethane for dissolving and separating out the solid is 8-14 times of the mass of the 4-bromo-2, 6-difluorobenzoic acid.
The post-treatment can adopt the following steps: and (3) after the reaction is finished, adding a saturated sodium bicarbonate solution into the reaction liquid, adjusting the pH value to 7-8, then extracting with dichloromethane, separating an organic layer, evaporating the solvent under reduced pressure, performing column chromatography separation, and evaporating the solvent by using petroleum ether as an eluent to obtain the intermediate shown in the formula (II).
In summary, the general reaction formula of the method for synthesizing difluoromethyleneoxy liquid crystal compounds according to the present invention can be represented as follows:
the synthesis method of the difluoromethyleneoxy liquid crystal compound is specifically recommended to be carried out according to the following steps:
(1) adding 4-bromo-2, 6-difluorobenzoic acid and 1, 3-propanedithiol into a mixed solvent of toluene and n-heptane under the atmosphere of nitrogen, heating to 40-60 ℃, dropwise adding trifluoromethanesulfonic acid, heating for azeotropic water carrying for 3-7 hours after dropwise adding is finished to remove water generated in the reaction, cooling the reaction system to room temperature after finishing the addition, dropwise adding methyl tert-butyl ether, continuously cooling to-5 ℃ after dropwise adding is finished, stirring for 0.5-1 hour, and separating out solids precipitated in the reaction system. Dissolving the precipitated solid in dichloromethane, cooling to-80 to-60 ℃ under the nitrogen atmosphere, dropwise adding a mixture of triethylamine and the fluorophenol shown in the formula (IV), reacting for 1-3 hours after dropwise adding, then dropwise adding triethylamine trihydrofluoride and bromine, reacting for 0.5-1.5 hours, heating to room temperature, adding a saturated sodium bicarbonate solution into a reaction liquid, adjusting the pH value to 7-8, extracting with dichloromethane, separating an organic layer, evaporating the solvent under reduced pressure, performing column chromatography separation, and evaporating the solvent by using petroleum ether as an eluent to obtain the intermediate shown in the formula (II). The feeding amount ratio of the 4-bromo-2, 6-difluorobenzoic acid to 1, 3-propanedithiol to trifluoromethanesulfonic acid to triethylamine to fluorophenol (IV) to triethylamine trihydrofluoride salt to bromine is 1: 1-1.5: 0.8-1.3: 1-1.5: 4-6.
(2) Reacting the intermediate (II) obtained in the step (1) and phenylboronic acid shown in the formula (III) in toluene at a reflux temperature for 4-16 hours in the presence of potassium carbonate and under the catalysis of bis (triphenylphosphine) palladium dichloride in nitrogen atmosphere, adding water into reaction liquid and stirring after the reaction is finished, then extracting with dichloromethane, separating an organic layer, evaporating the solvent under reduced pressure, performing column chromatography separation, collecting eluent containing a target compound by using petroleum ether as an eluent, and evaporating the solvent to obtain the difluoromethylenedioxy liquid crystal compound shown in the formula (I). The amount ratio of the intermediate (II) to the phenylboronic acid (III) to the bis (triphenylphosphine) palladium dichloride to the potassium carbonate is 1: 1.5-2.5: 0.01-0.05: 1.5-3.5
The difluoro methyleneoxy liquid crystal compound has higher optical anisotropy and dielectric anisotropy, higher clearing point, low melting point and low viscosity, can be used for preparing liquid crystal mixtures, and has wide application prospect.
(IV) detailed description of the preferred embodiments
The present invention is further illustrated by the following specific embodiments, but the scope of the invention is not limited thereto.
The structural formulas of the fluorophenol (IV) used in the following examples are respectively shown as formulas (IV-1) - (IV-3); the structural formula of the used phenylboronic acid (III) is respectively shown as formulas (III-1) and (III-2):
the structural formula of the prepared intermediate (II) is respectively shown as the formulas (II-1) - (II-3):
the structural formulas of the difluoromethyleneoxy liquid crystal compounds prepared correspondingly are respectively shown as the formulas (I-1) - (I-6):
example 15 preparation of- ((2, 6-difluoro-4-bromophenyl) difluoromethoxy) -1,2, 3-trifluorobenzene (II-1)
Dissolving 4-bromo-2, 6-difluorobenzoic acid (10 mmol) and 1, 3-propanedithiol (13 mmol) in a mixed solution of 15ml of toluene and 15ml of n-heptane under a nitrogen atmosphere, subsequently heating to 50 ℃, dropwise adding trifluoromethanesulfonic acid (13 mmol), after dropwise adding, heating to azeotropically take water for 4 hours to remove water generated in the reaction, after finishing adding, cooling the reaction system to room temperature, dropwise adding 20ml of methyl tert-butyl ether, after dropwise adding, continuously cooling to 0 ℃, stirring for 0.5 hours, and separating out solids precipitated in the reaction system. Dissolving the precipitated solid in 20ml of dichloromethane, cooling to-70 ℃ under the nitrogen atmosphere, dropwise adding a mixture consisting of 3,4, 5-trifluorophenol (IV-1, 11 mmol) and triethylamine (12 mmol), reacting for 2 hours after dropwise adding, dropwise adding triethylamine trihydrofluoride (50 mmol) and bromine (50 mmol), reacting for 1 hour, heating to room temperature, adding a saturated sodium bicarbonate solution into the reaction liquid, adjusting the pH to 7-8, extracting with dichloromethane, separating an organic layer, distilling off the solvent under reduced pressure, performing column chromatography separation, and distilling off the solvent by using petroleum ether as an eluent to obtain 5- ((2, 6-difluoro-4-bromophenyl) difluoromethoxy) -1,2, 3-trifluorophenyl (II-1), wherein the yield of the white solid is 45%.
1H NMR (500 MHz, CDCl3) δ: 7.21 (d, J = 8.6 Hz, 2H), 6.98-6.92 (m, 2H);MS (EI), m/z: 388.0 [M+], 240.9 [M+,100%]。
Example preparation of 25- ((2, 6-difluoro-4-bromophenyl) difluoromethoxy) -1, 3-difluorobenzene (II-2)
The reaction procedure was as in example 1, except that 3,4, 5-trifluorophenol was changed to 3, 5-difluorophenol (IV-2), to give 5- ((2, 6-difluoro-4-bromophenyl) difluoromethoxy) -1, 3-difluorobenzene (II-2) as a white solid in a yield of 44%.
1H NMR (500 MHz, CDCl3) δ: 7.70 (d, J = 8.4 Hz, 2H), 6.84 (dd, J = 7.5 Hz, 2H), 6.84-6.70 (m, 1H); MS (EI), m/z: 370.0 [M+], 241.0 [100%]。
Example 34 preparation of- ((2, 6-difluoro-4-bromophenyl) difluoromethoxy) -fluorobenzene (II-3)
The reaction procedure was as in example 1, except that 3,4, 5-trifluorophenol was changed to 4-fluorophenol (IV-3), to give 4- ((2, 6-difluoro-4-bromophenyl) difluoromethoxy) -fluorobenzene (II-3) as a yellow liquid in a yield of 46%.
1H NMR (500 MHz, CDCl3) δ: 6.84-6.70 (m, 1H) 7.19 (d, J = 8.3 Hz, 2H), 7.06 (d, J = 8.3 Hz,1H), 7.02-7.00 (m, 1H), 6.98-6.95 (m, 1H); MS (EI), m/z: 351.9 [M+], 241.0 [100%]
Example 44 '- (difluoro (3,4, 5-Trifluorophenoxy) methyl) -3',5 '-difluoro-2, 4, 6-trimethyl-1, 1' -Biphenyl (I-1) preparation
Adding 5- ((2, 6-difluoro-4-bromophenyl) difluoromethoxy) -1,2, 3-trifluorobenzene (II-1, 1 mmol), 2,4, 6-trimethylbenzene boric acid (III-1, 2 mmol), bis (triphenylphosphine) palladium dichloride (0.03 mmol) and potassium carbonate (2.5 mmol) into 3ml of toluene solution, refluxing for 12 hours under nitrogen atmosphere, adding water into the reaction solution after the reaction is finished, stirring, extracting with dichloromethane, separating an organic layer, evaporating the solvent under reduced pressure, performing column chromatography separation, collecting eluent containing a target compound by taking petroleum ether as an eluent, evaporating the solvent to obtain 4' - (difluoro (3,4, 5-trifluorophenoxy) methyl) -3',5' -difluoro-2, 4, 6-trimethyl-1, 1' -Biphenyl (I-1), white solid, m.p. 55.3 ℃ yield 44%.
1H NMR (500 MHz, CDCl3) δ: 7.03-7.01 (m, 2H), 6.97 (s, 2H), 6.84 (d, J= 9.7 Hz, 2H), 2,35 (s, 3H), 2.04 (s, 6H); MS (EI), m/z: 428.4 [M+], 281.3 [100%]。
Example 54 preparation of (- (3, 5-Difluorophenoxy) difluoromethyl) -3',5' -difluoro-2, 4, 6-trimethyl-1, 1' -biphenyl (I-2)
The reaction procedure is as in example 4 except that 5- ((2, 6-difluoro-4-bromophenyl) difluoromethoxy) -1,2, 3-trifluorobenzene (II-1) was changed to 5- ((2, 6-difluoro-4-bromophenyl) difluoromethoxy) -1, 3-difluorobenzene (II-2) to give 4'- ((3, 5-difluorophenoxy) difluoromethyl) -3',5 '-difluoro-2, 4, 6-trimethyl-1, 1' -biphenyl (I-2) as a white solid with a melting point of 63.2 ℃ and a yield of 40%.
1H NMR (500 MHz, CDCl3) δ: 6.97 (s, 2H), 6.92 (d, J = 7.3 Hz, 2H), 6.84 (d, J = 10.0 Hz, 2H), 6.77-6.72 (m, 1H), 2.35 (s, 3H), 2.05 (s, 6H); MS (EI), m/z: 410.4 [M+], 281.3 [100%]。
EXAMPLE 64 '- (difluoro (4-fluorophenoxy) methyl) -3',5 '-difluoro-2, 4, 6-trimethyl-1, 1' -biphenyl (I-3) preparation
The reaction procedure is as in example 4 except that 5- ((2, 6-difluoro-4-bromophenyl) difluoromethoxy) -1,2, 3-trifluorobenzene (II-1) was changed to 4- ((2, 6-difluoro-4-bromophenyl) difluoromethoxy) -fluorobenzene (II-3) to give 4'- (difluoro (4-fluorophenoxy) methyl) -3',5 '-difluoro-2, 4, 6-trimethyl-1, 1' -biphenyl (I-3) as a white solid with a melting point of 75.3 ℃ in 42% yield.
1H NMR (500 MHz, CDCl3) δ: 7.37 (m, 1H), 7.17 (d, J = 8.3 Hz, 1H), 7.11 (m, 1H), 7.09 (m, 3H), 6.84 (d, J = 9.7 Hz, 2H), 2.37 (s, 3H), 2.06 (s, 6H); MS (EI), m/z: 392.4 [M+], 281.3 [100%]。
Example 74 '- (difluoro (3,4, 5-Trifluorophenoxy) methyl) -3',5 '-difluoro-2, 4-dimethyl-1, 1' -Biphenyl (I-4) preparation
The procedure was as in example 4, except that 2,4, 6-trimethylphenylboronic acid (III-1) was changed to 2, 4-dimethylphenylboronic acid (III-2), and 4'- (difluoro (3,4, 5-trifluorophenoxy) methyl) -3',5 '-difluoro-2, 4-dimethyl-1, 1' -biphenyl (I-4) was obtained as a white solid with a melting point of 48.9 ℃ and a yield of 82%.
1H NMR (500 MHz, CDCl3) δ: 7.14 (s, 1H), 7.10 (s, 2H), 7.03-6.96 (m, 4H), 2.39 (s, 3H), 2.28 (s, 3H); MS (EI), m/z: 414.3 [M+], 267.3 [100%]。
Example 84 preparation of ((3, 5-Difluorophenoxy) difluoromethyl) -3',5' -difluoro-2, 4-dimethyl-1, 1' -biphenyl (I-5)
The reaction procedure was as in example 4, except that 5- ((2, 6-difluoro-4-bromophenyl) difluoromethoxy) -1,2, 3-trifluorobenzene (II-1) was changed to 5- ((2, 6-difluoro-4-bromophenyl) difluoromethoxy) -1, 3-difluorobenzene (II-2), and 2,4, 6-trimethylphenylboronic acid (III-1) was changed to 2, 4-dimethylbenzeneboronic acid (III-2), to give 4'- ((3, 5-difluorophenoxy) difluoromethyl) -3',5 '-difluoro-2, 4-dimethyl-1, 1' -biphenyl (I-5) as a white solid, melting point 51.4 ℃ and yield 76%.
1H NMR (500 MHz, CDCl3) δ: 7.14 (s, 1H), 7.11 (s, 2H), 6.97 (d, J = 10.2 Hz, 2H), 6.91 (dd, J = 7.45 Hz, 2H), 6.76-6.72 (m, 1H), 2.39 (s,3H), 2.28 (s, 3H); MS (EI), m/z: 396.3 [M+], 267.3 [M+, 100%]。
EXAMPLE 94 '- (difluoro (4-fluorophenoxy) methyl) -3',5 '-difluoro-2, 4-dimethyl-1, 1' -biphenyl (I-6) preparation
The reaction procedure was as in example 4 except that 5- ((2, 6-difluoro-4-bromophenyl) difluoromethoxy) -1,2, 3-trifluorobenzene (II-1) was changed to 4- ((2, 6-difluoro-4-bromophenyl) difluoromethoxy) -fluorobenzene (II-3), and 2,4, 6-trimethylbenzeneboronic acid (III-1) was changed to 2, 4-dimethylbenzeneboronic acid (III-2), to give 4'- (difluoro (4-fluorophenoxy) methyl) -3',5 '-difluoro-2, 4-dimethyl-1, 1' -biphenyl (I-6) as a white solid with a melting point of 61.3 ℃ and a yield of 85%.
1H NMR (500 MHz, CDCl3) δ: 7.38-7.33 (m, 1H), 7.16-7.09 (m, 5H), 7.01-6.96 (m, 3H), 2.39 (s, 3H), 2.29 (s, 3H); MS (EI), m/z: 378.3 [M+,10%], 267.3 [100%]。
EXAMPLE 10 Properties of Difluoromethyleneoxy-based liquid Crystal Compound
A liquid crystal composition was composed as shown in Table 1, and the clearing point of the composition was 108 ℃; the optical anisotropy Δ n was 0.1033 (589 nm, 20 ℃); dielectric anisotropy Δ ε was 17.2 (1 Khz, 25 ℃ C.); viscosity gamma1And 80 mpa.s.
TABLE 1 weight percentages of the components in the liquid crystal composition to which the compound of the present invention is added
Claims (8)
1. The difluoromethyleneoxy liquid crystal compound has a structure shown in a formula (I):
r in the formula (I)1Is CH3Or H; r2、R3And R4Is F or H, and at least one of them is F.
2. The difluoromethyleneoxy liquid crystal compound according to claim 1, which has a structural formula selected from the group consisting of the following formulas (I-1) to (I-6):
in the formulae (I-1) to (I-6), R1Is CH3Or H; r2、R3And R4Is F or H, and at least one of them is F.
3. The method for synthesizing difluoromethyleneoxy liquid crystal compounds as claimed in claim 1 or 2, wherein the intermediate represented by the formula (II) and the phenylboronic acid represented by the formula (III) are sufficiently reacted in toluene at a reflux temperature in the presence of bis (triphenylphosphine) palladium dichloride in a nitrogen atmosphere and in the presence of a base, and the difluoromethyleneoxy liquid crystal compound represented by the formula (I) is obtained through post-treatment:
in the formula (II), R2、R3And R4Is F or H, and at least one of them is F; in the formula (III), R1Is CH3Or H.
4. The method of claim 3, wherein: the alkali is one of sodium carbonate, sodium acetate, sodium bicarbonate, cesium carbonate and potassium carbonate, preferably potassium carbonate; the amount ratio of the intermediate (II) to phenylboronic acid (III) to bis (triphenylphosphine) palladium dichloride to potassium carbonate is 1: 1.5-2.5: 0.01-0.05: 1.5-3.5; the dosage of the solvent toluene is 5-20 times of the mass of the intermediate (II); the reaction time is recommended to be 4-16 hours.
5. The method of claim 3, wherein: the post-treatment can adopt the following steps: and (3) after the reaction is finished, adding water into the reaction liquid, stirring, extracting by using dichloromethane, separating an organic layer, evaporating the solvent under reduced pressure, performing column chromatography separation, collecting eluent containing the target compound by using petroleum ether as an eluent, and evaporating the solvent to obtain the difluoromethylenedioxy liquid crystal compound shown in the formula (I).
6. The method of any of claims 3-5, wherein: the intermediate (II) can be prepared according to the following method: under the nitrogen atmosphere, adding 4-bromo-2, 6-difluorobenzoic acid and 1, 3-propanedithiol into a mixed solvent of toluene and n-heptane, heating to 40-60 ℃, dropwise adding trifluoromethanesulfonic acid, after dropwise adding, heating for azeotropic carrying of water to remove water generated in the reaction, after finishing, cooling the reaction system to room temperature, dropwise adding methyl tert-butyl ether, after dropwise adding, continuously cooling to-5 ℃, stirring for 0.5-1 hour, and separating out solids precipitated in the reaction system; dissolving the precipitated solid in dichloromethane, cooling to-80 to-60 ℃ in a nitrogen atmosphere, dropwise adding a mixture of triethylamine and the fluorophenol shown in the formula (IV), reacting for 1-3 hours after dropwise adding, then dropwise adding triethylamine trihydrofluoride and bromine, reacting for 0.5-1.5 hours, heating to room temperature, and performing aftertreatment to obtain an intermediate shown in the formula (II);
in the formula (IV), R2、R3And R4Is F or H, and at least one of them is F.
7. The method of claim 6, wherein: the feeding amount ratio of the 4-bromo-2, 6-difluorobenzoic acid to 1, 3-propanedithiol to trifluoromethanesulfonic acid to triethylamine to fluorophenol (IV) to triethylamine trihydrofluoride salt to bromine is 1: 1-1.5: 0.8-1.3: 1-1.5: 4-6; the using amounts of the toluene solvent and the n-heptane solvent are respectively 4-6 times of the mass of the 4-bromo-2, 6-difluorobenzoic acid; the azeotropic water carrying time is 3-7 hours; the using amount of the methyl tert-butyl ether is 5-7 times of the mass of the 4-bromo-2, 6-difluorobenzoic acid; the using amount of the dichloromethane for dissolving and separating out the solid is 8-14 times of the mass of the 4-bromo-2, 6-difluorobenzoic acid.
8. The method of claim 6, wherein: the post-treatment after the dropwise addition of triethylamine trihydrofluoride and bromine adopts the following steps: and (3) after the reaction is finished, adding a saturated sodium bicarbonate solution into the reaction liquid, adjusting the pH value to 7-8, then extracting with dichloromethane, separating an organic layer, evaporating the solvent under reduced pressure, performing column chromatography separation, and evaporating the solvent by using petroleum ether as an eluent to obtain the intermediate shown in the formula (II).
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