CN102399117A - Method for synthesis of 2'-fluoro terphenyl liquid crystal - Google Patents
Method for synthesis of 2'-fluoro terphenyl liquid crystal Download PDFInfo
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Abstract
The present invention discloses a method for synthesis of 2'-fluoro terphenyl liquid crystal. With the present invention, problems of more reaction steps, low yield, heavy environmental hazard, expensive catalysts, or hazard on the human body in the prior art are solved. The technical scheme of the present invention is that: a catalyst is added to an organic solvent of the raw material to carry out a suzuki coupling reaction to realize the synthesis of the 2'-fluoro terphenyl liquid crystal. According to the present invention, 4-bromo-3-fluoro iodobenzene, a phenyl boronic acid derivative and a base are adopted as raw materials, and are subjected to two suzuki coupling reactions in the solvent under the effect of the catalyst at the reaction temperature of 70-100 DEG C to obtain the 2'-fluoro terphenyl liquid crystal, wherein the times of the two suzuki coupling reactions are respectively 4-10 hours and 10-20 hours. The method of the present invention has advantages of simple process, mild conditions, low preparation cost, high yield, environmental protection, and strong practicability.
Description
Technical field
The invention belongs to chemical field, it is related to liquid crystal intermediates and the synthetic method of monomer liquid crystal in a kind of electronic material, the method that more particularly to a kind of utilization suzuki coupling reactions prepare the Terphenyls liquid crystal Han 2 '-fluorine.
Background technology
Fluorine-containing Terphenyls monomer liquid crystal typically all has low fusing point, high clearing point and relatively low viscosity, at the same it is good with other monomers liquid crystal compatibility, so having substantial amounts of application in STN type liquid crystal displays, TFT type liquid crystal displays.The method for preparing fluorine-containing Terphenyls monomer liquid crystal in the prior art, include the synthetic method of fluorine-containing Terphenyls monomer liquid crystal disclosed in Patent No. US4696549, it is 1987, Merck companies method, it has the disadvantage, and reactions steps are more, yield is low, need in course of reaction to use expensive catalyst Pt O2.Its course of reaction has following two lines：
And the synthetic method of fluorine-containing Terphenyls monomer liquid crystal disclosed in Patent No. CN1966608, it is to carry out coupling reaction with chloride, catalyst uses part tri-butyl phosphine and crown ether etc., it has the disadvantage low yield, expensive catalyst and has high carcinogenic, and can not reclaim, it is impossible to carry out industrialized production.
Preparing fluorine-containing Terphenyls monomer liquid crystal, cumbersome, cost is high, yield is low, environmental pollution seriously brings very big technical problem to the field because synthesizing.
The content of the invention
The technical problem to be solved in the invention is to provide a kind of method of preparation Terphenyls liquid crystal Han 2 '-fluorine of simple high-efficiency environment friendly, the problem of to synthesize low, serious to environmental hazard cumbersome, yield, the expensive catalyst that uses present in prior art or be hazardous to the human body, it can reduce production cost, the pollution to environment is reduced, industrial monomer liquid crystal of the synthesis containing terphenyl is disclosure satisfy that.
In order to solve the above technical problems, the technical solution adopted in the present invention is：
A kind of method for synthesizing 2 '-fluorine Terphenyls liquid crystal, it is that raw material add catalyst in organic solvent, carry out the method realization of suzuki coupling reactions, using the bromo- 3- fluorine iodobenzenes of 4-, two kinds of phenyl boric acids as raw material, in the organic solvent environment of alkalescence in the presence of catalyst, respectively through 4-10 hours and 2 suzuki coupling reactions of 10-20 hours under 70~100 DEG C of reaction temperature, 2 '-fluorine Terphenyls liquid crystal is obtained, this synthetic route is as follows：
Step 1: heating generation suzuki coupling reactions in the presence of the first catalyst with the bromo- 3- fluorine iodobenzenes of 4- and the first phenyl boric acid and alkali in the first organic solvent, generate (I)：
Step 2: the intermediate product (I) for step one being obtained in the second organic solvent heats generation suzuki coupling reactions with the second phenyl boric acid and alkali in the presence of the second catalyst, generate target product (II) 2 '-fluorine Terphenyls monomer liquid crystal：
In the chemical formula of above-mentioned two steps description
Represent cyclohexyl, phenyl, pyrimidine, pyridine, 2, the one of which of 6 dioxane, R1、R2Respectively C1~C8 alkyl or alkoxy, alkenyl, F, Cl one of which, X1、X2、X3、X4Respectively H, F, Cl one of which, m, n=0 or 1.
Selected catalyst is tetra-triphenylphosphine palladium in suzuki cross-coupling reactions, the catalyst such as Pd/C, PdCl2.Alkali is sodium carbonate, potassium carbonate, potassium hydroxide, potassium phosphate etc., preferably potassium carbonate, the mol ratio 2: 1 of potassium carbonate and raw material phenyl boric acid.
Preferred catalyst is mol ratio 100-300: 1 of raw material and catalyst in tetrakis triphenylphosphine palladium, reaction in step one；Reaction dissolvent is the mixture of the organic solvents such as toluene, tetrahydrofuran, ethanol and water, wherein it is preferred that the mixed solvent of toluene or/and ethanol and water, 70~100 DEG C of reaction temperature, react 4-10 hours, preferably 6 hours by preferably 70~80 DEG C.
The catalyst optimized in step 2 is 5% Pd/C, mol ratio 200-500: 1 of raw material and catalyst in reaction；Reaction dissolvent is the mixture of tetrahydrofuran, DMF, DMA one of which or two or more materials and water,, wherein it is preferred that the mixed solvent of tetrahydrofuran and water, 70~100 DEG C of reaction temperature, it is preferred that 70~80 DEG C, react 10~20 hours, preferably 15 hours.
By adopting the above-described technical solution, the technological progress acquired by the present invention is：
The synthetic method of the terphenyl Han 2 '-fluorine of the present invention only needs cross-coupling reaction twice, and reaction scheme is short, and catalyst is cheap, to human body non-hazardous, and can repeatedly utilize, and yield and purity are all very high.Present invention process environmental protection is simple, cost is low, product is easy to purification, practical.The catalyst of the present invention does not use catalyst Pt O2, PdCl2 and part tri-butyl phosphine and the crown ether of carcinogenicity of costliness, and reusable 5 times of 5%Pd/C not only, greatlys save cost, reduces pollution.
Embodiment
The present invention is described in further details with reference to specific embodiment：
A kind of synthetic method for containing 2 '-fluorine Terphenyls liquid crystal, using the bromo- 3- fluorine iodobenzenes of 4-, two kinds of phenyl boric acids as raw material, in alkali environment in the presence of catalyst, in organic solvent, respectively through 4-10 hours and 2 suzuki cross-coupling reactions of 10-20 hours under 70~100 DEG C of reaction temperature, 2 '-fluorine Terphenyls liquid crystal is obtained, this synthetic route is as follows：
Step 1: heating generation suzuki coupling reactions in the presence of the first catalyst with the bromo- 3- fluorine iodobenzenes of 4- and the first phenyl boric acid and alkali in the first organic solvent：
Step 2: the intermediate product and the second phenyl boric acid and alkali that step one are obtained in the second organic solvent heat generation suzuki coupling reactions in the presence of the second catalyst, generate target 2 '-fluorine Terphenyls monomer liquid crystal：
In the chemical formula of foregoing description
Represent cyclohexyl, phenyl, pyrimidine, pyridine, 2, the one of which of 6 dioxane, R1、R2Respectively C1~C8 alkyl or alkoxy, alkenyl, F, Cl one of which, X1、X2、X3、X4Respectively H, F, Cl one of which, m, n are respectively 0 or 1.
Above-mentioned catalyst is one or both of tetrakis triphenylphosphine palladium, 5%Pd/C, PdCl2.
Above-mentioned alkali is the one of which of sodium carbonate, potassium carbonate, potassium hydroxide, potassium phosphate.And preferred potassium carbonate, the mol ratio 2: 1 of potassium carbonate and phenyl boric acid.
The first organic solvent in above-mentioned steps one is toluene, ethanol, benzene, tetrahydrofuran, methanol, isopropanol, the tert-butyl alcohol, diethylene glycol dimethyl ether, N, N-dimethylformamide, N, the mixture of one or more of materials and water formation in N dimethyl acetamide, 1-METHYLPYRROLIDONE, the bromo- 3- fluorine iodobenzenes of 4- and the first organic solvent weight are than 1: 2~1: 10.And the first organic solvent is preferably the mixture of toluene or ethanol and water, the weight ratio of the bromo- 3- fluorine iodobenzenes of 4- and toluene or the mixture of ethanol and water is 1: 5；Now the first catalyst is preferably tetrakis triphenylphosphine palladium, and the bromo- 3- fluorine iodobenzenes of 4- and the first catalyst molfraction ratio are 100: 1~300: 1；The temperature of suzuki cross-coupling reactions is preferably 70~80 DEG C, 4~10 hours reaction time, and the reaction time is 6 hours.
The second organic solvent in above-mentioned steps two is the mixture of tetrahydrofuran, DMF, DMA one of which or two or more materials and water, and intermediate product and the second organic solvent weight ratio are 1: 5~1: 15.And the second organic solvent is preferably the mixed solvent of tetrahydrofuran and water, intermediate product and the second organic solvent weight ratio preferably 1: 10.Second catalyst is preferably 5% Pd/C, intermediate product and the second catalyst molfraction ratio preferably 200: 1~500: 1；The temperature of suzuki cross-coupling reactions is preferably 70~80 DEG C, is reacted 10~20 hours, the reaction time is preferably 15 hours.
Fusing point (mp), the clearing point (mp) of product obtained by the method for the present invention are measured by DSC822e differential scanning calorimeters (DSC)；Mass spectrometric data (GC-MS) is measured with Agilent7890A-5975C types gas mass spectrometry (GC-MS), and gas chromatographic purity (GC) is measured with Agilent6890 gas chromatographs.
Embodiment one
The present embodiment obtains the fluoro- 4- bromo biphenyls of intermediate 4 '-propyl group -3- with the bromo- 3- fluorine iodobenzenes of 4- and propylbenzene acid reaction and synthesizes 4- ethyls -2 '-fluoro- 4 with ethylo benzene acid reaction again "-propyl group (1; 1 '; 4 '; 1 ") exemplified by terphenyl, the synthetic method to the present invention is further illustrated.
Step 1: the synthesis of the fluoro- 4- bromo biphenyls of 4 '-propyl group -3-
The bromo- 3- fluorine iodobenzene 150.5g (0.5mol) of 4-, potassium carbonate 138g, propyl group phenyl boric acid 86.1g (0.525mol), tetrakis triphenylphosphine palladium 3g (0.0026mol) are separately added into there-necked flask, and adds toluene 300g, ethanol 210g, water 240g；Then stir and be heated to 70 DEG C, keep the temperature at 70-75 DEG C and react 6 hours.Treat that solution is down to room temperature, carry out a point liquid processing, organic phase is washed to neutrality, and steam net toluene, decompression collects the cut under 150 DEG C/20Mpa, obtains the fluoro- 4- bromo biphenyls 110g of 4 '-propyl group -3-, yield is 75%.
It is 99%, mp=37.5 DEG C of fusing point, GC-MS data analyses such as table 1 through analyzing gas chromatographic purity GC.These data illustrate that the compound structure is correct.
Table 1
"-propyl group (the synthesis of 1,1 ', 4 ', 1 ") terphenyl Step 2: 4- ethyls -2 '-fluoro- 4
By the fluoro- 4- bromo biphenyls of 87.9g (0.3mol) 4 '-propyl group -3-, 49.5g (0.33mol) to ethyl phenyl boric acid, 5%Pd/C 1.5g (0.0007mol), potassium carbonate 83g, tetrahydrofuran 700g, water 180g, it is added in there-necked flask, it is warming up to 70 DEG C, backflow 15 hours, cooling adds 500ml toluene, point liquid, is washed to neutrality, net toluene is steamed, 95g grease is obtained.Product is purified through column chromatography, then adds 1 times of petroleum ether recrystallization to obtain product 76g, yield 80%, gas chromatographic purity GC 99.9% twice with 2 times of ethanol.mp：78.7℃cp：131.7℃.
GC-MS data results such as table 2.
Table 2
Fusing point, clearing point and the mass spectrometric data of product all support that the structure of matter is correct.
With the fluoro- 4- bromo biphenyls of 4 '-propyl group -3- and method of the amyl group phenyl boric acid according to step 2 "-propyl group (1,1 ', 4 ', the 1 ") terphenyl that synthesizes 4- amyl groups -2 '-fluoro- 4
GC-MS：360 (M+100) 331 (27.4) 303 (76.8) 274 (39.2) 137 (6.3), mp：63 DEG C, cp：141℃.
With the fluoro- 4- bromo biphenyls of 4 '-propyl group -3- and 3,4,5- trifluoro phenyl boric acids synthesize 2 ', 3,4, the 5- "-propyl group terphenyls of tetrafluoro 4 according to the method for step 2
GC-MS：344 (M+47.9) 315 (100) 293 (5.9) 275 (4.7) 183 (5.1) 157 (5.4), mp：62.3℃.
Embodiment two
Step 1: the synthesis of the fluoro- 4- bromo biphenyls of 4 '-ethyl -3-
The bromo- 3- fluorine iodobenzene 150.5g (0.5mol) of 4-, potassium carbonate 138g, ethyl phenyl boric acid 78.8g (0.0525mol), tetrakis triphenylphosphine palladium 3.5g (0.003mol) are separately added into there-necked flask, and adds toluene 300g, ethanol 210g, water 240g；Then stir and be heated to 70 DEG C, keep the temperature at 70-75 DEG C and react 6 hours.Treat that solution is down to room temperature, carry out a point liquid processing, organic phase is washed to neutrality, and steam net toluene, decompression collects the cut under 145 DEG C/20Mp, obtains the fluoro- 4- bromo biphenyls 103.2g of 4 '-ethyl -3-, yield is 74%.It is 99% through analyzing gas chromatographic purity GC.
"-ethyl (the synthesis of 1,1 ', 4 ', 1 ") terphenyl Step 2: 4- propyl group -2 '-fluoro- 4
By the fluoro- 4- bromo biphenyls of 83.7g (0.3mol) 4 '-ethyls -3-, 54.1g (0.33mol) to propyl group phenyl boric acid, 5%Pd/C 1.5g (0.0007mol), potassium carbonate 83g, tetrahydrofuran 660g, water 180g, it is added in there-necked flask, it is warming up to 70 DEG C, backflow 15 hours, cooling adds 500ml toluene, divide liquid, be washed to neutrality, steam net toluene.Product is purified through column chromatography, then obtains product 76.3g, yield 80%, gas chromatographic purity GC 99.9%mp twice with 2 times of ethanol, 1 times of petroleum ether recrystallization：70.9 DEG C, cp：133℃.
GC-MS data results such as table 3.
Table 3
| Molecular formula | Characteristic ion (M/Z+) and abundance (%) |
| C23H23F | 318(M+84.2)303(5.2)289(100)274(25.3)137(17.3) |
Fusing point, clearing point and the mass spectrometric data of product all support that the structure of matter is correct.
The fluoro- 4- bromo biphenyls of 4 '-ethyl -3- and butyl phenyl boric acid synthesize 4- butyl -2 '-fluoro- 4 according to the method for step 2 "-ethyl (1,1 ', 4 ', 1 ") terphenyl
mp：68.6 DEG C, cp：119.8℃.
The fluoro- 4- bromo biphenyls of 4 '-ethyl -3- and amyl group phenyl boric acid synthesize 4- amyl groups -2 '-fluoro- 4 according to the method for step 2 "-ethyl (1,1 ', 4 ', 1 ") terphenyl
GC-MS：346 (M+92.3) 331 (3.0) 289 (100) 274 (26.7) 137 (5.7), mp：55 DEG C, cp：128℃.
The fluoro- 4- bromo biphenyls of 4 '-ethyl -3- and pentylcyclohexyl phenyl boric acid synthesize the fluorine 4 of 4- (pentylcyclohexyl) 2 ' according to the method for step 2 "-ethyl (1,1 ', 4 ', 1 ") terphenyl
GC-MS：428 (M+100) 315 (10.0) 302 (15.8) 289 (18.6) 287 (16.2) 150 (5.9), mp：110 DEG C, cp：297℃.
The fluoro- 4- bromo biphenyls of 4 '-ethyl -3- and 3,4,5- trifluoro phenyl boric acids synthesize 2 ', 3,4, the 5- "-ethyl terphenyls of tetrafluoro 4 according to the method for step 2
mp：86.9℃.
Embodiment three
Step 1: the synthesis of the fluoro- 4- bromo biphenyls of 4 '-amyl group -3-
The difference of the step of this step of the present embodiment is with embodiment one one is：First phenyl boric acid is amyl group phenyl boric acid, and addition is 100.8g (0.525mol)；The fluoro- 4- bromo biphenyls 115.6g of 4 '-amyl group -3- can be so obtained, yield is 72%.
It is 99% through analyzing gas chromatographic purity GC.
"-amyl group (1,1 ', 4 ', 1 ") terphenyl Step 2: 4- ethyls -2 '-fluoro- 4
By the fluoro- 4- bromo biphenyls of 96.3g (0.3mol) 4 '-amyl groups -3-, 49.5g (0.33mol) to ethyl phenyl boric acid, 5%Pd/C 1.5g (0.0007mol), potassium carbonate 83g, tetrahydrofuran 750g, water 200g, it is added in there-necked flask, it is warming up to 70 DEG C, backflow 15 hours, cooling adds 500ml toluene, divide liquid, be washed to neutrality, steam net toluene.Product is purified through column chromatography, then obtains product 82g, yield 79%, gas chromatographic purity GC 99.9% twice with 2 times of ethanol, 1 times of petroleum ether recrystallization.mp：44 DEG C, cp：129.4℃.
GC-MS data results such as table 4.
Table 4
Fusing point, clearing point and the mass spectrometric data of product all support that the structure of matter is correct.
The fluoro- 4- bromo biphenyls of 4 '-amyl group -3- and propyl group phenyl boric acid synthesize 4- propyl group -2 '-fluoro- 4 according to the method for step 2 "-amyl group (1,1 ', 4 ', 1 ") terphenyl
GC-MS：360 (M+100) 331 (48.6) 303 (51.9) 274 (38.5) 137 (5.6), mp：63 DEG C, cp：141℃.
The fluoro- 4- bromo biphenyls of 4 '-amyl group -3- and 3,4,5- trifluoro phenyl boric acids synthesize 2 ', 3,4, the 5- "-amyl group terphenyls of tetrafluoro 4 according to the method for step 2
mp：55.4℃.
Example IV
Step one 4 '-propyl group 2 ', the synthesis of the fluoro- 4- bromo biphenyls of 3- bis-, structural formula
The bromo- 3- fluorine iodobenzene 150.5g (0.5mol) of 4-, potassium carbonate 138g, 4- propyl group 2- fluorobenzoic boric acids 95.5g (0.525mol), tetrakis triphenylphosphine palladium 4g (0..0034mol) are separately added into there-necked flask, and adds toluene 300g, ethanol 210g, water 240g；Then stir and be heated to 70 DEG C, keep the temperature at 70-75 DEG C and react 6 hours.Treat that solution is down to room temperature, carry out a point liquid processing, organic phase is washed to neutrality, and steam net toluene, the cut under 155 DEG C/20Mpa is collected in decompression, obtain 4 '-propyl group 2 ', the fluoro- 4- bromo biphenyls 118.2g of 3- bis-, yield is 76%.
It is 99% through analyzing gas chromatographic purity GC.
4 '-amyl group 2 ' of system, the fluoro- 4- bromo biphenyls of 3- bis- are reacted with the same bromo- 3- fluorine iodobenzenes of method 4- and 4- amyl group 2- fluorobenzoic boric acids
The synthesis of step 2 4- chlorine 2 ' 2 "-difluoro 4 "-propyl group terphenyl
By 93.3g (0.3mol) 4 '-propyl group 2 ', the fluoro- 4- bromo biphenyls of 3- bis-, 51.6g (0.33mol) are to chlorophenylboronic acid, 5%Pd/C 2g (0.0009mol), potassium carbonate 83g, tetrahydrofuran 700g, water 230g, it is added in there-necked flask, 70 DEG C are warming up to, is flowed back 15 hours, cooling adds 500ml toluene, divide liquid, neutrality is washed to, net toluene is steamed, obtains 100g grease.Product is purified through column chromatography, then obtains product 80.1g, yield 78%, gas chromatographic purity GC 99.9% twice with 2 times of ethanol, 1 times of petroleum ether recrystallization.mp：91 DEG C, cp：115℃.
GC-MS data results such as table 5.
Table 5
Fusing point, clearing point and the mass spectrometric data of product all support that the structure of matter is correct.
4 '-amyl group 2 ', the fluoro- 4- bromo biphenyls of 3- bis- according to the method for step 2 to chlorophenylboronic acid with synthesizing 4 '-chlorine 2,2 "-difluoro 4 "-ethyl terphenyl
GC-MS：370 (M+100) 372 (34.8) 313 (97) 315 (33.7) 277 (9.8), mp：61 DEG C, cp：113℃.
Embodiment five
The synthesis of step one 4 '-(4 "-pentylcyclohexyl) fluoro- 4- bromo biphenyls of -3-, structural formula
The bromo- 3- fluorine iodobenzene 150.5g (0.5mol) of 4-, potassium carbonate 138g, pentylcyclohexyl phenyl boric acid 143.8g, tetrakis triphenylphosphine palladium 5g (0.0043mol) are separately added into 500ml there-necked flasks, and adds toluene 300g, ethanol 210g, water 240g；Then stir and be heated to 70 DEG C, keep the temperature at 70-75 DEG C and react 6 hours.Treat that solution is down to room temperature, carry out a point liquid processing, organic phase is washed to neutrality, and steam net toluene, 2 times of petroleum ethers are recrystallized 2 times, obtain 4 '-(4 "-pentylcyclohexyl) the fluoro- 4- bromo biphenyls 151.1g of -3-, yield is 75%.
It is 99% through analyzing gas chromatographic purity GC,
"-pentylcyclohexyl (the synthesis of 1,1 ', 4 ', 1 ") terphenyl Step 2: 4- propyl group -2 '-fluoro- 4
By 120.9 (0.3mol) 4 '-(4 "-pentylcyclohexyl) the fluoro- 4- bromo biphenyls of -3-, 54.1g (0.33mol) to propyl group phenyl boric acid, 5%Pd/C 3g (0.0014mol), potassium carbonate 83g, tetrahydrofuran 900g, water 300g; be added in there-necked flask; be warming up to 70 DEG C; backflow 15 hours; cooling adds 500ml toluene, point liquid is washed to neutrality; steam net toluene.Product is purified through column chromatography, then obtains product 102.1g, yield 77%, gas chromatographic purity GC 99.9% twice with 2 times of ethanol, 1 times of petroleum ether recrystallization.mp：66℃cp：285℃
GC-MS data results such as table 6.
Table 6
Fusing point, clearing point and the mass spectrometric data of product all support that the structure of matter is correct.
Embodiment six
The synthesis of step one 4 '-(4 "-propyl group phenyl) fluoro- 4- bromo biphenyls of -3-, structural formula
The bromo- 3- fluorine iodobenzene 150.5g (0.5mol) of 4-, potassium carbonate 138g, pentylbiphenyl boric acid 126g, tetrakis triphenylphosphine palladium 5g (0.0043mol) are separately added into there-necked flask, and adds toluene 300g, ethanol 210g, water 240g；Then stir and be heated to 70 DEG C, keep the temperature at 70-75 DEG C and react 6 hours.Treat that solution is down to room temperature, carry out a point liquid processing, organic phase is washed to neutrality, and steam net toluene, column chromatography decolourizes with 2 times of toluene, 2 times of petroleum ethers recrystallizations, obtain 4 '-(4 "-propyl group phenyl) the fluoro- 4- bromo biphenyls 132.8g of -3-, yield is 72%.
It is 99% through analyzing gas chromatographic purity GC,
Step 2: " the synthesis of-(propyl octyl) terphenyl of 2 ', 3,4,5 three fluoro- 4
By 110.7g (0.3mol) 4 '-(4 "-propyl group phenyl) fluoro- 4- bromo biphenyls of -3-, 58g (0.33mol) to 3; 4; 5 trifluoro phenyl boric acids, 5%Pd/C 3g (0.0014mol), potassium carbonate 83g, tetrahydrofuran 850ml, water 250ml; be added in there-necked flask, 70 DEG C are warming up to, is flowed back 15 hours; cooling adds 500ml toluene; point liquid, neutrality is washed to, net toluene is steamed.Product is purified through column chromatography, then adds 2 times of petroleum ether recrystallizations to obtain product 88.2g, yield 70%, gas chromatographic purity GC 99.9%m p twice with 2 times of ethanol：135.2 DEG C, cp：249.3℃.
GC-MS data results such as table 7.
Table 7
| Molecular formula | Characteristic ion (M/Z+) and abundance (%) |
| C27H20F4 | 420 (M+72.1) 391 (100) 196 (23.3), |
Fusing point, clearing point and the mass spectrometric data of product all support that the structure of matter is correct.
Claims (8)
1. a kind of method for synthesizing 2 '-fluorine Terphenyls liquid crystal, is that raw material add catalyst in organic solvent, the method realization of suzuki coupling reactions is carried out, it is characterised in that：Using the bromo- 3- fluorine iodobenzenes of 4-, two kinds of phenyl boronic acid derivatives as raw material, in the organic solvent environment of alkalescence in the presence of catalyst, respectively through 4-10 hours and 2 suzuki coupling reactions of 10-20 hours under 70~100 DEG C of reaction temperature, 2 '-fluorine Terphenyls liquid crystal is obtained, this synthetic route is as follows：
Step 1: heating generation suzuki coupling reactions in the presence of the first catalyst with the bromo- 3- fluorine iodobenzenes of 4- and the first phenyl boric acid and alkali in the first organic solvent：
Step 2: the intermediate product and the second phenyl boric acid and alkali that step one are obtained in the second organic solvent heat generation suzuki coupling reactions in the presence of the second catalyst, generate target 2 '-fluorine Terphenyls monomer liquid crystal：
In the chemical formula of foregoing description
Represent cyclohexyl, phenyl, pyrimidine, pyridine, 2, the one of which of 6 dioxane, R1、R2Respectively C1~C8 alkyl or alkoxy, alkenyl, F, Cl one of which, X1、X2、X3、X4Respectively H, F, Cl one of which, m, n=0 or 1.
2. a kind of method for synthesizing 2 '-fluorine Terphenyls liquid crystal according to claim 1, it is characterised in that：The catalyst is one or both of tetrakis triphenylphosphine palladium, 5%Pd/C, PdCl2.
3. a kind of method for synthesizing 2 '-fluorine Terphenyls liquid crystal according to claim 1, it is characterised in that：The alkali is the one of which of sodium carbonate, potassium carbonate, potassium hydroxide, potassium phosphate.
4. a kind of method for synthesizing 2 '-fluorine Terphenyls liquid crystal according to claim 3, it is characterised in that：The mol ratio 2: 1 of the preferred potassium carbonate of alkali, potassium carbonate and phenyl boric acid.
5. a kind of method for synthesizing 2 '-fluorine Terphenyls liquid crystal according to claim 1, it is characterised in that：The first organic solvent in the step one is toluene, ethanol, benzene, tetrahydrofuran, methanol, isopropanol, the tert-butyl alcohol, diethylene glycol dimethyl ether, N, N-dimethylformamide, N, the mixture of one or more of materials and water formation in N dimethyl acetamide, 1-METHYLPYRROLIDONE, the bromo- 3- fluorine iodobenzenes of 4- and the first organic solvent weight are than 1: (2~10).
6. a kind of method of synthesis 2 '-fluorine Terphenyls liquid crystal according to any one of Claims 1 to 5, it is characterised in that：First organic solvent is the mixture of toluene and ethanol and water, and the weight ratio of the bromo- 3- fluorine iodobenzenes of 4- and toluene and the mixture of ethanol and water is 1: 5；First catalyst is tetrakis triphenylphosphine palladium, and the bromo- 3- fluorine iodobenzenes of 4- and the first catalyst molfraction ratio are (100~300): 1；Reaction temperature is 70~80 DEG C, and the reaction time is 6 hours.
7. a kind of method for synthesizing 2 '-fluorine Terphenyls liquid crystal according to claim 1, it is characterised in that：The second organic solvent in the step 2 is the mixture of tetrahydrofuran, DMF, DMA one of which or two or more materials and water, and intermediate product and the second organic solvent weight ratio are 1: (5~15).
8. a kind of method of synthesis 2 '-fluorine Terphenyls liquid crystal according to Claims 1 to 4 or 7 any one, it is characterised in that：Second organic solvent is the mixed solvent of tetrahydrofuran and water, and intermediate product and the second organic solvent weight ratio are 1: 10；Second catalyst is 5%Pd/C, and intermediate product and the second catalyst molfraction ratio are (200~500): 1；Reaction temperature is 70~80 DEG C, and the reaction time is 15 hours.
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| CN103058886A (en) * | 2013-01-29 | 2013-04-24 | 石家庄诚志永华显示材料有限公司 | Poly-fluorine poly-cyanogen liquid crystal compound as well as preparation method and application thereof |
| CN103086842A (en) * | 2013-02-07 | 2013-05-08 | 江苏联化科技有限公司 | Synthesis method of 3,3',4,4',5,5'-hexafluorobiphenyl |
| CN104003852A (en) * | 2014-06-06 | 2014-08-27 | 北京八亿时空液晶科技股份有限公司 | Liquid crystal compound containing terphenyl/quaterphenyl structure and application thereof |
| CN104262119A (en) * | 2014-09-05 | 2015-01-07 | 石河子大学 | Method for synthesizing asymmetric terphenyl compound |
| CN104478669A (en) * | 2014-09-05 | 2015-04-01 | 石河子大学 | Asymmetric terphenyl liquid crystal compound |
| WO2016115719A1 (en) * | 2015-01-23 | 2016-07-28 | 北京欣奕华科技有限公司 | Liquid crystal compound and preparation method therefor, liquid crystal composition and liquid crystal display panel |
| EP3312257A1 (en) | 2016-10-18 | 2018-04-25 | Merck Patent GmbH | Liquid-crystalline medium and high-frequency components comprising same |
| CN114671745A (en) * | 2020-12-24 | 2022-06-28 | 江苏和成新材料有限公司 | Green method for synthesizing compound containing biaryl structure through Suzuki coupling reaction |
| CN114671744A (en) * | 2020-12-24 | 2022-06-28 | 江苏和成新材料有限公司 | Green method for synthesizing compound containing biaryl structure through Suzuki coupling reaction |
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| CN101768447A (en) * | 2010-01-14 | 2010-07-07 | 石家庄开发区永生华清液晶有限公司 | Polyfluoric terphenyl liquid crystal compound and synthesis method and use thereof |
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| CN1966608A (en) * | 2006-11-20 | 2007-05-23 | 烟台万润精细化工有限责任公司 | Method for preparing biphenyl monomer liquid crystal by using cross-coupling reaction |
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| CN103058886A (en) * | 2013-01-29 | 2013-04-24 | 石家庄诚志永华显示材料有限公司 | Poly-fluorine poly-cyanogen liquid crystal compound as well as preparation method and application thereof |
| CN103086842B (en) * | 2013-02-07 | 2015-04-29 | 联化科技股份有限公司 | Synthesis method of 3,3',4,4',5,5'-hexafluorobiphenyl |
| CN103086842A (en) * | 2013-02-07 | 2013-05-08 | 江苏联化科技有限公司 | Synthesis method of 3,3',4,4',5,5'-hexafluorobiphenyl |
| CN104003852A (en) * | 2014-06-06 | 2014-08-27 | 北京八亿时空液晶科技股份有限公司 | Liquid crystal compound containing terphenyl/quaterphenyl structure and application thereof |
| CN104003852B (en) * | 2014-06-06 | 2016-04-06 | 北京八亿时空液晶科技股份有限公司 | A kind ofly contain three or the liquid crystalline cpd of quaterphenyl structure and application thereof |
| CN104262119A (en) * | 2014-09-05 | 2015-01-07 | 石河子大学 | Method for synthesizing asymmetric terphenyl compound |
| CN104478669A (en) * | 2014-09-05 | 2015-04-01 | 石河子大学 | Asymmetric terphenyl liquid crystal compound |
| WO2016115719A1 (en) * | 2015-01-23 | 2016-07-28 | 北京欣奕华科技有限公司 | Liquid crystal compound and preparation method therefor, liquid crystal composition and liquid crystal display panel |
| EP3312257A1 (en) | 2016-10-18 | 2018-04-25 | Merck Patent GmbH | Liquid-crystalline medium and high-frequency components comprising same |
| CN114671745A (en) * | 2020-12-24 | 2022-06-28 | 江苏和成新材料有限公司 | Green method for synthesizing compound containing biaryl structure through Suzuki coupling reaction |
| CN114671744A (en) * | 2020-12-24 | 2022-06-28 | 江苏和成新材料有限公司 | Green method for synthesizing compound containing biaryl structure through Suzuki coupling reaction |
| CN114671744B (en) * | 2020-12-24 | 2024-04-05 | 江苏和成新材料有限公司 | Green method for synthesizing biaryl structure-containing compound through Suzuki coupling reaction |
| CN114671745B (en) * | 2020-12-24 | 2024-04-05 | 江苏和成新材料有限公司 | Green method for synthesizing biaryl structure-containing compound through Suzuki coupling reaction |
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