CN113443974B - Method for preparing phenanthrene derivative from biphenyl ketene - Google Patents
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Abstract
The invention relates to a method for preparing phenanthrene derivatives from biphenyl ketene, which takes biphenyl ketene shown in a formula 1 as a raw material, dissolves biphenyl ketene in a solvent, and performs intramolecular cyclization reaction in the presence of organic base and under ultraviolet radiation to synthesize phenanthrene derivatives shown in a formula 2, wherein the reaction formula is as follows:wherein R is 1 、R 2 、R 3 Each independently selected from hydrogen, methyl, trifluoromethyl, chlorine, bromine, iodine, nitrite. The method for preparing the phenanthrene derivative from the biphenyl ketene has the advantages of simple reaction steps, no use of transition metal catalyst, high conversion rate and environment friendliness, and ultraviolet light is used for catalyzing intramolecular cyclization reaction.
Description
Technical Field
The invention belongs to the technical field of fully or partially hydrogenated phenanthrene derivatives, and relates to a method for preparing phenanthrene derivatives from biphenyl ketene.
Background
Phenanthrene (phenanthrene) is a polycyclic aromatic hydrocarbon containing three benzene rings, and is present in coal tar. The centers of the three rings of the phenanthrene are not on the same straight line, are isomers of anthracene, and are white, glossy and fluorescent flaky crystals. Phenanthrene has wide application, and can be used as a pulp antifogging agent in the paper industry; on the military industry, phenanthrene can also be used for nitrifying glycerol explosive and nitrifying cellulose stabilizer and manufacturing smoke screen bullets; in medicine, fei-kea synthesizes medicine with special physiological functions of alkaloid, morphine and caffeine, dimethyl morphine and a plurality of reproductive organs. In the dye industry, phenanthrene can be used for preparing 2-amino phenanthrene ketone, benzanthrone, sulfur vat dyes (blue Bo, black BB and brown), and the like. In the plastics industry, phenanthrene is used as a main intermediate for polyimide resins that are resistant to high temperatures. In addition, phenanthrene can be hydrogenated under high temperature and high pressure to obtain phenanthrene, which is a fuel for advanced jet aircraft. The solid oxide of phenanthrene can be used to prepare electric insulating material and filler with good flame resistance. On the aspect of pesticides, phenanthrenequinone prepared by oxidizing phenanthrenequinone is used for producing efficient and low-toxicity synthetic pesticides. Resin spectacle lenses produced from phenanthrene have been developed in recent years.
Because of the difficulty in preparing phenanthrene, many enterprises in the past and China stay at the level of preparing crude phenanthrene, the product is only used for preparing carbon black or used as general fuel, and part of crude phenanthrene is used as a concrete additive, so that the benefit is low. Therefore, the research, development and production of downstream products of phenanthrene with high added value are important to domestic related enterprises.
Typical methods of constructing phenanthrene cores include transition metal catalyzed cycloisomerisation starting from aromatic hydrocarbons, ortho-alkynyl-biaryl or substituted N-toluenesulfonyl. The Namrata Rastoni team proposes an intramolecular cyclization process of visible light catalytic oxidation of alpha-bromo-chalcone, and the phenanthrene compound can be obtained by reacting for 3 hours in anhydrous N, N-Dimethylformamide (DMF), and the phenanthrene compound has a wide substrate range and good regioselectivity. However, the alpha-bromo chalcone substrate used in the reaction needs to use toxic and volatile bromine to carry out bromination reaction on the prepared chalcone substrate, the operation is complicated and difficult, and the heavy metal catalyst used in the reaction has great harm to the environment.
The invention provides a novel method for preparing phenanthrene derivatives from biphenyl ketene, which adopts photocatalysis to carry out intramolecular cyclization reaction to obtain phenanthrene derivatives with high yield, and has the advantages of simple operation and environmental protection.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for synthesizing intramolecular cyclization phenanthrene compounds by taking biphenyl ketene compounds as raw materials, which has the advantages of simplicity, few reaction steps, easy operation, small consumption of organic solvents, simple post-treatment, high product purity, small environmental protection pressure and suitability for industrial production.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a process for preparing phenanthrene derivative from biphenyl ketene features that the biphenyl ketene as shown in formula 1 is dissolved in solvent, and the intramolecular cyclization reaction is carried out in the presence of organic alkali and ultraviolet radiation
A phenanthrene derivative represented by formula 2, which has the following reaction formula:
wherein R is 1 、R 2 、R 3 Independently selected from hydrogen, methyl, trifluoromethyl, chlorine, bromine, iodine, nitrite (-NO) 2 )。
According to the scheme, the solvent is one or more of toluene, chlorobenzene, ethanol and anisole.
Preferably, air is introduced into the reaction system during the intramolecular cyclization reaction. Oxygen in the air can improve the reaction conversion rate.
Preferably, the concentration of the biphenyl ketene represented by formula 1 in the solvent is 0.1 to 0.25mmol/mL.
According to the scheme, the organic base is one of 1, 8-diazabicyclo undec-7-ene (DBU), triethylamine and KOH, and the addition amount of the organic base is 2-4 times of the molar amount of the biphenyl ketene shown in the formula 1.
Preferably, the ultraviolet radiation is emitted by an ultraviolet lamp with the ultraviolet radiation condition of 20-40W for 4-8 hours.
The preparation method of the phenanthrene derivative from the biphenyl ketene comprises the following specific steps: adding the biphenyl ketene shown in the formula 1 into a reaction bottle, adding a solvent and an organic base, carrying out intramolecular cyclization reaction under ultraviolet radiation, tracking the reaction completion by a TLC (thin layer chromatography) plate, adding a dichloromethane dissolution product into the reaction liquid, extracting with water to collect an organic phase, adding silica gel powder (for drying) into the organic phase, removing the solvent by rotary evaporation under reduced pressure to obtain a crude product, separating the obtained crude product by a column chromatography method, and drying to obtain the phenanthrene derivative shown in the formula 2.
According to the scheme, the preparation method of the biphenyl ketene shown in the formula 1 comprises the following steps:
1) 2-bromobenzaldehyde and phenylboronic acid suzuki coupling reaction: dissolving 2-bromobenzaldehyde (compound 1) and phenylboronic acid (compound 2) in a mixed solution of N, N-Dimethylformamide (DMF) and water, and adding K 2 CO 3 And palladium acetate, and carrying out reaction under the ice water bath condition, and purifying to obtain biphenyl-2-formaldehyde (compound 3);
2) Aldehyde ketone condensation reaction: mixing the biphenyl-2-formaldehyde prepared in the step 1) with R 1 、R 2 、R 3 Dissolving substituted acetophenone (compound 4) in ethanol, adding K 3 PO 4 ·3H 2 O, stirring at room temperature, reacting, separating and purifying to obtain the biphenyl ketene (compound 5) shown in the formula 1.
The specific reaction formula is as follows:
preferably, the reaction time in step 1) is 30 to 60 minutes.
Preferably, the reaction time in step 2) is 10 to 14 hours.
According to the invention, the biphenyl ketene shown in formula 1 is used as a raw material, hydrogen electrons on a biphenyl ketene double bond are converted into an active state to be cyclized with a benzene ring under the excitation of ultraviolet light, an aliphatic ring is generated, and simultaneously, hydrogen on the aliphatic ring is pulled off under the action of organic alkali to generate the phenanthrene compound.
The invention has the beneficial effects that: the method for preparing the phenanthrene derivative from the biphenyl ketene has the advantages of simple reaction steps, no use of transition metal catalyst, high conversion rate and environment friendliness, and ultraviolet light is used for catalyzing intramolecular cyclization reaction.
Drawings
FIG. 1 is a schematic illustration of compound 5a of example 1 of the present invention 1 H NMR chart;
FIG. 2 is a diagram of compound 5a of example 1 13 C NMR chart;
FIG. 3 is a diagram of compound 6a of example 1 1 H NMR chart;
FIG. 4 is a diagram of compound 6a of example 1 13 C NMR chart;
FIG. 5 is a diagram of compound 5b of example 2 1 H NMR chart;
FIG. 6 is a diagram of compound 5b of example 2 13 C NMR chart;
FIG. 7 is a diagram of compound 6b of example 2 1 H NMR chart;
FIG. 8 is a diagram of compound 6b of example 2 13 C NMR chart;
FIG. 9 is a photograph of compound 5c of example 3 1 H NMR chart;
FIG. 10 is a photograph of compound 5c of example 3 13 C NMR chart;
FIG. 11 is a photograph of compound 6c of example 3 1 H NMR chart;
FIG. 12 is a photograph of compound 6c of example 3 13 C NMR chart;
FIG. 13 is a photograph of compound 5d of example 4 1 H NMR chart;
FIG. 14 is a photograph of compound 5d of example 4 13 C NMR chart;
FIG. 15 is a photograph of compound 6d of example 4 1 H NMR chart;
FIG. 16 is a schematic diagram of example 4Compound 6d 13 C NMR chart.
FIG. 17 is a photograph of compound 5e of example 5 1 H NMR chart;
FIG. 18 is a photograph of compound 5e of example 5 13 C NMR chart;
FIG. 19 is a photograph of compound 6e of example 5 1 H NMR chart;
FIG. 20 is a photograph of compound 6e of example 5 13 C NMR chart;
FIG. 21 is a photograph of compound 5f of example 6 1 H NMR chart;
FIG. 22 is a photograph of compound 5f of example 6 13 C NMR chart;
FIG. 23 is a photograph of compound 6f of example 6 1 H NMR chart;
FIG. 24 is a photograph of compound 6f of example 6 13 C NMR chart;
FIG. 25 shows 5g of the compound of example 7 1 H NMR chart;
FIG. 26 is a chart of 5g of the compound of example 7 13 C NMR chart;
FIG. 27 is a photograph of 6g of the compound of example 7 1 H NMR chart;
FIG. 28 is a photograph of 6g of the compound of example 7 13 C NMR chart.
Detailed Description
The present invention will be described in further detail with reference to examples for better understanding of the technical scheme of the present invention to those skilled in the art.
Example 1
A preparation method of a phenanthrene derivative comprises the following specific steps:
1) 2.0mmol of 2-bromobenzaldehyde (compound 1), 2.1mmol of phenylboronic acid (compound 2) and 2.0mmol of K 2 CO 3 Put into a 100mL flask, then a mixed solution of 20mL of N, N-Dimethylformamide (DMF) and 10mL of water is poured into the flask, the flask is put into ice water mixed solution and stirred, 0.1mmol of palladium acetate is weighed and added into the flask, the reaction is carried out for 30min, a proper amount of dichloromethane dissolution product is added into the reaction solution, then the organic phase is collected by extraction with water, the solvent is removed by distillation under reduced pressure, and the obtained crude product is separated by column chromatography and dried to obtain a compound 3;
2) Weigh 1.0mmol of Compound 3, 2.2mmol of 2-chloroacetophenone (Compound 4 a), 0.2mmol of K 3 PO 4 ·3H 2 Placing O into a 25mL flask, pouring 10mL of ethanol, stirring at room temperature for reaction for 12 hours, adding a proper amount of dichloromethane dissolution product into the reaction liquid, extracting with water to collect an organic phase, distilling under reduced pressure to remove a solvent, separating the obtained crude product by column chromatography, and drying to obtain a compound 5a;
3) 318mg of Compound 5a (1.0 mmol) was added to an open reaction flask, 10mL of chlorobenzene was added to the reaction flask, DBU (2.5 mmol) was added, the reaction flask was left under a 40W ultraviolet lamp and stirred at room temperature for 8 hours, TLC plate was followed by completion of the reaction, then 30mL of dichloromethane dissolution product was added to the reaction solution, the mixed solution was extracted with water to collect the organic phase, silica gel powder was added to the organic phase and the solvent was removed by rotary evaporation under reduced pressure to give a crude product, which was isolated by column chromatography and suspended by rotary evaporator at 35℃to give Compound 6a (288 mg, yield 88%).
The reaction formula is as follows:
characterization data for compound 5a are as follows:
1 H NMR(500MHz,CDCl 3 )：δ7.82(d,J＝7.7Hz,1H),7.48(t,J＝9.0Hz,2H),7.44(d,J＝12.1Hz,2H),7.41–7.38(m,3H),7.38–7.35(m,2H),7.33(d,J＝8.0Hz,1H),7.30(d,J＝7.7Hz,2H),7.28(d,J＝7.3Hz,1H),7.08(d,J＝16.1Hz,1H)。 1 the H NMR spectrum is shown in FIG. 1.
13 C NMR(126MHz,CDCl 3 )：δ194.37,146.27,143.52,139.56,138.96,132.56,131.08,131.02,130.52,130.48,130.08,129.84,129.01,128.22,127.80,127.56,127.47,126.99,126.68。 13 The C NMR spectrum is shown in FIG. 2.
Characterization data for compound 6a are as follows:
1 H NMR(500MHz,CDCl 3 )：δ8.84(t,1H),8.73(t,1H),8.67(d,J＝8.4Hz,1H),7.84(s,1H),7.79(d,J＝7.9Hz,1H),7.73(t,J＝5.8Hz,1H),7.72–7.66(m,2H),7.57(t,J＝7.8Hz,2H),7.47(d,J＝3.5Hz,2H),7.41–7.34(m,1H)。 1 the H NMR spectrum is shown in FIG. 3.
13 C NMR(126MHz,CDCl 3 )：δ196.99,139.77,133.85,132.37,132.34,131.79,130.91,130.49,130.47,130.17,129.87,129.39,128.89,127.82,127.38,127.12,126.88,126.82,122.88,122.79。 13 The C NMR spectrum is shown in FIG. 4.
The DBU of step 3) of this example was replaced with an equimolar amount of triethylamine, the remaining conditions unchanged, to give the product as compound 6a (238 mg, 75% yield).
The DBU of step 3) of this example was replaced with an equimolar amount of KOH, the remaining conditions unchanged, to give the product as compound 6a (219 mg, 69% yield).
Example 2
A preparation method of a phenanthrene derivative comprises the following specific steps:
1) 1.0mmol of Compound 3 (preparation method is the same as in example 1), 2.2mmol of 2' -bromoacetophenone (Compound 4 b) and 0.2mmol of K were weighed out 3 PO 4 ·3H 2 Placing O into a 25mL flask, pouring 10mL of ethanol, stirring at room temperature for reaction for 12 hours, adding a proper amount of dichloromethane dissolution product into the reaction liquid, extracting with water to collect an organic phase, distilling under reduced pressure to remove a solvent, separating the obtained crude product by column chromatography, and drying to obtain a compound 5b;
2) 362mg of Compound 5b (1.0 mmol) was added to an open reaction flask, 10mL of chlorobenzene was added to the reaction flask, 381mg of DBU (2.5 mmol) was added, air was introduced, the reaction flask was left under a 20W ultraviolet lamp and stirred at room temperature for 8 hours, TLC plate was followed by completion of the reaction, then 30mL of dichloromethane dissolved product was added to the reaction solution, the mixed solution was extracted with water to collect the organic phase, silica gel powder was added to the organic phase and the solvent was removed by rotary evaporation under reduced pressure to obtain a crude product, and the obtained crude product was separated by column chromatography and dried to obtain Compound 6b (318 mg, yield 75%).
The reaction formula is as follows:
characterization data for compound 5b are as follows:
1 H NMR(500MHz,CDCl 3 ): delta 7.81 (d, j=7.6 hz, 1H), 7.56 (t, j=10.3 hz, 1H), 7.53-7.47 (m, 1H), 7.44 (ddd, j=10.4, 6.0,1.4hz, 2H), 7.41-7.27 (m, 8H), 7.27-7.21 (m, 1H), 7.04 (t, j=11.3 hz, 1H), the spectra are shown in fig. 5.
13 C NMR(126MHz,CDCl 3 ): delta 189.37,144.67,143.63,139.99,136.85,133.01,131.87,130.75,130.29,130.10,129.86,128.45,127.82,127.76,127.74,127.21,122.93, spectrum is shown in figure 6.
Characterization data for compound 6b are as follows:
1 H NMR(500MHz,CDCl 3 ): δ8.76 (d, j=8.4 hz, 1H), 8.73 (d, j=8.4 hz, 1H), 8.07 (d, j=8.2 hz, 1H), 7.89 (d, j=7.9 hz, 1H), 7.82 (s, 1H), 7.80 (d, j=8.2 hz, 2H), 7.76 (t, j=7.7 hz, 1H), 7.70 (t, j=7.6 hz, 1H), 7.65 (d, j=7.4 hz, 1H), 7.61 (d, j=8.4 hz, 2H), 7.58 (d, j=7.5 hz, 1H), the spectrum being shown in fig. 7.
13 C NMR(126MHz,CDCl 3 ): delta 196.84,136.99,134.81,131.92,131.89,131.42,130.67,129.98,129.59,129.38,129.15,128.70,128.56,127.34,127.28,126.51,123.05,122.77, spectrum is shown in figure 8.
Example 3
A preparation method of a phenanthrene derivative comprises the following specific steps:
1) 1.0mmol of Compound 3 (preparation method is the same as in example 1), 2.2mmol of 3' -iodoacetophenone (Compound 4 c), 0.2mmol of K were weighed out 3 PO 4 ·3H 2 O was put into a 25mL flask, followed by pouring 10mL of ethanol, stirring at room temperature for reaction for 12 hours, and then an appropriate amount of dichloromethane dissolution product was added to the reaction solution, usingExtracting with water, collecting organic phase, distilling under reduced pressure to remove solvent, separating the crude product by column chromatography, and drying to obtain compound 5c;
2) 412mg of Compound 5c (1.0 mmol) was added to an open reaction flask, 10mL of chlorobenzene was added to the reaction flask, DBU (2.5 mmol) was added, air was introduced, the reaction flask was left under a 40W ultraviolet lamp and stirred at room temperature for 8 hours, TLC plate was followed by completion of the reaction, then an appropriate amount of dichloromethane dissolution product was added to the reaction solution, the mixed solution was extracted with water to collect the organic phase, silica gel powder was added to the organic phase and the solvent was removed by rotary evaporation under reduced pressure to obtain a crude product, and the obtained crude product was separated by column chromatography and dried to obtain Compound 6c (340 mg, yield 83%).
The reaction formula is as follows:
characterization data for compound 5c are as follows:
1 H NMR(500MHz,CDCl 3 ): delta 8.27 (s, 1H), 7.88 (dt, j=7.2, 5.2hz, 4H), 7.56-7.42 (m, 6H), 7.39-7.32 (m, 3H), 7.21 (t, j=7.8 hz, 1H), the spectrum is shown in figure 9 of the specification.
13 C NMR(126MHz,CDCl 3 ): delta 189.08,144.91,143.67,141.42,139.99,139.96,137.38,132.91,130.78,130.35,130.28,129.83,128.49,127.79,127.78,127.65,127.33,122.94,94.47, the spectrum is shown in fig. 10.
Characterization data for compound 6c are as follows:
1 H NMR(500MHz,CDCl 3 ): δ8.80 (d, j=8.4 hz, 1H), 8.76 (d, j=8.4 hz, 1H), 8.14 (d, j=8.2 hz, 1H), 7.92 (d, j=7.9 hz, 1H), 7.87 (s, 1H), 7.83 (s, 1H), 7.78 (t, j=7.7 hz, 1H), 7.73 (t, j=7.8 hz, 2H), 7.67 (t, j=7.4 hz, 1H), 7.61 (t, j=7.6 hz, 1H), 7.46 (d, j=7.5 hz, 1H), 7.37 (t, j=7.6 hz, 1H), 2.42 (s, 3H), see the spectrum of fig. 11.
13 C NMR(126MHz,CDCl 3 ): delta 200.09(s), 139.30(s), 138.63(s), 135.73(s), 131.91(s), 131.82(s), 131.52(s), 131.34(s), 130.81(s), 130.03(s), 129.85(s), 129.22(s), 128.80(s), 127.52(s), 127.21(s), 127.09(s), 126.74(s), 125.53(s), 122.91(s), 122.73(s), 20.86(s), and the spectra are shown in FIG. 12.
Example 4
A preparation method of a phenanthrene derivative comprises the following specific steps:
1) 1.0mmol of Compound 3 (preparation method is the same as in example 1), 2.2mmol of 4-nitroacetophenone (Compound 4 d), 0.2mmol of K were weighed out 3 PO 4 ·3H 2 Placing O into a 25mL flask, pouring 10mL of ethanol, stirring at room temperature for reaction for 12 hours, adding a proper amount of dichloromethane dissolution product into the reaction liquid, extracting with water to collect an organic phase, distilling under reduced pressure to remove a solvent, separating the obtained crude product by column chromatography, and drying to obtain a compound 5d;
2) 329mg of Compound 5d (1.0 mmol) was added to an open reaction flask, 10mL of chlorobenzene was added to the reaction flask, 381mg of DBU (2.5 mmol) was added, air was introduced, the reaction flask was left under a 40W ultraviolet lamp and stirred at room temperature for 8 hours, TLC plate was followed by completion of the reaction, then an appropriate amount of dichloromethane dissolution product was added to the reaction solution, the mixture was extracted with water to collect an organic phase, silica gel powder was added to the organic phase and the solvent was removed by rotary evaporation under reduced pressure to obtain a crude product, and the obtained crude product was separated by column chromatography and dried to obtain Compound 6d (230 mg, yield 70%).
The reaction formula is as follows:
characterization data for compound 5d are as follows:
1 H NMR(500MHz,CDCl 3 )：δ7.82(d,J＝7.7Hz,1H),7.48(dd,J＝15.9,94hz, 2H), 7.44 (d, j=12.1 hz, 2H), 7.41-7.38 (m, 3H), 7.38-7.35 (m, 2H), 7.33 (d, j=8.0 hz, 1H), 7.30 (d, j=7.7 hz, 2H), 7.29-7.25 (m, 1H), 7.08 (d, j=16.1 hz, 1H), the spectra are shown in fig. 13.
13 C NMR(126MHz,CDCl 3 ): delta 189.28,149.94,146.22,143.87,142.98,139.82,132.58,130.79,130.68,129.80,129.42,129.32,128.45,127.83,127.21,123.89,123.75,122.85, spectrum is shown in fig. 14.
Characterization data for compound 6d are as follows:
1 H NMR(500MHz,CDCl 3 ): δ8.82 (d, j=8.4 hz, 1H), 8.77 (d, j=8.4 hz, 1H), 8.35 (d, j=8.5 hz, 2H), 8.19 (d, j=8.3 hz, 1H), 8.10 (d, j=8.4 hz, 2H), 7.92 (d, j=7.9 hz, 1H), 7.88 (s, 1H), 7.82 (t, j=7.7 hz, 1H), 7.77 (t, j=7.6 hz, 1H), 7.69 (t, j=7.5 hz, 1H), 7.65 (t, j=7.6 hz, 1H), the spectrum being shown in fig. 15.
13 C NMR(126MHz,CDCl 3 ): delta 195.97,150.38,143.24,133.86,131.77,131.23,130.81,130.78,129.80,129.73,129.11,128.87,127.60,127.58,127.45,126.39,123.77,123.17,122.85, spectrum is shown in figure 16.
Example 5
A preparation method of a phenanthrene derivative comprises the following specific steps:
1) 1.0mmol of Compound 3 (preparation method is the same as in example 1), 2.2mmol of 4-bromoacetophenone (Compound 4 e) and 0.2mmol of K were weighed out 3 PO 4 ·3H 2 Placing O into a 25mL flask, pouring 10mL of ethanol, stirring at room temperature for reaction for 12 hours, adding a proper amount of dichloromethane dissolution product into the reaction liquid, extracting with water to collect an organic phase, distilling under reduced pressure to remove a solvent, separating the obtained crude product by column chromatography, and drying to obtain a compound 5e;
2) 363mg of compound 5e (1.0 mmol) was added to an open reaction flask, 10mL of chlorobenzene was added to the reaction flask, 381mg of DBU (2.5 mmol) was added, air was introduced, the reaction flask was left under a 40W violet lamp and stirred at room temperature for 8 hours, TLC plate was followed by completion of the reaction, then an appropriate amount of dichloromethane dissolution product was added to the reaction solution, the mixture was extracted with water to collect an organic phase, silica gel powder was added to the organic phase and the solvent was removed by rotary evaporation under reduced pressure to obtain a crude product, and the obtained crude product was separated by column chromatography and dried to obtain compound 6e (218 mg, yield 60%).
The reaction formula is as follows:
characterization data for compound 5e are as follows:
1 H NMR(500MHz,CDCl 3 ): delta 7.83 (ddd, j=10.0, 9.0,5.2hz, 4H), 7.66-7.59 (m, 2H), 7.53-7.40 (m, 6H), 7.40-7.33 (m, 3H), map see fig. 17.
13 C NMR(126MHz,CDCl 3 ): delta 189.39,144.67,143.61,139.97,136.83,133.00,131.85,130.73,130.26,130.07,129.83,128.42,127.79,127.73,127.72,127.18,122.94, map is shown in FIG. 18.
Characterization data for compound 6e are as follows:
1 H NMR(500MHz,CDCl 3 ): δ8.79 (d, j=8.4 hz, 1H), 8.75 (d, j=8.4 hz, 1H), 8.12 (d, j=8.2 hz, 1H), 7.91 (d, j=7.9 hz, 1H), 7.86 (s, 1H), 7.83 (d, j=8.1 hz, 2H), 7.78 (t, j=7.7 hz, 1H), 7.73 (t, j=7.6 hz, 1H), 7.68 (d, j=7.5 hz, 1H), 7.64 (d, j=7.4 hz, 2H), 7.61 (d, j=7.4 hz, 1H), the map is shown in fig. 19.
13 C NMR(126MHz,CDCl 3 ): delta 196.78,137.00,134.81,131.91,131.88,131.41,130.67,129.98,129.59,129.39,129.16,128.69,128.55,127.34,127.27,126.52,123.06,122.77, map is shown in FIG. 20.
Example 6
A preparation method of a phenanthrene derivative comprises the following specific steps:
1) 1.0mmol of Compound 3 (preparation method is the same as in example 1), 2.2mmol of 4-fluoroacetophenone (Compound 4 f), 0.2mmol of K are weighed out 3 PO 4 ·3H 2 O was placed in a 25mL flask, followed by pouring 10mL of ethanol at room temperatureStirring and reacting for 12 hours, then adding a proper amount of dichloromethane dissolution product into the reaction liquid, extracting with water, collecting an organic phase, distilling under reduced pressure to remove a solvent, separating the obtained crude product by a column chromatography, and drying to obtain a compound 5f;
2) 302mg of compound 5f (1.0 mmol) was added to an open reaction flask, 10mL of chlorobenzene was added to the reaction flask, DBU (2.5 mmol) was added, air was introduced, the reaction flask was left under a 20W violet lamp at room temperature and stirred for 4 hours, the TLC plate was followed by completion of the reaction, then an appropriate amount of dichloromethane dissolution product was added to the reaction solution, the mixture was extracted with water to collect an organic phase, silica gel powder was added to the organic phase and the solvent was removed by rotary evaporation under reduced pressure to obtain a crude product, and the obtained crude product was separated by column chromatography and dried to obtain compound 6f (250 mg, yield 73%).
Characterization data for compound 5f are as follows:
1 H NMR(500MHz,CDCl 3 ): delta 7.96 (dd, j=7.2, 5.6hz, 2H), 7.82 (d, j=7.9 hz, 1H), 7.80 (s, 1H), 7.46 (dd, j=14.4, 7.1hz, 2H), 7.41 (d, j=8.9 hz, 3H), 7.39-7.35 (m, 2H), 7.33 (d, j=7.7 hz, 2H), 7.17-7.08 (m, 2H), the pattern is shown in fig. 21.
13 C NMR(126MHz,CDCl 3 ): delta 188.93,166.54,164.52,144.33,143.56,140.01,134.45,134.43,133.08,131.15,131.08,130.71,130.15,129.83,128.40,127.71,127.68,127.13,123.11,115.74,115.57, map is shown in FIG. 22.
Characterization data for compound 6f are as follows:
1 H NMR(500MHz,CDCl 3 )：δ8.80(d,J＝8.4Hz,1H),8.76(d,J＝8.4Hz,1H),8.09(d,J＝8.3Hz,1H),8.01(d,J＝5.8Hz,1H),8.00(d,J＝5.7Hz,1H),7.93(d,J＝7.9Hz,1H),7.85(d,J＝12.5Hz,1H),7.79(t,J＝7.7Hz,1H),7.74(t,J＝7.6hz,1 h), 7.68 (t, j=7.4 hz,1 h), 7.62 (t, j=7.6 hz,1 h), 7.17 (t, j=8.1 hz,2 h), the map is shown in fig. 23.
13 C NMR(126MHz,CDCl 3 ): delta 196.34(s), 167.02(s), 164.98(s), 135.16(s), 134.57(s), 134.55(s), 133.10(s), 133.03(s), 131.32(s), 130.65(s), 130.05(s), 129.51(s), 129.22(s), 128.93(s), 128.41(s), 127.28(s), 127.23(s), 126.52(s), 123.03(s), 122.75(s), 115.83(s), 115.65(s), and the map is shown in fig. 24.
Example 7
A preparation method of a phenanthrene derivative comprises the following specific steps:
1) 1.0mmol of Compound 3 (preparation method is the same as in example 1), 2.2mmol of p-trifluoromethyl acetophenone (Compound 4 g), 0.2mmol of K were weighed out 3 PO 4 ·3H 2 Placing O into a 25mL flask, pouring 10mL of ethanol, stirring at room temperature for reaction for 12 hours, adding a proper amount of dichloromethane dissolution product into the reaction liquid, extracting with water to collect an organic phase, distilling under reduced pressure to remove a solvent, separating the obtained crude product by column chromatography, and drying to obtain 5g of a compound;
2) 352mg of compound 5g (1.0 mmol) was added to an open reaction flask, 10mL chlorobenzene was added to the reaction flask, 381mg of DBU (2.5 mmol) was added, air was introduced, the reaction flask was left under a 40W violet lamp and stirred at room temperature for 8 hours, TLC plate was followed by completion of the reaction, then an appropriate amount of dichloromethane dissolution product was added to the reaction solution, the mixture was extracted with water to collect an organic phase, silica gel powder was added to the organic phase and the solvent was removed by rotary evaporation under reduced pressure to obtain a crude product, and the obtained crude product was separated by column chromatography and dried to obtain 6g of compound (275 mg, yield 78%).
Characterization data for compound 5g are as follows:
1 H NMR(500MHz,CDCl 3 ): delta 8.04 (t, j=11.9 hz, 2H), 7.90 (dd, j=23.4, 8.5hz, 1H), 7.85 (s, 1H), 7.74 (d, j=7.9 hz, 2H), 7.52 (t, j=7.4 hz, 1H), 7.49 (s, 1H), 7.48-7.44 (m, 3H), 7.43 (d, j=8.6 hz, 1H), 7.39 (d, j=16.9 hz, 1H), 7.37-7.31 (m, 2H), the map is shown in fig. 25.
13 C NMR(126MHz,CDCl 3 ): delta 189.81,145.48,143.76,140.99,139.91,132.81,130.76,130.46,129.82,128.79,128.43,127.79,127.76,127.18,125.63,125.60,125.57,125.54,123.05, map is shown in FIG. 26.
Characterization data for 6g of compound was as follows:
1 H NMR(500MHz,CDCl 3 ): δ8.81 (d, j=8.4 hz, 1H), 8.77 (d, j=8.4 hz, 1H), 8.17 (d, j=8.2 hz, 1H), 8.07 (d, j=8.0 hz, 2H), 7.93 (d, j=7.9 hz, 1H), 7.88 (s, 1H), 7.83-7.79 (m, 1H), 7.78 (d, j=7.7 hz, 2H), 7.75 (d, j=8.1 hz, 1H), 7.69 (t, j=7.4 hz, 1H), 7.64 (t, j=7.6 hz, 1H), the map is shown in fig. 27.
13 C NMR(126MHz,CDCl 3 ): delta 196.69,141.21,134.38,131.61,130.73,130.63,130.20,129.87,129.70,129.06,128.81,127.46,127.33,126.47,125.63,125.60,123.09,122.80, map is shown in FIG. 28.
Claims (9)
1. A method for preparing phenanthrene derivatives from biphenyl ketene is characterized in that biphenyl ketene shown in a formula 1 is taken as a raw material, biphenyl ketene is dissolved in a solvent, and intramolecular cyclization reaction is carried out under the condition of existence of organic base and ultraviolet radiation to synthesize the phenanthrene derivatives shown in a formula 2, wherein the reaction formula is as follows:
；
wherein R is 1 、R 2、 R 3 Each independently selected from hydrogen, methyl, trifluoromethyl, chloro, bromo, iodo, nitrite;
the organic base is one of 1, 8-diazabicyclo undec-7-ene, triethylamine and KOH;
and the ultraviolet radiation condition is that an ultraviolet lamp with the ultraviolet radiation of 20-40W radiates for 4-8 hours.
2. The method for preparing phenanthrene derivatives from biphenyl ketene according to claim 1, wherein the solvent is one or more of toluene, chlorobenzene, ethanol, anisole.
3. The method for producing a phenanthrene derivative from a biphenylene ketone according to claim 1, wherein air is introduced into the reaction system during the intramolecular cyclization reaction.
4. The method for producing a phenanthrene derivative from a biphenylene ketone according to claim 1, wherein a concentration of the biphenylene ketone represented by formula 1 in a solvent is 0.1 to 0.25mmol/mL.
5. The method for preparing a phenanthrene derivative from a biphenyl ketene according to claim 1, wherein the organic base is added in an amount of 2-4 times the molar amount of the biphenyl ketene represented by formula 1.
6. The method for preparing phenanthrene derivatives from biphenyl ketene according to claim 1, characterized by the specific steps of: adding the biphenyl ketene shown in the formula 1 into a reaction bottle, adding a solvent and an organic base, carrying out intramolecular cyclization reaction under ultraviolet radiation, tracking the reaction completion by a TLC (thin layer chromatography) plate, adding a dichloromethane dissolution product into the reaction liquid, extracting with water to collect an organic phase, adding silica gel powder into the organic phase, removing the solvent by rotary evaporation under reduced pressure to obtain a crude product, separating the obtained crude product by a column chromatography method, and drying to obtain the phenanthrene derivative shown in the formula 2.
7. The method for producing a phenanthrene derivative from a biphenylene ketone according to claim 1, wherein the biphenylene ketone represented by formula 1 is produced by:
1) 2-bromobenzaldehyde and phenylboronic acid suzuki coupling reaction: dissolving 2-bromobenzaldehyde and phenylboronic acid in a mixed solution of N, N-dimethylformamide and water, and adding K 2 CO 3 And palladium acetate inCarrying out reaction under the ice water bath condition, and purifying to obtain biphenyl-2-formaldehyde;
2) Aldehyde ketone condensation reaction: mixing the biphenyl-2-formaldehyde prepared in the step 1) with R 1 、R 2 、R 3 Dissolving substituted acetophenone in ethanol, adding K 3 PO 4 ∙3H 2 O, stirring at room temperature for reaction, and separating and purifying to obtain the biphenyl ketene shown in the formula 1.
8. The method for preparing phenanthrene derivatives from biphenyl ketene according to claim 7, wherein the reaction time of step 1) is 30-60 min.
9. The method for preparing phenanthrene derivatives from biphenyl ketene according to claim 7, wherein the reaction time of step 2) is 10-14 h.
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| Photoredox/Cobalt-Catalyzed C(sp3)-H Bond Functionalization toward Phenanthrene Skeletons with Hydrogen Evolution;Guo, Jia-Dong等;Organic Letters;第22卷(第24期);第9627-9632页 * |
| Synthesis of Phenanthrenes through Visible-Light Photoredox Catalyzed Intramolecular Cyclization of α-Bromochalcones;Nagode, Savita B.等;European Journal of Organic Chemistry;第2018卷(第13期);Supporting Information第3-4页 * |
| Synthesis of Substituted Phenanthrene by Iron(III)-Catalyzed Intramolecular Alkyne-Carbonyl Metathesis;Bera, Krishnendu等;Journal of Organic Chemistry;第77卷(第19期);第8780-8786页 * |
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