A process for the coupling of methyl biphenyl-4-carboxylate with a bromoalkane to form a biphenyl benzyl alcohol
Patent Information
- Application Number
- CN202611283732.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-08-24
- Publication Date
- 2026-10-30
AI Technical Summary
[0010]综上，现有的联苯苄醇及其衍生物的合成方法尽管能简单、高效合成联苯苄醇及其衍生物，底物适用范围广泛，但是普遍存在几个缺点：反应过程中使用过渡金属或者贵金属催化剂，一定程度上造成了成本的负担和环境的污染；有的反应需要使用光照，产生的光污染对反应放大化生产造成很大阻碍
[0024]本发明的有益效果为：本发明为合成联苯苄醇提供了一个新的思路，与现有的合成工艺相比，绿色安全、经济简便，无需使用剧毒的金属（如：铬）或高毒的化学试剂；也无需使用贵金属（如：钯）；无需高温或者光照条件；使用廉价易得的溴代烷烃和联苯-4-甲酸甲酯作为原料，成本低；设备简单；反应条件温和；可放大化生产，故本发明公开的方法可广泛应用于药物及新材料的工业化生产。
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Abstract
Description
Technical Field
[0001] This invention belongs to the field of organic synthesis technology, and particularly relates to a method for coupling methyl biphenyl-4-carboxylate with bromoalkane to synthesize biphenylbenzyl alcohol. Background Technology
[0002] Biphenylbenzyl alcohol, a typical aromatic secondary alcohol, possesses strong derivatization capabilities due to its intramolecular biphenyl conjugated structure and active hydroxyl groups. Current industrial applications are mainly concentrated in six areas: First, in the pharmaceutical field, it is used as a core intermediate in the industrial production of the broad-spectrum antifungal active pharmaceutical ingredient bifonazole, and further extended to construct novel drug molecules with anti-inflammatory and anti-tumor properties; second, in agricultural plant protection, it is used to synthesize agricultural fungicides and storage antifungal agents; third, as a building block in organic synthesis, it is used to prepare ester fragrances, azo dyes, and fluorescent whitening agents; fourth, it participates in polymer polymerization modification to synthesize liquid crystal monomers, weather-resistant and anti-corrosion coating resins, and optoelectronic functional materials; fifth, it is used in daily chemical washing and care systems as an antibacterial, preservative, and fragrance fixing raw material; in addition, it can also be used to prepare chromatographic derivatization reagents, metal corrosion inhibitors, and catalytic ligands, among other specialty chemicals. Therefore, the green and efficient preparation process of biphenylbenzyl alcohol and its derivatives has significant industrial value.
[0003] Given the versatile applications of biphenylbenzyl alcohol, the synthesis of its compounds and derivatives has attracted widespread interest. According to literature reports, the existing synthetic methods for biphenylbenzyl alcohol and its derivatives mainly include the following:
[0004] The Suzuki coupling of phenylboronic acid and aryl bromides can efficiently yield benzyl aldehydes or ketone intermediates. Subsequent reduction with NaBH4 yields the benzyl alcohol compound. This reaction offers advantages such as high catalytic efficiency and stable, well-established reaction conditions. However, it requires the use of the transition metal palladium, resulting in high reaction costs and environmental unfriendliness. (Bioorg. Med. Chem., 2008, 16, 7715-7727)
[0005]
[0006] Aliphatic amines were pre-activated into pyridine salt precursors, and then nucleophilic addition to biphenylaldehyde was achieved in the presence of chromium chloride, yielding biphenylbenzyl alcohol in excellent yield. However, this method requires the use of excess heavy metals (2.5 equiv), which can cause serious metal pollution to the environment. (Org. Lett., 2023, 25, 4934-4939)
[0007]
[0008] This transformation utilizes inexpensive and stable potassium cyclohexylfluoroborate and biphenylaldehyde as raw materials, with a Lewis acid as the catalyst. The radical addition reaction can be completed under visible light irradiation without the need for a photosensitizer, yielding the corresponding target compound. However, the reaction requires light irradiation, making its scale-up a significant challenge. (Org. Chem. Front., 2024, 11, 3988-3996)
[0009]
[0010] In summary, although existing methods for synthesizing biphenylbenzyl alcohol and its derivatives are simple, efficient, and have a wide range of applicable substrates, they generally have several drawbacks: the use of transition metal or noble metal catalysts in the reaction process leads to a certain degree of cost burden and environmental pollution; some reactions require the use of light, and the resulting light pollution greatly hinders the scale-up of the reaction. Summary of the Invention
[0011] The purpose of this invention is to provide a method for coupling methyl biphenyl-4-carboxylate with bromoalkane to synthesize biphenyl benzyl alcohol, thereby solving the problems mentioned in the background art.
[0012] The technical solution adopted by this invention to solve its technical problem is:
[0013] A method for coupling methyl biphenyl-4-carboxylate with a bromoalkane to synthesize biphenylbenzyl alcohol includes the following steps: In an electrochemical catalytic reactor, methyl biphenyl-4-carboxylate, a bromoalkane, and an electrolyte are dissolved in a solvent, electrodes are connected, and the reaction is carried out at room temperature with stirring. After the reaction, the mixture is subjected to vacuum distillation, extraction, combination of organic phases, drying, filtration, concentration, and purification to obtain the biphenylbenzyl alcohol compound. The anode material is one of zinc, manganese, platinum, magnesium, iron, nickel, copper, cobalt, tin, or titanium; the cathode material is one of carbon, graphite felt, zinc, manganese, platinum, magnesium, iron, nickel, copper, cobalt, tin, or titanium; and the electrolyte is a salt composed of cations and anions. The reaction formula is as follows:
[0014]
[0015] As a preferred embodiment of the present invention, the molar ratio of methyl biphenyl-4-carboxylate to bromoalkane, electrolyte and solvent is 1:1.2~5.0:1.2~5.0:100~500.
[0016] As a preferred embodiment of the present invention, the methyl biphenyl-4-carboxylate is a compound of formula (1), the bromoalkane is a compound of formula (2), and the biphenyl benzyl alcohol product is a compound of formula (3); wherein, R is an alkyl group.
[0017]
[0018] As a preferred embodiment of the present invention, the alkyl group is a chain alkyl group, a cycloalkyl group, an alkyl group containing any element selected from halogen, oxygen, nitrogen, silicon, phosphorus, and sulfur, or an alkyl group containing aromatic hydrocarbons or heterocyclic aromatic hydrocarbons.
[0019] As a preferred embodiment of the present invention, the solvent is one or a mixture of multiple of the following: acetonitrile, dichloromethane, dichloroethane, trichloromethane, carbon tetrachloride, N,N-dimethylformamide (DMF), 1,4-dioxane, methanol, ethanol, isopropanol, hexafluoroisopropanol, trifluoroethanol, acetone, dimethyl sulfoxide (DMSO), tetrahydrofuran, and water.
[0020] As a preferred embodiment of the present invention, the electrolyte is one or more of lithium perchlorate, ammonium perchlorate, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium tetrafluoroborate, tetraethylammonium tetrafluoroborate, and tetraethylammonium chloride.
[0021] As a preferred embodiment of the present invention, the electrode is in the form of a sheet, block, rod, or mesh.
[0022] As a preferred embodiment of the present invention, the energizing reaction is carried out under constant current or constant voltage conditions, with a current intensity of 20mA to 10A and a reaction temperature of -20 to 100℃.
[0023] As a preferred embodiment of the present invention, the purification process specifically includes column chromatography, vacuum distillation, or recrystallization.
[0024] The beneficial effects of this invention are as follows: This invention provides a new approach for the synthesis of biphenylbenzyl alcohol. Compared with existing synthesis processes, it is green, safe, economical, and simple, requiring no use of highly toxic metals (such as chromium) or highly toxic chemical reagents; it also requires no use of precious metals (such as palladium); it does not require high temperature or light conditions; it uses inexpensive and readily available bromoalkanes and methyl biphenyl-4-carboxylate as raw materials, resulting in low cost; the equipment is simple; the reaction conditions are mild; and it can be scaled up for production. Therefore, the method disclosed in this invention can be widely applied to the industrial production of pharmaceuticals and new materials. Attached Figure Description
[0025] Figure 1 This is a selection of bromoalkanes and their yields investigated in this invention;
[0026] Figure 2 This is the nuclear magnetic resonance spectrum of Embodiment 1 of the present invention;
[0027] Where 3aa~3bx are product numbers, and Ⅰ is... 1 H NMR spectrum, II is 13 C NMR. Detailed Implementation
[0028] The method of the present invention will be further described below through embodiments, but the present invention is not limited to these embodiments.
[0029] Example 1
[0030]
[0031] Methyl biphenyl-4-carboxylate (212.0 mg, 1.0 mmol, 1.0 eq.) and tert-butyl bromide (204.0 mg, 1.5 mmol, 1.5 eq.) were placed in a three-necked flask; MeCN (8 mL) was added and stirred to dissolve; TBAC (333.5 mg, 1.2 mmol, 1.2 eq.) was added; electrodes were inserted into the three-necked flask (zinc rod or zinc sheet as anode, tin rod or tin sheet as cathode), and the reaction was carried out at a constant current of 40 mA for about 2 h. After the reaction was completed, the solvent was recovered by distillation, H2O (15 mL) was added, and the mixture was extracted with ethyl acetate (3 x 15 mL). The organic phases were combined, dried over anhydrous sodium sulfate, filtered, and the residue after solvent recovery was separated by column chromatography to obtain the product, with a yield of 95%.
[0032] Structural identification of compound 3bq:
[0033] Nuclear magnetic resonance data:
[0034] 1 H NMR (500 MHz, Chloroform-d) δ 7.61 (d, J = 7.2 Hz, 2H), 7.56 (d, J= 8.2 Hz, 2H), 7.45 (t, J = 7.7 Hz, 2H), 7.37 (dd, J = 16.1, 7.8 Hz, 3H), 4.46 (d, J = 2.4 Hz, 1H), 1.91 (d, J = 2.8 Hz, 1H), 0.97 (s, 9H). 13 C NMR (126MHz, Chloroform-d) δ 141.41, 141.02, 140.27, 128.89, 128.18, 127.35, 127.17,126.41, 82.33, 35.88, 26.10.
[0035] Compound 3bq 1 H NMR, 13 C NMR such as Figure 2 As shown in the figure, the analysis results indicate that the target product obtained is correct.
[0036] Example 2:
[0037]
[0038] Methyl biphenyl-4-carboxylate (212.0 mg, 1.0 mmol, 1.0 eq.) and 1-bromoadamantane (321.0 mg, 1.5 mmol, 1.5 eq.) were placed in a three-necked flask; N,N-dimethylformamide (8 mL) was added and stirred to dissolve; tetrabutylammonium bromide (967.1 mg, 3.0 mmol, 3.0 eq.) was added; electrodes were inserted into the three-necked flask (zinc rod or zinc sheet as anode, tin rod or tin sheet as cathode), and the reaction was carried out at a constant current of 40 mA for about 2 h. After the reaction was completed, the solvent was recovered by distillation, H2O (15 mL) was added, and the mixture was extracted with ethyl acetate (3 x 15 mL). The organic phases were combined, dried over anhydrous sodium sulfate, filtered, and the residue after solvent recovery was separated by column chromatography to obtain the product, with a yield of 97%.
[0039] Structural identification of compound 3bs:
[0040] Nuclear magnetic resonance data:
[0041] 1 H NMR (500 MHz, Chloroform-d) δ 7.63 – 7.30 (m, 2H), 7.56 (d, J =8.2 Hz, 2H), 7.44 (t, J = 7.7 Hz, 2H), 7.34 (t, J = 8.0 Hz, 3H), 4.26 (s,1H), 1.99 (s, 3H), 1.88 (s, 1H), 1.68 (d, J = 12.1 Hz, 5H), 1.61 (d, J = 11.1Hz, 3H), 1.54 (d, J = 10.2 Hz, 3H). 13 C NMR (126 MHz, Chloroform-d) δ 141.05,140.40, 140.19, 128.88, 128.34, 127.32, 127.16, 126.30, 82.91, 38.30, 37.42,37.22, 28.50.
[0042] Example 3:
[0043]
[0044] Methyl biphenyl-4-carboxylate (212.0 mg, 1.0 mmol, 1.0 eq.) and bromocyclopentane (179.0 mg, 1.2 mmol, 1.2 eq.) were placed in a three-necked flask; MeCN (6 mL) was added and stirred to dissolve; tetraethylammonium tetrafluoroborate (542.5 mg, 2.5 mmol, 2.5 eq.) was added; electrodes (magnesium sheet as anode, tin rod or tin sheet as cathode) were inserted into the three-necked flask, and the reaction was carried out at a constant current of 40 mA for about 2 h. After the reaction was completed, the solvent was recovered by distillation, H2O (15 mL) was added, and the mixture was extracted with ethyl acetate (3 x 15 mL). The organic phases were combined, dried over anhydrous sodium sulfate, filtered, and the residue after solvent recovery was separated by column chromatography to obtain the product, with a yield of 85%.
[0045] Structural identification of compound 3ay:
[0046] Nuclear magnetic resonance data:
[0047] 1 H NMR (500 MHz, Chloroform-d) δ 7.62 – 7.55 (m, 4H), 7.47 – 7.41 (m,4H), 7.34 (t, J = 7.3 Hz, 1H), 4.46 (d, J = 8.4 Hz, 1H), 2.27 (q, J = 8.2 Hz,1H), 1.92 (d, J = 13.9 Hz, 2H), 1.66 – 1.60 (m, 2H), 1.50 – 1.40 (m, 2H),1.22 (td, J = 15.5, 12.6, 9.4 Hz, 2H). 13 C NMR (126 MHz, Chloroform-d) δ143.60, 141.02, 140.56, 128.89, 127.37, 127.21, 127.20, 127.07, 79.01, 47.77,29.63, 25.70, 25.58.
[0048] Comparative Example 1:
[0049]
[0050] A magnetic stir bar was placed in a dried 10 mL Schlenk tube, and 4-biphenylaldehyde (18.2 mg, 0.1 mmol, 1.0 eq.) and 1-cyclopentyl-2,4,6-triphenylpyridine-1-onium tetrafluoroborate (92.6 mg, 0.2 mmol, 2.0 eq.) were added. The reaction tube was evacuated and purged with argon, and this process was repeated three times. N,N-dimethylformamide (DMF, 1.0 mL) was added, followed by CrCl2 (61.5 mg, 0.5 mmol, 5.0 eq.). The reaction mixture was stirred in a 90 °C oil bath for 24 hours. After the reaction solution cooled to room temperature, the reaction was quenched in 10 mL of water, and extracted with ethyl acetate (3 × 5.0 mL). The organic phases were combined, washed with saturated brine, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography to give a colorless oil in 51% yield.
[0051] Example 4:
[0052]
[0053] Methyl biphenyl-4-carboxylate (1.06 g, 5.0 mmol, 1.0 eq.) and 5-bromo-1-pentene (1.49 g, 10.0 mmol, 2.0 eq.) were placed in a three-necked flask; MeCN (50 mL) was added and stirred to dissolve; TBAC (1.66 g, 6 mmol, 1.2 eq.) was added; electrodes were inserted into the three-necked flask (zinc rod or zinc sheet as anode, tin rod or tin sheet as cathode), and the reaction was carried out at a constant current of 200 mA for about 3 h. After the reaction was completed, the solvent was recovered by distillation, H2O (75 mL) was added, and the mixture was extracted with ethyl acetate (3 x 75 mL). The organic phases were combined, dried over anhydrous sodium sulfate, filtered, and the residue after solvent recovery was separated by column chromatography to obtain the product, with a yield of 71%.
[0054] Structural identification of compound 3al:
[0055] Nuclear magnetic resonance data:
[0056] 1H NMR (500 MHz, Chloroform-d) δ 7.60 – 7.58 (m, 4H), 7.46-7.41 (q,J = 7.8 Hz, 4H), 7.36 – 7.34 (m, 1H), 5.80 (td, J = 16.8, 6.6 Hz, 1H), 4.99(dd, J = 26.8, 13.7 Hz, 2H), 4.73 (t, J = 6.5 Hz, 1H), 2.11 (q, J = 6.9 Hz,2H), 1.87 – 1.82 (m, 1H), 1.79 – 1.72 (m, 1H), 1.63 – 1.52 (m, 1H), 1.44 (dd,J = 15.2, 8.3 Hz, 1H). 13 C NMR (126 MHz, Chloroform-d) δ 143.95, 140.97,140.62, 138.68, 128.90, 127.40, 127.35, 127.20, 126.46, 114.88, 74.42, 38.62,33.73, 25.24.
[0057] Example 5:
[0058]
[0059] Methyl biphenyl-4-carboxylate (212.0 mg, 1.0 mmol, 1.0 eq.) and 9-bromo-1-nonene (1.28 g, 5.0 mmol, 5.0 eq.) were placed in a three-necked flask; MeCN (12 mL) was added and stirred to dissolve; TBAC (692.5 mg, 2.5 mmol, 2.5 eq.) was added; electrodes (zinc rod or zinc sheet as anode and zinc rod or zinc sheet as cathode) were inserted into the three-necked flask, and the reaction was carried out at a constant current of 40 mA for about 2 h. After the reaction was completed, the solvent was recovered by distillation, H2O (15 mL) was added, and the mixture was extracted with ethyl acetate (3 x 15 mL). The organic phases were combined, dried over anhydrous sodium sulfate, filtered, and the residue after solvent recovery was separated by column chromatography to obtain the product, with a yield of 85%.
[0060] Structural identification of compound 3am:
[0061] Nuclear magnetic resonance data:
[0062] 1H NMR (500 MHz, Chloroform-d) δ 7.62 – 7.56 (m, 4H), 7.44 (q, J =7.8 Hz, 4H), 7.35 (t, J = 7.4 Hz, 1H), 5.87 – 5.75 (m, 1H), 5.02 – 4.89 (m,2H), 4.71 (d, J = 6.6 Hz, 1H), 2.04 (q, J = 6.9 Hz, 2H), 1.91 – 1.81 (m, 2H),1.79 – 1.72 (m, 1H), 1.50 – 1.42 (m, 1H), 1.30 (d, J = 19.2 Hz, 8H). 13 C NMR(126 MHz, Chloroform-d) δ 144.11, 141.01, 140.56, 139.35, 128.89, 127.38,127.32, 127.21, 126.48, 114.25, 74.59, 39.25, 33.94, 29.63, 29.56, 29.25,29.06, 25.99.
[0063] Example 6:
[0064]
[0065] Methyl biphenyl-4-carboxylate (2.12 g, 10.0 mmol, 1.0 eq.) and bromomethylcyclohexane (8.85 g, 50.0 mmol, 5.0 eq.) were placed in a three-necked flask; acetonitrile (250 mL) was added and stirred to dissolve; TBAC (13.85 g, 50.0 mmol, 5.0 eq.) was added; electrodes were inserted into the three-necked flask (zinc rod or zinc sheet as anode, tin rod or tin sheet as cathode), and the reaction was carried out at a constant current of 300 mA for about 2 h. After the reaction was completed, the solvent was recovered by distillation, H2O (150 mL) was added, and the mixture was extracted with ethyl acetate (3 x 150 mL). The organic phases were combined, dried over anhydrous sodium sulfate, filtered, and the residue after solvent recovery was separated by column chromatography to obtain the product, with a yield of 82%.
[0066] Structural identification of compound 3ah:
[0067] Nuclear magnetic resonance data:
[0068] 1H NMR (500 MHz, Chloroform-d) δ 7.59 (t, J = 7.3 Hz, 4H), 7.47 –7.39 (m, 4H), 7.35 (t, J = 7.3 Hz, 1H), 4.84 (d, J = 13.3 Hz, 1H), 1.84 (s,1H), 1.78 – 1.76 (m, 1H), 1.71 (d, J = 9.9 Hz, 2H), 1.62 – 1.53 (m, 2H), 1.47(dd, J = 9.5, 7.1 Hz, 1H), 1.30 – 1.19 (m, 3H), 1.16 (dd, J = 13.8, 10.8 Hz,1H), 1.02 – 0.94 (m, 2H). 13 C NMR (126 MHz, Chloroform-d) δ 144.53, 141.00,140.53, 128.89, 127.38, 127.36, 127.20, 126.42, 71.97, 47.18,34.40, 34.13,33.07, 26.72, 26.43, 26.29.
[0069] Example 7:
[0070]
[0071] Methyl biphenyl-4-carboxylate (212.0 mg, 1.0 mmol, 1.0 eq.) and 4-phenyl-1-butyl bromide (318.0 mg, 1.5 mmol, 1.5 eq.) were placed in a three-necked flask; 1,4-dioxane (8.0 mL) was added and stirred to dissolve; TBAC (333.5 mg, 1.2 mmol, 1.2 eq.) was added; electrodes (graphite felt anode and graphite felt cathode) were inserted into the three-necked flask, and the reaction was carried out at a constant current of 40 mA for about 2 h. After the reaction was completed, the solvent was recovered by distillation, H2O (15 mL) was added, and the mixture was extracted with ethyl acetate (3 x 15 mL). The organic phases were combined, dried over anhydrous sodium sulfate, filtered, and the residue after solvent recovery was separated by column chromatography to obtain the product, with a yield of 79%.
[0072] Structural identification of compound 3aj:
[0073] Nuclear magnetic resonance data:
[0074] 1H NMR (500 MHz, Chloroform-d) δ 7.59 (t, J = 7.5 Hz, 4H), 7.53 –7.40 (m, 4H), 7.36 (t, J = 7.4 Hz, 1H), 7.29 – 7.26 (m, 2H), 7.18 (t, J = 8.6Hz, 3H), 4.72 (t, J = 6.1 Hz, 1H), 2.67 – 2.57 (m, 2H), 1.94 – 1.83 (m, 2H), 1.83 – 1.76 (m, 1H), 1.73 – 1.65 (m, 2H), 1.56 – 1.49 (m, 1H), 1.44 – 1.36(m, 1H). 13 C NMR (126 MHz, Chloroform-d) δ 144.01, 142.69, 140.99, 140.63,128.90, 128.52, 128.41, 127.40, 127.35, 127.21, 126.46, 125.80, 74.47, 39.06,35.99, 31.54, 25.68.
[0075] Example 8:
[0076]
[0077] Methyl biphenyl-4-carboxylate (21.2 g, 100 mmol, 1.0 eq.) and 5-bromo-1-pentene (22.2 mg, 150 mmol, 1.5 eq.) were placed in a 1 L beaker; MeCN (500.0 mL) was added and stirred until dissolved; TBAC (55.4 g, 200 mmol, 2.0 eq.) was added; electrodes (zinc rod or zinc sheet as anode, tin rod or tin sheet as cathode) were inserted into the 1 L beaker, and the reaction was carried out at a constant current of 10 A for about 4 h. After the reaction was completed, the solvent was recovered by distillation, H2O (500 mL) was added, and the mixture was extracted with ethyl acetate (3 x 500 mL). The organic phases were combined, dried over anhydrous sodium sulfate, filtered, and the residue after solvent recovery was separated by column chromatography to obtain the product, with a yield of 65%.
[0078] Appendix Table 1: Yield profile of the reaction under different conditions (This invention is not limited to the reaction conditions listed in the table).
[0079]
[0080] Table 1 Performance Test Result Evaluation Table
[0081]
[0082] Notes: The amount of methyl biphenyl-4-carboxylate in Examples 1, 2, 3, 5, and 7 in this table is 1.0 mmol; the amount of methyl biphenyl-4-carboxylate in Example 4 is 5.0 mmol; the amount of methyl biphenyl-4-carboxylate in Example 6 is 10.0 mmol; the amount of methyl biphenyl-4-carboxylate in Example 8 is 100.0 mmol; the dimensions of the rod electrodes in Examples 1, 2, 3, 5, and 6 are: diameter 0.8 cm, length 10 cm; the dimensions of the sheet electrodes are: length × width × height 2 cm × 1 cm × 0.5 cm; the dimensions of the graphite felt electrode in Example 7 are: length × width × height 1 cm × 5 cm; the dimensions of the rod electrode in Example 8 are: diameter 3.0 cm, length 15 cm; the dimensions of the sheet electrode are: length × width × height 8 cm × 1 cm × 15 cm; TBAC stands for tetrabutylammonium chloride; TBAB stands for tetrabutylammonium bromide; Et4NBF4 stands for tetraethylammonium tetrafluoroborate; DMF stands for N,N-dimethylformamide.
[0083] As can be seen from the results in Table 1, the synthesis method provided by the present invention can greatly improve the yield of biphenylbenzyl alcohol, which can reach 97%. Moreover, the process is simple, the cost is low, and it has a wide range of industrial applications.
[0084] The above description is a preferred embodiment of the present invention and should not be construed as limiting the scope of the present invention. It should be noted that those skilled in the art can make several improvements and modifications without departing from the principle of the present invention, and these improvements and modifications are also considered to be within the scope of protection of the present invention.
Claims
1. A method for coupling methyl biphenyl-4-carboxylate with a bromoalkane to synthesize biphenyl benzyl alcohol, characterized in that, include: In an electrochemical catalytic reactor, methyl biphenyl-4-carboxylate, bromoalkane, and electrolyte are dissolved in a solvent, connected to electrodes, and reacted by stirring at room temperature. After the reaction, the mixture is subjected to vacuum distillation, extraction, merging of organic phases, drying, filtration, concentration, and purification to obtain the biphenyl benzyl alcohol compound. The anode material is one of zinc, manganese, platinum, magnesium, iron, nickel, copper, cobalt, tin, or titanium, and the cathode material is one of carbon, graphite felt, zinc, manganese, platinum, magnesium, iron, nickel, copper, cobalt, tin, or titanium. The electrolyte is a salt composed of cations and anions.
2. The method according to claim 1, characterized in that, The molar ratio of methyl biphenyl-4-carboxylate to bromoalkanes, electrolytes, and solvents is 1:1.2~5.0:1.2~5.0:100~500.
3. The method according to claim 1, characterized in that, The methyl biphenyl-4-carboxylate is a compound shown in formula (1), the bromoalkane is a compound shown in formula (2), and the biphenyl benzyl alcohol product is a compound shown in formula (3); wherein, R is an alkyl group.
4. The method according to claim 3, characterized in that, Alkyl groups are alkanes, cycloalkyl groups, alkyl groups containing any of the elements of halogen, oxygen, nitrogen, silicon, phosphorus, and sulfur, or alkyl groups containing aromatics or heterocyclic aromatics.
5. The method according to claim 1, characterized in that, The solvent is one or a mixture of more than one of acetonitrile, dichloromethane, dichloroethane, trichloromethane, carbon tetrachloride, N,N-dimethylformamide, 1,4-dioxane, methanol, ethanol, isopropanol, hexafluoroisopropanol, trifluoroethanol, acetone, dimethyl sulfoxide, tetrahydrofuran, and water.
6. The method according to claim 1, characterized in that, The electrolyte is one or more of lithium perchlorate, ammonium perchlorate, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium tetrafluoroborate, tetraethylammonium tetrafluoroborate, and tetraethylammonium chloride.
7. The method according to claim 1, characterized in that, The electrode can be in the form of a sheet, block, rod, or mesh.
8. The method according to any one of claims 1 to 7, characterized in that, The energizing reaction is carried out under constant current or constant voltage conditions, with a current intensity of 20mA~10A and a reaction temperature of -20~100℃.
9. The method according to any one of claims 1 to 7, characterized in that, The purification process specifically includes column chromatography, vacuum distillation, or recrystallization.