CN116283516B - Eutectic solvent and preparation method and application thereof - Google Patents

Eutectic solvent and preparation method and application thereof Download PDF

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CN116283516B
CN116283516B CN202310309027.8A CN202310309027A CN116283516B CN 116283516 B CN116283516 B CN 116283516B CN 202310309027 A CN202310309027 A CN 202310309027A CN 116283516 B CN116283516 B CN 116283516B
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reaction
eutectic solvent
caprolactam
sorbitol
halogen
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CN116283516A (en
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岳刚
刘宝友
史磊
王志强
陈少华
康凯明
郑科阳
刘银豹
王利民
关登仕
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Ningxia Zhongxing Display Materials Co ltd
Hebei University of Science and Technology
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Ningxia Zhongxing Display Materials Co ltd
Hebei University of Science and Technology
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Abstract

The invention relates to the technical field of organic synthesis, and particularly discloses a eutectic solvent and a preparation method and application thereof. The eutectic solvent is prepared from caprolactam and sorbitol, is suitable for suzuki reaction with various bromoaromatic hydrocarbon and phenylboric acid as substrates, can achieve the purposes of obviously improving the reaction rate and reducing the catalyst consumption, and the product after the reaction is not mutually dissolved with the caprolactam/sorbitol eutectic solvent, so that the post-treatment process of the reaction is simplified, the target product can be obtained by simple extraction, and the caprolactam/sorbitol eutectic solvent can also effectively fix a palladium metal catalyst and reduce the loss of the catalyst in the liquid separation process; besides, the method can inhibit the coupling reaction of the phenylboronic acid, improve the selectivity of the suzuki reaction and reduce the occurrence of side reactions, thereby improving the yield and purity of the target product, and has good application prospect and extremely high popularization and application value in the suzuki reaction.

Description

Eutectic solvent and preparation method and application thereof
Technical Field
The invention relates to the technical field of organic synthesis, and particularly discloses a eutectic solvent and a preparation method and application thereof.
Background
Suzuki-Miyaura cross-coupling reaction (Suzuki reaction for short) is a cross-coupling reaction between an organoboride and a halogenated benzene, and is a general method for forming a carbon-carbon bond compound. Under the catalysis of Pd and other transition metals, the organoboride and the halogenated benzene can undergo cross-coupling reaction under mild conditions, and are commonly used for synthesizing multiolefin, styrene and biphenyl derivatives. The biphenyl derivative is an extremely important chemical intermediate and has been widely applied to the fields of molecular organic synthesis such as nano materials, electronic technology and pharmaceutical engineering.
However, the existing Suzuki reaction generally uses Pd (PPh 3) 4 As a catalyst, palladium is expensive, so that the reaction cost is high. In addition, most of the reaction solvents used in the suzuki reaction are volatile solvents, the reaction solvents are not easy to recycle and reuse, and the reaction activity of the suzuki reaction cannot be effectively improved. Therefore, a green solvent system which is environment-friendly, can be recycled and can effectively improve the suzuki reaction activity is developed, so that the use amount of a catalyst and a reaction solvent can be reduced, and the method has very important significance for expanding the application range of the suzuki reaction.
Disclosure of Invention
Aiming at the problems that the reaction solvent of the Suzuki reaction in the prior art cannot effectively improve the reaction activity, is difficult to recycle, has certain toxicity, is poor in environmental friendliness and the like, the invention provides a eutectic solvent and a preparation method and application thereof. The invention takes the eutectic solvent with specific composition as the reaction solvent of the Suzuki reaction, effectively reduces the reaction time and the catalyst consumption of the Suzuki reaction, simultaneously realizes repeated use of the reaction solvent, has no toxicity and harm, low price, good adaptability to the substrates of phenylboronic acid and bromoarene, and has wide application prospect in the Suzuki reaction.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
in a first aspect, the present invention provides a eutectic solvent prepared from caprolactam and sorbitol.
The eutectic solvent disclosed by the invention takes caprolactam and sorbitol as raw materials to obtain the eutectic solvent, has good thermal stability, moderate viscosity and good application prospect, is low in raw material cost and wide in source, contains natural substances, has good biocompatibility, and is a green natural eutectic solvent.
Preferably, the molar ratio of the caprolactam to the sorbitol is 2-4:1.
Preferably, the molar ratio of caprolactam to sorbitol is 3:1.
The preferred proportions of caprolactam and sorbitol provide the eutectic solvent with excellent solubility and thermal stability.
In a second aspect, the present invention also provides a method for preparing a eutectic solvent, comprising the steps of: and adding caprolactam and sorbitol into a long-chain alkane solvent, heating until the system is uniform and transparent, and distilling to remove the long-chain alkane solvent to obtain the eutectic solvent.
The eutectic solvent is prepared by adding caprolactam and sorbitol into long-chain alkane solvent and removing the solvent through heating and dissolving and rotary steaming, so that the defects of uneven heating of raw materials, difficult coordination of hydrogen bonds and low purity of the solvent can be effectively avoided, and meanwhile, the raw materials comprise natural substances, are nontoxic and harmless, have low cost and simple preparation process, and the obtained eutectic solvent has high purity and is suitable for industrial large-scale production.
Preferably, the long-chain alkane solvent is n-heptane or n-octane.
Preferably, the ratio of the volume of the long-chain alkane solvent to the total mass of caprolactam and sorbitol is (2-3) mL to 1g.
Preferably, the heating temperature is 80 ℃ to 100 ℃.
The preferable reaction solvent, the addition amount of the reaction solvent and the reaction temperature can fully dissolve caprolactam and sorbitol and promote the full reaction of the caprolactam and the sorbitol, thus obtaining the uniform and transparent eutectic solvent.
Preferably, the long-chain alkane solvent is removed by adopting a decompression rotary evaporation mode, the temperature of the decompression rotary evaporation is 40-50 ℃, the pressure is minus 0.09MPa to minus 0.05MPa, and the time is 1.5-2.5 h.
The preferred time and temperature of the reduced pressure spin-evaporation can further improve the purity of the eutectic solvent and the uniformity of the hydrogen bond donor and hydrogen bond acceptor.
In a third aspect, the invention also provides an application of the eutectic solvent in suzuki reaction.
In combination with the above, the eutectic solvent is used as a reaction medium in the suzuki reaction.
The eutectic solvent provided by the invention can form a supermolecular grid space structure through intermolecular hydrogen bond association, stabilize the palladium catalyst of the Suzuki reaction, promote the oxidation addition reaction in the Suzuki reaction process, and convert 0-valent palladium into 2-valent palladium, so that the palladium catalyst is dispersed into the solvent, and promote the reaction mass transfer; in addition, the eutectic solvent provided by the invention has excellent dissolution and dispersion properties on a reaction substrate, and can effectively reduce the reaction activation energy, so that the reaction rate is greatly improved, the reaction time is shortened, and the dosage of a catalyst is reduced; in addition, the product after the reaction is not mutually soluble with the caprolactam/sorbitol eutectic solvent, the post-treatment process of the reaction is simplified, the target product can be obtained only by simple extraction, the product shows excellent performance in the boll wood reaction taking phenylboronic acid and bromoarene as substrates, and the popularization and application values are higher.
In combination with the above, the substrate of the suzuki reaction is bromoarene shown in formula (I) and phenylboric acid shown in formula (II);
wherein R is 1 Is H, methyl or cyano; r is R 2 Is H, methyl or halogen; r is R 3 Is H, methyl, methoxy, halogen, nitro or phenyl; r is R 4 Is H or halogen;
R 5 、R 6 、R 8 is H or halogen; r is R 7 Is H, halogen or ethoxy.
Illustratively, the catalyst for the suzuki reaction comprises at least one of tetrakis (triphenylphosphine) palladium, palladium chloride, or palladium acetate.
The eutectic solvent provided by the invention has good applicability to Suzuki reaction substrates, is suitable for cross-coupling reaction of various functional group substituted halogenated aromatic hydrocarbon and phenylboric acid, can achieve the excellent effects of effectively improving the reaction activity and obviously reducing the catalyst dosage, can realize repeated use of the reaction solvent, effectively reduces the reaction cost, and has extremely high practical value.
In a fourth aspect, the present invention also provides a method for preparing a biphenyl derivative, comprising the steps of: adding the eutectic solvent in any one of the above into water, uniformly mixing, sequentially adding an acid binding agent, bromoaromatic hydrocarbon shown in formula (I), phenylboric acid shown in formula (II) and a palladium catalyst, and reacting at 90-100 ℃ for 24-42 min under an inert atmosphere to obtain a biphenyl derivative shown in formula (III);
wherein R is 1 Is H, methyl or cyano; r is R 2 Is H, methyl or halogen; r is R 3 Is H, methyl, methoxy, halogen, nitro or phenyl; r is R 4 Is H or halogen;
R 5 、R 6 、R 8 is H or halogen; r is R 7 Is H, halogen or ethoxy.
In combination with the above, the volume ratio of the eutectic solvent to water is 0.5-1.5:1.
In combination with the above, the acid binding agent is potassium carbonate, and the mass ratio of the acid binding agent to water is 1:3-5.
In combination with the above, the molar ratio of the acid binding agent, the bromoaromatic hydrocarbon and the phenylboronic acid is 1.5-2.5:1:1.
In combination with the above, the ratio of the palladium catalyst to the phenylboronic acid is (0.14 to 0.3) g/1 mol.
Compared with the existing solvent, the eutectic solvent provided by the invention has the advantages that the reaction rate is improved by 9.6 times, the addition amount of the catalyst is reduced by 80%, and meanwhile, after the reaction medium is recycled for 4 times, the product still has higher yield and purity, and has extremely high application value in industrial production, especially in the production of industrial products mainly comprising the Suzuki reaction.
Drawings
FIG. 1 is a diagram showing the eutectic solvent prepared in example 1 of the present invention 1 H NMR chart;
FIG. 2 is a diagram showing the eutectic solvent prepared in example 1 of the present invention 13 C NMR chart;
FIG. 3 is an FT-IR chart of the eutectic solvent prepared in example 1 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In order to better illustrate the present invention, the following examples are provided for further illustration.
Example 1
The embodiment of the invention provides a eutectic solvent, which is prepared from caprolactam and sorbitol in a molar ratio of 3:1, and specifically comprises the following steps:
0.174mol (19.69 g) of caprolactam and 0.058mol (10.57 g) of sorbitol are added into 60mL of n-heptane, heated to 80 ℃ and kept at a constant temperature until the system is uniform and transparent, then the reaction solution is transferred to a rotary evaporator and rotary-evaporated at 45 ℃ and-0.09 MPa for 2h, and the n-heptane is removed to obtain the caprolactam/sorbitol eutectic solvent.
The caprolactam/sorbitol eutectic solvent prepared in this example 1 H NMR chart, 13 The CNMR and FT-IR patterns are shown in FIGS. 1-3, respectively. It was confirmed by characterization that caprolactam and sorbitol formed a eutectic solvent by the above preparation method.
Example 2
The embodiment of the invention provides a eutectic solvent, which is prepared from caprolactam and sorbitol in a molar ratio of 2:1, and specifically comprises the following steps:
0.116mol (13.13 g) of caprolactam and 0.058mol (10.57 g) of sorbitol are added into 50mL of n-heptane, heated to 90 ℃ and kept at a constant temperature until the system is uniform and transparent, then the reaction solution is transferred to a rotary evaporator, and the n-heptane is removed after rotary evaporation for 1.5h at 40 ℃ and-0.09 MPa, thus obtaining the caprolactam/sorbitol eutectic solvent.
Example 3
The embodiment of the invention provides a eutectic solvent, which is prepared from caprolactam and sorbitol in a molar ratio of 4:1, and specifically comprises the following steps:
0.232mol (26.25 g) of caprolactam and 0.058mol (10.57 g) of sorbitol are added into 109mL of n-heptane, heated to 100 ℃ and kept at a constant temperature until the system is uniform and transparent, then the reaction solution is transferred to a rotary evaporator, and the n-heptane is removed after rotary evaporation for 2.5h at 50 ℃ and-0.09 MPa, thus obtaining the caprolactam/sorbitol eutectic solvent.
Example 4
The caprolactam/sorbitol eutectic solvent prepared in example 1 is used as a reaction medium in suzuki reaction, 4-methoxybromobenzene and phenylboronic acid are selected as reaction substrates, and the specific suzuki reaction steps are as follows:
adding 8g of potassium carbonate and 30g of ultrapure water into a three-port bottle, mixing and dissolving, recovering to room temperature of 25 ℃, adding 30g of caprolactam/sorbitol eutectic solvent, then sequentially adding 3.6g of phenylboric acid and 0.04g (1 g/mol) of tetrakis (triphenylphosphine) palladium, uniformly mixing, introducing nitrogen, heating under stirring, gradually dropwise adding 5.5g of 4-methoxybromobenzene in the heating process, stopping introducing nitrogen when the system starts to reflux, and carrying out reflux reaction for 4 hours at 100 ℃.
After the reaction is finished, transferring the reaction solution into a 500mL separating funnel, cooling to 40-60 ℃, adding 150mL of n-heptane, adding 100mL of ultrapure water after full oscillation, separating the solution, repeatedly extracting and separating the solution for 2 times, combining n-heptane phases, standing for 10min, carrying out suction filtration, transferring the filtrate into a round bottom flask, mounting the round bottom flask on a rotary steaming instrument, carrying out rotary steaming for 1.5-2.5 h at 40-50 ℃ under-0.09 MPa, and weighing after the n-heptane phase is evaporated. The product yield was calculated.
Product yield= (actual yield of target product/theoretical yield of target product) ×100%.
According to the same reaction conditions as those described above, different eutectic solvents were used as the reaction medium for the suzuki reaction, that is, the reaction conditions were the same except for the reaction medium, and the yields and purities of the specific products are shown in table 1.
TABLE 1 yield purity data for different eutectic solvents as reaction medium
The preparation method of each of the eutectic solvents in numbers 2 to 6 is exactly the same as that of the caprolactam/sorbitol eutectic solvent of example 1, and the molar ratio of the hydrogen bond donor and the hydrogen bond acceptor in each of the eutectic solvents is adjusted in order to ensure the optimal effect of each of the eutectic solvents as shown in the above table.
As can be seen from the above table, the caprolactam/sorbitol eutectic solvent prepared in example 1 was used as the reaction medium for suzuki reaction, and the yield and purity of the prepared product were significantly higher than those of the other eutectic solvents.
To further determine that the caprolactam/sorbitol eutectic solvent was the reaction medium for the suzuki reaction, the following test was performed on the optimal conditions for the suzuki reaction.
Suzuki reaction was performed under exactly the same reaction conditions as above, except that the reaction times were 10min, 15min, 20min, 25min, 30min and 60min, respectively, and the remaining conditions were exactly the same. The results are shown in Table 2.
TABLE 2 product yield purity data for different reaction times
Suzuki reaction was carried out under exactly the same reaction conditions as above except that the catalyst was added in an amount of 0.02g/mol, 0.08g/mol, 0.14g/mol, 0.30g/mol, the reaction time was 25 minutes, and the remaining conditions were exactly the same. The results are shown in Table 3.
TABLE 3 product yield purity data for different catalyst loadings
Additive amount 0.02g/mol 0.08g/mol 0.14g/mol 0.30g/mol
Yield is good 38.4％ 76.9％ 99.4％ 99.4％
Purity of 16.3％ 50.4％ 99.0％ 99.0％
Suzuki reaction was carried out under exactly the same reaction conditions as above except that the reaction temperature was 60℃and 70℃and 80℃and 90℃and 100℃respectively, the catalyst addition was 0.14g/mol, the reaction time was 25 minutes, and the remaining conditions were exactly the same. The results are shown in Table 4.
TABLE 4 product yield purity data for different reaction temperatures
Temperature (temperature) 60℃ 70℃ 80℃ 90℃ 100℃
Yield is good 35.7％ 57.1％ 91.1％ 97.3％ 99.8％
Purity of 15.4％ 26.9％ 86.4％ 95.5％ 99.0％
From the above test results, it is clear that caprolactam/sorbitol eutectic solvent is used as a reaction medium for Suzuki reaction (4-methoxybromobenzene and phenylboronic acid are used as substrates), and the optimal reaction conditions are as follows: the reaction temperature is 100 ℃, the reaction time is 25min, and the catalyst addition amount is 0.14g/mol (0.03 mol%). The addition amount of the existing report catalyst is 0.5mol percent to 2.5mol percent, so that the caprolactam/sorbitol eutectic solvent provided by the embodiment of the invention is used as a reaction medium, the dosage of the catalyst can be obviously reduced, and the reaction cost is reduced.
Under the reaction conditions: the Suzuki reaction was carried out at 80℃for 25 minutes with the addition of 0.14g/mol of the catalyst and using different solvents as the reaction medium in the Suzuki reaction, and 4-methoxybromobenzene and phenylboronic acid as substrates in the same steps and conditions (except for the temperature, the other reaction conditions were the same) as described above, and the results are shown in Table 5.
TABLE 5 product yield purity of different reaction solvents
Note that: since the reflux temperature of toluene, ethanol and water is 80 ℃, the reaction temperature is uniformly selected to 80 ℃ in order to enhance the comparability.
As can be seen from the above results, caprolactam/sorbitol eutectic solvent and ionic liquid ([ BMIM) were obtained in example 1 of the present invention]BF 4 、[BMIM]PF 6 ) Molecular organic solvent (mixed system of toluene, ethanol and water) is used as reaction medium, and the yield of product is caprolactam/sorbitol eutectic solvent > molecular organic solvent > [ Bmim ] under the same reaction condition]PF 6 ＞[Bmim]BF 4 And the yield of the caprolactam/sorbitol eutectic solvent is far greater than that of other solvents.
Example 5
The recycling performance:
the Suzuki reaction was carried out under the optimum reaction conditions (reaction temperature 100 ℃, reaction time 25min, catalyst addition 0.14 g/mol) in example 4 with 4-methoxybromobenzene and phenylboronic acid as substrates and with caprolactam/sorbitol eutectic solvent as reaction medium. The method comprises the following specific steps:
adding 8g of potassium carbonate and 30g of ultrapure water into a three-port bottle, mixing and dissolving, recovering to room temperature of 25 ℃, adding 30g of caprolactam/sorbitol eutectic solvent, then sequentially adding 3.6g of phenylboric acid and 4.2mg (0.14 g/mol) of tetrakis (triphenylphosphine) palladium, uniformly mixing, introducing nitrogen, heating under stirring, gradually dropwise adding 5.5g of 4-methoxybromobenzene in the heating process, stopping introducing nitrogen when the system starts to reflux, and carrying out reflux reaction at 100 ℃ for 25min.
After the suzuki reaction is finished, the product and the eutectic solvent in the reaction liquid are in a layered state, the upper-layer product and the lower-layer eutectic solvent are separated, the lower-layer substance obtained by separating is the eutectic solvent and the metal palladium catalyst embedded in the grid of the eutectic solvent, the equal volume of n-heptane is added into the upper-layer substance obtained by separating for extraction, the extraction is repeated for three times, the n-heptane phases are combined, the equal volume of water is added for washing, and the product is obtained by standing and separating.
And taking the mixed solution containing the eutectic solvent and the metal palladium catalyst obtained by liquid separation as a reaction medium of the next suzuki reaction, namely directly adding the equal volume of water and the equal proportion of substrate into the mixed solution to react (without adding the palladium catalyst), recycling for 5 times, and obtaining the yield and purity data of the product shown in Table 6.
TABLE 6 product yield and purity for 5 cycles
Number of cycles 1 time 2 times 3 times 4 times 5 times
Yield is good 99.7％ 98.1％ 95.8％ 94.5％ 90.7％
Purity of 98.6％ 96.9％ 93.5％ 91.1％ 85.9％
As a result, the caprolactam/sorbitol eutectic solvent provided by the invention can be recycled for 4 times, so that the suzuki reaction still has higher reaction rate, and the yield and purity of the prepared product can still reach more than 90%.
Example 6
Effect comparison of different reaction substrates:
the suzuki reaction was carried out under the optimum reaction conditions (reaction temperature 100 ℃ C., reaction time 25min, catalyst addition amount 0.14 g/mol) in example 4 using the caprolactam/sorbitol eutectic solvent prepared in example 1 as a reaction medium, according to the following reaction conditions:
29.4mmol of bromoarene, 29.4mmol of phenylboric acid, 58.8mmol of potassium carbonate, 0.0035mmol of tetra (triphenylphosphine) palladium, 30g of caprolactam/sorbitol eutectic solvent and 30g of ultrapure water are added into a three-necked flask, after the reaction is finished, the reaction solution is transferred into a separating funnel, 80mL of n-heptane is added after the reaction is finished, 80mL of ultrapure water is added after the reaction solution is cooled to 40-60 ℃, the solution is separated, the extraction and the separation are repeated for 2 times, the n-heptane phases are combined, the mixture is stood for 10min and filtered in a pumping way, the filtrate is transferred into a round bottom flask, the round bottom flask is mounted on a rotary steaming instrument, the rotary steaming is carried out for 1.5-2.5 h at 40-50 ℃, and the mixture is weighed after the n-heptane phase is evaporated. The product yield was calculated. The results are shown in Table 7.
TABLE 7 comparison of different reaction substrates
The caprolactam/sorbitol eutectic solvents prepared in examples 2-3 can achieve substantially the same technical effect as example 1 when applied to the suzuki reaction.
In conclusion, the caprolactam/sorbitol eutectic solvent provided by the invention has good substrate applicability, is suitable for suzuki reaction with various bromoaromatic hydrocarbons and phenylboric acid as substrates, can achieve the purposes of obviously improving the reaction rate and reducing the catalyst dosage, and the product after the reaction is not mutually dissolved with the caprolactam/sorbitol eutectic solvent, so that the post-treatment process of the reaction is simplified, the target product can be obtained only by simple extraction, and the caprolactam/sorbitol eutectic solvent provided by the invention can also effectively fix the palladium metal catalyst and reduce the loss of the catalyst in the liquid separation process; in addition, the caprolactam/sorbitol eutectic solvent provided by the invention can inhibit the coupling reaction of phenyl boric acid, improve the selectivity of the suzuki reaction and reduce the occurrence of side reactions, thereby improving the yield and purity of the target product, showing good application prospect in the suzuki reaction and having extremely high popularization and application value.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, or alternatives falling within the spirit and principles of the invention.

Claims (9)

1. The eutectic solvent is characterized by being prepared from caprolactam and sorbitol in a molar ratio of 2-4:1.
2. The eutectic solvent of claim 1, wherein the molar ratio of caprolactam to sorbitol is 3:1.
3. A method for preparing a eutectic solvent according to any one of claims 1 to 2, comprising the steps of: and adding caprolactam and sorbitol into a long-chain alkane solvent, heating until the system is uniform and transparent, and distilling to remove the long-chain alkane solvent to obtain the eutectic solvent.
4. A method of preparing a eutectic solvent according to claim 3, wherein the long-chain alkane solvent is n-heptane or n-octane; and/or
The ratio of the volume of the long-chain alkane solvent to the total mass of the caprolactam and the sorbitol is (2-3) mL, 1g; and/or
The heating temperature is 80-100 ℃; and/or
Removing the long-chain alkane solvent by adopting a decompression rotary evaporation mode, wherein the decompression rotary evaporation temperature is 40-50 ℃, the pressure is-0.09 MPa to-0.05 MPa, and the time is 1.5-2.5 h.
5. Use of the eutectic solvent according to any one of claims 1-2 in a suzuki reaction.
6. The use according to claim 5, wherein the eutectic solvent is used as a reaction medium.
7. The use according to claim 5, wherein the substrate for the suzuki reaction is a bromoarene of formula (i) and a phenylboronic acid of formula (ii);
wherein R is 1 Is H, methyl or cyano; r is R 2 Is H, methyl or halogen; r is R 3 Is H, methyl, methoxy, halogen, nitro or phenyl; r is R 4 Is H or halogen;
R 5 、R 6 、R 8 is H or halogen; r is R 7 Is H, halogen or ethoxy.
8. A process for producing a biphenyl derivative, comprising the steps of: adding the eutectic solvent according to any one of claims 1-2 into water, uniformly mixing, sequentially adding an acid binding agent, bromoaromatic hydrocarbon shown in formula (I), phenylboric acid shown in formula (II) and palladium catalyst, and reacting at 90-100 ℃ for 24-42 min in an inert atmosphere to obtain biphenyl derivatives shown in formula (III);
wherein R is 1 Is H, methyl or cyano; r is R 2 Is H, methyl or halogen; r is R 3 Is H, methyl, methoxy, halogen, nitro or phenyl; r is R 4 Is H or halogen;
R 5 、R 6 、R 8 is H or halogen; r is R 7 Is H, halogen or ethoxy.
9. The method for preparing a biphenyl derivative according to claim 8, wherein the volume ratio of the eutectic solvent to water is 0.5-1.5:1; and/or
The acid binding agent is potassium carbonate, and the mass ratio of the acid binding agent to water is 1:3-5; and/or
The mol ratio of the acid binding agent, the bromoarene and the phenylboric acid is 1.5-2.5:1:1; and/or
The ratio of the palladium catalyst to the phenylboronic acid is (0.14-0.3) g/1 mol.
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