P-terphenyl derivative and synthesis method thereof

Abstract

The invention relates to a novel method for high-selectivity synthesis of a p-terphenyl derivative through cascade cyclization of dimethyl sulfoxide (DMSO) serving as two C sources and aryl ketone in a multi-component form under the promotion of potassium tert-butoxide. According to the method, only strong base potassium tert-butoxide is used as an accelerant, and complex ligands and expensive metal reagents are prevented from being used. Meanwhile, the formal [1 + 2 + 2 + 1] cascade cyclization reaction is suitable for various substrates, has good tolerance to various substituent groups, and can provide p-terphenyl derivatives which are easy to obtain at a good yield. In addition, the reaction also has the characteristics of low additive price, simple reaction conditions, easily available initial raw materials and the like. According to the method, a multi-group hierarchical cyclization protocol is carried out on starting raw materials which are easy to purchase commercially at lower cost, and the p-terphenyl compounds with multiple substituent groups are synthesized.

Description

[Technical field]

[0001] The invention belongs to the field of organic synthesis and relates to a terphenyl derivative and a synthesis method thereof. [Background technology]

[0002] Terphenyl compounds are composed of three benzene rings connected and are a class of small molecular polycyclic aromatic hydrocarbons. They exist in three isomers: ortho, meta and para. In nature, they mainly exist in the form of para structure. Compounds containing terphenyl structure have good biological activity. In addition, this type of compound also performs well in liquid crystal and electroluminescence, and is widely used in liquid crystal materials. p-Terphenyl is composed of a C-18 tricyclic or polycyclic C-18 aromatic skeleton, and its structure varies due to the connection mode between the middle benzene ring and the benzene rings on both sides and the connection changes with the main skeleton. In recent years, studies have found that p-terphenyl has a variety of biological activities, including cytotoxicity, α-glucosidase inhibition, antioxidant and antibacterial activity. In addition, p-terphenyl also plays an important role in membrane chemistry, supramolecular organic materials, covalent organic polymers and other fields. Due to its special configuration, it has been widely used in material preparation, such as laser dyes and single-molecule spectroscopy. p-Terphenyl also plays an important role in organic superconductors (HTOS). By doping it with potassium ions, the conductive properties can be effectively improved. Due to its non-planar structure, p-terphenyl can be used as a simple molecular rotor. At the same time, it performs well in electroluminescence and is often used as a scintillator for detecting ionizing radiation.

[0003] Despite the wide application of p-terphenyl in the fields of medicine and materials, chemists are still studying its efficient synthesis methods. Existing synthesis methods mainly include coupling reactions or cyclization reactions between aryl halides, aryl boronic acids or Grignard reagents. However, these methods usually require expensive noble metal catalysts or complex ligands, which are costly and environmentally unfriendly. In addition, cyclization reactions often require complex substrates, which increases the reaction cost. Therefore, it is of great research value to design a synthesis method for p-terphenyl that does not require transition metal catalysts and ligands and has a simple substrate structure. We hope to develop a practical, efficient and easy-to-operate method that directly uses commercially available starting materials to avoid the problems of limited substitution categories, expensive synthesis costs and multi-step synthesis of starting materials. To this end, we developed a method for realizing multi-component cascade cyclization reactions using dimethyl sulfoxide as a synthon and reaction reagent, and using commercially available aryl ketone derivatives under the promotion of potassium tert-butoxide. This method does not use additional metal catalysts and ligands, is easy to operate, has good substrate adaptability, high yield, and the starting materials can be directly purchased commercially.

[0004] At present, there are no public documents or patent applications at home and abroad on the [1+2+2+1] cascade cyclization of multiple components to obtain terphenyl in the absence of metal catalysts. [Summary of the invention]

[0005] Therefore, the present invention uses DMSO as two carbon sources and aryl ketone derivatives as raw materials to develop a non-metal-catalyzed cyclization reaction for efficiently synthesizing p-terphenyl derivatives. The reaction utilizes readily available aryl ketones, dimethyl sulfoxide, and potassium tert-butoxide through a multi-component [1+2+2+1] cascade cyclization method to obtain p-terphenyl compounds with high functional group tolerance in a relatively high yield. The method has the advantages of no metal and ligand catalysis, cheap and readily available raw materials, simple operation, and a wide range of functional group tolerance, and provides a new method and idea for the synthesis of p-terphenyl. Further, the present invention also uses DMSO as one carbon source and aryl ketone derivatives substituted with multiple alkanes at the α position as raw materials to develop a non-metal-catalyzed cyclization reaction for efficiently synthesizing p-terphenyl derivatives containing extendable side chains.

[0006] To achieve the above object, the technical solution of the present invention is as follows:

[0007] A selective synthesis method for a class of p-terphenyl derivatives comprises the following steps: in an air atmosphere, potassium tert-butoxide is used as a promoter, DMSO is used as a carbon source and a reaction solvent, and aromatic ketone derivatives are stirred at 160° C. for 12 hours to obtain p-terphenyl derivatives.

[0008] A further improvement is that the product containing the p-terphenyl derivative is diluted with ethyl acetate, water is added, and then extracted three times with ethyl acetate, the organic phases are collected and combined, and then anhydrous Na2SO4 is added to dehydrate the combined organic phases, and then concentrated under reduced pressure to obtain a crude product. The crude product is separated by column chromatography on silica gel to obtain a purified p-terphenyl derivative.

[0009] In a further improvement, the molar ratio of potassium tert-butoxide to the aryl ketone derivative is 1:2×0.5.

[0010] In a further improvement, the ketone is one of propiophenone, 3'-methylpropiophenone, 4'-methylpropiophenone, 4'-ethylpropiophenone, 4'-fluoropropiophenone, 3'-trifluoromethylpropiophenone, butyrophenone, valerophenone, hexanophenone, heptanone, lauryl ketone (dodecyl ketone), stearyl ketone (octadecyl ketone), acetophenone, 2'-methylacetophenone, 3'-methylacetophenone, 4'-methylacetophenone, 4'-ethylacetophenone, 4'-n-butylacetophenone, 4'-n-pentylacetophenone, 4'-isopropylacetophenone, 2'-acetonaphthone, 3',4'-dimethylacetophenone, 4'-fluoroacetophenone, 3'-trifluoromethylacetophenone, 2'-acetylpyridine, 2'-acetylthiophene, and 2'-acetylfuran.

[0011] A class of p-terphenyl derivatives, wherein the chemical formula of the p-terphenyl derivatives is as shown in formula (1) or formula (2):

[0012]

[0013] Wherein, R is a substituent group selected from H, Me, Et, F, CF3 or Ph. Wherein n=1, 2, 3, 4, 5, 10 or 16.

[0014] The advantages of the present invention are as follows:

[0015] The present invention discloses a novel method for synthesizing p-terphenyl derivatives by cascade cyclization in a multi-component form with high selectivity under the promotion of potassium tert-butoxide, using dimethyl sulfoxide (DMSO) as two C sources and aromatic ketones. The method only uses strong base potassium tert-butoxide as a promoter, avoiding the use of complex ligands and expensive metal reagents. At the same time, this formal [1+2+2+1] cascade cyclization reaction is applicable to a variety of substrates, has good tolerance to a variety of substituents, and can provide easily available p-terphenyl derivatives with good yield. In addition, the reaction also has the characteristics of low additive price, simple reaction conditions, and easy availability of starting materials. A multi-component cascade cyclization protocol is achieved at a relatively low cost from commercially available starting materials, and p-terphenyl compounds with a variety of substituents are synthesized. In addition, a novel method for synthesizing p-terphenyl derivatives containing extendable side chains with high selectivity is developed. A new approach is provided for the synthesis of p-terphenyl derivatives containing extendable side chains with potential application value in the field of materials.

Brief Description of the Drawings

[0016] Figure 1 It is the reaction diagram of the present invention.

[0017] Figure 2 The figure is the chemical formula of the terphenyl derivatives of the present invention. [Specific implementation method]

[0018] Reaction formula of the present invention is as follows:

[0019]

[0020] Embodiment 1:

[0021] Potassium tert-butoxide (1 mmol, 2.0 equiv.) was added to a 10 mL Schlenk tube equipped with a magnetic stirrer. Then, phenylacetone (2×0.5 mmol) and 2.0 mL of solvent dimethyl sulfoxide (DMSO) were added under an air atmosphere. The mixture was stirred at 160°C for 12 hours (constant temperature oil bath). After the reaction was completed, it was cooled to room temperature, diluted with ethyl acetate, and an appropriate amount of water was added. The mixture was extracted three times with ethyl acetate, the organic phase was collected, and an appropriate amount of anhydrous Na2SO4 was added to dehydrate the combined organic layers, and concentrated under reduced pressure. The crude product was separated and purified by column chromatography on silica gel (petroleum ether / ethyl acetate = 100:1) to obtain purified 2'-methyl-1,1':4',1"-triphenylene appearance: yellow solid; yield: 51% (62.2 mg); 1 H NMR (400MHz, CDCl3) δ7.65–7.59(m,2H),7.49(t,J=2.4Hz,1H),7.46–7.38(m,5H),7.37–7.29(m,5H),2.34(s,3H). 13 C NMR (101MHz, CDCl3) δ141.69,141.05,141.03,140.26,135.81,130.39,129.31,129.21,128.84,128.21,127.31,127.20,126.93,124.64,20.74.

[0022] Embodiment 2:

[0023] Potassium tert-butoxide (1 mmol, 2.0 equivalents) was added to a 10 mL Schlenk tube equipped with a magnetic stirrer. Then, 3'-methylpropiophenone (2×0.5 mmol) and 2.0 mL of solvent dimethyl sulfoxide (DMSO) were added under an air atmosphere. The mixture was stirred at 160°C for 12 hours (constant temperature oil bath). After the reaction was completed, it was cooled to room temperature, diluted with ethyl acetate, and then an appropriate amount of water was added. The mixture was extracted three times with ethyl acetate, the organic phase was collected, and an appropriate amount of anhydrous Na2SO4 was added to dehydrate the combined organic layers, and concentrated under reduced pressure. The crude product was separated by column chromatography on silica gel (petroleum ether / ethyl acetate=100:1) to obtain purified 2',3,3"-methyl-1,1':4',1"-triphenyl. Appearance: yellow solid; Yield: 58% (78.8 mg); 1 H NMR (400MHz, CDCl3) δ7.55(d,J=1.8Hz,1H),7.54–7.47(m,3H),7.43–7.33(m,3H),7.23(d,J=8.6Hz,4H),2.48(d,J=8.2Hz,6H),2.41(s,3H). 13C NMR (101MHz, CDCl3) δ141.66,141.06,141.04,140.24,138.37,137.75,135.72,130.29,130.05, 129.15,128.73,128.05,128.03,127.98,127.62,126.38,124.58,124.30,21.65,21.59,20.75.

[0024] Embodiment 3:

[0025] Potassium tert-butoxide (1 mmol, 2.0 equiv.) was added to a 10 mL Schlenk tube equipped with a magnetic stirrer. Then, 4'-methylpropiophenone (2 x 0.5 mmol) and 2.0 mL of dimethyl sulfoxide (DMSO) were added under an air atmosphere. The mixture was stirred at 160°C for 12 hours (constant temperature oil bath). After the reaction was completed, it was cooled to room temperature, diluted with ethyl acetate, and then an appropriate amount of water was added. The mixture was extracted three times with ethyl acetate, the organic phase was collected, and an appropriate amount of anhydrous Na2SO4 was added to dehydrate the combined organic layers, and concentrated under reduced pressure. The crude product was separated by column chromatography on silica gel (petroleum ether / ethyl acetate = 100:1) to obtain purified 2',4,4'-trimethyl-1,1':4',1"-triphenyl. Appearance: white solid; Yield: 61% (82.9 mg); 1 H NMR (400MHz, CDCl3) δ7.53(d,J=7.7Hz,2H),7.49–7.43(m,2H),7.31–7.21(m,8H),2.41(d,J=4.5Hz,6H),2.35(s,3H). 13 C NMR (101MHz, CDCl3) δ140.63,139.92,138.71,138.10,136.94,136.44,135.71, 130.30,129.46,129.11,128.90,128.82,126.93,124.34,21.19,21.12,20.71.

[0026] Embodiment 4:

[0027] Potassium tert-butoxide (1 mmol, 2.0 equivalents) was added to a 10 mL Schlenk tube equipped with a magnetic stirrer. Then, 4'-ethylpropiophenone (2×0.5 mmol) and 2.0 mL of dimethyl sulfoxide (DMSO) were added under an air atmosphere. The mixture was stirred at 160°C for 12 hours (constant temperature oil bath). After the reaction was completed, it was cooled to room temperature, diluted with ethyl acetate, and then an appropriate amount of water was added. The mixture was extracted three times with ethyl acetate, the organic phase was collected, and an appropriate amount of anhydrous Na2SO4 was added to dehydrate the combined organic layers, and concentrated under reduced pressure. The crude product was separated by column chromatography on silica gel (petroleum ether / ethyl acetate=100:1) to obtain purified 4,4"-ethyl-2'-methyl-1,1':4',1"-terphenyl. Appearance: black liquid; Yield: 69% (103.5 mg); 1 HNMR (400MHz, CDCl3) δ7.63(dd,J=8.4,2.4Hz,2H),7.56(d,J=1.9Hz,1H),7.52(dd,J=7.9,2.0Hz,1H ),7.35(dd,J=9.2,7.0Hz,7H),2.78(dt,J=7.6,3.8Hz,4H),2.42(s,3H),1.36(td,J=7.6,5.1Hz,7H). 13 C NMR (101MHz, CDCl3) δ143.36,142.81,140.73,140.01,139.00,138.44,135.79,130.41 ,129.26,129.04,128.35,127.67,127.11,124.47,28.66,28.62,20.83,15.68,15.60.

[0028] Embodiment 5:

[0029] Potassium tert-butoxide (1 mmol, 2.0 equivalents) was added to a 10 mL Schlenk tube equipped with a magnetic stirrer. Then, 4'-fluoropropiophenone (2×0.5 mmol) and 2.0 mL of dimethyl sulfoxide (DMSO) were added under an air atmosphere. The mixture was stirred at 160°C for 12 hours (constant temperature oil bath). After the reaction was completed, it was cooled to room temperature, diluted with ethyl acetate, and then an appropriate amount of water was added. The mixture was extracted three times with ethyl acetate, the organic phase was collected, and an appropriate amount of anhydrous Na2SO4 was added to dehydrate the combined organic layers, and concentrated under reduced pressure. The crude product was separated by column chromatography on silica gel (petroleum ether / ethyl acetate=100:1) to obtain purified 4,4"-fluoro-2'-methyl-1,1':4',1"-triphenyl. Appearance: yellow solid; Yield: 22% (30.8 mg); 1H NMR (400MHz, CDCl3) δ7.61 (dd, J = 8.4, 5.3Hz, 2H), 7.50–7.42 (m, 2H), 7.38–7.27 (m, 4H), 7.21–7.10 (m, 4H), 2.35 (s, 3H). 13 C NMR (101MHz, CDCl3) δ163.72,163.23,161.27,139.95,139.36,137.39,137.36,136.95,136.92,135. 91,130.78,130.70,130.37,129.04,128.67,128.59,124.47,115.76,115.55,115.18,114.97,20.63.

[0030] Embodiment 6:

[0031] Potassium tert-butoxide (1 mmol, 2.0 equivalents) was added to a 10 mL Schlenk tube equipped with a magnetic stirrer. Then, 3'-trifluoromethylpropiophenone (2×0.5 mmol) and 2.0 mL of dimethyl sulfoxide (DMSO) were added under an air atmosphere. The mixture was stirred at 160°C for 12 hours (constant temperature oil bath). After the reaction was completed, it was cooled to room temperature, diluted with ethyl acetate, and then an appropriate amount of water was added. The mixture was extracted three times with ethyl acetate, the organic phase was collected, and an appropriate amount of anhydrous Na2SO4 was added to dehydrate the combined organic layers, and concentrated under reduced pressure. The crude product was separated by column chromatography on silica gel (petroleum ether / ethyl acetate=100:1) to obtain purified 2'-methyl-3,3"-trifluoromethyl-1,1':4',1"-triphenyl. Appearance: white solid; Yield: 40% (76.0 mg); 1 H NMR (400MHz, CDCl3) δ7.88(s,1H),7.81(d,J=7.6Hz,1H),7.68–7.46(m,9H),7.34(d,J=7.8Hz,1H),2.36(s,3H). 13 C NMR (101MHz, CDCl3) δ142.04,141.50,140.20,139.38,136.08,132.51,130.43,130.40,129.35,129.31,128.72,124.82,20.53.

[0032] Embodiment 7:

[0033] Potassium tert-butoxide (1 mmol, 2.0 equiv.) was added to a 10 mL Schlenk tube equipped with a magnetic stirrer. Then, phenylbutyrophenone (2×0.5 mmol) and 2.0 mL of dimethyl sulfoxide (DMSO) were added under an air atmosphere. The mixture was stirred at 160°C for 12 hours (constant temperature oil bath). After the reaction was completed, it was cooled to room temperature, diluted with ethyl acetate, and then an appropriate amount of water was added. The mixture was extracted three times with ethyl acetate, the organic phase was collected, and an appropriate amount of anhydrous Na2SO4 was added to dehydrate the combined organic layers, and concentrated under reduced pressure. The crude product was separated by column chromatography on silica gel (petroleum ether / ethyl acetate=100:1) to obtain purified 2'-ethyl-6'-methyl-1,1':4',1"-triphenyl. Appearance: white solid; Yield: 65% (88.4 mg); 1 H NMR (400MHz, CDCl3) δ7.64 (dd, J=8.1, 1.4Hz, 2H), 7.45–7.36 (m, 5H), 7.35–7.30 (m ,3H),7.21–7.17(m,2H),2.42(q,J=7.5Hz,2H),2.07(s,3H),1.06(t,J=7.5Hz,3H). 13 C NMR (101MHz, CDCl3) δ142.79,141.45,140.66,140.59,140.30,136.75,129.45, 128.79,128.41,127.26,127.21,126.80,126.16,124.71,27.06,21.25,15.79.

[0034] Embodiment 8:

[0035] Potassium tert-butoxide (1 mmol, 2.0 equiv.) was added to a 10 mL Schlenk tube equipped with a magnetic stirrer. Then, valerophenone (2×0.5 mmol) and 2.0 mL of solvent dimethyl sulfoxide (DMSO) were added under an air atmosphere. The mixture was stirred at 160°C for 12 hours (constant temperature oil bath). After the reaction was completed, it was cooled to room temperature, diluted with ethyl acetate, and then an appropriate amount of water was added. The mixture was extracted three times with ethyl acetate, the organic phase was collected, and an appropriate amount of anhydrous Na2SO4 was added to dehydrate the combined organic layers, and concentrated under reduced pressure. The crude product was separated by column chromatography on silica gel (petroleum ether / ethyl acetate=100:1) to obtain purified 2'-ethyl-6'-propyl-1,1':4',1"-triphenyl. Appearance: yellow solid; Yield: 50% (75.0 mg); 1H NMR(400MHz, CDCl3)δ7.72(dd,J=7.7,1.8Hz,2H),7.53–7.45(m,4H),7.42(dt,J=7.8,2.5Hz,4H),7.28(d ,J=1.7Hz,2H),2.50–2.36(m,4H),1.58–1.51(m,2H),1.13(t,J=7.6Hz,3H),0.85(td,J=7.3,1.4Hz,3H). 13 C NMR (101MHz, CDCl3) δ142.82,141.54,141.29,140.24,140.18,129.74,128.72,12 8.07,127.22,127.12,126.70,125.26,124.54,36.03,27.09,24.50,15.66,14.18.

[0036] Embodiment 9:

[0037] Potassium tert-butoxide (1 mmol, 2.0 equivalents) was added to a 10 mL Schlenk tube equipped with a magnetic stirrer. Then, hexanophenone (2×0.5 mmol) and 2.0 mL of dimethyl sulfoxide (DMSO) were added under an air atmosphere. The mixture was stirred at 160°C for 12 hours (constant temperature oil bath). After the reaction was completed, it was cooled to room temperature, diluted with ethyl acetate, and then an appropriate amount of water was added. The mixture was extracted three times with ethyl acetate, the organic phase was collected, and an appropriate amount of anhydrous Na2SO4 was added to dehydrate the combined organic layers, and concentrated under reduced pressure. The crude product was separated by column chromatography on silica gel (petroleum ether / ethyl acetate=100:1) to obtain purified 2'-butyl-6'-propyl-1,1':4',1"-triphenyl. Appearance: white solid; Yield: 50% (82.0 mg); 1 H NMR (400MHz, CDCl3) δ7.78(d,J=7.5Hz,1H),7.55(dt,J=14.6,7.4Hz,2H),7.47(d,J=5.8Hz,2H),7.33(s,1H ), 2.48 (d, J = 8.6Hz, 2H), 1.57 (dt, J = 15.1, 7.6Hz, 2H), 1.31 (q, J = 7.5Hz, 1H), 0.90 (dt, J = 14.3, 7.3Hz, 3H). 13C NMR (101MHz, CDCl3) δ141.56,141.53,141.29,140.41,140.23,139.96,129.81,128.71,12 8.00,127.21,127.09,126.67,125.24,125.21,36.08,33.64,24.50,22.63,14.18,13.84.

[0038] Embodiment 10:

[0039] Potassium tert-butoxide (1 mmol, 2.0 equivalents) was added to a 10 mL Schlenk tube equipped with a magnetic stirrer. Then, phenylheptanone (2×0.5 mmol) and 2.0 mL of dimethyl sulfoxide (DMSO) were added under an air atmosphere. The mixture was stirred at 160°C for 12 hours (constant temperature oil bath). After the reaction was completed, it was cooled to room temperature, diluted with ethyl acetate, and an appropriate amount of water was added. The mixture was extracted three times with ethyl acetate, the organic phase was collected, and an appropriate amount of anhydrous Na2SO4 was added to dehydrate the combined organic layers, and concentrated under reduced pressure. The crude product was separated by column chromatography on silica gel (petroleum ether / ethyl acetate=100:1) to obtain purified 2'-butyl-6'-pentyl-1,1':4',1"-triphenyl. Appearance: yellow liquid; Yield: 47% (83.6 mg); 1 H NMR (400MHz, CDCl3) δ7.67–7.62(m,2H),7.48–7.38(m,4H),7.35(d,J=6.7Hz,4H),7.21–7.18(m,2H),2.36(dd d,J=8.3,6.8,3.7Hz,4H),1.43(tdd,J=12.5,6.9,3.6Hz,4H),1.20–1.11(m,6H),0.77(dt,J=12.5,7.1Hz,6H). 13 C NMR (101MHz, CDCl3) δ141.58,141.52,141.48,140.31,140.14,139.94,129.77,128.68,127.96,1 27.18,127.06,126.64,125.16,125.14,33.92,33.61,31.76,31.08,22.60,22.33,13.94,13.83.

[0040] Embodiment 11:

[0041] Potassium tert-butoxide (1 mmol, 2.0 equivalents) was added to a 10 mL Schlenk tube equipped with a magnetic stirrer. Then, lauryl ketone (dodecyl ketone) (2×0.5 mmol) and 2.0 mL of solvent dimethyl sulfoxide (DMSO) were added under an air atmosphere. The mixture was stirred at 160°C for 12 hours (constant temperature oil bath). After the reaction was completed, it was cooled to room temperature, diluted with ethyl acetate, and an appropriate amount of water was added. The mixture was extracted three times with ethyl acetate, the organic phase was collected, and an appropriate amount of anhydrous Na2SO4 was added to dehydrate the combined organic layers, and concentrated under reduced pressure. The crude product was separated by column chromatography on silica gel (petroleum ether / ethyl acetate=100:1) to obtain purified 2'-decyl-6'-nonyl-1,1':4',1"-triphenyl. Appearance: green liquid; Yield: 40% (99.2 mg); 1 H NMR (400MHz, CDCl3) δ7.70 (d, J=7.6Hz, 2H), 7.49–7.39 (m, 8H), 7.24 (s, 2H) ,2.46–2.36(m,5H),1.48(d,J=8.2Hz,4H),1.35–1.28(m,27H),0.93(s,6H). 13 C NMR (101MHz, CDCl3) δ141.62,141.51,140.32,140.17,139.98,129.80,128.70,127.99, 127.21,125.18,33.98,31.99,31.96,31.93,31.43,29.56,29.50,22.76,22.74,14.18.

[0042] Embodiment 12:

[0043] Potassium tert-butoxide (1 mmol, 2.0 equivalents) was added to a 10 mL Schlenk tube equipped with a magnetic stirrer. Then, stearyl ketone (octadecyl ketone) (2×0.5 mmol) and 2.0 mL of solvent dimethyl sulfoxide (DMSO) were added under an air atmosphere. The mixture was stirred at 160°C for 12 hours (constant temperature oil bath). After the reaction was completed, it was cooled to room temperature, diluted with ethyl acetate, and an appropriate amount of water was added. The mixture was extracted three times with ethyl acetate, the organic phase was collected, and an appropriate amount of anhydrous Na2SO4 was added to dehydrate the combined organic layers, and concentrated under reduced pressure. The crude product was separated by column chromatography on silica gel (petroleum ether / ethyl acetate=100:1) to obtain purified 2'-hexadecyl-6'-pentadecyl-1,1':4',1"-triphenyl. Appearance: green liquid; Yield: 40% (132.8 mg); 1H NMR(400MHz, CDCl3)δ7.67(d,J=7.6Hz,2H),7.46–7.36(m,8H),7.21(d,J=7.3 Hz, 2H), 2.41–2.32 (m, 4H), 1.44 (d, J = 8.3Hz, 4H), 1.28 (s, 51H), 0.90 (s, 6H). 13 CNMR(101MHz,CDCl3)δ141.60,141.49,140.29,140.15,139.96,129.78,128.68,127 .97,127.19,125.16,33.96,31.97,31.41,29.75,29.71,29.66,29.41,22.74,14.17.

[0044] Embodiment 13:

[0045] Potassium tert-butoxide (1 mmol, 2.0 equivalents) was added to a 10 mL Schlenk tube equipped with a magnetic stirrer. Then, acetophenone (2×0.5 mmol) and 2.0 mL of dimethyl sulfoxide (DMSO) were added under an air atmosphere. The mixture was stirred at 160° C. for 12 hours (constant temperature oil bath). After the reaction was completed, it was cooled to room temperature, the mixture was diluted with ethyl acetate, an appropriate amount of water was added, and then extracted three times with ethyl acetate, the organic phase was collected, and an appropriate amount of anhydrous Na2SO4 was added to dehydrate the combined organic layers, and concentrated under reduced pressure. The crude product was separated and purified by column chromatography on silica gel (petroleum ether / ethyl acetate=100:1) to obtain terphenyl as a white solid. Yield: 74% (85.1 mg); 1 HNMR (400MHz, CDCl3) δ7.68 (s, 4H), 7.66–7.62 (m, 4H), 7.46 (t, J = 7.7Hz, 4H), 7.39–7.33 (m, 2H). 13 C NMR (101MHz, CDCl3) δ140.70,140.11,128.79,127.48,127.32,127.03.

[0046] Embodiment 14:

[0047] Potassium tert-butoxide (1 mmol, 2.0 equivalents) was added to a 10 mL Schlenk tube equipped with a magnetic stirrer. Then, 2'-methylacetophenone (2×0.5 mmol) and 2.0 mL of dimethyl sulfoxide (DMSO) were added under an air atmosphere. The mixture was stirred at 160°C for 12 hours (constant temperature oil bath). After the reaction was completed, it was cooled to room temperature, diluted with ethyl acetate, and then an appropriate amount of water was added. The mixture was extracted three times with ethyl acetate, the organic phase was collected, and an appropriate amount of anhydrous Na2SO4 was added to dehydrate the combined organic layers, and concentrated under reduced pressure. The crude product was separated by column chromatography on silica gel (petroleum ether / ethyl acetate=100:1) to obtain purified 2,2,-dimethyl-p-terphenyl. Appearance: white solid; Yield: 55% (70.9 mg); 1 H NMR (400MHz, CDCl3) δ7.39(s,4H),7.32–7.29(m,8H),2.37(s,6H). 13 C NMR (101MHz, CDCl3) δ141.69,140.39,135.46,130.42,129.92,128.92,127.29,125.84,20.62.

[0048] Embodiment 15:

[0049] Potassium tert-butoxide (1 mmol, 2.0 equivalents) was added to a 10 mL Schlenk tube equipped with a magnetic stirrer. Then, 3'-methylacetophenone (2×0.5 mmol) and 2.0 mL of dimethyl sulfoxide (DMSO) were added under air atmosphere. The mixture was stirred at 160°C for 12 hours (constant temperature oil bath). After the reaction was completed, it was cooled to room temperature, diluted with ethyl acetate, and then an appropriate amount of water was added. The mixture was extracted three times with ethyl acetate, the organic phase was collected, and an appropriate amount of anhydrous Na2SO4 was added to dehydrate the combined organic layer, and concentrated under reduced pressure. The crude product was separated by column chromatography on silica gel (petroleum ether / ethyl acetate=100:1) to obtain purified 3,3,-dimethyl-p-terphenyl. Appearance: yellow solid; Yield: 62% (71.5 mg);. 1 H NMR (400MHz, CDCl3) δ7.74(s,4H),7.53(d,J=8.9Hz,4H),7.43(t,J=7.5Hz,2H),7.26(d,J=7.5Hz,2H),2.52(s,6H). 13 C NMR (101MHz, CDCl3) δ140.79,140.20,138.41,128.75,128.11,127.88,127.49,124.20,21.60.

[0050] Embodiment 16:

[0051] Potassium tert-butoxide (1 mmol, 2.0 equivalents) was added to a 10 mL Schlenk tube equipped with a magnetic stirrer. Then, 4'-methylacetophenone (2×0.5 mmol) and 2.0 mL of dimethyl sulfoxide (DMSO) were added under air atmosphere. The mixture was stirred at 160°C for 12 hours (constant temperature oil bath). After the reaction was completed, it was cooled to room temperature, diluted with ethyl acetate, and then an appropriate amount of water was added. The mixture was extracted three times with ethyl acetate, the organic phase was collected, and an appropriate amount of anhydrous Na2SO4 was added to dehydrate the combined organic layer, and concentrated under reduced pressure. The crude product was separated by column chromatography on silica gel (petroleum ether / ethyl acetate=100:1) to obtain purified 4,4,-dimethyl-p-terphenyl. Appearance: white solid; Yield: 72% (92.8 mg);. 1 H NMR (400MHz, CDCl3) δ7.65 (s, 4H), 7.54 (d, J = 7.8Hz, 4H), 7.27 (d, J = 8.0Hz, 4H), 2.41 (s, 6H). 13 C NMR (101MHz, CDCl3) δ139.78, 137.90, 137.05, 129.51, 127.24, 126.85, 21.11.

[0052] Embodiment 17:

[0053] Potassium tert-butoxide (1 mmol, 2.0 equivalents) was added to a 10 mL Schlenk tube equipped with a magnetic stirrer. Then, 4'-ethylacetophenone (2×0.5 mmol) and 2.0 mL of dimethyl sulfoxide (DMSO) were added under an air atmosphere. The mixture was stirred at 160°C for 12 hours (constant temperature oil bath). After the reaction was completed, it was cooled to room temperature, diluted with ethyl acetate, and then an appropriate amount of water was added. The mixture was extracted three times with ethyl acetate, the organic phase was collected, and an appropriate amount of anhydrous Na2SO4 was added to dehydrate the combined organic layers, and concentrated under reduced pressure. The crude product was separated by column chromatography on silica gel (petroleum ether / ethyl acetate=100:1) to obtain purified 4,4,-diethyl-p-terphenyl. Appearance: yellow solid; Yield: 79% (112.9 mg); 1 H NMR (400MHz, CDCl3) δ7.64(d,J=2.0Hz,4H),7.59–7.52(m,4H),7.28(d,J=7.7Hz,4H),2.70(q,J=7.7Hz,4H),1.28(t,J=7.6Hz,6H). 13C NMR(101MHz, CDCl3)δ143.44,139.81,138.16,128.34,127.29,126.95,28.56,15.59.HRMS-ESI(m / z)[M+H] + Calcd for C 22 H 22 286.1722; Found, 286.1725.

[0054] Embodiment 18:

[0055] Potassium tert-butoxide (1 mmol, 2.0 equivalents) was added to a 10 mL Schlenk tube equipped with a magnetic stirrer. Then, 4'-n-butylacetophenone (2×0.5 mmol) and 2.0 mL of dimethyl sulfoxide (DMSO) were added under an air atmosphere. The mixture was stirred at 160°C for 12 hours (constant temperature oil bath). After the reaction was completed, it was cooled to room temperature, diluted with ethyl acetate, and then an appropriate amount of water was added. The mixture was extracted three times with ethyl acetate, the organic phase was collected, and an appropriate amount of anhydrous Na2SO4 was added to dehydrate the combined organic layers, and concentrated under reduced pressure. The crude product was separated by column chromatography on silica gel (petroleum ether / ethyl acetate=100:1) to obtain purified 4,4,-di-n-butyl-p-terphenyl. Appearance: yellow liquid; Yield: 79% (135.1 mg); 1 H NMR (400MHz, CDCl3) δ7.65 (s, 4H), 7.55 (d, J = 8.1Hz, 4H), 7.26 (d, J = 7.9Hz, 4H), 2.6 6(t,J=7.8Hz,4H),1.71–1.59(m,4H),1.40(h,J=7.4Hz,4H),0.95(t,J=7.3Hz,6H). 13 C NMR (101MHz, CDCl3) δ142.12,139.78,138.09,128.88,127.27,126.85,35.33,33.66,22.44,14.00.

[0056] Embodiment 19:

[0057] Potassium tert-butoxide (1 mmol, 2.0 equivalents) was added to a 10 mL Schlenk tube equipped with a magnetic stirrer. Then, 4'-n-pentylacetophenone (2×0.5 mmol) and 2.0 mL of solvent dimethyl sulfoxide (DMSO) were added under an air atmosphere. The mixture was stirred at 160°C for 12 hours (constant temperature oil bath). After the reaction was completed, it was cooled to room temperature, diluted with ethyl acetate, and then an appropriate amount of water was added. The mixture was extracted three times with ethyl acetate, the organic phase was collected, and an appropriate amount of anhydrous Na2SO4 was added to dehydrate the combined organic layers, and concentrated under reduced pressure. The crude product was separated by column chromatography on silica gel (petroleum ether / ethyl acetate=100:1) to obtain purified 4,4,-di-n-pentyl-p-terphenyl. Appearance: yellow liquid; Yield: 70% (129.5 mg); 1 H NMR (400MHz, CDCl3) δ7.26 (d, J=1.1Hz, 3H), 7.17 (dd, J=8.1, 1.3Hz, 4H), 6.88 (d, J=7.7 Hz,5H),2.26(t,J=7.8Hz,4H),1.30–1.23(m,4H),1.02–0.91(m,8H),0.56–0.48(m,6H). 13 C NMR (101MHz, CDCl3) δ142.17,139.78,138.08,128.89,127.28,126.86,35.63,31.60,31.23,22.61,14.09.

[0058] Embodiment 20:

[0059] Potassium tert-butoxide (1 mmol, 2.0 equivalents) was added to a 10 mL Schlenk tube equipped with a magnetic stirrer. Then, 4'-isopropylacetophenone (2×0.5 mmol) and 2.0 mL of dimethyl sulfoxide (DMSO) were added under an air atmosphere. The mixture was stirred at 160°C for 12 hours (constant temperature oil bath). After the reaction was completed, it was cooled to room temperature, diluted with ethyl acetate, and then an appropriate amount of water was added. The mixture was extracted three times with ethyl acetate, the organic phase was collected, and an appropriate amount of anhydrous Na2SO4 was added to dehydrate the combined organic layers, and concentrated under reduced pressure. The crude product was separated by column chromatography on silica gel (petroleum ether / ethyl acetate=100:1) to obtain purified 4,4,-diisopropyl-p-terphenyl. Appearance: white solid Yield: 65% (102.1 mg); 1 HNMR (400MHz, CDCl3) δ7.67 (s, 4H), 7.60 (d, J = 8.2Hz, 4H), 7.35 (d, J = 7.9Hz, 4H), 2.98 (q, J = 6.9Hz, 2H), 1.33 (d, J = 6.9Hz, 13H). 13C NMR (101MHz, CDCl3) δ148.07,139.83,138.34,127.33,126.98,126.93,33.87,24.06.

[0060] Embodiment 21:

[0061] Potassium tert-butoxide (1 mmol, 2.0 equivalents) was added to a 10 mL Schlenk tube equipped with a magnetic stirrer. Then, 2'-naphthyl acetonide (2 x 0.5 mmol) and 2.0 mL of dimethyl sulfoxide (DMSO) were added under an air atmosphere. The mixture was stirred at 160 ° C for 12 hours (constant temperature oil bath). After the reaction was completed, it was cooled to room temperature, diluted with ethyl acetate, and then an appropriate amount of water was added. The mixture was extracted three times with ethyl acetate, the organic phase was collected, and an appropriate amount of anhydrous Na2SO4 was added to dehydrate the combined organic layer, and concentrated under reduced pressure. The crude product was separated by column chromatography on silica gel (petroleum ether / ethyl acetate = 100:1) to obtain purified 4,4,-dinaphthylbenzene. Appearance: white solid; Yield: 68% (112.2 mg); 1 H NMR (400MHz, CDCl3) δ8.11–8.06(m,2H),7.93(ddd,J=16.8,7.6,1.7Hz,4H),7.64(s,4H),7.61–7.49(m,8H). 13 C NMR (101MHz, CDCl3) δ140.05,139.77,133.96,131.73,130.03,128.40,127.79,127.12,126.17,126.14,125.89,125.50.

[0062] Embodiment 22:

[0063] Potassium tert-butoxide (1 mmol, 2.0 equivalents) was added to a 10 mL Schlenk tube equipped with a magnetic stirrer. Then, 3',4'-dimethylacetophenone (2×0.5 mmol) and 2.0 mL of dimethyl sulfoxide (DMSO) were added under an air atmosphere. The mixture was stirred at 160°C for 12 hours (constant temperature oil bath). After the reaction was completed, it was cooled to room temperature, diluted with ethyl acetate, and then an appropriate amount of water was added. The mixture was extracted three times with ethyl acetate, the organic phase was collected, and an appropriate amount of anhydrous Na2SO4 was added to dehydrate the combined organic layers, and concentrated under reduced pressure. The crude product was separated by column chromatography on silica gel (petroleum ether / ethyl acetate=100:1) to obtain purified 3,3,4,4,-tetraethyl-p-terphenyl. Appearance: white solid; Yield: 63% (90.1 mg); 1HNMR (400MHz, CDCl3) δ7.64(d,J=1.1Hz,4H),7.43(s,2H),7.39(d,J=8.1Hz,2H),7.23(d,J=7.7Hz,2H),2.34(d,J=12.1Hz,12H). 13 C NMR (101MHz, CDCl3) δ139.82,138.42,136.96,135.75,130.11,128.31,127.24,124.39,19.99,19.49.

[0064] Embodiment 23:

[0065] Potassium tert-butoxide (1 mmol, 2.0 equivalents) was added to a 10 mL Schlenk tube equipped with a magnetic stirrer. Then, 4'-fluoroacetophenone (2×0.5 mmol) and 2.0 mL of solvent dimethyl sulfoxide (DMSO) were added under an air atmosphere. The mixture was stirred at 160°C for 12 hours (constant temperature oil bath). After the reaction was completed, it was cooled to room temperature, diluted with ethyl acetate, and then an appropriate amount of water was added. The mixture was extracted three times with ethyl acetate, the organic phase was collected, and an appropriate amount of anhydrous Na2SO4 was added to dehydrate the combined organic layers, and concentrated under reduced pressure. The crude product was separated by column chromatography on silica gel (petroleum ether / ethyl acetate=100:1) to obtain purified 4,4,-difluoro-p-terphenyl. Appearance: white solid; Yield: 63% (83.7 mg); 1 HNMR (400MHz, CDCl3) δ7.62 (s, 4H), 7.61–7.56 (m, 4H), 7.15 (t, J = 8.7Hz, 4H). 13 C NMR (101MHz, CDCl3) δ 162.55 (d, J = 248.4Hz), 139.16, 136.72 (d, J = 3.3Hz), 128.57 (d, J = 8.1Hz), 127.41, 115.71 (d, J = 21.2Hz).

[0066] Embodiment 24:

[0067] Potassium tert-butoxide (1 mmol, 2.0 equivalents) was added to a 10 mL Schlenk tube equipped with magnetic stirring. Then, 3'-trifluoromethylacetophenone (2×0.5 mmol) and 2.0 mL of dimethyl sulfoxide (DMSO) were added under air atmosphere. The mixture was stirred at 160° C. for 12 hours (constant temperature oil bath). After the reaction was completed, it was cooled to room temperature, diluted with ethyl acetate, and then an appropriate amount of water was added. The mixture was extracted three times with ethyl acetate, the organic phase was collected, and an appropriate amount of anhydrous Na2SO4 was added to dehydrate the combined organic layer, and concentrated under reduced pressure. The crude product was purified by column chromatography on silica gel (petroleum ether / ethyl acetate=100:1) to obtain 3,3 ， -Ditrifluoromethyl-p-terphenyl. Appearance: yellow solid; Yield: 32% (58.5 mg); 1 H NMR (400MHz, CDCl3) δ7.56 (s, 2H), 7.49 (d, J = 7.6Hz, 2H), 7.38 (s, 4H), 7.28 (dt, J = 15.3, 7.7Hz, 4H). 13 C NMR (101MHz, CDCl3) δ141.23,139.42,130.35,129.39,127.80,124.25,124.22,123.88,123.84.

[0068] Embodiment 25:

[0069] Potassium tert-butoxide (1 mmol, 2.0 equivalents) was added to a 10 mL Schlenk tube equipped with a magnetic stirrer. Then, 2'-acetylpyridine (2 x 0.5 mmol) and 2.0 mL of dimethyl sulfoxide (DMSO) were added under an air atmosphere. The mixture was stirred at 160 ° C for 12 hours (constant temperature oil bath). After the reaction was completed, it was cooled to room temperature, the mixture was diluted with ethyl acetate, an appropriate amount of water was added, and then extracted with ethyl acetate three times, the organic phase was collected, and an appropriate amount of anhydrous Na2SO4 was added to dehydrate the combined organic layer, and concentrated under reduced pressure. The crude product was separated by column chromatography on silica gel (petroleum ether / ethyl acetate = 100: 1) to obtain purified 4,4,-bipyridinebenzene. Appearance: yellow liquid; Yield: 43% (49.8 mg); 1 H NMR (400MHz, CDCl3) δ8.76–8.68(m,2H),8.13(s,4H),7.82–7.75(m,4H),7.28–7.22(m,2H). 13 C NMR (101MHz, CDCl3) δ156.89, 149.76, 139.80, 136.83, 127.28, 122.33, 120.69.

[0070] Embodiment 26:

[0071] Potassium tert-butoxide (1 mmol, 2.0 equivalents) was added to a 10 mL Schlenk tube equipped with a magnetic stirrer. Then, 2'-acetylthiophene (2 x 0.5 mmol) and 2.0 mL of dimethyl sulfoxide (DMSO) were added under an air atmosphere. The mixture was stirred at 160°C for 12 hours (constant temperature oil bath). After the reaction was completed, it was cooled to room temperature, diluted with ethyl acetate, and then an appropriate amount of water was added, and then extracted three times with ethyl acetate, the organic phase was collected, and an appropriate amount of anhydrous Na2SO4 was added to dehydrate the combined organic layer, and concentrated under reduced pressure. The crude product was separated by column chromatography on silica gel (petroleum ether / ethyl acetate = 100:1) to obtain purified 4,4,-dithiophenebenzene. Appearance: white solid; Yield: 59% (71.3 mg); 1 H NMR (400MHz, CDCl3) δ7.62 (s, 4H), 7.34 (d, J = 3.6Hz, 2H), 7.29 (d, J = 5.1Hz, 2H), 7.10 (dd, J = 5.1, 3.6Hz, 2H). 13 CNMR(101MHz,CDCl3)δ143.95,133.53,128.16,126.34,124.95,123.14.

[0072] Embodiment 27:

[0073] Potassium tert-butoxide (1 mmol, 2.0 equivalents) was added to a 10 mL Schlenk tube equipped with a magnetic stirrer. Then, 2'-acetylfuran (2×0.5 mmol) and 2.0 mL of solvent dimethyl sulfoxide (DMSO) were added under an air atmosphere. The mixture was stirred at 160°C for 12 hours (constant temperature oil bath). After the reaction was completed, it was cooled to room temperature, diluted with ethyl acetate, and then an appropriate amount of water was added. The mixture was extracted three times with ethyl acetate, the organic phase was collected, and an appropriate amount of anhydrous Na2SO4 was added to dehydrate the combined organic layers, and concentrated under reduced pressure. The crude product was separated by column chromatography on silica gel (petroleum ether / ethyl acetate=100:1) to obtain purified 4,4,-difuranbenzene. Appearance: yellow solid; Yield: 60% (63.0 mg); 1 H NMR (400MHz, CDCl3) δ7.69 (s, 4H), 7.48 (d, J = 1.8Hz, 2H), 6.70–6.64 (m, 2H), 6.49 (dd, J = 3.3, 1.8Hz, 2H). 13 CNMR(101MHz,CDCl3)δ153.72,142.13,129.69,124.03,111.75,105.12.

Claims

1. A terphenyl derivative, characterized in that: The chemical structural formula of the terphenyl derivative is as shown in formula (1) or formula (2): Wherein, R is a substituent group selected from H, Me, Et, i Pr, n butyl, n Pentyl, F, CF3, or Ph. Wherein, R is a substituent group selected from H, Me, Et, F, CF3 or Ph.

2. The terphenyl derivative according to claim 1, characterized in that: n=1, 2, 3, 4, 5, 10 or 16.

3. A method for synthesizing a terphenyl derivative, characterized in that: The steps include: In an air atmosphere, potassium tert-butoxide is used as a promoter, DMSO is used as a carbon source and a reaction solvent, and the ketone is stirred at 160° C. for 12-48 hours to obtain a product containing a terphenyl derivative.

4. The method for synthesizing the terphenyl derivatives according to claim 3, characterized in that: The product containing the terphenyl derivatives is purified by the following purification method: The product containing the terphenyl derivatives was diluted with ethyl acetate, and then water was added, and then extracted three times with ethyl acetate. The organic phases were collected and combined, and then anhydrous Na2SO4 was added to dehydrate the combined organic phases, and then concentrated under reduced pressure to obtain a crude product. The crude product was separated by column chromatography on silica gel to obtain a purified terphenyl derivative.

5. The method for synthesizing the terphenyl derivatives according to claim 3, characterized in that: The molar ratio of the potassium tert-butoxide to the aryl ketone derivative is 1:

1.

6. The method for synthesizing a terphenyl derivative according to claim 3, characterized in that: The ketone is one of propiophenone, 3'-methylpropiophenone, 4'-methylpropiophenone, 4'-ethylpropiophenone, 4'-fluoropropiophenone, 3'-trifluoromethylpropiophenone, butyrophenone, valerophenone, hexanophenone, heptanone, lauryl ketone (dodecyl ketone), stearyl ketone (octadecyl ketone), acetophenone, 2'-methylacetophenone, 3'-methylacetophenone, 4'-methylacetophenone, 4'-ethylacetophenone, 4'-n-butylacetophenone, 4'-n-pentylacetophenone, 4'-isopropylacetophenone, 2'-acetonaphthone, 3',4'-dimethylacetophenone, 4'-fluoroacetophenone, 3'-trifluoromethylacetophenone, 2'-acetylpyridine, 2'-acetylthiophene, and 2'-acetylfuran.

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