CN111205152B - Preparation method of m-terphenyl compound - Google Patents
Preparation method of m-terphenyl compound Download PDFInfo
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Abstract
The invention provides a method for synthesizing m-terphenyl compounds by taking aryl methyl ketone and triethyl orthoformate as raw materials, which comprises the steps of heating a mixture of the aryl methyl ketone and the triethyl orthoformate to 50 ℃ under the protection of inert gas, adding trifluoromethanesulfonic acid for reaction, and separating after the reaction is finished to obtain the m-terphenyl compounds. The synthesis method has the advantages of easily available raw materials, low cost, mild reaction conditions, simple and easily-controlled operation, no need of any metal catalyst or solvent, short reaction time, good economic benefit and suitability for industrial mass production.
Description
Technical Field
The invention belongs to the technical field of drug synthesis and chemical product synthesis, and particularly relates to a method for synthesizing m-terphenyl compounds by taking aryl methyl ketone and triethyl orthoformate as raw materials.
Background
The m-terphenyl compound generally has excellent photoelectric and optical properties, is widely applied to the field of material science, and is used for manufacturing conductive polymers, liquid crystal materials, heat storage and transfer materials, laser dyes, textile dye carriers and the like.
For example, nine-nitro-terphenyl (NONA) is a high-temperature resistant explosive with good safety performance, the heat resistance degree can reach more than 300 ℃, 100% detonation can be ensured at high temperature, and the NONA-nitro-terphenyl (NONA) belongs to special explosives for aerospace.
Meanwhile, some m-terphenyl compounds also have certain biological activity, for example, natural products such as carbofuran (Mulberrofuran R), trifluorocresol (Trifucol), Simonsinol (Simonsinol) and the like contain m-terphenyl structural units.
The synthesis method of the m-terphenyl compound is various. The earliest method was to start with cyclohexanedione, react with twice the amount of aromatic grignard reagent and finally catalytically dehydrogenate to produce benzene ring.
The most common method is by metal coupling reactions. For example, Suzuki coupling reaction in which aryl organic compounds of boron, magnesium, tin, zinc and the like and halogenated aromatic compounds are catalyzed by using a transition metal catalyst to obtain terphenyl products, Ullmarm coupling reaction in which halogenated aromatic hydrocarbons are catalyzed by using copper powder as a catalyst to generate coupling reaction to generate terphenyl compounds, oxidation coupling reaction in which p-cresol is oxidized into phenoxy free radicals by using ferric trichloride as a metal oxidant and then coupling is performed to obtain target products, and the like.
The compound can also be prepared by a [2+2+2] or [4+2] cycloaddition reaction. For example, under the action of a manganese catalyst, the terminal alkyne compound can perform cyclization reaction with certain special enol substances to obtain a terphenyl product.
However, the methods reported in these known documents have certain disadvantages, such as severe reaction conditions, expensive catalysts, narrow substrate range, and poor chemical or regioselectivity. In view of the important use of m-terphenyl compounds, further development of new synthetic methods with high efficiency and simplicity is needed. The patent reports a novel synthesis method of m-terphenyl compounds, which can prepare and synthesize target compounds in one step without solvents or any metal catalysts.
Disclosure of Invention
The invention aims to provide a method for preparing a m-terphenyl compound by using aryl methyl ketone and triethyl orthoformate as raw materials and trifluoromethanesulfonic acid as a catalytic condition through one-step reaction.
The purpose of the invention can be realized by the following technical scheme:
a process for preparing an m-terphenyl compound: in the presence of organic acid, acetophenone shown in the general formula (I) and triethyl orthoformate are heated and condensed in a solvent or without any solvent to obtain an m-terphenyl compound shown in the general formula (II), wherein the chemical reaction formula (A) is shown as follows:
wherein R is1Is H, halogen or C1-C6Straight or branched alkyl, R2Is H, halogen or C1-C6Linear or branched alkyl of (a); or R1And R2Adjacent carbon atoms are connected together to form a benzene ring; the organic acid is selected from CF3COOH, TsOH or TfOH; the solvent is ethanol or tetrahydrofuran; the molar ratio of the acetophenone, triethyl orthoformate and the organic acid is 1: (2-6): (0.05-3).
Preferably, R1Is H, methyl, ethyl or chlorine, R2Is H, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl or chlorine; or R1And R2And adjacent carbon atoms thereof are linked together to form a benzene ring.
Preferably, the molar ratio of the acetophenone, triethyl orthoformate and the organic acid is 1: (2-5): (0.05-1); more preferably, the molar ratio of acetophenone, triethyl orthoformate and the organic acid is 1: 4: 0.1, the organic acid is TfOH.
The method for preparing the m-terphenyl compound has the advantages that the reaction temperature is 40-100 ℃, and the reaction time is 1-4 hours; preferably, the reaction temperature is 50 ℃ and the reaction time is 2 h.
The method for preparing the m-terphenyl compound is characterized in that the reaction is carried out under the protection of inert gas; the reaction is carried out in the absence of any solvent.
The method for preparing the m-terphenyl compound comprises the following specific operation steps: under the protection of inert gas, heating and stirring the acetophenone and the triethyl orthoformate uniformly in the solvent or without any solvent, adding trifluoromethanesulfonic acid for reaction, and separating and purifying after the reaction is finished to obtain the m-terphenyl compound.
Preferably, the specific operation steps are as follows: stirring the acetophenone and the triethyl orthoformate for 0.5h at 50 ℃ under the protection of inert gas, adding trifluoromethanesulfonic acid for reaction, adding saturated sodium carbonate aqueous solution for quenching after the reaction is finished, extracting with dichloromethane, combining organic phases, drying with sodium sulfate, concentrating under reduced pressure, and separating the obtained concentrate by silica gel column chromatography to obtain the m-terphenyl compound.
Compared with the existing synthesis method of the m-terphenyl compound, the synthesis method has the following advantages:
(1) the m-terphenyl compound is obtained by heating acetophenone and triethyl orthoformate in a solvent or without any solvent for the first time to perform condensation reaction.
(2) The method can efficiently synthesize a series of m-terphenyl compounds, has the advantages of simple and easily obtained raw materials, mild reaction conditions (reaction temperature is 50 ℃), one-pot reaction, simple operation, short reaction time (about 2 hours), reduction of production cost, contribution to industrial production and practical application value.
(3) The method disclosed by the invention does not need any metal catalyst, only needs catalytic amount of organic acid for catalytic reaction, and even does not need any solvent, so that the synthesis cost and the pollution of the organic solvent to the environment are reduced, and the method has the advantages of environmental friendliness, safety and convenience in operation and the like, and has good application and popularization potentials.
In conclusion, the synthesis method can obtain a series of m-terphenyl compounds by one-pot reaction, the required raw materials are simple and easy to obtain, expensive metal catalysts (organic acid catalytic reaction with catalytic amount) are not needed, even any solvent is not needed, the reaction condition is mild, the operation is simple, the reaction time is short (about 2 hours), the method is green and environment-friendly, the production cost is greatly saved, and the method has good economic benefit, is suitable for industrial large-scale production and has good application and popularization potential.
Detailed Description
The present invention is illustrated in detail by the following examples, but the present invention is not limited to the examples.
Example 1: synthesis of m-terphenyl compound IIa
A25 mL two-necked flask under nitrogen blanket was charged with triethyl orthoformate (4.0mmol), acetophenone (1.0mmol) and ethanol (5 mL). After stirring for 0.5h, trifluoromethanesulfonic acid (0.1mmol) was added to the mixture, the reaction was monitored by TLC and quenched after completion by addition of saturated sodium carbonate solution (10mL) to give a biphasic solution which was extracted with dichloromethane (3X 10 mL). The organic layer obtained by extraction was dried over anhydrous sodium sulfate, then concentrated by rotary evaporation under reduced pressure, and finally separated directly by silica gel column chromatography (using ethyl acetate-hexane as eluent) to obtain m-terphenyl compound Ia as a white solid, with a yield of 73%, melting point: 83-84 ℃.
1H NMR(600MHz,CDCl3)δ7.83(t,J＝1.7Hz,1H),7.71–7.63(m,4H),7.60(dd,J＝7.1,1.6Hz,2H),7.53(dd,J＝8.3,7.0Hz,1H),7.48(dd,J＝10.6,4.8Hz,4H),7.39(t,J＝7.4Hz,2H)；13C NMR(151MHz,CDCl3)δ141.82,141.22,129.23,128.84,127.44,127.30,126.20,126.17.
Example 2: synthesis of m-terphenyl compound IIa
A25 mL two-necked flask under nitrogen blanket was charged with triethyl orthoformate (4.0mmol) and acetophenone (1.0 mmol). After stirring for 0.5h, trifluoromethanesulfonic acid (0.1mmol) was added to the mixture, the reaction was monitored by TLC and quenched after completion by addition of saturated sodium carbonate solution (10mL) to give a biphasic solution which was extracted with dichloromethane (3X 10 mL). The organic layer obtained by extraction was dried over anhydrous sodium sulfate, then concentrated by rotary evaporation under reduced pressure, and finally separated directly by silica gel column chromatography (using ethyl acetate-hexane as eluent) to obtain m-terphenyl compound Ia as a white solid, with a yield of 81%, melting point: 83-84 ℃.
Example 3: synthesis of m-terphenyl compound IIa
A25 mL two-necked flask under nitrogen blanket was charged with triethyl orthoformate (4.0mmol), acetophenone (1.0mmol) and THF (5 mL). After stirring for 0.5h, trifluoromethanesulfonic acid (0.1mmol) was added to the mixture, the reaction was monitored by TLC and quenched after completion by addition of saturated sodium carbonate solution (10mL) to give a biphasic solution which was extracted with dichloromethane (3X 10 mL). The organic layer obtained by extraction was dried over anhydrous sodium sulfate, then concentrated by rotary evaporation under reduced pressure, and finally separated directly by silica gel column chromatography (using ethyl acetate-hexane as eluent) to obtain m-terphenyl compound Ia as a white solid, with a yield of 61%, melting point: 83-84 ℃.
Example 4: synthesis of m-terphenyl compound IIa
A25 mL two-necked flask under nitrogen blanket was charged with triethyl orthoformate (4.0mmol) and acetophenone (1.0 mmol). After stirring for 0.5h, CF was added to the mixture3COOH (1.5mmol), the reaction was monitored by TLC and quenched after completion by addition of saturated sodium carbonate solution (10mL) to give a biphasic solution which was extracted with dichloromethane (3X 10 mL). Extract (Cuiyu)Drying the obtained organic layer with anhydrous sodium sulfate, performing rotary evaporation and concentration under reduced pressure, and finally directly performing silica gel column chromatography (using ethyl acetate-hexane as an eluent) to separate to obtain the m-terphenyl compound Ia as a white solid, wherein the yield is 54%, and the melting point is as follows: 83-84 ℃.
Example 5: synthesis of m-terphenyl compound IIa
A25 mL two-necked flask under nitrogen blanket was charged with triethyl orthoformate (4.0mmol) and acetophenone (1.0 mmol). After stirring for 0.5h, p-toluenesulfonic acid (0.5mmol) was added to the mixture, the reaction was monitored by TLC and quenched after completion with saturated sodium carbonate solution (10mL) to give a biphasic solution which was extracted with dichloromethane (3X 10 mL). The organic layer obtained by extraction was dried over anhydrous sodium sulfate, then concentrated by rotary evaporation under reduced pressure, and finally separated directly by silica gel column chromatography (using ethyl acetate-hexane as eluent) to obtain m-terphenyl compound Ia as a white solid, with a yield of 56%, melting point: 83-84 ℃.
Example 6: synthesis of m-terphenyl Compound IIb
Triethyl orthoformate (4mmol) and p-methylacetophenone Ib (1mmol) were added to a 25mL two-necked flask under nitrogen, and after stirring at 50 ℃ for 0.5 hour, trifluoromethanesulfonic acid (0.1mmol) was added. The progress of the reaction was monitored by TLC, and after completion of the reaction, it was quenched by addition of saturated aqueous sodium carbonate (10mL) and extracted with dichloromethane (3X 10 mL). The dichloromethane solution obtained by the mixed extraction was dried over sodium sulfate and concentrated under reduced pressure. The resulting oil was separated by silica gel column chromatography to give the desired product IIb as a white solid in 73% yield, melting point: 105 ℃ and 106 ℃.
1H NMR(600MHz,CDCl3)δ7.78(s,1H),7.59–7.52(m,6H),7.52–7.46(m,1H),7.28(d,J＝7.7Hz,4H),2.42(s,6H)；13C NMR(151MHz,CDCl3)δ141.64,138.36,137.15,129.50,129.09,127.09,125.77,125.68,21.12.
Example 7: synthesis of m-terphenyl Compound IIc
Triethyl orthoformate (4mmol) and m-methylacetophenone Ic (1mmol) were added to a 25mL two-necked flask under nitrogen, and after stirring at 50 ℃ for 0.5 hour, trifluoromethanesulfonic acid (0.1mmol) was added. The progress of the reaction was monitored by TLC, and after completion of the reaction, it was quenched by addition of saturated aqueous sodium carbonate (10mL) and extracted with dichloromethane (3X 10 mL). The dichloromethane solution obtained by the mixed extraction was dried over sodium sulfate and concentrated under reduced pressure. The obtained oil was separated by silica gel column chromatography to obtain the objective product IIc as a colorless oil in a yield of 81%.
1H NMR(600MHz,CDCl3)δ7.82(s,1H),7.59(d,J＝7.6Hz,2H),7.55–7.45(m,5H),7.38(t,J＝7.5Hz,2H),7.22(d,J＝7.4Hz,2H),2.47(s,6H)；13C NMR(151MHz,CDCl3)δ141.82,141.21,138.36,129.05,128.69,128.11,128.05,126.16,126.04,124.36,21.55.
Example 8: synthesis of m-terphenyl Compound IId
Triethyl orthoformate (4mmol) and p-ethylacetophenone Id (1mmol) were added to a 25mL two-necked flask under nitrogen, stirred at 50 ℃ for 0.5 hour, and then trifluoromethanesulfonic acid (0.1mmol) was added. The progress of the reaction was monitored by TLC, and after completion of the reaction, it was quenched by addition of saturated aqueous sodium carbonate (10mL) and extracted with dichloromethane (3X 10 mL). The dichloromethane solution obtained by the mixed extraction was dried over sodium sulfate and concentrated under reduced pressure. The obtained oily substance is separated by silica gel column chromatography to obtain the target product IId which is colorless crystals, the yield is 75 percent, and the melting point is as follows: and (6) from 66 to 67 ℃.
1H NMR(600MHz,cdcl3)δ7.82(s,1H),7.59(dd,J＝17.9,7.6Hz,6H),7.54–7.48(m,1H),7.33(d,J＝7.9Hz,4H),2.83–2.63(m,4H),1.32(t,J＝7.6Hz,6H)；13C NMR(151MHz,CDCl3)δ143.55,141.71,138.67,129.12,128.36,127.21,125.90,125.75,28.58,15.64.
Example 9: synthesis of m-terphenyl Compound II e
Triethyl orthoformate (4mmol) and p-propyl acetophenone Ie (1mmol) were added to a 25mL two-neck flask under nitrogen, and after stirring at 50 ℃ for 0.5 hour, trifluoromethanesulfonic acid (0.1mmol) was added. The progress of the reaction was monitored by TLC, and after completion of the reaction, it was quenched by addition of saturated aqueous sodium carbonate (10mL) and extracted with dichloromethane (3X 10 mL). The dichloromethane solution obtained by the mixed extraction was dried over sodium sulfate and concentrated under reduced pressure. The obtained oily substance is separated by silica gel column chromatography to obtain the target product IIe which is a white solid, the yield is 82 percent, and the melting point is as follows: 51-52 ℃.
1H NMR(600MHz,cdcl3)δ7.82(s,1H),7.58(dd,J＝13.5,7.7Hz,6H),7.55–7.43(m,1H),7.29(d,J＝7.9Hz,4H),2.67(t,J＝7.7Hz,4H),1.72(dd,J＝15.1,7.5Hz,4H),1.01(t,J＝7.3Hz,6H)；13C NMR(151MHz,CDCl3)δ141.96,141.66,138.61,129.06,128.90,127.06,125.84,125.68,37.71,24.58,13.90.
Example 10: synthesis of m-terphenyl Compound II f
Triethyl orthoformate (4mmol) and p-isopropylacetophenone If (1mmol) were added to a 25mL two-necked flask under nitrogen, and after stirring at 50 ℃ for 0.5 hour, trifluoromethanesulfonic acid (0.1mmol) was added. The progress of the reaction was monitored by TLC, and after completion of the reaction, it was quenched by addition of saturated aqueous sodium carbonate (10mL) and extracted with dichloromethane (3X 10 mL). The dichloromethane solution obtained by the mixed extraction was dried over sodium sulfate and concentrated under reduced pressure. The obtained oil was separated by silica gel column chromatography to obtain the target product IIf as a white solid, in 69% yield, melting point: 79 to 80 ℃.
1H NMR(600MHz,CDCl3)δ7.79(d,J＝1.6Hz,1H),7.58(d,J＝8.2Hz,4H),7.56–7.52(m,2H),7.48(dd,J＝8.2,6.9Hz,1H),7.33(d,J＝8.1Hz,4H),2.97(dt,J＝13.8,6.9Hz,2H),1.31(d,J＝6.9Hz,12H)；13C NMR(151MHz,CDCl3)δ148.16,141.71,138.84,129.12,127.23,126.94,125.95,125.79,33.88,24.09；HRMS(ESI)calcd for C18H13(M+H)+:229.1012,Found:229.1010.
Example 11: synthesis of m-terphenyl Compound II g
Triethyl orthoformate (4mmol) and p-n-butylacetophenone Ig (1mmol) were added to a 25mL two-necked flask under nitrogen, and after stirring at 50 ℃ for 0.5 hour, trifluoromethanesulfonic acid (0.1mmol) was added. The progress of the reaction was monitored by TLC, and after completion of the reaction, it was quenched by addition of saturated aqueous sodium carbonate (10mL) and extracted with dichloromethane (3X 10 mL). The dichloromethane solution obtained by the mixed extraction was dried over sodium sulfate and concentrated under reduced pressure. The obtained oily substance was separated by silica gel column chromatography to obtain the target product IIg as a white solid, in a yield of 78%, melting point: 27-28 ℃.
1H NMR(600MHz,CDCl3)δ7.81(d,J＝1.4Hz,1H),7.62–7.53(m,6H),7.52–7.44(m,1H),7.29(d,J＝7.8Hz,4H),2.68(t,J＝7.8Hz,4H),1.74–1.61(m,4H),1.42(dd,J＝14.9,7.4Hz,4H),0.97(t,J＝7.4Hz,6H)；13C NMR(151MHz,CDCl3)δ142.21,141.70,138.60,129.10,128.89,127.11,125.87,125.71,35.35,33.70,22.46,14.02.
Example 12: synthesis of m-terphenyl Compound IIh
Triethyl orthoformate (4mmol) and p-isobutylacetophenone Ih (1mmol) were added to a 25mL two-necked flask under nitrogen, and after stirring at 50 ℃ for 0.5 hour, trifluoromethanesulfonic acid (0.1mmol) was added. The progress of the reaction was monitored by TLC, and after completion of the reaction, it was quenched by addition of saturated aqueous sodium carbonate (10mL) and extracted with dichloromethane (3X 10 mL). The dichloromethane solution obtained by the mixed extraction was dried over sodium sulfate and concentrated under reduced pressure. The obtained oily substance is separated by silica gel column chromatography to obtain the target product IIh which is a white solid, the yield is 79 percent, and the melting point is as follows: 47-48 ℃.
1H NMR(600MHz,CDCl3)δ7.83(d,J＝1.5Hz,1H),7.58(dd,J＝13.9,4.9Hz,6H),7.55–7.44(m,1H),7.33–7.18(m,4H),2.55(d,J＝7.2Hz,4H),1.94(dt,J＝13.5,6.8Hz,2H),0.97(d,J＝6.6Hz,12H)；13C NMR(151MHz,CDCl3)δ141.68,141.00,138.63,129.60,129.11,126.95,125.86,125.70,45.14,30.31,22.47；HRMS(ESI)calcd for C26H31(M+H)+:343.2420,Found:343.2425.
Example 13: synthesis of m-terphenyl compound IIi
Triethyl orthoformate (4mmol) and p-pentylacetophenone Ii (1mmol) were added to a 25mL two-necked flask under nitrogen, and after stirring at 50 ℃ for 0.5 hour, trifluoromethanesulfonic acid (0.1mmol) was added. The progress of the reaction was monitored by TLC, and after completion of the reaction, it was quenched by addition of saturated aqueous sodium carbonate (10mL) and extracted with dichloromethane (3X 10 mL). The dichloromethane solution obtained by the mixed extraction was dried over sodium sulfate and concentrated under reduced pressure. The obtained oily substance is separated by silica gel column chromatography to obtain the target product IIi which is a white solid, the yield is 75%, and the melting point is as follows: 36-37 ℃.
1H NMR(600MHz,CDCl3)δ7.81(s,1H),7.61–7.53(m,6H),7.49(dd,J＝8.2,7.1Hz,1H),7.29(d,J＝8.0Hz,4H),2.78–2.55(m,4H),1.75–1.64(m,4H),1.47–1.32(m,8H),0.93(t,J＝6.8Hz,6H)；13C NMR(151MHz,CDCl3)δ142.25,141.69,138.60,129.10,128.88,127.11,125.87,125.71,35.64,31.61,31.24,22.61,14.09.
Example 14: synthesis of m-terphenyl Compound II j
Triethyl orthoformate (4mmol) and 3, 4-dimethylacetophenone Ij (1mmol) were added to a 25mL two-necked flask under nitrogen, and after stirring at 50 ℃ for 0.5 hour, trifluoromethanesulfonic acid (0.1mmol) was added. The progress of the reaction was monitored by TLC, and after completion of the reaction, it was quenched by addition of saturated aqueous sodium carbonate (10mL) and extracted with dichloromethane (3X 10 mL). The dichloromethane solution obtained by the mixed extraction was dried over sodium sulfate and concentrated under reduced pressure. The obtained oily substance is separated by silica gel column chromatography to obtain the target product IIj which is a yellow solid, the yield is 71 percent, and the melting point is as follows: 37-38 ℃.
1H NMR(600MHz,CDCl3)δ7.78(t,J＝1.7Hz,1H),7.56–7.51(m,2H),7.50–7.46(m,1H),7.44(s,2H),7.40(dd,J＝7.7,1.8Hz,2H),7.24(d,J＝7.7Hz,2H),2.36(s,6H),2.33(s,6H)；13C NMR(151MHz,CDCl3)δ141.73,138.91,136.93,135.79,130.07,128.99,128.53,125.82,125.63,124.60,19.94,19.45；HRMS(ESI)calcd for C22H23(M+H)+:287.1794,Found:287.1791.
Example 15: synthesis of m-terphenyl Compound II k
Triethyl orthoformate (4mmol) and p-chloroacetophenone Ik (1mmol) were added to a 25mL two-necked flask under nitrogen, and after stirring at 50 ℃ for 0.5 hour, trifluoromethanesulfonic acid (0.1mmol) was added. The progress of the reaction was monitored by TLC, and after completion of the reaction, it was quenched by addition of saturated aqueous sodium carbonate (10mL) and extracted with dichloromethane (3X 10 mL). The dichloromethane solution obtained by the mixed extraction was dried over sodium sulfate and concentrated under reduced pressure. The obtained oily substance is separated by silica gel column chromatography to obtain the target product IIk which is a white solid, the yield is 68 percent, and the melting point is as follows: 92-93 ℃.
1H NMR(600MHz,CDCl3)δ7.71(t,J＝1.5Hz,1H),7.59–7.49(m,7H),7.47–7.40(m,4H)；HRMS(ESI)calcd for C18H13Cl2(M+H)+:299.0389,Found:299.0388.
Example 16: synthesis of m-terphenyl Compound II l
Triethyl orthoformate (4mmol) and m-chloroacetophenone Il (1mmol) were added to a 25mL two-necked flask under nitrogen, and after stirring at 50 ℃ for 0.5 hour, trifluoromethanesulfonic acid (0.1mmol) was added. The progress of the reaction was monitored by TLC, and after completion of the reaction, it was quenched by addition of saturated aqueous sodium carbonate (10mL) and extracted with dichloromethane (3X 10 mL). The dichloromethane solution obtained by the mixed extraction was dried over sodium sulfate and concentrated under reduced pressure. The obtained oil was separated by silica gel column chromatography to obtain the objective product IIl as a yellow oil in 74% yield.
1H NMR(600MHz,CDCl3)δ7.73(s,1H),7.63(s,2H),7.57(d,J＝6.8Hz,2H),7.53(dd,J＝10.2,7.7Hz,3H),7.40(t,J＝7.8Hz,2H),7.38–7.33(m,2H)；13C NMR(151MHz,CDCl3)δ142.77,140.58,134.78,130.10,129.50,127.57,127.39,126.65,126.01,125.42.
Example 17: synthesis of m-terphenyl compound IIm
Triethyl orthoformate (4mmol) and acetophenone Im (1mmol) were added to a 25mL two-necked flask under nitrogen, and after stirring at 50 ℃ for 0.5 hour, trifluoromethanesulfonic acid (0.1mmol) was added. The progress of the reaction was monitored by TLC, and after completion of the reaction, it was quenched by addition of saturated aqueous sodium carbonate (10mL) and extracted with dichloromethane (3X 10 mL). The dichloromethane solution obtained by the mixed extraction was dried over sodium sulfate and concentrated under reduced pressure. The obtained oily substance was separated by silica gel column chromatography to obtain the target product IIm as a white solid, in 67% yield, melting point: 124 ℃ and 125 ℃.
1H NMR(600MHz,CDCl3)δ8.15(s,2H),8.08(s,1H),7.96(dd,J＝14.4,8.2Hz,4H),7.91(d,J＝7.7Hz,2H),7.86(d,J＝8.4Hz,2H),7.76(d,J＝7.6Hz,2H),7.62(t,J＝7.6Hz,1H),7.58–7.48(m,4H)；13C NMR(151MHz,CDCl3)δ141.80,138.50,133.69,132.71,129.38,128.51,128.23,127.67,126.64,126.48,126.36,126.02,125.97,125.65。
Claims (9)
1. A method of preparing an m-terphenyl compound, characterized in that: in the presence of organic acid, acetophenone shown in the general formula (I) and triethyl orthoformate are heated and condensed in a solvent or without any solvent to obtain an m-terphenyl compound shown in the general formula (II), wherein the chemical reaction formula (A) is shown as follows:
wherein R is1Is H, halogen or C1-C6Straight or branched alkyl, R2Is H, halogen or C1-C6Linear or branched alkyl of (a); or R1And R2Adjacent carbon atoms are connected together to form a benzene ring; the organic acid is selected from CF3COOH, TsOH or TfOH; the solvent is ethanol or tetrahydrofuran; the molar ratio of the acetophenone, triethyl orthoformate and the organic acid is 1: (2-6): (0.05-3), the reaction temperature is 40-50 ℃, and the reaction time is 1-4 h.
2. The method for preparing m-terphenyl compound according to claim 1, wherein R1Is H, methyl, ethyl or chlorine, R2Is H, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl or chlorine; or R1And R2And adjacent carbon atoms thereof are linked together to form a benzene ring.
3. The method of preparing an m-terphenyl compound according to claim 1, wherein the molar ratio of the acetophenone, triethyl orthoformate and the organic acid is 1: (2-5): (0.05-1).
4. The method of preparing an m-terphenyl compound according to claim 3, wherein the molar ratio of the acetophenone, triethyl orthoformate and the organic acid is 1: 4: 0.1, the organic acid is TfOH.
5. The method for preparing an m-terphenyl compound according to claim 1, wherein the reaction temperature is 50 ℃ and the reaction time is 2 hours.
6. The method of claim 1, wherein the reaction is carried out under an inert gas atmosphere.
7. The method for preparing an m-terphenyl compound according to claim 1, wherein the reaction is carried out without any solvent.
8. The process for the preparation of m-terphenyl compounds according to any one of claims 1 to 6, comprising the following specific operating steps: under the protection of inert gas, heating and stirring the acetophenone and the triethyl orthoformate uniformly in the solvent or without any solvent, adding trifluoromethanesulfonic acid for reaction, and separating and purifying after the reaction is finished to obtain the m-terphenyl compound.
9. The method for preparing m-terphenyl compound according to claim 8, which comprises the following steps: stirring the acetophenone and the triethyl orthoformate for 0.5h at 50 ℃ under the protection of inert gas, adding trifluoromethanesulfonic acid for reaction, adding saturated sodium carbonate aqueous solution for quenching after the reaction is finished, extracting with dichloromethane, combining organic phases, drying with sodium sulfate, concentrating under reduced pressure, and separating the obtained concentrate by silica gel column chromatography to obtain the m-terphenyl compound.
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Non-Patent Citations (3)
| Title |
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| Acid-Catalyzed Reaction of Acetylferrocene with Triethyl Orthoformate;Yukihiko Sasaki等;《J. Org. Chem.》;19731231;第38卷(第21期);第3723-3726页 * |
| Highly Branched Polyphenylenes with 1,3,5-Triphenylbenzene Fragments via Cyclocondensation of Acetylaromatic Compounds and Ni0-Catalyzed Dehalogenation: Synthesis and Light Emission;Irina A. Khotina等;《Macromolecules》;20031002;第36卷;第8353-8360页 * |
| Metal-free and solvent-free synthesis of m-terphenyls through tandem cyclocondensation of aryl methyl ketones with triethyl orthoformate;Xiaoqin Xiao等;《RSC Advances》;20200325;第10卷;第12113-12118页 * |
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