CN116426295A - Preparation method of side fluorine-containing terphenyl liquid crystal monomer - Google Patents
Preparation method of side fluorine-containing terphenyl liquid crystal monomer Download PDFInfo
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- CN116426295A CN116426295A CN202211472086.9A CN202211472086A CN116426295A CN 116426295 A CN116426295 A CN 116426295A CN 202211472086 A CN202211472086 A CN 202211472086A CN 116426295 A CN116426295 A CN 116426295A
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- coupling reaction
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- triphenylphosphine
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 38
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 36
- 239000000178 monomer Substances 0.000 title claims abstract description 34
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 title claims abstract description 32
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000011737 fluorine Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000005859 coupling reaction Methods 0.000 claims abstract description 69
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 21
- QWXYZCJEXYQNEI-OSZHWHEXSA-N intermediate I Chemical compound COC(=O)[C@@]1(C=O)[C@H]2CC=[N+](C\C2=C\C)CCc2c1[nH]c1ccccc21 QWXYZCJEXYQNEI-OSZHWHEXSA-N 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 8
- AGYWDGVTLKNTBS-UHFFFAOYSA-N 4-bromo-1-chloro-2-fluorobenzene Chemical compound FC1=CC(Br)=CC=C1Cl AGYWDGVTLKNTBS-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000004996 alkyl benzenes Chemical class 0.000 claims abstract description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000004327 boric acid Substances 0.000 claims abstract description 6
- BMIBJCFFZPYJHF-UHFFFAOYSA-N 2-methoxy-5-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine Chemical compound COC1=NC=C(C)C=C1B1OC(C)(C)C(C)(C)O1 BMIBJCFFZPYJHF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 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 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 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 description 12
- ZBRJXVVKPBZPAN-UHFFFAOYSA-L nickel(2+);triphenylphosphane;dichloride Chemical group [Cl-].[Cl-].[Ni+2].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 ZBRJXVVKPBZPAN-UHFFFAOYSA-L 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- 239000012074 organic phase Substances 0.000 claims description 8
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 6
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000005191 phase separation Methods 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 4
- 239000012071 phase Substances 0.000 claims description 4
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- -1 alkyl phenylboronic acid Chemical compound 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- HXITXNWTGFUOAU-UHFFFAOYSA-N dihydroxy-phenylborane Natural products OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 238000009776 industrial production Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000000741 silica gel Substances 0.000 description 5
- 229910002027 silica gel Inorganic materials 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000002523 gelfiltration Methods 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 2
- HTGQCLJTWPSFNL-UHFFFAOYSA-N (2-methylphenoxy)boronic acid Chemical compound CC1=CC=CC=C1OB(O)O HTGQCLJTWPSFNL-UHFFFAOYSA-N 0.000 description 1
- URFPRAHGGBYNPW-UHFFFAOYSA-N 1-bromo-4-ethylbenzene Chemical compound CCC1=CC=C(Br)C=C1 URFPRAHGGBYNPW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006880 cross-coupling reaction Methods 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 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
- C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
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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
- C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
- C09K2019/121—Compounds containing phenylene-1,4-diyl (-Ph-)
- C09K2019/123—Ph-Ph-Ph
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
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- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
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- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method of a side fluorine-containing terphenyl liquid crystal monomer, which belongs to the technical field of liquid crystal materials, and comprises the steps of carrying out a first-step coupling reaction on alkylbenzene boric acid and 3-fluoro-4-chloro-bromobenzene, carrying out a second-step coupling reaction on an obtained intermediate I and bisboronic acid pinacol ester, and carrying out a third-step coupling reaction on an obtained intermediate II and bromoarene. The method is simple, the reaction condition is mild, the catalyst is low in price, the method is safe and environment-friendly, can be used for multiple times, and is suitable for industrial production.
Description
Technical Field
The invention relates to preparation of a liquid crystal material, in particular to a preparation method of a side fluorine-containing terphenyl liquid crystal monomer.
Background
The fluorine-containing terphenyl liquid crystal monomer generally has lower melting point, higher clearing point and lower viscosity, and can be well compatible with other liquid crystal monomers, so that the fluorine-containing terphenyl liquid crystal monomer is widely applied to STN type liquid crystal displays and TFT type liquid crystal displays.
The invention patent No. US4696549 discloses a preparation method of fluorine-containing terphenyl monomer liquid crystal, which has the advantages of multiple reaction steps, low yield and high price of catalyst PtO in the reaction process 2 The specific method comprises the following steps:
the invention patent with publication number of CN1966608 discloses a method for preparing biphenyl monomer liquid crystal by cross coupling reaction, which uses chloride for coupling reaction, and uses ligand tri-tert-butylphosphine, crown ether and the like as a catalyst, but the method still has the defects of low yield, expensive catalyst, high carcinogenicity of raw materials, incapability of recycling and the like, and is not suitable for industrial production, and the specific method is as follows:
disclosure of Invention
The invention provides a preparation method of a side fluorine-containing terphenyl liquid crystal monomer aiming at the problems.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the preparation method comprises the steps of firstly carrying out a first-step coupling reaction on alkylbenzene boric acid and 3-fluoro-4-chloro-bromobenzene, then carrying out a second-step coupling reaction on an obtained intermediate I and bisboronic acid pinacol ester, and then carrying out a third-step coupling reaction on an obtained intermediate II and bromoaromatic hydrocarbon, thus obtaining the side-position fluorine-containing terphenyl liquid crystal monomer, wherein the specific chemical reaction formula is as follows:
wherein R is 1 Alkyl, preferably methyl, ethyl, propyl, butyl or pentyl;
R 2 =h or F
R 3 =alkyl or F
R 4 =h or F.
Further, in the first coupling reaction, the catalyst is bis (triphenylphosphine) nickel dichloride, tetrakis (triphenylphosphine) palladium acetate, bis (tricyclohexyl) phosphine palladium dichloride or bis (triphenylphosphine) palladium dichloride, preferably bis (triphenylphosphine) nickel dichloride;
in the second coupling reaction, the catalyst is bis (triphenylphosphine) nickel dichloride, tetra (triphenylphosphine) palladium, palladium acetate, bis (tricyclohexyl) phosphine palladium dichloride or bis (triphenylphosphine) palladium dichloride, preferably bis (triphenylphosphine) palladium dichloride;
in the third coupling reaction, the catalyst is bis (triphenylphosphine) nickel dichloride, tetra (triphenylphosphine) palladium, palladium acetate, bis (tricyclohexyl) phosphine palladium dichloride or bis (triphenylphosphine) palladium dichloride, preferably tetra (triphenylphosphine) palladium.
Furthermore, in the second coupling reaction, auxiliary catalyst sodium bromide is also added; the mol ratio of the intermediate I to the sodium bromide is 1:0.08-0.12.
Further, in the first coupling reaction, the molar ratio of the alkylbenzene boric acid to the bis (triphenylphosphine) nickel dichloride is 1:0.00008-0.0005;
in the second coupling reaction, the molar ratio of the intermediate I to the bis (triphenylphosphine) palladium dichloride is 1:0.0001-0.0005;
in the third coupling reaction, the molar ratio of the intermediate II to the tetrakis (triphenylphosphine) palladium is 1:0.00008-0.0002.
Furthermore, all three-step coupling reactions are required to be carried out under alkaline conditions.
Furthermore, in the first coupling reaction, an inorganic strong base, preferably sodium hydroxide or potassium hydroxide, needs to be added;
in the second coupling reaction, strong alkali weak acid salt, preferably sodium acetate, needs to be added;
in the third coupling reaction, a strong base weak acid salt, preferably sodium carbonate, is added.
Further, in the first coupling reaction, the molar ratio of the alkylbenzene boric acid to the 3-fluoro-4-chloro-bromobenzene is 1:1.0-1.2;
in the second coupling reaction, the molar ratio of the intermediate I to the pinacol diboronate is 1:1.3-1.5;
in the third coupling reaction, the mol ratio of the intermediate II to the bromoarene is 1.0-1.2:1.
Furthermore, the solvents of the first coupling reaction and the third coupling reaction are solvent systems formed by toluene and water;
the solvent of the second coupling reaction is N, N-dimethylformamide (hereinafter referred to as DMF).
Further, the first coupling reaction and the third coupling reaction are both carried out under reflux conditions;
the temperature of the coupling reaction in the second step is 85-90 ℃.
Furthermore, the three-step coupling reaction is carried out under the protection of inactive gas;
after the coupling reaction in the first step is completed, the catalyst is recovered by adopting bonded silica gel filtration, phase separation is directly carried out, an organic phase is washed to be neutral by water, and then the intermediate I is obtained by concentration and column separation;
after the coupling reaction is completed in the second step, the catalyst is filtered and recovered by adopting bonded silica gel, then the organic solvent is added for extraction, phase separation is carried out, and the organic phase is washed to be neutral by water and then is concentrated and separated by a column, thus obtaining an intermediate II;
and thirdly, after the coupling reaction is finished, filtering and recovering the catalyst by adopting bonded silica gel, directly separating phases, washing an organic phase to be neutral by using water, and concentrating and separating by using a column to obtain the side fluorine-containing terphenyl liquid crystal monomer.
The preparation method of the side fluorine-containing terphenyl liquid crystal monomer has the beneficial effects that:
according to the invention, alkyl phenylboronic acid, 3-fluoro-4-chloro-bromobenzene, pinacol ester of biboronate and bromoarene are taken as raw materials, and a specific catalyst is utilized to prepare the side fluorine-containing terphenyl liquid crystal monomer through three steps of coupling reactions, so that the purity of the obtained side fluorine-containing terphenyl liquid crystal monomer product is high and can reach more than 99.12%, and the yield can reach more than 78.77%; the method is simple, the reaction condition is mild, the catalyst is low in price, the method is safe and environment-friendly, can be used for multiple times, and is suitable for industrial production.
Drawings
FIG. 1 is a nuclear magnetic resonance diagram of a side-position fluorine-containing terphenyl liquid crystal monomer YJ7 prepared in example 7 of the present invention;
FIG. 2 is a nuclear magnetic resonance diagram of a side-position fluorine-containing terphenyl liquid crystal monomer YJ8 prepared in example 8 of the present invention;
FIG. 3 is a nuclear magnetic resonance chart of a side-position fluorine-containing terphenyl liquid crystal monomer YJ9 prepared in example 9 of the present invention.
Detailed Description
The following description of the technical solution in the embodiments of the present invention is clear and complete. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways other than those described herein, and persons skilled in the art will readily appreciate that the present invention is not limited to the specific embodiments disclosed below.
Example 1 preparation method of side-position fluorine-containing terphenyl liquid Crystal monomer
The embodiment is a preparation method of a side fluorine-containing terphenyl liquid crystal monomer, and the specific preparation process comprises the following steps in sequence:
1) First step coupling reaction
29.91g (0.22 mol) of methylphenylboric acid, 46.08g (0.22 mol) of 3-fluoro-4-chloro-bromobenzene, 20g (0.5 mol) of sodium hydroxide, 180mL of distilled water, 150mL of toluene and 0.0144g (0.000022 mol) of catalyst bis (triphenylphosphine) nickel dichloride are added into a 500mL three-necked flask, nitrogen is introduced into the three-necked flask to replace air in the three-necked flask to fill the three-necked flask with nitrogen, the temperature is raised to reflux for carrying out the first-step coupling reaction, after the reaction is basically consumed, bonded silica gel is adopted for filtration and recovery of catalyst bis (triphenylphosphine) nickel dichloride, a small amount of water washing [ the catalyst bis (triphenylphosphine) nickel dichloride is used for the next first-step coupling reaction after water washing and drying ], the filtrate is combined for phase separation, the organic phase is washed to be neutral with water, a spin-dried solvent is separated through a column to obtain 47.04g of intermediate I, the yield 96.90%, the content of 99.89%, and the specific chemical reaction formula is as follows:
2) Second step coupling reaction
33.10 (0.15 mol) of intermediate I, 50.79g (0.2 mol) of bisboronic acid pinacol ester, 120mL of DMF, 28.71g (0.35 mol) of sodium acetate, 0.0105 (0.000015 mol) of catalyst bis (triphenylphosphine) palladium dichloride, 1.543g (0.015 mol) of auxiliary catalyst sodium bromide are added into a 500mL three-port bottle, nitrogen is introduced to replace air in the three-port bottle to fill the three-port bottle with nitrogen, the temperature is increased to 85 ℃ for carrying out a second coupling reaction, after the intermediate I is basically consumed, 300mL of water is added, a small amount of water is used for filtering and recovering catalyst bis (triphenylphosphine) palladium dichloride, a small amount of water washing [ catalyst bis (triphenylphosphine) palladium dichloride is used for the next second coupling reaction after water washing and drying ], 300mL of dichloromethane is added into the combined filtrate for extraction twice, the obtained dichloromethane phase is combined, water is washed to be neutral, a spin-dried solvent is separated by a column, 40.g of intermediate II, 86.42%, and the specific purity of the chemical formula is as follows:
3) Third step of coupling reaction
34.34g (0.11 mol) of intermediate II, 18.51g (0.1 mol) of p-ethyl bromobenzene, 150mL of toluene, 27.56g (0.26 mol) of sodium carbonate, 130mL of distilled water and 0.0127g (0.000011 mol) of catalyst tetra (triphenylphosphine) palladium are added into a 500mL three-port bottle, nitrogen is introduced into the three-port bottle to replace air in the three-port bottle to be filled with nitrogen, the temperature is increased to reflux for carrying out a third-step coupling reaction, after the p-ethyl bromophenyl is consumed, the catalyst tetra (triphenylphosphine) palladium is recovered by adopting bonded silica gel filtration, a small amount of water is used for the next third-step coupling reaction after the catalyst tetra (triphenylphosphine) palladium is washed and dried, the filtrate is combined for phase separation, the organic phase is washed to be neutral, and a spin-dried solvent is separated by a column to obtain 27.82g of side fluorine-containing terphenyl liquid crystal monomer which is marked as YJ1, and the yield 95.81%, and the specific chemical reaction formula is as follows:
the overall yield of the three-step coupling reaction was 80.23%.
Examples 2 to 9 preparation method of side-position fluorine-containing terphenyl liquid Crystal monomer
Examples 2 to 9 are a preparation method of a side fluorine-containing terphenyl liquid crystal monomer, and the steps are basically the same as example 1, except that the raw material consumption and the process parameters are different, and the specific details are shown in tables 1 to 2:
table 1 list of process parameters in examples 2 to 6
Table 2 list of process parameters in examples 7 to 9
Wherein, the steps and process parameters of the other parts of examples 2 to 9 are the same as those of example 1; the specific structural formulas of YJ1 to YJ9 are as follows:
YJ1：
YJ2：/>
YJ3：/>
YJ4/>
YJ5/>
YJ6/>
YJ7/>
YJ8/>
YJ9/>
to save time for examination, only three nuclear magnetic patterns of the compounds are randomly selected for introduction, and the method is specifically as follows:
the nuclear magnetic resonance hydrogen spectrum of YJ7 is shown in figure 1; the nuclear magnetic resonance hydrogen spectrum of YJ8 is shown in figure 2; the nuclear magnetic resonance hydrogen spectrum of YJ9 is shown in FIG. 3.
It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Claims (10)
1. The preparation method is characterized in that firstly, alkyl phenylboronic acid and 3-fluoro-4-chloro-bromobenzene are subjected to a first coupling reaction, then the obtained intermediate I and bisboronic acid pinacol ester are subjected to a second coupling reaction, and the obtained intermediate II and bromoarene are subjected to a third coupling reaction, so that the side fluorine-containing terphenyl liquid crystal monomer is obtained, wherein the specific chemical reaction formula is as follows:
wherein R is 1 An alkyl group;
R 2 =h or F
R 3 =alkyl or F
R 4 =h or F.
2. The method for preparing the side-position fluorine-containing terphenyl liquid crystal monomer according to claim 1, wherein in the first coupling reaction, the catalyst is bis (triphenylphosphine) nickel dichloride, tetrakis (triphenylphosphine) palladium acetate, bis (tricyclohexyl) phosphine palladium dichloride or bis (triphenylphosphine) palladium dichloride;
in the second coupling reaction, the catalyst is bis (triphenylphosphine) nickel dichloride, tetra (triphenylphosphine) palladium, palladium acetate, bis (tricyclohexyl) phosphine palladium dichloride or bis (triphenylphosphine) palladium dichloride;
in the third coupling reaction, the catalyst is bis (triphenylphosphine) nickel dichloride, tetrakis (triphenylphosphine) palladium, palladium acetate, bis (tricyclohexyl) phosphine palladium dichloride or bis (triphenylphosphine) palladium dichloride.
3. The preparation method of the side fluorine-containing terphenyl liquid crystal monomer according to claim 2, wherein in the second coupling reaction, sodium bromide as an auxiliary catalyst is also added; the mol ratio of the intermediate I to the sodium bromide is 1:0.08-0.12.
4. The method for preparing a side-position fluorine-containing terphenyl liquid crystal monomer according to claim 2 or 3, wherein,
in the first coupling reaction, the molar ratio of the alkylbenzene boric acid to the bis (triphenylphosphine) nickel dichloride is 1:0.00008-0.0005;
in the second coupling reaction, the molar ratio of the intermediate I to the bis (triphenylphosphine) palladium dichloride is 1:0.0001-0.0005;
in the third coupling reaction, the molar ratio of the intermediate II to the tetrakis (triphenylphosphine) palladium is 1:0.00008-0.0002.
5. The method for preparing a side-position fluorine-containing terphenyl liquid crystal monomer according to any one of claims 1-3, wherein the three-step coupling reaction is performed under alkaline conditions.
6. The method for preparing a side-position fluorine-containing terphenyl liquid crystal monomer according to claim 5, wherein in the first coupling reaction, inorganic strong base is required to be added;
in the second coupling reaction, strong alkali weak acid salt is needed to be added;
in the third coupling reaction, strong alkali weak acid salt needs to be added.
7. The method for preparing a side-position fluorine-containing terphenyl liquid crystal monomer according to claim 1, 2, 3 or 6, wherein,
in the first coupling reaction, the molar ratio of the alkylbenzene boric acid to the 3-fluoro-4-chloro-bromobenzene is 1:1.0-1.2;
in the second coupling reaction, the molar ratio of the intermediate I to the pinacol diboronate is 1:1.3-1.5;
in the third coupling reaction, the mol ratio of the intermediate II to the bromoarene is 1.0-1.2:1.
8. The method for preparing a side-position fluorine-containing terphenyl liquid crystal monomer according to claim 1, 2, 3 or 6, wherein,
the solvents of the first coupling reaction and the third coupling reaction are solvent systems formed by toluene and water;
the solvent of the second coupling reaction is N, N-dimethylformamide.
9. The method for preparing a side-position fluorine-containing terphenyl liquid crystal monomer according to claim 1, 2, 3 or 6, wherein,
the first step of coupling reaction and the third step of coupling reaction are carried out under the reflux condition;
the temperature of the coupling reaction in the second step is 85-90 ℃.
10. The method for preparing a side-position fluorine-containing terphenyl liquid crystal monomer according to claim 1, 2, 3 or 6, wherein the three-step coupling reaction is carried out under the protection of inactive gas;
after the coupling reaction in the first step is completed, phase separation is carried out, and an organic phase is concentrated and separated by a column to obtain an intermediate I;
after the coupling reaction is completed in the second step, adding water, adding an organic solvent for extraction, separating phases, and concentrating and separating an organic phase by a column to obtain an intermediate II;
and thirdly, after the coupling reaction is finished, directly separating phases, and concentrating and separating an organic phase by a column to obtain the side fluorine-containing terphenyl liquid crystal monomer.
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