CN1293084C - Process for synthesizing liquid crystal compound by catalytic cross-coupling of diphenyl-phosphino- palladium acetate - Google Patents
Process for synthesizing liquid crystal compound by catalytic cross-coupling of diphenyl-phosphino- palladium acetate Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000006880 cross-coupling reaction Methods 0.000 title claims abstract description 18
- 150000001875 compounds Chemical class 0.000 title claims abstract description 16
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 15
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 10
- 230000003197 catalytic effect Effects 0.000 title claims description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical class C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000003118 aryl group Chemical group 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000010290 biphenyl Nutrition 0.000 claims abstract description 7
- 239000004305 biphenyl Substances 0.000 claims abstract description 7
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000005191 phase separation Methods 0.000 claims abstract description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 24
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 10
- 229910052763 palladium Inorganic materials 0.000 claims description 8
- GJOGRUGECVQJBK-UHFFFAOYSA-N 2-diphenylphosphanylacetic acid Chemical compound C=1C=CC=CC=1P(CC(=O)O)C1=CC=CC=C1 GJOGRUGECVQJBK-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000012071 phase Substances 0.000 claims description 5
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 5
- 235000011009 potassium phosphates Nutrition 0.000 claims description 5
- 239000008346 aqueous phase Substances 0.000 claims description 4
- 238000004440 column chromatography Methods 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- -1 4-n-propyl-cyclohexyl Chemical group 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- 239000003446 ligand Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- XWUIMCCTFNHVCQ-UHFFFAOYSA-M sodium;2-diphenylphosphanylacetate Chemical compound [Na+].C=1C=CC=CC=1P(CC(=O)[O-])C1=CC=CC=C1 XWUIMCCTFNHVCQ-UHFFFAOYSA-M 0.000 claims description 2
- JPWKWIRNTXBCSQ-UHFFFAOYSA-N C(C)(=O)O.C1(=CC=CC=C1)PC1=CC=CC=C1 Chemical compound C(C)(=O)O.C1(=CC=CC=C1)PC1=CC=CC=C1 JPWKWIRNTXBCSQ-UHFFFAOYSA-N 0.000 claims 2
- 125000003545 alkoxy group Chemical group 0.000 claims 2
- 125000000217 alkyl group Chemical group 0.000 claims 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims 2
- 229910052739 hydrogen Inorganic materials 0.000 claims 2
- 239000001257 hydrogen Substances 0.000 claims 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- 150000004768 bromobenzenes Chemical group 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 239000003426 co-catalyst Substances 0.000 claims 1
- 125000000113 cyclohexyl group Chemical class [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims 1
- 229910052731 fluorine Inorganic materials 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
- OSCBARYHPZZEIS-UHFFFAOYSA-N phenoxyboronic acid Chemical group OB(O)OC1=CC=CC=C1 OSCBARYHPZZEIS-UHFFFAOYSA-N 0.000 claims 1
- 239000000376 reactant Substances 0.000 claims 1
- 239000007787 solid Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 239000012847 fine chemical Substances 0.000 abstract description 2
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical group C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 abstract 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 abstract 2
- 235000010338 boric acid Nutrition 0.000 abstract 1
- 229960002645 boric acid Drugs 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 239000000243 solution Substances 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- LBUNNMJLXWQQBY-UHFFFAOYSA-N 4-fluorophenylboronic acid Chemical compound OB(O)C1=CC=C(F)C=C1 LBUNNMJLXWQQBY-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000006384 oligomerization reaction Methods 0.000 description 2
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- FLKDFHOPNIOCOU-UHFFFAOYSA-N 1-fluoro-4-phenylcyclohexa-2,4-diene-1-carbaldehyde Chemical group FC1(CC=C(C=C1)C1=CC=CC=C1)C=O FLKDFHOPNIOCOU-UHFFFAOYSA-N 0.000 description 1
- AFMPMSCZPVNPEM-UHFFFAOYSA-N 2-bromobenzonitrile Chemical compound BrC1=CC=CC=C1C#N AFMPMSCZPVNPEM-UHFFFAOYSA-N 0.000 description 1
- WLPATYNQCGVFFH-UHFFFAOYSA-N 2-phenylbenzonitrile Chemical group N#CC1=CC=CC=C1C1=CC=CC=C1 WLPATYNQCGVFFH-UHFFFAOYSA-N 0.000 description 1
- ZRYZBQLXDKPBDU-UHFFFAOYSA-N 4-bromobenzaldehyde Chemical compound BrC1=CC=C(C=O)C=C1 ZRYZBQLXDKPBDU-UHFFFAOYSA-N 0.000 description 1
- 238000007341 Heck reaction Methods 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 238000003477 Sonogashira cross-coupling reaction Methods 0.000 description 1
- 238000006619 Stille reaction Methods 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- 238000006579 Tsuji-Trost allylation reaction Methods 0.000 description 1
- 150000001543 aryl boronic acids Chemical class 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- JRTIUDXYIUKIIE-UHFFFAOYSA-N cycloocta-1,5-diene;nickel Chemical group [Ni].C1CC=CCCC=C1.C1CC=CCCC=C1 JRTIUDXYIUKIIE-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical group Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910000033 sodium borohydride Chemical group 0.000 description 1
- 239000012279 sodium borohydride Chemical group 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention belongs to the technical field of fine chemical industry and provides a preparing method of a catalyst for catalyzing cross-coupling reaction, and a technique realizing catalytic reaction. The catalyst is a diphenylphosphine palladium acetate type coordination compound; the preparation method has the advantages of simplicity, convenience, high activity, good selectivity and stability in the air. The cross-coupling reaction is characterized in that at room temperature or little higher temperature than room temperature, at normal pressure, under the alkaline condition, in water/organic two phases, diphenylphosphine palladium acetate type coordination compound is used for catalyzing the cross-coupling reaction between aromatic bromo compounds and aromatic boracic acid for generating biphenyl type compounds, particularly biphenyl shape liquid crystal compounds used for TFT-LCD, and the yield is high; products and the catalyst can be separated through simple phase separation, and the catalyst can be circularly used. The present invention provides a green chemical method for synthesizing biphenyl shape liquid crystal compounds used for TFT-LCD.
Description
Technical Field
The invention belongs to the technical field of fine chemical engineering and material chemistry, and relates to a liquid crystal compound for synthesizing a TFT-LCD (thin film transistor-liquid crystal display), in particular to a greening technology for synthesizing the liquid crystal compound by using a coordination catalysis method.
Background
Many biarylenes have liquid crystalline properties and have been used in TFT-LCDs. The biaryl compound prepared by the classical organic synthesis method has long route, low total yield, poor selectivity and serious pollution. The coordination catalysis has the advantages of mild reaction conditions, good selectivity and the like, and provides an important means for greening organic synthesis. The coordination catalysis method is mostly adopted for the green chemical industry accepted by the world at present.
Coupling reactions catalyzed by the zero-valent palladium complex, such as Heck reaction, Suzuki reaction, Stille reaction, Sonogashira reaction, Tsuji-Trost reaction and the like,are effective methods for forming C-C bonds in organic synthesis. Among them, Pd (PPh) was discovered by Suzuki in 19813)4The method for preparing asymmetric diaryl or polyaromatic hydrocarbon by catalyzing the cross coupling of aromatic bromide and aromatic boric acid forms CSP2--CSP2One of the important methods for aromatic bonding.
Diphenylphosphinoacetic acid has been used as ligand in SHOP process for synthesizing linear α -olefin by oligomerization of ethylene, it, nickel chloride and sodium borohydride form a catalytic system to catalyze the oligomerization of ethylene in 1, 4-butanediol solution [ USP3,686,351 Shell Dev. Co., 1972.1.18], it and bis-1, 5 cyclooctadiene nickel form a catalytic system to catalyze the isomerization of α -olefin double bond [ Ger. Offen 2,120,977 Shell International research, 18, Nov 1971].
Branstein, p. et al report the synthesis of palladium diphenylphosphinoacetate. 2mmol of sodium diphenylphosphinoacetate were suspended in CH at room temperature2Cl2In (1 mmol of PdCl is added2(PhCN)2. Reaction ofThe reaction time is 4 hours,obtaining the earthy yellow cis-Pd (Ph)2PCH2COO)243% yield [ Braunstein, P., Matt, D., Nobel, D., J.Organomet. chem., 301(1986)]401-]。
Buchecker, r. catalyzed cross-coupling of 4-bromobenzaldehyde and 4-fluorobenzeneboronic acid to synthesize 4-fluoro, 4-formylbiphenyl liquid crystal compound with 5% palladium on carbon in alkaline condition and benzene/ethanol mixed solvent, yield 93.2% [ DE 4,307,243(Hoffmann La Roche, f., und co.a-G1993]. Herrmann, w. catalyzed cross-coupling of 2-bromobenzonitrile and phenylboronic acid in toluene solution in the presence of potassium carbonate to obtain 2-cyanobiphenyl, yield 93% [ EP 690,046, Hoechst ag, 1996].
Disclosure of Invention
The invention aims to provide a catalyst and a method for synthesizing a biphenyl type liquid crystal compound for TFT-LCD by catalytic cross-coupling reaction.
Technical scheme of the invention
1. Catalyst synthesis method
At room temperature, Ph2PCH2Adding Na dropwise into COONa solution4PdCl4In the solution, a yellow precipitate is obtained, see reaction formula (1).
2. Cross-coupling reaction
The reaction is carried out at room temperature in a two-phase aqueous/organic phase, see equation (2).
The invention has the advantages that:
1. the catalyst has simple preparation method, high activity, good selectivity and stability in air.
2. The cross-coupling reaction is catalyzed in two phases of room temperature or slightly higher reaction temperature, normal pressure, alkalinity and water/organic phase, the reaction condition is mild, and the selectivity is good.
3. The reaction products are in the organic phase and the catalyst is in the aqueous phase, which can be separated by simple phase separation, and the catalyst in the aqueous phase can be recycled. The reaction is carried out in two phases but the use of a phase transfer agent is not necessary.
Detailed Description
EXAMPLE 1 preparation of catalyst
A ground plug with a crescent piston is arranged on one side port of the 100ml three-mouth flask and is connected with ultra-pure nitrogen. The other side opening is provided with a constant pressure dropping funnel. The flask was fitted with a stirring magnet and then stoppered, and the flask was mounted on a magnetic stirrer. The whole set of the apparatus is evacuated and filled with nitrogen for three times, and the subsequent operation is carried out according to the method for treating sensitive substances in the air.
1mmol of N was added under stirring at room temperature4PdCl4Dissolved in 10ml of deoxygenated water; 2mmol Ph was added to a constant pressure dropping funnel2PCH2COONa dissolved in 5ml deoxygenated water. Ph is2PCH2Adding Na dropwise into COONa solution4PdCl4In the solution, a yellowish brown precipitate rapidly formed, and stirring was continued for 10 min. Filter pressing and vacuum drying to obtain the product with the yield of 93 percent.
EXAMPLE 2 Synthesis of biphenyl type Compound
A ground plug with a crescent piston is arranged on one side port of the 50ml two-port flask and is connected with ultra-pure nitrogen. The flask was fitted with a stirring magnet and then stoppered, and the flask was mounted on a magnetic stirrer. The whole set of the apparatus is evacuated and filled with nitrogen for three times, and the subsequent operation is carried out according to the method for treating sensitive substances in the air.
5ml of deoxygenated water and 5ml of tetrahydrofuran were placed in a two-neck flask. 1.0mmol of aromatic bromide, 1.5mmol of arylboronic acid, 3.0mmol of potassium phosphate and 0.02mmol of catalyst are added into a bottle in sequence and stirred for a certain time at room temperature. The reaction mixture is extracted with ether or ethyl acetate, the lower layer is water-soluble of the catalystThe liquid can be reused after being separated. Washing the upper layer of extract with saturated NaCl solution, and Mg2SO4Drying, filtering and evaporating the solvent. The obtained product is subjected to column chromatographyPurifying by a method, wherein a developing agent is n-hexane and ethyl acetate which are 7: 1, and obtaining the product. The results are shown in Table 1
TABLE 1cis-Pd (Ph)2PCH2COO)2Catalytic cross-coupling synthesis of biphenyl compound
Note: isolated yields are shown in the table.
Example 3
One side port of the 100ml two-port flask is provided with a ground plug with a crescent piston and is connected with ultra-pure nitrogen. The flask was fitted with a stirring magnet and then stoppered, and the flask was mounted on a magnetic stirrer. The whole set of the apparatus is evacuated and filled with nitrogen for three times, and the subsequent operation is carried out according to the method for treating sensitive substances in the air.
20ml of deoxygenated water and 20ml of tetrahydrofuran were added to a two-neck flask, 5.0mmol of aromatic bromide, 7.5mmol of aromatic boric acid, 15mmol of potassium phosphate and 0.05mmol of catalyst were sequentially added to the flask, and the mixture was stirred at room temperature for a certain period of time. The reaction mixture is extracted with ether or ethyl acetate, the lower layer is the aqueous solution of the catalyst, and the catalyst can be reused after being separated. The upper layer was washed with saturated NaCl solution, dried over Mg2SO4, filtered and the solvent was evaporated. Purifying the obtained product by column chromatography, wherein the developing agent is n-hexane and ethyl acetate which are 7: 1, and obtaining the product. The results are shown in Table 2
TABLE 2cis-Pd (Ph)2PCH2COO)2Liquid crystal compound for synthesizing TFT-LCD (thin film transistor-liquid crystal display) by catalytic cross-coupling
Note: isolated yields are shown in the table.
Example 4 catalyst reuse
One side port of the 100ml two-port flask is provided with a ground plug with a crescent piston and is connected with ultra-pure nitrogen. The flask was fitted with a stirring magnet and then stoppered, and the flask was mounted on a magnetic stirrer. The whole set of the apparatus is evacuated and filled with nitrogen for three times, and the subsequent operation is carried out according to the method for treating sensitive substances in the air.
50ml of deoxygenated water and 50ml of tetrahydrofuran were added to a two-necked flask, and 10.0mmol of 4-propyl- (4' -cyclohexyl) -bromobenzene, 15.0mmol of 4-fluorobenzeneboronic acid, 30mmol of potassium phosphate and 0.1mmol of catalyst were sequentially added to the flask, and the mixture was stirred at 70 ℃ for 4 hours without precipitation of palladium black. The reaction mixture is extracted with toluene or ether, the lower layer is the aqueous solution of the catalyst, and the catalyst can be reused after being separated. Washing the upper layer of extract with saturated NaCl solution, and Mg2SO4Drying, filtering and evaporating the solvent. The obtained product is purified by column chromatography, the developing agent is n-hexane and ethyl acetate which are 7: 1, and the separation yield is 84%.
The instrument was mounted and handled as described above. Adding the catalyst separated from the previous experiment into a two-neck flaskThe aqueous solution was supplemented with 50ml of tetrahydrofuran. 10.0mmol of 4-propyl- (4' -cyclohexyl) -bromobenzene, 15.0mmol of 4-fluorobenzeneboronic acid, 30mmol of potassium phosphate and 0.1mmol of catalyst were added in succession to a bottle and stirred at 70 ℃ for 4 h. The reaction mixture is extracted with toluene or diethyl ether and the lower catalyst aqueous solution is separated. Washing the upper layer of extract with saturated NaCl solution, and Mg2SO4Drying, filtering and evaporating the solvent. The obtained product was purified by column chromatography with a developing solvent of n-hexane and ethyl acetate of 7: 1, isolated in 93% yield.
Claims (2)
1. The method for synthesizing the liquid crystal compound by the palladium diphenylphosphinoacetate catalytic cross-coupling is characterized by comprising the following steps: the palladium diphenylphosphinoacetate type complex catalyzes the cross-coupling reaction between the aromatic bromide and the aromatic boric acid to generate a liquid crystal compound for the biphenyl TFT-LCD; the cross coupling reaction is carried out in water/organic two phases under the conditions of room temperature, normal pressure and alkalinity; after the reaction, the product is extracted by ether or ethyl acetate or toluene, the product is on the upper layer, the catalyst is on the lower layer, and the separation can be realized by phase separation;evaporating the solvent in the upper layer material to obtain a product, and performing column chromatography to obtain a pure product; the lower catalyst aqueous solution can catalyze the reaction again;
(1) the aromatic bromide is the derivative of bromobenzene substituted by R group at ortho-position and para-position, and R is hydrogen, straight-chain alkyl, alkoxy, carbonyl, fluorine or cyclohexane derivative of 1-12 carbon atoms;
(2) the aromatic boric acid is a derivative of phenyl boric acid substituted by R group; r is hydrogen, straight-chain alkyl of ortho-or para-1-12 carbon, alkoxy, carbonyl, 4-n-propyl-cyclohexyl, 4-fluoro, 3, 4-difluoro, 3, 4, 5-trifluoro;
(3) the biphenyl type liquid crystal compound for TFT-LCD is generated by the reactant through cross coupling reaction.
2. The method for synthesizing a liquid crystal compound by palladium diphenylphosphinoacetate catalytic cross-coupling according to claim 1, which is characterized in that: the main catalyst is a palladium diphenylphosphine acetate type complex,
(1) the ligand of the palladium diphenylphosphine acetate type catalyst is as follows: ph2P(CH2)nCO2H，n＝1-3；
(2) The complex is prepared from 1 mol of NaPdCl4Reaction with 2 moles of a sodium diphenylphosphinoacetate type ligand at room temperature in an aqueous phase to obtain a yellow solid with cis-Pd (Ph)2PCH2COO)2Structure;
(3) the catalyst is used under alkaline conditions, the base being potassium phosphate or potassium carbonate, which is a co-catalyst.
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| CN1966608B (en) * | 2006-11-20 | 2010-09-01 | 烟台万润精细化工股份有限公司 | Method for preparing biphenyl-like monomer liquid crystal using cross-coupling reaction |
| TW200911821A (en) * | 2007-06-08 | 2009-03-16 | Solvay | Light emitting material |
| CN101328108B (en) * | 2008-08-04 | 2012-01-11 | 上海万溯化学有限公司 | Preparation of 1-(3',5'- difluoro) phenyl-4-(4''- -alkylphenyl)-2-fluorobenzene |
| CN102617657A (en) * | 2012-02-22 | 2012-08-01 | 徐州师范大学 | Method and reaction device for synthesizing 1-bromo-2,3,4,6-tetra-acetyl glucopyranose |
| CN104744208A (en) * | 2015-02-04 | 2015-07-01 | 宜春学院 | Biphenyl-type fluorine-containing liquid crystal monomer as well as catalyst and preparation method thereof |
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| US6392047B1 (en) * | 1999-07-13 | 2002-05-21 | Clariant Gmbh | Process for preparing biaryls in the presence of palladophosphacyclobutane catalysts |
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2004
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6392047B1 (en) * | 1999-07-13 | 2002-05-21 | Clariant Gmbh | Process for preparing biaryls in the presence of palladophosphacyclobutane catalysts |
| CN1263084A (en) * | 1999-12-29 | 2000-08-16 | 中国科学院上海有机化学研究所 | 1-trifluoromethyl-2-alkylvinylaniline derivative and its synthesis |
| US6583307B2 (en) * | 2001-03-07 | 2003-06-24 | University Of New Orleans Research And Technology Foundation, Inc. | Convenient and efficient Suzuki-Miyaura cross-coupling catalyzed by a palladium/diazabutadiene system |
| US6660821B2 (en) * | 2001-03-29 | 2003-12-09 | Kwangju Institute Of Science And Technology | Vinyl-phenyl pyridine monomers and polymers prepared thereform |
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