CN113234447A - Preparation method of biphenyl liquid crystal material - Google Patents
Preparation method of biphenyl liquid crystal material Download PDFInfo
- Publication number
- CN113234447A CN113234447A CN202110278256.9A CN202110278256A CN113234447A CN 113234447 A CN113234447 A CN 113234447A CN 202110278256 A CN202110278256 A CN 202110278256A CN 113234447 A CN113234447 A CN 113234447A
- Authority
- CN
- China
- Prior art keywords
- compound
- liquid crystal
- crystal material
- reaction
- stirring
- 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.)
- Withdrawn
Links
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 24
- 239000000463 material Substances 0.000 title claims abstract description 23
- 235000010290 biphenyl Nutrition 0.000 title claims abstract description 22
- 239000004305 biphenyl Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 63
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 150000001875 compounds Chemical class 0.000 claims abstract description 28
- 238000003756 stirring Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 18
- 229940125904 compound 1 Drugs 0.000 claims abstract description 16
- 239000003208 petroleum Substances 0.000 claims abstract description 16
- 238000001914 filtration Methods 0.000 claims abstract description 15
- 239000000706 filtrate Substances 0.000 claims abstract description 14
- 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 abstract description 14
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 14
- 229940125782 compound 2 Drugs 0.000 claims abstract description 12
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 9
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 9
- 239000012074 organic phase Substances 0.000 claims abstract description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 238000002425 crystallisation Methods 0.000 claims abstract description 6
- 230000008025 crystallization Effects 0.000 claims abstract description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 36
- 239000008213 purified water Substances 0.000 claims description 18
- 239000012044 organic layer Substances 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000010992 reflux Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 12
- 229940126214 compound 3 Drugs 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- HCUZNQLIMDDCHF-UHFFFAOYSA-N 2,6-difluoro-4-iodoaniline Chemical compound NC1=C(F)C=C(I)C=C1F HCUZNQLIMDDCHF-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000010410 layer Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 6
- ZWZVWGITAAIFPS-UHFFFAOYSA-N thiophosgene Chemical compound ClC(Cl)=S ZWZVWGITAAIFPS-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- 229940125898 compound 5 Drugs 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- ZNTJVJSUNSUMPP-UHFFFAOYSA-N 1-ethyl-4-ethynylbenzene Chemical group CCC1=CC=C(C#C)C=C1 ZNTJVJSUNSUMPP-UHFFFAOYSA-N 0.000 claims description 3
- -1 4-iodophenylboronic acid ester Chemical class 0.000 claims description 3
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 3
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 3
- FXORZKOZOQWVMQ-UHFFFAOYSA-L dichloropalladium;triphenylphosphane Chemical compound Cl[Pd]Cl.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 FXORZKOZOQWVMQ-UHFFFAOYSA-L 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- VDFVNEFVBPFDSB-UHFFFAOYSA-N 1,3-dioxane Chemical compound C1COCOC1 VDFVNEFVBPFDSB-UHFFFAOYSA-N 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 claims description 2
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 6
- BWGRDBSNKQABCB-UHFFFAOYSA-N 4,4-difluoro-N-[3-[3-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)-8-azabicyclo[3.2.1]octan-8-yl]-1-thiophen-2-ylpropyl]cyclohexane-1-carboxamide Chemical compound CC(C)C1=NN=C(C)N1C1CC2CCC(C1)N2CCC(NC(=O)C1CCC(F)(F)CC1)C1=CC=CS1 BWGRDBSNKQABCB-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- LFZAGIJXANFPFN-UHFFFAOYSA-N N-[3-[4-(3-methyl-5-propan-2-yl-1,2,4-triazol-4-yl)piperidin-1-yl]-1-thiophen-2-ylpropyl]acetamide Chemical compound C(C)(C)C1=NN=C(N1C1CCN(CC1)CCC(C=1SC=CC=1)NC(C)=O)C LFZAGIJXANFPFN-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- 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
- C09K19/14—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain
- C09K19/18—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain the chain containing carbon-to-carbon triple bonds, e.g. tolans
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C263/00—Preparation of derivatives of isocyanic acid
- C07C263/10—Preparation of derivatives of isocyanic acid by reaction of amines with carbonyl halides, e.g. with phosgene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C263/00—Preparation of derivatives of isocyanic acid
- C07C263/16—Preparation of derivatives of isocyanic acid by reactions not involving the formation of isocyanate groups
-
- 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
- C09K19/14—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain
- C09K19/18—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain the chain containing carbon-to-carbon triple bonds, e.g. tolans
- C09K2019/183—Ph-Ph-C≡C-Ph
Landscapes
- 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
本发明提供了一种联苯基液晶材料的制备方法，该方法工艺简单，产率高；所述的联苯基液晶材料结构式为：通过化合物1与化合物2合成；所述的化合物1结构式为：
所述的化合物2结构式为：
合成过程如下：在反应容器中投入化合物1，化合物2，以及4‑二氧六环，粉末状碳酸钾，四(三苯基膦)钯升温回流反应一段时间，反应完毕降温至10‑20℃，加入乙酸乙酯，过滤除去盐，滤液浓缩至干；加入乙酸乙酯和水，搅拌一段时间后静置分层，水层再用乙酸乙酯萃取，合并有机相浓缩至干，加石油醚升温回流一段时间，降温至0‑5℃，搅拌结晶，过滤干燥得到化合物。The invention provides a preparation method of biphenyl liquid crystal material, which has simple process and high yield; the structural formula of the biphenyl liquid crystal material is: 
Synthesized by compound 1 and compound 2; the structural formula of compound 1 is: Described compound 2 structural formula is: The synthesis process is as follows: in the reaction vessel, drop into compound 1, compound 2, and 4-dioxane, powdered potassium carbonate, and tetrakis (triphenylphosphine) palladium is heated and refluxed for a period of time, and the reaction is completed and cooled to 10-20 ℃ , ethyl acetate was added, the salt was removed by filtration, and the filtrate was concentrated to dryness; ethyl acetate and water were added, and after stirring for a period of time, the layers were left to stand, the aqueous layer was extracted with ethyl acetate, the combined organic phases were concentrated to dryness, and petroleum ether was added. The temperature is heated and refluxed for a period of time, cooled to 0-5° C., stirred for crystallization, filtered and dried to obtain the compound.
Description
Technical Field
The invention belongs to the technical field of liquid crystal materials, and particularly relates to a preparation method of a biphenyl liquid crystal material.
Background
The existing preparation method of the liquid crystal compound has a complex process, so that the yield of a reaction product is low, and the industrial production cannot be met; the method has simple process and high yield of the target compound.
Disclosure of Invention
The invention provides a brand new method for synthesizing biphenyl liquid crystal material, which comprises the following steps:
a preparation method of biphenyl liquid crystal material is disclosed, wherein the biphenyl liquid crystal material is a compound 3, and the structural formula of the biphenyl liquid crystal material is as follows:
the compound 3 is synthesized by a compound 1 and a compound 2;
the structural formula of the compound 1 is as follows:
the structural formula of the compound 2 is as follows:
the synthesis process is as follows: adding a compound 1, a compound 2, 4-dioxane, powdered potassium carbonate and tetrakis (triphenylphosphine) palladium into a reaction vessel, heating and refluxing for reaction for a period of time, cooling to 10-20 ℃ after the reaction is finished, adding ethyl acetate, filtering to remove salts, and concentrating the filtrate to be dry;
adding ethyl acetate and water, stirring for a period of time, standing for layering, extracting the water layer with ethyl acetate, mixing the organic phases, concentrating to dryness, adding petroleum ether, heating and refluxing for a period of time, cooling to 0-5 ℃, stirring for crystallization, filtering, and drying to obtain the compound.
Preferably, the preparation method of the biphenyl liquid crystal material comprises the following steps:
introducing nitrogen into a dry clean reaction vessel, adding 4-ethyl phenylacetylene, 4-iodophenylboronic acid ester and tetrahydrofuran, heating to 60 ℃ under the protection of nitrogen, adding triphenylphosphine palladium dichloride, cuprous iodide and triethylamine, and carrying out reflux reaction for a period of time;
after the reaction is finished, adding activated carbon for decoloring for a period of time, filtering the filtrate, concentrating the filtrate until the filtrate is dried to obtain a light yellow solid, adding petroleum ether, heating to 50-55 ℃, stirring for a period of time, cooling to 0-5 ℃, crystallizing, filtering and drying to obtain the off-white compound 1.
Preferably, the preparation method of the biphenyl liquid crystal material comprises the following steps:
adding 2, 6-difluoro-4-iodoaniline, dichloromethane, sodium bicarbonate and purified water into a reaction container, stirring and cooling to 10-15 ℃; dropwise adding a mixed solution of thiophosgene and dichloromethane for about 4-5h, and keeping the temperature at 10-20 ℃ for 4h to completely react after the dropwise adding;
adding purified water, stirring, standing for layering, washing the organic layer with purified water for several times, concentrating the organic layer until petroleum ether is added for dispersion and crystallization to obtain a compound 2.
On the basis of adopting the intermediate compound 1, the applicant provides another preparation method of biphenyl liquid crystal material, wherein the biphenyl liquid crystal material is a compound 3,
the compound 3 is synthesized by synthesizing a compound 4 from a compound 1 and a compound 5;
the structural formula of the compound 5 is as follows:
the structural formula of the compound 4 is as follows:
the synthesis process of the compound 3 comprises the following steps:
adding the compound 4, dichloromethane, sodium bicarbonate and purified water into a reaction vessel, and stirring and cooling to 10-15 ℃;
dropwise adding a mixed solution of thiophosgene and dichloromethane for about 4-5h, and then preserving heat at 10-20 ℃ until the reaction is complete;
adding purified water, stirring, standing for layering, washing an organic layer with purified water, concentrating the organic layer until the organic layer is dry, adding petroleum ether, dispersing and crystallizing to obtain a compound 3.
Preferably, in the preparation method of the biphenyl liquid crystal material, the synthesis process of the compound 4 comprises the following steps:
putting a compound 1, 2, 6-difluoro-4-iodoaniline, 1, 4-dioxane, powdered potassium carbonate and tetrakis (triphenylphosphine) palladium into a reaction vessel, heating for reflux reaction, cooling to 10-20 ℃ after the reaction is finished, adding ethyl acetate, filtering to remove salts, and concentrating the filtrate to be dry;
adding ethyl acetate and water, stirring, standing for layering, extracting water layer with ethyl acetate, mixing organic phases, concentrating to dryness, adding petroleum ether, heating for refluxing, and cooling to 0-5 deg.C; the crystals were stirred, filtered and dried to give compound 4.
Detailed Description
The present invention will be described in further detail with reference to examples, which are illustrative of the present invention and are not to be construed as being limited thereto.
Example 1:
synthesis of Compound 1
Introducing nitrogen into a dry and clean 5L four-neck flask, adding 135g of 4-ethyl phenylacetylene, 330g of 4-iodophenylboronic acid ester and 3500ml of tetrahydrofuran, heating to 60 ℃ under the protection of nitrogen, adding 0.3g of triphenylphosphine palladium dichloride, 0.3g of cuprous iodide and 200ml of triethylamine, and carrying out reflux reaction for 6 hours. After the reaction is finished, 15g of activated carbon is added for decolorization for 30min, the filtrate is filtered and concentrated to be dry to obtain a light yellow solid, 600ml of petroleum ether is added, the temperature is raised to 50-55 ℃, the mixture is stirred for 30min, the temperature is lowered to 0-5 ℃, crystallization is carried out for 6h, and the white-like compound 1285.7 g is obtained after filtration and drying, with the yield of 86%.
Synthesis of Compound 2
255g of 2, 6-difluoro-4-iodoaniline, 4000ml of dichloromethane, 400g of sodium bicarbonate and 1500ml of purified water are put into a 10L glass reaction bottle, and the temperature is reduced to 10-15 ℃ by stirring. And dropwise adding a mixed solution of 150g of thiophosgene and 500ml of dichloromethane, dropwise adding for about 4-5h, and keeping the temperature at 10-20 ℃ for 4h to completely react after dropwise adding. Adding 1500ml of purified water, stirring for 30 minutes, standing for layering, washing an organic layer with 1500ml of purified water once, concentrating the organic layer until the organic layer is dry, adding 400ml of petroleum ether, dispersing and crystallizing to obtain the compound 2247 g, wherein the yield is 83.2%.
Synthesis of Compound 3
1166 g of compound, 2150 g of compound, 3000ml of 1, 4-dioxane, 300g of powdered potassium carbonate and 0.1g of tetrakis (triphenylphosphine) palladium are put into a 5L four-neck flask, the mixture is heated and refluxed for 7 hours, the temperature is reduced to 10-20 ℃ after the reaction is finished, 500ml of ethyl acetate is added, the salt is removed by filtration, the filtrate is concentrated to be dry, 2500ml of ethyl acetate and 1500ml of water are added, the mixture is stirred for 30 minutes and kept stand for layering, the water layer is extracted by 1000ml of ethyl acetate, the combined organic phase is concentrated to be dry, 1000ml of petroleum ether is added, the temperature is increased and refluxed for 30 minutes, the temperature is reduced to 0-5 ℃, the mixture is stirred and crystallized for 2 hours, and the compound is filtered and dried to obtain 3153.6 g of compound, and the yield is 81.6%.
Example 2:
synthesis of compound 4 into a 5L four-neck flask are added 1166 g of compound, 130g of 2, 6-difluoro-4-iodoaniline, 3000ml of 1, 4-dioxane, 300g of powdered potassium carbonate and 0.1g of tetrakis (triphenylphosphine) palladium, the temperature is raised and the reflux reaction is carried out for 7h, after the reaction is finished, the temperature is reduced to 10-20 ℃, 500ml of ethyl acetate is added, the salt is removed by filtration, the filtrate is concentrated to be dry, 2500ml of ethyl acetate and 1500ml of water are added, the mixture is stirred for 30min and kept stand for layering, the water layer is extracted by 1000ml of ethyl acetate, the organic phases are combined and concentrated to be dry, 1000ml of petroleum ether is added, the temperature is raised and the reflux is carried out for 30min, the temperature is reduced to 0-5 ℃, the mixture is crystallized for 2h by stirring, and the compound is obtained by filtration and drying, 4121.6 g of compound, and the yield is 73.4%.
Synthesis of Compound 3
4120 g of the compound, 2000ml of dichloromethane, 180g of sodium bicarbonate and 700ml of purified water were put into a 5L glass reaction flask, and the temperature was lowered to 10-15 ℃ with stirring. And dropwise adding a mixed solution of 75g of thiophosgene and 300ml of dichloromethane, dropwise adding for about 4-5h, and keeping the temperature at 10-20 ℃ for 4h to completely react after dropwise adding. Adding 1500ml of purified water, stirring for 30 minutes, standing for layering, washing an organic layer with 1500ml of purified water once, concentrating the organic layer until the organic layer is dry, adding 400ml of petroleum ether, dispersing and crystallizing to obtain 399.3 g of a compound, wherein the yield is 73%.
In addition, it is to be noted that specific examples described in the present specification may differ in the names of compounds and the like. All equivalent or simple modifications made according to the principles described in the present patent concepts are included in the scope of protection of the present patent. Various modifications, additions and substitutions for the specific embodiments described may be made by those skilled in the art without departing from the scope of the invention as defined in the accompanying claims.
Claims (5)
1. A preparation method of biphenyl liquid crystal material is disclosed, wherein the biphenyl liquid crystal material is a compound 3, and the structural formula of the biphenyl liquid crystal material is as follows:
the method is characterized in that: the compound 3 is synthesized by a compound 1 and a compound 2;
the structural formula of the compound 1 is as follows:
the structural formula of the compound 2 is as follows:
the synthesis process is as follows: adding a compound 1, a compound 2, 4-dioxane, powdered potassium carbonate and tetrakis (triphenylphosphine) palladium into a reaction vessel, heating and refluxing for reaction for a period of time, cooling to 10-20 ℃ after the reaction is finished, adding ethyl acetate, filtering to remove salts, and concentrating the filtrate to be dry;
adding ethyl acetate and water, stirring for a period of time, standing for layering, extracting the water layer with ethyl acetate, mixing the organic phases, concentrating to dryness, adding petroleum ether, heating and refluxing for a period of time, cooling to 0-5 ℃, stirring for crystallization, filtering, and drying to obtain the compound.
2. The method of producing a biphenyl liquid crystal material according to claim 1, wherein:
the preparation method of the compound 1 comprises the following steps:
introducing nitrogen into a dry clean reaction vessel, adding 4-ethyl phenylacetylene, 4-iodophenylboronic acid ester and tetrahydrofuran, heating to 60 ℃ under the protection of nitrogen, adding triphenylphosphine palladium dichloride, cuprous iodide and triethylamine, and carrying out reflux reaction for a period of time;
after the reaction is finished, adding activated carbon for decoloring for a period of time, filtering the filtrate, concentrating the filtrate until the filtrate is dried to obtain a light yellow solid, adding petroleum ether, heating to 50-55 ℃, stirring for a period of time, cooling to 0-5 ℃, crystallizing, filtering and drying to obtain the off-white compound 1.
3. The method of producing a biphenyl liquid crystal material according to claim 1, wherein:
the preparation method of the compound 2 comprises the following steps:
adding 2, 6-difluoro-4-iodoaniline, dichloromethane, sodium bicarbonate and purified water into a reaction container, stirring and cooling to 10-15 ℃; dropwise adding a mixed solution of thiophosgene and dichloromethane for about 4-5h, and keeping the temperature at 10-20 ℃ for 4h to completely react after the dropwise adding;
adding purified water, stirring, standing for layering, washing the organic layer with purified water for several times, concentrating the organic layer until petroleum ether is added for dispersion and crystallization to obtain a compound 2.
4. A method for preparing biphenyl liquid crystal material, the biphenyl liquid crystal material is compound 3,
the method is characterized in that: the compound 3 is synthesized by synthesizing a compound 4 from a compound 1 and a compound 5;
the structural formula of the compound 5 is as follows:
the structural formula of the compound 4 is as follows:
the synthesis process of the compound 3 comprises the following steps:
adding the compound 4, dichloromethane, sodium bicarbonate and purified water into a reaction vessel, and stirring and cooling to 10-15 ℃;
dropwise adding a mixed solution of thiophosgene and dichloromethane for about 4-5h, and then preserving heat at 10-20 ℃ until the reaction is complete;
adding purified water, stirring, standing for layering, washing an organic layer with purified water, concentrating the organic layer until the organic layer is dry, adding petroleum ether, dispersing and crystallizing to obtain a compound 3.
5. The method of producing a biphenyl liquid crystal material according to claim 4, wherein:
the synthesis process of the compound 4 comprises the following steps:
putting a compound 1, 2, 6-difluoro-4-iodoaniline, 1, 4-dioxane, powdered potassium carbonate and tetrakis (triphenylphosphine) palladium into a reaction vessel, heating for reflux reaction, cooling to 10-20 ℃ after the reaction is finished, adding ethyl acetate, filtering to remove salts, and concentrating the filtrate to be dry;
adding ethyl acetate and water, stirring, standing for layering, extracting water layer with ethyl acetate, mixing organic phases, concentrating to dryness, adding petroleum ether, heating for refluxing, and cooling to 0-5 deg.C; the crystals were stirred, filtered and dried to give compound 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110278256.9A CN113234447A (en) | 2021-03-15 | 2021-03-15 | Preparation method of biphenyl liquid crystal material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110278256.9A CN113234447A (en) | 2021-03-15 | 2021-03-15 | Preparation method of biphenyl liquid crystal material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113234447A true CN113234447A (en) | 2021-08-10 |
Family
ID=77130308
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110278256.9A Withdrawn CN113234447A (en) | 2021-03-15 | 2021-03-15 | Preparation method of biphenyl liquid crystal material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113234447A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117004405A (en) * | 2022-04-27 | 2023-11-07 | 西安近代化学研究所 | Liquid crystal composition having a refractive index of wide Wen Gaoshuang, optical communication element, and high-frequency module |
-
2021
- 2021-03-15 CN CN202110278256.9A patent/CN113234447A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117004405A (en) * | 2022-04-27 | 2023-11-07 | 西安近代化学研究所 | Liquid crystal composition having a refractive index of wide Wen Gaoshuang, optical communication element, and high-frequency module |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6799037B2 (en) | Chemical method | |
| KR101488550B1 (en) | Process and intermediates for preparing integrase inhibitors | |
| JP2013047248A (en) | Process and intermediates for preparing integrase inhibitor | |
| WO2017096772A1 (en) | Method for preparing anti-heart-failure medicine lcz696 | |
| KR20190035680A (en) | Polymorphism of binalinostet and its production method | |
| CN113234447A (en) | Preparation method of biphenyl liquid crystal material | |
| CN102395591A (en) | Method for preparing prasugrel | |
| CN104016954B (en) | Preparation and purification method of nebivolol intermediate | |
| CN106146485B (en) | Method for preparing tedizolid and tedizolid crystal obtained by method | |
| CN104557752A (en) | Synthetic method of 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione compound | |
| CN111961083B (en) | Montelukast sodium intermediate compound | |
| CN109912651B (en) | Preparation method of benzyltriphenylphosphonium chloride | |
| CN104262202B (en) | The preparation technology of bambuterol intermediate | |
| CN111635368B (en) | A kind of preparation method of amine compound | |
| JP6516576B2 (en) | Process for the preparation of (3R, 4S) -1- (4-fluorophenyl)-[3 (S) -hydroxy-3- (4-fluorophenyl) propyl]-[4- (phenylmethoxy) phenyl] -2-azetidinone | |
| CN103910668B (en) | A kind of preparation method of 3 alkyl-indol | |
| CN118459425B (en) | A method for preparing pyrrolidine-1-amine-dihydrochloride | |
| CN114195737B (en) | 5-(Phenyl)-1,3,2,4-dioxathiazole 2-oxide and its preparation | |
| CN116514867A (en) | Monophosphine compound and preparation method thereof | |
| KR101525296B1 (en) | Lamivudine oxalate and preparation method thereof | |
| CN109970703A (en) | Preparation method and application of 1,3-heterocyclic substituted aromatic ketones | |
| CN107973714A (en) | A kind of preparation method of monomethyl ester salt | |
| CN119707933A (en) | Synthesis method of 1- (-) -3- [5- (-) -1H-tetrazol-1-yl ] -1H-pyrazole-5-carboxylic acid | |
| CN107522763B (en) | Preparation method of (2'R) -2' -deoxy-2 '-fluoro-2' -methyluridine | |
| CN118164846A (en) | A method for synthesizing dexketoprofen, intermediates thereof and uses thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20210810 |