A terphenyl derivative and a method for synthesizing the same

Abstract

The application is a new method for synthesizing p-terphenyl derivatives by cascade cyclization of aryl ketone multi-component form with dimethyl sulfoxide (DMSO) as two C sources under the promotion of potassium tert-butoxide. The method only uses strong base potassium tert-butoxide as a promoter, avoids the use of complex ligands and expensive metal reagents. At the same time, this formal [1+2+2+1] cascade cyclization reaction is suitable for a variety of substrates, has good tolerance to a variety of substituents, and can provide easily obtained p-terphenyl derivatives with good yield. In addition, the reaction also has the characteristics of low price of additives, simple reaction conditions, easy availability of starting materials, etc. The multi-component cascade cyclization protocol is realized by using easily commercially available starting materials at a lower cost, and a variety of substituted p-terphenyl compounds are synthesized.

Description

[Technical Field]

[0001] This invention belongs to the field of organic synthesis and relates to a terphenyl derivative and its synthesis method. [Background Technology]

[0002] Terphenyl compounds are a class of small-molecule polycyclic aromatic hydrocarbons composed of three linked benzene rings. They exist as three isomers: ortho, meta, and para. In nature, they mainly exist in the para configuration. Compounds containing the terphenyl structure exhibit good biological activity. Furthermore, these compounds also demonstrate excellent liquid crystal and electroluminescence properties, and are widely used in liquid crystal materials. p-Terphenyl consists of a C-18 tricyclic or polycyclic C-18 aromatic skeleton, and its structure varies depending on the connection between the central and flanking benzene rings and its connection to the main skeleton. Recent studies have revealed that p-terphenyl possesses various biological activities, including cytotoxicity, α-glucosidase inhibition, antioxidant, and antibacterial activities. In addition, p-terphenyl plays an important role in membrane chemistry, supramolecular organic materials, and covalent organic polymers. Due to its unique configuration, it is now widely used in material preparation, such as laser dyes and single-molecule spectroscopy. p-Terphenyl also plays an important role in organic superconductors (HTOS). Potassium ion doping can effectively improve its conductivity. Due to its non-planar arrangement, terphenyl can be used as a simple molecular rotor. Furthermore, it exhibits good electroluminescence properties and is often used as a scintillator for detecting ionizing radiation.

[0003] Despite the wide applications of terphenyl in the pharmaceutical and materials fields, chemists continue to research efficient synthetic methods for it. Existing synthetic methods mainly involve coupling or cyclization reactions between aryl halides, arylboronic acids, or Grignard reagents. However, these methods typically require expensive noble metal catalysts or complex ligands, resulting in high costs and environmental pollution. Furthermore, cyclization reactions often require complex substrates, increasing reaction costs. Therefore, designing a terphenyl synthesis method that does not require transition metal catalysts and ligands and uses simple substrate structures is of significant research value. We aim to develop a practical, efficient, and easy-to-operate method that directly utilizes commercially available starting materials, avoiding the limitations of substitution categories, high synthetic costs, and the hassle of multi-step synthesis of starting materials. To this end, we have developed a method using dimethyl sulfoxide as a synthon and reactant, promoted by potassium tert-butoxide, to achieve a multi-component cascade cyclization reaction using commercially available aryl ketone derivatives. This method does not use additional metal catalysts or ligands, is simple to operate, has good substrate adaptability, high yield, and uses commercially available starting materials.

[0004] Currently, there are no published documents or patent applications, either domestically or internationally, regarding the formation of [1+2+2+1] cascades of p-terphenyl without metal catalysts. [Summary of the Invention]

[0005] Therefore, this invention develops a metal-free cyclization reaction for the efficient synthesis of p-terphenyl derivatives using DMSO as two carbon sources and aryl ketone derivatives as raw materials. This reaction utilizes readily available aryl ketones, dimethyl sulfoxide, and potassium tert-butoxide via a multi-component [1+2+2+1] cascade cyclization method to obtain p-terphenyl compounds with high functional group tolerance in high yield. This method has advantages such as being metal-free and ligand-based, using inexpensive and readily available raw materials, being simple to operate, and having a wide range of functional group tolerances. Furthermore, it provides a new method and approach for the synthesis of p-terphenyl. Further, this invention also develops a metal-free cyclization reaction for the efficient synthesis of p-terphenyl derivatives containing extendable side chains using DMSO as one carbon source and aryl ketone derivatives with polyalkane substitution at the α-position as raw materials.

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

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

[0008] Further improvements involved diluting the product containing the para-terphenyl derivative with ethyl acetate, adding water, and extracting it three times with ethyl acetate. The organic phases were collected and combined, and then anhydrous Na2SO4 was added to dehydrate the combined organic phases. The mixture was then concentrated under reduced pressure to obtain a crude product. The crude product was then separated by column chromatography on silica gel to obtain purified para-terphenyl derivatives.

[0009] Further improvements were made, with the molar ratio of potassium tert-butoxide to aryl ketone derivatives being 1:2×0.5.

[0010] A further improvement is that the ketone is one of acetone, 3'-methylacetone, 4'-methylacetone, 4'-ethylacetone, 4'-fluoroacetone, 3'-trifluoromethylacetone, phenylbutanone, phenylpentanone, phenylhexanone, phenylheptanone, 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'-naphthylacetophenone, 3',4'-dimethylacetophenone, 4'-fluoroacetophenone, 3'-trifluoromethylacetophenone, 2'-acetylpyridine, 2'-acetylthiophene, and 2'-acetylfuran.

[0011] A class of para-terphenyl derivatives, the chemical formula of which is 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 this invention are as follows:

[0015] This invention presents a novel method for the highly selective synthesis of p-terphenyl derivatives via a multi-component cascade cyclization of dimethyl sulfoxide (DMSO) with aryl ketones, using potassium tert-butoxide as the promoter and two carbon sources. This method utilizes only the strong base potassium tert-butoxide as the promoter, avoiding the use of complex ligands and expensive metal reagents. Furthermore, this formal [1+2+2+1] cascade cyclization reaction is applicable to a variety of substrates, exhibits good tolerance to various substituents, and provides readily available p-terphenyl derivatives in good yields. In addition, the reaction features inexpensive additives, simple reaction conditions, and readily available starting materials. It realizes a multi-component cascade cyclization protocol using readily available starting materials at a lower cost, synthesizing p-terphenyl compounds with various substituents. Furthermore, it develops a novel method for the highly selective synthesis of p-terphenyl derivatives containing extended side chains. This provides a new route for the synthesis of p-terphenyl derivatives with extended side chains, which have potential applications in the materials science field. [Attached Image Description]

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

[0017] Figure 2 This is a chemical formula diagram of the terphenyl derivatives of the present invention.

Detailed Implementation Methods

[0018] The reaction formula of this invention is as follows:

[0019]

[0020] Example 1:

[0021] Potassium tert-butoxide (1 mmol, 2.0 equivalent) was added to a 10 mL Schlenk tube equipped with a magnetic stirrer. Then, acetone (2 × 0.5 mmol) and 2.0 mL of dimethyl sulfoxide (DMSO) were added under air. The mixture was stirred at 160 °C for 12 hours (using a constant-temperature oil bath). After the reaction was complete, the mixture was cooled to room temperature, diluted with ethyl acetate, 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. The mixture was concentrated under reduced pressure. The crude product was purified by column chromatography on silica gel (petroleum ether / ethyl acetate = 100:1) to give purified 2'-methyl-1,1':4',1”-triphenyl. 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] Example 2:

[0023] Potassium tert-butoxide (1 mmol, 2.0 equivalent) was added to a 10 mL Schlenk tube equipped with a magnetic stirrer. Then, 3'-methylphenylacetone (2 × 0.5 mmol) and 2.0 mL of dimethyl sulfoxide (DMSO) were added under air. The mixture was stirred at 160 °C for 12 hours (using an oil bath). After the reaction was complete, the mixture was cooled to room temperature, diluted with ethyl acetate, and then extracted three times with ethyl acetate. The organic phase was collected, and the combined organic layers were dehydrated with an appropriate amount of anhydrous Na₂SO₄ and concentrated under reduced pressure. The crude product was separated by column chromatography on silica gel (petroleum ether / ethyl acetate = 100:1) to give 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] Example 3:

[0025] Potassium tert-butoxide (1 mmol, 2.0 equivalent) was added to a 10 mL Schlenk tube equipped with a magnetic stirrer. Then, 4'-methylphenylacetone (2 × 0.5 mmol) and 2.0 mL of dimethyl sulfoxide (DMSO) were added under air. The mixture was stirred at 160 °C for 12 hours (using a constant-temperature oil bath). After the reaction was complete, the mixture was cooled to room temperature, diluted with ethyl acetate, and then extracted three times with ethyl acetate. The organic phase was collected, and the combined organic layers were dehydrated with an appropriate amount of anhydrous Na₂SO₄ and concentrated under reduced pressure. The crude product was separated by column chromatography on silica gel (petroleum ether / ethyl acetate = 100:1) to give 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] Example 4:

[0027] Potassium tert-butoxide (1 mmol, 2.0 equivalent) was added to a 10 mL Schlenk tube equipped with a magnetic stirrer. Then, 4'-ethylphenylacetone (2 × 0.5 mmol) and 2.0 mL of dimethyl sulfoxide (DMSO) were added under air. The mixture was stirred at 160 °C for 12 hours (using an oil bath). After the reaction was complete, the mixture was cooled to room temperature, diluted with ethyl acetate, and then extracted three times with ethyl acetate. The organic phase was collected, and the combined organic layers were dehydrated with an appropriate amount of anhydrous Na₂SO₄ and concentrated under reduced pressure. The crude product was separated by column chromatography on silica gel (petroleum ether / ethyl acetate = 100:1) to give 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] Example 5:

[0029] Potassium tert-butoxide (1 mmol, 2.0 equivalent) was added to a 10 mL Schlenk tube equipped with a magnetic stirrer. Then, 4'-fluorophenylacetone (2 × 0.5 mmol) and 2.0 mL of dimethyl sulfoxide (DMSO) were added under air. The mixture was stirred at 160 °C for 12 hours (using a constant-temperature oil bath). After the reaction was complete, the mixture was cooled to room temperature, diluted with ethyl acetate, and then extracted three times with ethyl acetate. The organic phase was collected, and the combined organic layers were dehydrated with an appropriate amount of anhydrous Na₂SO₄ and concentrated under reduced pressure. The crude product was separated by column chromatography on silica gel (petroleum ether / ethyl acetate = 100:1) to give 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] Example 6:

[0031] Potassium tert-butoxide (1 mmol, 2.0 equivalent) was added to a 10 mL Schlenk tube equipped with a magnetic stirrer. Then, 3'-trifluoromethylphenylacetone (2 × 0.5 mmol) and 2.0 mL of dimethyl sulfoxide (DMSO) were added under air. The mixture was stirred at 160 °C for 12 hours (using a constant-temperature oil bath). After the reaction was complete, the mixture was cooled to room temperature, diluted with ethyl acetate, and then extracted three times with ethyl acetate. The organic phase was collected, and the combined organic layers were dehydrated with an appropriate amount of anhydrous Na₂SO₄ and concentrated under reduced pressure. The crude product was separated by column chromatography on silica gel (petroleum ether / ethyl acetate = 100:1) to give 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] Example 7:

[0033] Potassium tert-butoxide (1 mmol, 2.0 equivalent) was added to a 10 mL Schlenk tube equipped with a magnetic stirrer. Then, phenylbutanone (2 × 0.5 mmol) and 2.0 mL of dimethyl sulfoxide (DMSO) were added under air. The mixture was stirred at 160 °C for 12 hours (using a constant-temperature oil bath). After the reaction was complete, the mixture was cooled to room temperature, diluted with ethyl acetate, and then extracted three times with ethyl acetate. The organic phase was collected, and the combined organic layers were dehydrated with an appropriate amount of anhydrous Na₂SO₄ and concentrated under reduced pressure. The crude product was separated by column chromatography on silica gel (petroleum ether / ethyl acetate = 100:1) to give 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] Example 8:

[0035] Potassium tert-butoxide (1 mmol, 2.0 equivalent) was added to a 10 mL Schlenk tube equipped with a magnetic stirrer. Then, phenylpentanone (2 × 0.5 mmol) and 2.0 mL of dimethyl sulfoxide (DMSO) were added under air. The mixture was stirred at 160 °C for 12 hours (using a constant-temperature oil bath). After the reaction was complete, the mixture was cooled to room temperature, diluted with ethyl acetate, and then extracted three times with ethyl acetate. The organic phase was collected, and the combined organic layers were dehydrated with an appropriate amount of anhydrous Na₂SO₄ and concentrated under reduced pressure. The crude product was separated by column chromatography on silica gel (petroleum ether / ethyl acetate = 100:1) to give 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] Example 9:

[0037] Potassium tert-butoxide (1 mmol, 2.0 equivalent) 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 air. The mixture was stirred at 160 °C for 12 hours (using a constant-temperature oil bath). After the reaction was complete, the mixture was cooled to room temperature, diluted with ethyl acetate, and then extracted three times with ethyl acetate. The organic phase was collected, and the combined organic layers were dehydrated with an appropriate amount of anhydrous Na₂SO₄ and concentrated under reduced pressure. The crude product was separated by column chromatography on silica gel (petroleum ether / ethyl acetate = 100:1) to give 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] Example 10:

[0039] Potassium tert-butoxide (1 mmol, 2.0 equivalent) 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 air. The mixture was stirred at 160 °C for 12 hours (using a constant-temperature oil bath). After the reaction was complete, the mixture was cooled to room temperature, diluted with ethyl acetate, and then extracted three times with ethyl acetate. The organic phase was collected, and the combined organic layers were dehydrated with an appropriate amount of anhydrous Na₂SO₄ and concentrated under reduced pressure. The crude product was separated by column chromatography on silica gel (petroleum ether / ethyl acetate = 100:1) to give 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] Example 11:

[0041] Potassium tert-butoxide (1 mmol, 2.0 equivalent) 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 dimethyl sulfoxide (DMSO) were added under air. The mixture was stirred at 160 °C for 12 hours (using a constant-temperature oil bath). After the reaction was complete, the mixture was cooled to room temperature, diluted with ethyl acetate, and then extracted three times with ethyl acetate. The organic phase was collected, and the combined organic layers were dehydrated with an appropriate amount of anhydrous Na₂SO₄ and concentrated under reduced pressure. The crude product was separated by column chromatography on silica gel (petroleum ether / ethyl acetate = 100:1) to give 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] Example 12:

[0043] Potassium tert-butoxide (1 mmol, 2.0 equivalent) 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 dimethyl sulfoxide (DMSO) were added under air. The mixture was stirred at 160 °C for 12 hours (using a constant-temperature oil bath). After the reaction was complete, the mixture was cooled to room temperature, diluted with ethyl acetate, and then extracted three times with ethyl acetate. The organic phase was collected, and the combined organic layers were dehydrated with an appropriate amount of anhydrous Na₂SO₄ and concentrated under reduced pressure. The crude product was separated by column chromatography on silica gel (petroleum ether / ethyl acetate = 100:1) to give purified 2'-hexadecyl-6'-pentadecanyl-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] Example 13:

[0045] Potassium tert-butoxide (1 mmol, 2.0 equivalent) 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 air. The mixture was stirred at 160 °C for 12 hours (using a constant-temperature oil bath). After the reaction was complete, the mixture was cooled to room temperature, diluted with ethyl acetate, and then extracted three times with ethyl acetate. The organic phase was collected, and the combined organic layers were dehydrated with an appropriate amount of anhydrous Na₂SO₄ and concentrated under reduced pressure. The crude product was purified by column chromatography on silica gel (petroleum ether / ethyl acetate = 100:1) to give p-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] Example 14:

[0047] Potassium tert-butoxide (1 mmol, 2.0 equivalent) 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 air. The mixture was stirred at 160 °C for 12 hours (using a constant-temperature oil bath). After the reaction was complete, the mixture was cooled to room temperature, diluted with ethyl acetate, and then extracted three times with ethyl acetate. The organic phase was collected, and the combined organic layers were dehydrated with an appropriate amount of anhydrous Na₂SO₄ and concentrated under reduced pressure. The crude product was separated by column chromatography on silica gel (petroleum ether / ethyl acetate = 100:1) to give 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] Example 15:

[0049] Potassium tert-butoxide (1 mmol, 2.0 equivalent) 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. The mixture was stirred at 160 °C for 12 hours (using a constant-temperature oil bath). After the reaction was complete, the mixture was cooled to room temperature, diluted with ethyl acetate, and then extracted three times with ethyl acetate. The organic phase was collected, and the combined organic layers were dehydrated with an appropriate amount of anhydrous Na₂SO₄ and concentrated under reduced pressure. The crude product was separated by column chromatography on silica gel (petroleum ether / ethyl acetate = 100:1) to give 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] Example 16:

[0051] Potassium tert-butoxide (1 mmol, 2.0 equivalent) 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. The mixture was stirred at 160 °C for 12 hours (using an oil bath). After the reaction was complete, the mixture was cooled to room temperature, diluted with ethyl acetate, and then extracted three times with ethyl acetate. The organic phase was collected, and the combined organic layers were dehydrated with an appropriate amount of anhydrous Na₂SO₄ and concentrated under reduced pressure. The crude product was separated by column chromatography on silica gel (petroleum ether / ethyl acetate = 100:1) to give 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] Example 17:

[0053] Potassium tert-butoxide (1 mmol, 2.0 equivalent) 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 air. The mixture was stirred at 160 °C for 12 hours (using an oil bath). After the reaction was complete, the mixture was cooled to room temperature, diluted with ethyl acetate, and then extracted three times with ethyl acetate. The organic phase was collected, and the combined organic layers were dehydrated with an appropriate amount of anhydrous Na₂SO₄ and concentrated under reduced pressure. The crude product was separated by column chromatography on silica gel (petroleum ether / ethyl acetate = 100:1) to give 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] Example 18:

[0055] Potassium tert-butoxide (1 mmol, 2.0 equivalent) 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 air. The mixture was stirred at 160 °C for 12 hours (using a constant-temperature oil bath). After the reaction was complete, the mixture was cooled to room temperature, diluted with ethyl acetate, and then extracted three times with ethyl acetate. The organic phase was collected, and the combined organic layers were dehydrated with an appropriate amount of anhydrous Na₂SO₄ 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] Example 19:

[0057] Potassium tert-butoxide (1 mmol, 2.0 equivalent) 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 dimethyl sulfoxide (DMSO) were added under air. The mixture was stirred at 160 °C for 12 hours (using an oil bath). After the reaction was complete, the mixture was cooled to room temperature, diluted with ethyl acetate, and then extracted three times with ethyl acetate. The organic phase was collected, and the combined organic layers were dehydrated with an appropriate amount of anhydrous Na₂SO₄ and concentrated under reduced pressure. The crude product was separated by column chromatography on silica gel (petroleum ether / ethyl acetate = 100:1) to give 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] Example 20:

[0059] Potassium tert-butoxide (1 mmol, 2.0 equivalent) 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 air. The mixture was stirred at 160 °C for 12 hours (using a constant-temperature oil bath). After the reaction was complete, the mixture was cooled to room temperature, diluted with ethyl acetate, and then extracted three times with ethyl acetate. The organic phase was collected, and the combined organic layers were dehydrated with an appropriate amount of anhydrous Na₂SO₄ and concentrated under reduced pressure. The crude product was separated by column chromatography on silica gel (petroleum ether / ethyl acetate = 100:1) to give 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] Example 21:

[0061] Potassium tert-butoxide (1 mmol, 2.0 equivalent) was added to a 10 mL Schlenk tube equipped with a magnetic stirrer. Then, 2'-naphthyl ethyl ketone (2 × 0.5 mmol) and 2.0 mL of dimethyl sulfoxide (DMSO) were added under air. The mixture was stirred at 160 °C for 12 hours (using a constant-temperature oil bath). After the reaction was complete, the mixture was cooled to room temperature, diluted with ethyl acetate, and then extracted three times with ethyl acetate. The organic phase was collected, and the combined organic layers were dehydrated with an appropriate amount of anhydrous Na₂SO₄ and concentrated under reduced pressure. The crude product was separated by column chromatography on silica gel (petroleum ether / ethyl acetate = 100:1) to give 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] Example 22:

[0063] Potassium tert-butoxide (1 mmol, 2.0 equivalent) 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 air. The mixture was stirred at 160 °C for 12 hours (using an oil bath). After the reaction was complete, the mixture was cooled to room temperature, diluted with ethyl acetate, and then extracted three times with ethyl acetate. The organic phase was collected, and the combined organic layers were dehydrated with an appropriate amount of anhydrous Na₂SO₄ and concentrated under reduced pressure. The crude product was separated by column chromatography on silica gel (petroleum ether / ethyl acetate = 100:1) to give 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] Example 23:

[0065] Potassium tert-butoxide (1 mmol, 2.0 equivalent) 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 dimethyl sulfoxide (DMSO) were added under air. The mixture was stirred at 160 °C for 12 hours (using a constant-temperature oil bath). After the reaction was complete, the mixture was cooled to room temperature, diluted with ethyl acetate, and then extracted three times with ethyl acetate. The organic phase was collected, and the combined organic layers were dehydrated with an appropriate amount of anhydrous Na₂SO₄ and concentrated under reduced pressure. The crude product was separated by column chromatography on silica gel (petroleum ether / ethyl acetate = 100:1) to give 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] Example 24:

[0067] Potassium tert-butoxide (1 mmol, 2.0 equivalent) was added to a 10 mL Schlenk tube equipped with a magnetic stirrer. Then, 3'-trifluoromethylacetophenone (2 × 0.5 mmol) and 2.0 mL of dimethyl sulfoxide (DMSO) were added under air. The mixture was stirred at 160 °C for 12 hours (using a constant-temperature oil bath). After the reaction was complete, the mixture was cooled to room temperature, diluted with ethyl acetate, and then extracted three times with ethyl acetate. The organic phase was collected, and the combined organic layers were dehydrated with an appropriate amount of anhydrous Na₂SO₄ and concentrated under reduced pressure. The crude product was purified by column chromatography on silica gel (petroleum ether / ethyl acetate = 100:1) to obtain purified 3,3'-trifluoromethylacetophenone. ， -Di(trifluoromethyl)-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] Example 25:

[0069] Potassium tert-butoxide (1 mmol, 2.0 equivalent) was added to a 10 mL Schlenk tube equipped with a magnetic stirrer. Then, 2'-acetylpyridine (2 × 0.5 mmol) and 2.0 mL of dimethyl sulfoxide (DMSO) were added under air. The mixture was stirred at 160 °C for 12 hours (using an oil bath). After the reaction was complete, the mixture was cooled to room temperature, diluted with ethyl acetate, and then extracted three times with ethyl acetate. The organic phase was collected, and the combined organic layers were dehydrated with an appropriate amount of anhydrous Na₂SO₄ and concentrated under reduced pressure. The crude product was separated by column chromatography on silica gel (petroleum ether / ethyl acetate = 100:1) to give purified 4,4'-dipyridinebenzene. 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] Example 26:

[0071] Potassium tert-butoxide (1 mmol, 2.0 equivalent) was added to a 10 mL Schlenk tube equipped with a magnetic stirrer. Then, 2'-acetylthiophene (2 × 0.5 mmol) and 2.0 mL of dimethyl sulfoxide (DMSO) were added under air. The mixture was stirred at 160 °C for 12 hours (using a constant-temperature oil bath). After the reaction was complete, the mixture was cooled to room temperature, diluted with ethyl acetate, 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. The mixture was 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] Example 27:

[0073] Potassium tert-butoxide (1 mmol, 2.0 equivalent) 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 dimethyl sulfoxide (DMSO) were added under air. The mixture was stirred at 160 °C for 12 hours (using a constant-temperature oil bath). After the reaction was complete, the mixture was cooled to room temperature, diluted with ethyl acetate, and then extracted three times with ethyl acetate. The organic phase was collected, and the combined organic layers were dehydrated with an appropriate amount of anhydrous Na₂SO₄ and concentrated under reduced pressure. The crude product was separated by column chromatography on silica gel (petroleum ether / ethyl acetate = 100:1) to give 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 method for synthesizing terphenyl derivatives, characterized in that, Includes the following steps: In an air atmosphere, using potassium tert-butoxide as a promoter and DMSO as a carbon source and reaction solvent, the product containing p-terphenyl derivatives is obtained by stirring with ketones at 160°C for 12-48 hours. The chemical structural formulas of the terphenyl derivatives are shown in formula (1) or formula (2): （1） Wherein, R is a substituent group selected from Me, Et, i Pr, n butyl n Pentyl, F, CF3, or Ph; （2） Wherein, R is a substituent group selected from H, Me, Et, F, CF3 or Ph; n = 1, 2, 3, 4, 5, 10 or 16; The ketone is one of acetone, 3'-methylacetone, 4'-methylacetone, 4'-ethylacetone, 3'-trifluoromethylacetone, phenylbutanone, phenylpentanone, phenylhexanone, phenylheptanone, 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, 3',4'-dimethylacetophenone, and 4'-fluoroacetophenone.

2. The method for synthesizing terphenyl derivatives as described in claim 1, characterized in that, The products containing para-terphenyl derivatives were purified using the following method: The product containing the para-terphenyl derivatives was diluted with ethyl acetate, water was added, and the product was 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. The product was then concentrated under reduced pressure to obtain the crude product. The crude product was separated by column chromatography on silica gel to obtain the purified para-terphenyl derivatives.

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

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