CN112812097B - Method for synthesizing 3- (2-pyridine) substituted pyrrole compound by visible light catalysis - Google Patents
Method for synthesizing 3- (2-pyridine) substituted pyrrole compound by visible light catalysis Download PDFInfo
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Abstract
The invention belongs to the technical field of synthesis of pyrrole compounds, and particularly relates to a method for synthesizing a 3- (2-pyridine) substituted pyrrole compound by visible light catalysis. The visible light catalysis synthesis method of 3- (2-pyridine) substituted pyrrole compounds is specifically to synthesize the compound shown in the formulaN-aryl-substituted glycine,βThe- (2-pyridine) -1, 3-eneyne, the visible light catalyst DPZ and the additive sodium dihydrogen phosphate are uniformly mixed in a solvent, and after the reaction under the irradiation of visible light, the substituted pyrrole compound is obtained by separation and purification. The synthetic method has the advantages of simple reaction substrate, mild reaction conditions, no heavy metal participation and high yield.
Description
Technical Field
The invention belongs to the technical field of synthesis of pyrrole compounds, and particularly relates to a method for synthesizing a 3- (2-pyridine) substituted pyrrole compound by visible light catalysis.
Background
The 3- (2-pyridine) substituted pyrrole compound has wide application in the fields of synthetic drugs, natural products, functional materials and the like. In the research of green organic synthetic chemistry, the development of a method for synthesizing the 3- (2-pyridine) substituted pyrrole compound with environmental protection and high efficiency has important significance. The prior art methods for synthesizing 3- (2-pyridine) substituted pyrroles are mainly the serial cyclization of 1-phenyl-3- (2-pyridine) enone, nitromethane and ammonium acetate (Coskun, a.; yilmaz, m.d.; akkaya, e.u.: org.lett.,2007,9, 607-609) and the cycloaddition reaction of methyl benzenesulfonylmethylisocyanitrile with 2-vinylpyridine (Smith, n.d.; huang, d.; cosford, n.d.p.: org.lett.,2002,4, 3537-3539). It is noted that these processes have poor step economics and atom economics, generally low yields, and limited functional group compatibility.
In recent years, the visible light catalytic reaction is widely applied to the field of organic synthesis due to greenness, high efficiency and mildness. Because the reaction condition has no heavy metal residue, the product does not need to be removed by heavy metal, and the visible light is used for catalyzing the free radical addition-cyclization reaction of the N-aryl substituted glycine and the beta- (2-pyridine) -1, 3-eneyne.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention provides a method for synthesizing a 3- (2-pyridine) substituted pyrrole compound by visible light catalysis. The synthesis method has the advantages of simple reaction substrate, mild reaction conditions, no heavy metal participation and high yield.
In order to realize the purpose, the technical scheme of the invention is as follows:
a method for synthesizing 3- (2-pyridine) substituted pyrrole compounds by visible light catalysis is characterized by uniformly mixing N-aryl substituted glycine shown in a formula I, beta- (2-pyridine) -1, 3-eneyne shown in a formula II, a visible light catalyst DPZ and additive sodium dihydrogen phosphate in a solvent under the protection of inert gas, reacting under the irradiation of visible light, and separating and purifying to obtain substituted pyrrole compounds shown in a formula III;
in the formulae I, II and III, ar represents an aryl group such as phenyl, p-methoxyphenyl, p-trifluoromethoxyphenyl, 3, 4-dimethoxyphenyl, 2-chloro-4-methoxyphenyl, 2-tert-butylphenyl, 2-methyl-4-bromophenyl, 1-naphthyl, 4-methoxyphenyl, 1, 4-diphenyl, R 1 And R 2 Represents H, alkyl or aryl, such as phenyl, 3-thienyl, 4-pentyl, 2-furan, 3-fluorophenyl.
Preferably, the reaction is carried out under the irradiation of visible light, the reaction temperature is 20-30 ℃, and the reaction time is 24-72h; more preferably, the reaction temperature is 25 ℃ and the reaction time is 48h.
Preferably, the solvent is a mixed solvent of 1, 2-dichloroethane and tetrahydrofuran, and the volume ratio of the 1, 2-dichloroethane to the tetrahydrofuran is (0.5-1.5): (0.5-1.5); further preferably 1.
Preferably, the molar ratio of the N-aryl substituted glycine to the beta- (2-pyridine) -1, 3-enyne is (1-2) to (0.5-1.5); more preferably 1.5.
Preferably, the molar ratio of the visible-light-driven photocatalyst DPZ to the beta- (2-pyridine) -1, 3-eneyne is (0.001-0.01): 1; more preferably 0.005.
Preferably, the mole ratio of the additive sodium dihydrogen phosphate to the beta- (2-pyridine) -1, 3-eneyne is (0.5-1.5) to (0.5-1.5); further preferably 1.
Preferably, the ratio of the volume of the solvent to the amount of β - (2-pyridine) -1, 3-enyne material is 30 to 50mL; further preferably 40mL.
The visible light catalyst DPZ selected by the invention has small relative molecular mass, is easy to synthesize and has high catalytic efficiency.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention uses metal-free DPZ photocatalyst in the reaction, the catalyst consumption is very little, the catalytic efficiency is high, and the product conversion rate is high;
2. compared with the existing synthesis method, the synthesis method provided by the invention uses a metal-free DPZ photocatalyst, is mild in reaction condition, fast and efficient, high in yield, green and environment-friendly, and has great popularization and application values.
Drawings
FIG. 1 is a hydrogen spectrum of the product of example 1;
FIG. 2 is a carbon spectrum of the product of example 1;
FIG. 3 is a high resolution mass spectrum of the product of example 1;
FIG. 4 is a hydrogen spectrum of the product of example 2;
FIG. 5 is a carbon spectrum of the product of example 2;
FIG. 6 is a high resolution mass spectrum of the product of example 2.
Detailed Description
The invention is further illustrated, but not limited, by the following examples and figures.
The visible-light photocatalyst DPZ in the examples can be referred to literature (Yu Zhao,
Chenhao Zhang,
kek Foo Chin, old \711richPytela, guo Wei, hongjun Liu, filip Bures and Zhiyong Jiang RSC adv.,2014,4, 30062); sodium dihydrogen phosphate was purchased from carbofuran.
Example 1
The visible light catalytic synthesis process of N-phenyl-3- (2-pyridyl) -2-benzyl-4-phenyl pyrrole has the following reaction formula:
the preparation method comprises the following specific steps: 1mg of visible light photocatalyst DPZ dissolved in 200. Mu.L of toluene was extracted 35.5. Mu.L (0.0005mmol, 0.005 eq.) into a 25mL Schlenktube (Schlenktube), and toluene was blown dry with an air pump; subsequently, 22.7mg (0.15 mmol) of N-phenylglycine, 28.1mg (0.10 mmol) of 2- (2-pyridine) -1, 4-diphenyl-1, 3-enyne, 12mg (0.10 mmol) of sodium dihydrogenphosphate were added, followed by 4mL of purified and dried particles in a volume ratio of 1:1 tetrahydrofuran and 1, 2-dichloroethane are subjected to vacuum-freezing (freezing at-200 ℃ for 20 min) -room temperature (5 min) -argon protection for three times in sequence, the reaction bottle is placed in a thermostat at 25 ℃, and is stirred for 48 hours under the irradiation condition of a 3W blue LED lamp; after the reaction is finished, evaporating tetrahydrofuran and 1, 2-dichloroethane by using a rotary evaporator, and directly separating by column chromatography, wherein an eluent is a mixed solvent of n-hexane and ethyl acetate, and the volume ratio of gradient concentrations of n-hexane and ethyl acetate is 50-5 (specifically: the volume ratio of n-hexane to ethyl acetate is 50.
Characterization data for the synthesized N-phenyl-3- (2-pyridyl) -2-benzyl-4-phenylpyrrole are as follows:
the nuclear magnetic data are: 1 H NMR(300MHz,CDCl 3 ) δ 8.63 (d, J =4.0hz, 1h), 7.48 (t, J =6.9hz, 1h), 7.35-7.29 (m, 3H), 7.23 (d, J =4.2hz, 4h), 7.18 (s, 3H), 7.12-7.06 (m, 2H), 7.02 (d, J =6.2hz, 3h), 6.90 (s, 1H), 6.78-6.67 (m, 2H), 4.24 (s, 2H) (as shown in fig. 1); 13 C NMR(75MHz,CDCl 3 ) Delta 155.6,149.2,140.1,139.7,135.7,135.4,132.1,128.9,128.2,128.1, 127.9,127.6,126.7,125.7,125.6,125.5,124.3,121.8,120.8,120.6,30.6 (as shown in FIG. 2).
The high resolution data is: HRMS (ESI) M/z 387.1854 (M + H) + ),calc.for C 28 H 22 N 2 387.1856 (as shown in fig. 3).
Example 2
The visible light catalytic synthesis process of N-p-methoxyphenyl-3- (2-pyridyl) -2-benzyl-4-phenylpyrrole has the following reaction formula:
the preparation method comprises the following specific steps: in this example, N-phenylglycine in example 1 was replaced with N- (4-methoxyphenyl) glycine, and otherwise the same as in example 1, N-p-methoxyphenyl-3- (2-pyridyl) -2-benzyl-4-phenylpyrrole was obtained in 38.3mg as a yellow oil in 92% yield.
Characterization data for the synthesized N-p-methoxyphenyl-3- (2-pyridyl) -2-benzyl-4-phenylpyrrole are as follows:
the nuclear magnetic data are: 1 H NMR(300MHz,CDCl 3 ) δ 8.64 (dd, J =5.3,1.8hz, 1h), 7.49 (td, J =7.7,1.8hz, 1h), 7.23 (d, J =3.9hz, 4h), 7.18 (dd, J =5.1,3.5hz, 1h), 7.11-7.07 (m, 4H), 7.05 (d, J =7.2hz, 3h), 6.85 (dd, J =7.1,1.6hz, 3h), 6.77-6.73 (m, 2H), 4.22 (s, 2H), 3.83 (s, 3H) (as shown in fig. 4); 13 C NMR(75MHz,CDCl 3 ) Delta 158.9,155.6,149.1,140.2,135.8,135.5,132.6,132.4,128.2,128.1,128.0,127.9,125.7,125.6,125.5,123.9,121.0,120.6,114.0,55.5,30.5 (as shown in FIG. 5).
The high resolution data is: HRMS (ESI) M/z 417.1959 (M + H) + ),calc.for C 29 H 24 N 2 O417.1961 (as shown in fig. 6).
Example 3
The visible light catalytic synthesis process of N-p-trifluoro-methoxyphenyl-3- (2-pyridyl) -2-benzyl-4-phenyl pyrrole has the following reaction formula:
the preparation method comprises the following specific steps: in this example, N- (p-trifluoromethoxyphenyl) -3- (2-pyridyl) -2-benzyl-4-phenylpyrrole 40mg was obtained as a yellow oil in 85% yield in the same manner as in example 1 except that N-phenylglycine in example 1 was replaced with N- (4-trifluoromethoxyphenyl) glycine.
Characterization data for the synthesized N-p-trifluoromethoxyphenyl-3- (2-pyridyl) -2-benzyl-4-phenylpyrrole are as follows:
the nuclear magnetic data are: 1 H NMR(300MHz,CDCl 3 )δ8.64(dd,J＝5.1,1.8Hz,1H),7.50(td,J＝7.7,1.8Hz,1H),7.25–7.21(m,4H),7.20–7.16(m,5H),7.12–7.08(m,2H),7.03(dd,J＝5.8,4.2Hz,3H),6.87(s,1H),6.72(dd,J＝7.1,2.2Hz,2H),4.22(s,2H)； 13 C NMR(75MHz,CDCl 3 )δ155.3,149.3,148.2,139.7,138.3,135.8,135.1,132.2,128.3,128.2,128.1,128.1,128.0,125.8,125.7,124.7,121.4,120.8,120.6,30.7。
the high resolution data is: HRMS (ESI) M/z 471.1676 (M + H) + ),calc.for C 29 H 21 F 3 N 2 O 471.1679。
Example 4
Visible light catalytic synthesis method of N- (3, 4-dimethoxyphenyl) -3- (2-pyridyl) -2-benzyl-4-phenylpyrrole, which has the following reaction formula:
the preparation method comprises the following specific steps: in this example, N-phenylglycine in example 1 was replaced with N- (3, 4-dimethoxyphenyl) glycine in the same manner as in example 1 to give N- (3, 4-dimethoxyphenyl) -3- (2-pyridyl) -2-benzyl-4-phenylpyrrole 42.8mg as a yellow oil in a yield of 96%.
Characterization data for the synthesized N- (3, 4-dimethoxyphenyl) -3- (2-pyridyl) -2-benzyl-4-phenylpyrrole are as follows:
the nuclear magnetic data are: 1 H NMR(300MHz,CDCl 3 )δ8.66–8.61(m,1H),7.49(td,J＝7.8,1.9Hz,1H),7.25–7.21(m,4H),7.20–7.15(m,1H),7.14–7.04(m,5H),6.93(s,1H),6.89–6.82(m,2H),6.43(t,J＝2.3Hz,1H),6.34(d,J＝2.3Hz,2H),4.26(s,2H),3.63(s,6H)； 13 C NMR(75MHz,CDCl 3 )δ160.7,155.5,149.3,141.3,140.5,135.7,135.3,131.6,128.2,128.1,128.0,125.6,125.6,125.5,124.2,120.6,104.8,100.5,55.3,30.7。
the high resolution data is: HRMS (ESI) M/z 447.2062 (M + H) + ),calc.for C 30 H 26 N 2 O 2 447.2067。
Example 5
The visible light catalytic synthesis process of N- (2-chloro-4-methoxyphenyl) -3- (2-pyridyl) -2-benzyl-4-phenyl pyrrole has the following reaction formula:
the preparation method comprises the following specific steps: in this example, N-phenylglycine in example 1 was replaced with N- (2-chloro-4-methoxyphenyl) glycine, and the same procedures as in example 1 were repeated to give 37.4mg of N- (2-chloro-4-methoxyphenyl) -3- (2-pyridyl) -2-benzyl-4-phenylpyrrole as a yellow oil in 83% yield.
Characterization data for the synthesized N- (2-chloro-4-methoxyphenyl) -3- (2-pyridyl) -2-benzyl-4-phenylpyrrole are as follows:
the nuclear magnetic data are: 1 H NMR(300MHz,CDCl 3 )δ8.66(dd,J＝5.4,1.6Hz,1H),7.52(td,J＝7.7,1.6Hz,1H),7.23(d,J＝4.1Hz,4H),7.20–7.16(m,1H),7.15–7.10(m,2H),7.06–6.99(m,4H),6.96(d,J＝2.8Hz,1H),6.77(s,1H),6.76–6.70(m,3H),4.25(d,J＝16.1Hz,1H),4.04(d,J＝15.8Hz,1H),3.82(s,3H)； 13 C NMR(75MHz,CDCl 3 )δ159.7,155.6,149.3,139.6,135.6,135.4,133.4,133.00,130.6,129.9,128.3,128.1,127.8,125.7,125.6,125.5,124.0,120.9,120.5,114.9,112.8,55.7,30.7。
the high resolution data is: HRMS (ESI) M/z 447.2062 (M + H) + ),calc.for C 30 H 26 N 2 O 2 447.2067。
Example 6
The visible light catalytic synthesis process of N- (2-tert-butyl phenyl) -3- (2-pyridyl) -2-benzyl-4-phenyl pyrrole has the following reaction formula:
the preparation method comprises the following specific steps: in this example, the same procedures used in example 1 were repeated except for replacing N-phenylglycine used in example 1 with N- (2-tert-butylphenyl) glycine to give 38mg of N- (2-tert-butylphenyl) -3- (2-pyridyl) -2-benzyl-4-phenylpyrrole as a yellow oil in a yield of 86%.
Characterization data for the synthesized N- (2-tert-butylphenyl) -3- (2-pyridyl) -2-benzyl-4-phenylpyrrole are as follows:
the nuclear magnetic data are: 1 H NMR(300MHz,CDCl 3 )δ8.63(d,J＝4.1Hz,1H),7.58(dd,J＝8.1,1.2Hz,1H),7.48(td,J＝7.7,1.8Hz,1H),7.37–7.31(m,1H),7.23(t,J＝6.6Hz,4H),7.20–7.15(m,1H),7.09(dd,J＝11.3,5.1Hz,2H),7.03(dd,J＝7.1,3.3Hz,4H),6.85(s,1H),6.80–6.70(m,3H),4.43(d,J＝15.7Hz,1H),3.71(d,J＝15.8Hz,1H),1.22(s,9H)； 13 C NMR(75MHz,CDCl 3 )δ147.3,139.7,138.9,136.8,135.6,132.00,128.7,128.7,128.5,128.3,128.1,127.8,125.9,125.8,125.5,123.4,122.2,120.4,36.0,31.7,31.3。
the high resolution data is: HRMS (ESI) M/z 443.2479 (M + H) + ),calc.for C 32 H 30 N 2 443.2482。
Example 7
The visible light catalyzed process of synthesizing N- (2-methyl-4 bromophenyl) -3- (2-pyridyl) -2-benzyl-4-phenyl pyrrole has the following reaction formula:
the preparation method comprises the following specific steps: in this example, N-phenylglycine in example 1 was replaced with N- (2-methyl-4-bromophenyl) glycine, and the procedure was otherwise as in example 1 to give 40.6mg of N- (2-methyl-4-bromophenyl) -3- (2-pyridyl) -2-benzyl-4-phenylpyrrole as a brown solid, melting point 82-83 ℃ and yield 85%.
Characterization data for the synthesized N- (2-methyl-4-bromophenyl) -3- (2-pyridyl) -2-benzyl-4-phenylpyrrole are as follows:
the nuclear magnetic data are: 1 HNMR(300MHz,CDCl 3 )δ8.68(d,J＝4.2Hz,1H),7.53(td,J＝7.8,1.8Hz,1H),7.34(s,1H),7.31(dd,J＝8.1,2.1Hz,1H),7.26–7.21(m,4H),7.19(dd,J＝6.1,2.4Hz,1H),7.15(d,J＝3.2Hz,1H),7.13(s,1H),7.06–7.00(m,3H),6.96(d,J＝8.2Hz,1H),6.73–6.63(m,3H),4.08(s,2H),1.79(s,3H)； 13 C NMR(75MHz,CDCl 3 )δ155.3,149.1,139.4,138.8,137.5,135.9,135.3,133.5,132.7,130.0,129.5,129.3,128.4,128.3,128.2,127.9,125.8,125.7,125.7,124.3,122.2,120.7,120.2,116.3,30.7,17.1。
the high resolution data is: HRMS (ESI) M/z 479.1115 (M + H) + ),calc.for C 29 H 23 BrN 2 479.1117。
Example 8
The visible light catalytic synthesis process of N- (1-naphthyl) -3- (2-pyridyl) -2-benzyl-4-phenyl pyrrole has the following reaction formula:
the preparation method comprises the following specific steps: in this example, N-phenylglycine in example 1 was replaced with N- (1-naphthyl) glycine, and the same procedures as in example 1 were repeated to give 34.4mg of N- (1-naphthyl) -3- (2-pyridyl) -2-benzyl-4-phenylpyrrole as a yellow oil in a yield of 79%.
Characterization data for the synthesized N- (1-naphthyl) -3- (2-pyridyl) -2-benzyl-4-phenylpyrrole are as follows:
the nuclear magnetic data are: 1 H NMR(300MHz,CDCl 3 )δ8.68(d,J＝4.8Hz,1H),7.87(d,J＝7.8Hz,2H),7.55(td,J＝8.0,1.3Hz,1H),7.48(dd,J＝7.7,5.7Hz,2H),7.42(d,J＝4.7Hz,1H),7.37(d,J＝8.1Hz,1H),7.26–7.23(m,4H),7.22(s,1H),7.18(d,J＝7.7Hz,2H),7.13(d,J＝7.6Hz,1H),6.94(s,1H),6.88–6.83(m,3H),6.53(dd,J＝6.1,2.5Hz,2H),4.30(d,J＝16.0Hz,1H),3.85(d,J＝15.9Hz,1H)； 13 C NMR(75MHz,CDCl 3 )δ155.63,149.18,139.81,135.99,135.43,133.85,131.05,128.72,128.29,128.18,128.12,127.73,127.61,127.09,126.45,125.84,125.62,125.33,124.87,124.04,123.44,121.79,120.63,77.42,77.00,76.58,30.82。
the high resolution data is: HRMS (ESI) M/z 437.2011 (M + H) + ),calc.for C 32 H 24 N 2 437.2012。
Example 9
The visible light catalytic synthesis process of N- (4-methoxyphenyl) -3- (2-pyridyl) -5-methyl-2-benzyl-4-phenylpyrrole has the following reaction formula:
the preparation method comprises the following specific steps: in this example, N-phenylglycine in example 1 was replaced with N- (4-methoxyphenyl) alanine, and the same procedures as in example 1 were repeated to give 32.7mg of N- (4-methoxyphenyl) -3- (2-pyridyl) -5-methyl-2-benzyl-4-phenylpyrrole as a yellow oil in a yield of 76%.
Characterization data for the synthesized N- (4-methoxyphenyl) -3- (2-pyridyl) -5-methyl-2-benzyl-4-phenylpyrrole are as follows:
the nuclear magnetic data are: 1 HNMR(300MHz,CDCl 3 )δ8.55(d,J＝4.9Hz,1H),7.40–7.34(m,1H),7.24–7.20(m,2H),7.16(d,J＝2.9Hz,2H),7.14(s,1H),6.99(dd,J＝4.9,2.1Hz,4H),6.96(s,1H),6.93(d,J＝2.1Hz,1H),6.89(d,J＝7.9Hz,1H),6.84–6.80(m,2H),6.68–6.63(m,2H),4.15(s,2H),3.80(s,3H),1.96(s,3H)； 13 C NMR(75MHz,CDCl 3 )δ159.1,155.7,148.6,140.5,136.2,135.7,131.2,131.0,130.3,129.8,128.3,127.9,127.7,127.1,125.4,125.3,125.3,120.4,120.1,114.0,55.4,30.9,11.5。
the high resolution data is: HRMS (ESI) M/z 431.2110 (M + H) + ),calc.for C 30 H 26 N 2 O 431.2118。
Example 10
The visible light catalytic synthesis process of N- (4-methoxyphenyl) -3- (2-pyridyl) -5-ethyl-2-benzyl-4-phenylpyrrole has the following reaction formula:
the preparation method comprises the following specific steps: in this example, N-phenylglycine in example 1 was replaced with N- (4-methoxyphenyl) butynoic acid, and the same operation as in example 1 was repeated except for obtaining 36mg of N- (4-methoxyphenyl) -3- (2-pyridyl) -5-ethyl-2-benzyl-4-phenylpyrrole as a yellow oil in a yield of 81%.
Characterization data for the synthesized N- (4-methoxyphenyl) -3- (2-pyridyl) -5-ethyl-2-benzyl-4-phenylpyrrole are as follows:
the nuclear magnetic data are: 1 H NMR(300MHz,CDCl 3 )δ8.61(d,J＝4.9Hz,1H),7.42(dd,J＝7.7,6.0Hz,1H),7.36(dd,J＝7.2,4.6Hz,1H),7.32–7.30(m,1H),7.29(s,1H),7.28–7.22(m,3H),7.08(s,1H),7.05(dd,J＝4.8,2.0Hz,3H),7.02(s,1H),6.93(d,J＝8.0Hz,1H),6.91–6.85(m,2H),6.73(dd,J＝7.1,2.2Hz,2H),4.21(s,2H),3.89(s,3H),2.47(q,J＝7.4Hz,2H),0.84(t,J＝7.4Hz,3H)； 13 C NMR(75MHz,CDCl 3 )δ159.1,156.0,148.9,140.6,136.5,135.4,133.2,131.7,131.1,130.9,130.4,130.2,128.3,127.9,127.7,125.4,125.3,125.2,120.3,119.9,113.8,55.4,30.8,18.1,15.1。
the high resolution data is: HRMS (ESI) M/z 445.2267 (M + H) + ),calc.for C 31 H 28 N 2 O 445.2274。
Example 11
The visible light catalytic synthesis process of N- (4-methoxyphenyl) -3- (2-pyridyl) -2, 5-dibenzyl-4-phenylpyrrole has the following reaction formula:
the preparation method comprises the following specific steps: in this example, N-phenylglycine in example 1 was replaced with N- (4-methoxyphenyl) -DL- β -homophenylalanine, and the same procedures as in example 1 were repeated to give 41.5mg of N- (4-methoxyphenyl) -3- (2-pyridyl) -2, 5-dibenzyl-4-phenylpyrrole as a yellow oil in a yield of 82%.
Characterization data for the synthesized N- (4-methoxyphenyl) -3- (2-pyridyl) -2, 5-dibenzyl-4-phenylpyrrole are as follows:
the nuclear magnetic data are: 1 H NMR(300MHz,CDCl 3 )δ8.59(d,J＝4.1Hz,1H),7.41(dd,J＝7.6,6.4Hz,1H),7.24(d,J＝4.3Hz,4H),7.19(dd,J＝8.8,4.9Hz,2H),7.02(dd,J＝4.5,2.8Hz,6H),6.99(d,J＝1.7Hz,2H),6.92(d,J＝8.0Hz,1H),6.71–6.67(m,2H),6.64(d,J＝3.3Hz,4H),4.18(s,2H),3.81(s,2H),3.76(s,3H)； 13 C NMR(75MHz,CDCl 3 )δ158.9,140.4,140.2,136.0,130.5,130.4,130.0,129.6,128.2,128.1,128.1,127.8,127.7,125.7,125.5,125.4,125.3,122.3,120.1,113.5,55.4,30.9。
the high resolution data is: HRMS (ESI) M/z 507.2424 (M + H) + ),calc.for C 36 H 30 N 2 O 507.2431。
Example 12
The visible light catalytic synthesis process of N- (4-methoxyphenyl) -3- (2-pyridyl) -2-benzyl-4, 5-diphenyl pyrrole has the following reaction formula:
the preparation method comprises the following specific steps: in this example, N-phenylglycine in example 1 was replaced with N- (4-methoxyphenyl) -phenylacetic acid, and the same operation as in example 1 was conducted to give 38.4mg of N- (4-methoxyphenyl) -3- (2-pyridyl) -2-benzyl-4, 5-diphenylpyrrole as a yellow oil in a yield of 78%.
Characterization data for the synthesized N- (4-methoxyphenyl) -3- (2-pyridyl) -2-benzyl-4, 5-diphenylpyrrole are as follows:
the nuclear magnetic data are: 1 HNMR(300MHz,CDCl 3 )δ8.61(d,J＝4.9Hz,1H),7.42(td,J＝7.7,1.8Hz,1H),7.12–7.06(m,6H),7.02(dd,J＝6.8,4.1Hz,6H),6.94(dd,J＝11.6,5.8Hz,3H),6.88–6.82(m,4H),6.68–6.65(m,2H),4.21(s,2H),3.74(s,3H)； 13 C NMR(75MHz,CDCl 3 )δ158.7,155.8,149.1,140.5,135.6,135.5,132.3,131.9,131.2,130.8,130.3,128.3,127.9,127.6,127.4,126.2,125.7,125.5,125.3,122.1,120.4,116.4,114.8,113.4,55.3,30.8。
the high resolution data is: HRMS (ESI) M/z 493.2261 (M + H) + ),calc.for C 35 H 28 N 2 O 493.2274。
Example 13
The visible light catalytic synthesis process of N- (4-methoxyphenyl) -3- (2-pyridyl) -2-benzyl-4-phenyl-5- (4-fluorophenyl) pyrrole has the following reaction formula:
the preparation method comprises the following specific steps: in this example, N-phenylglycine in example 1 was replaced with N- (4-methoxyphenyl) -4-fluorophenylacetic acid, and the same operation as in example 1 was repeated to give 40.3mg of N- (4-methoxyphenyl) -3- (2-pyridyl) -2-benzyl-4-phenyl-5- (4-fluorophenyl) pyrrole as a yellow oil in 79% yield.
Characterization data for the synthesized N- (4-methoxyphenyl) -3- (2-pyridyl) -2-benzyl-4-phenyl-5- (4-fluorophenyl) pyrrole are as follows:
the nuclear magnetic data are: 1 H NMR(300MHz,CDCl 3 )δ8.61(d,J＝4.4Hz,1H),7.44(t,J＝7.0Hz,1H),7.08(dd,J＝8.9,4.4Hz,7H),7.01(dd,J＝6.8,2.6Hz,2H),6.96(d,J＝7.9Hz,1H),6.89(d,J＝2.9Hz,1H),6.84(dd,J＝10.6,4.4Hz,5H),6.75–6.66(m,4H),4.21(s,2H),3.76(s,3H)； 13 C NMR(75MHz,CDCl 3 )δ163.0,159.7,158.8,140.3,135.8,135.3,132.8,132.7,130.9,130.7,130.3,128.3,127.9,127.7,125.8,125.5,122.2,120.5,114.7,114.4,113.5,55.3,30.8。
the high resolution data is: HRMS (ESI) M/z 511.2172 (M + H) + ),calc.for C 35 H 27 FN 2 O 511.2180。
Example 14
The visible light catalysis process of synthesizing N- (4-methoxy phenyl) -3- (2-pyridyl) -2-benzyl-4-phenyl-5- (3-chlorophenyl) pyrrole has the following reaction formula:
the preparation method comprises the following specific steps: in this example, N-phenylglycine in example 1 was replaced with N- (4-methoxyphenyl) -3-chlorophenylacetic acid, and the same procedures as in example 1 were repeated to give 43.1mg of N- (4-methoxyphenyl) -3- (2-pyridyl) -2-benzyl-4-phenyl-5- (3-chlorophenyl) pyrrole as a yellow oil in 82% yield.
Characterization data for the synthesized N- (4-methoxyphenyl) -3- (2-pyridyl) -2-benzyl-4-phenyl-5- (3-chlorophenyl) pyrrole are as follows:
the nuclear magnetic data are: 1 H NMR(300MHz,CDCl 3 )δ8.61(dd,J＝4.9,0.8Hz,1H),7.44(td,J＝7.8,1.6Hz,1H),7.11(dd,J＝5.1,3.1Hz,4H),7.07(s,2H),7.05–7.00(m,3H),7.00–6.97(m,1H),6.95(s,1H),6.93–6.90(m,2H),6.85(dd,J＝5.4,3.4Hz,4H),6.79(dd,J＝7.5,1.4Hz,1H),6.70(d,J＝8.9Hz,2H),4.22(s,2H),3.76(s,3H)； 13 C NMR(75MHz,CDCl 3 )δ158.9,140.2,135.0,134.1,133.2,131.0,130.7,130.7,130.4,130.2,129.3,128.7,128.3,127.9,127.8,126.5,125.8,125.8,125.6,122.8,120.6,113.6,55.4,30.8。
the high resolution data is: HRMS (ESI) M/z 527.1876 (M + H) + ),calc.for C 35 H 27 ClN 2 O 527.1885。
Example 15
The visible light catalytic synthesis process of N- (4-methoxyphenyl) -3- (2-pyridyl) -2-benzyl-4-phenyl-5- (4-methoxyphenyl) pyrrole has the following reaction formula:
the preparation method comprises the following specific steps: in this example, the same procedures as in example 1 were repeated except for replacing N-phenylglycine in example 1 with N- (4-methoxyphenyl) -4-methoxyphenylacetic acid to give 45.9mg of N- (4-methoxyphenyl) -3- (2-pyridyl) -2-benzyl-4-phenyl-5- (4-methoxyphenyl) pyrrole as a yellow oil in 88% yield.
Characterization data for the synthesized N- (4-methoxyphenyl) -3- (2-pyridyl) -2-benzyl-4-phenyl-5- (4-methoxyphenyl) pyrrole are as follows:
the nuclear magnetic data are: 1 H NMR(300MHz,CDCl 3 )δ8.61(d,J＝4.9Hz,1H),7.45–7.39(m,1H),7.11–7.06(m,6H),7.05–7.02(m,3H),6.96(d,J＝7.9Hz,1H),6.85(dd,J＝8.7,3.7Hz,6H),6.67(d,J＝8.9Hz,2H),6.56(d,J＝8.8Hz,2H),4.21(s,2H),3.75(s,3H),3.67(s,3H)； 13 C NMR(75MHz,CDCl 3 )δ158.6,157.9,155.8,148.9,140.5,135.7,135.6,132.3,132.0,131.7,131.2,130.8,130.3,128.3,127.9,127.6,125.7,125.4,125.2,124.7,121.6,120.3,113.4,112.9,55.3,54.9,30.8。
the high resolution data is: HRMS (ESI) M/z 523.2366 (M + H) + ),calc.for C 36 H 30 N 2 O 2 523.2380。
Example 16
Visible light catalytic synthesis method of 1, 4-diphenyl-3- (2-pyridyl) -2- (3-thienylmethylene) pyrrole, which has the following reaction formula:
the preparation method comprises the following specific steps: in this example, the 2- (2-pyridine) -1, 4-diphenyl-1, 3-enyne in example 1 was replaced with 2- (2-pyridine) -1-phenyl-4- (3-thiophene) -1, 3-enyne, and the same procedure as in example 1 was repeated except for obtaining 31mg of 1, 4-diphenyl-3- (2-pyridyl) -2- (3-thienylmethylene) pyrrole as a yellow oil in 79% yield.
Characterization data for the synthesized 1, 4-diphenyl-3- (2-pyridyl) -2- (3-thienylmethylene) pyrrole are as follows:
the nuclear magnetic data are: 1 HNMR(300MHz,CDCl 3 )δ8.66(d,J＝4.2Hz,1H),7.50(td,J＝7.7,1.7Hz,1H),7.38(t,J＝5.9Hz,3H),7.25(s,2H),7.24–7.21(m,4H),7.19–7.15(m,1H),7.10(dd,J＝11.3,6.4Hz,2H),7.01(dd,J＝4.9,3.0Hz,1H),6.89(s,1H),6.46(dd,J＝20.2,3.3Hz,2H),4.21(s,2H)； 13 C NMR(75MHz,CDCl 3 )δ155.5,149.1,140.3,139.7,135.8,135.3,132.0,129.00,128.3,128.2,128.00,127.7,126.7,125.7,124.7,124.3,120.7,120.7,120.6,25.6。
the high resolution data is: HRMS (ESI) M/z 393.1414 (M + H) + ),calc.for C 26 H 20 N 2 S 393.1420。
Example 17
Visible light catalytic synthesis method of 1, 4-diphenyl-3- (2-pyridyl) -2-hexyl pyrrole, which has the following reaction formula:
the preparation method comprises the following specific steps: in this example, the 2- (2-pyridine) -1, 4-diphenyl-1, 3-enyne in example 1 was replaced with 2- (2-pyridine) -1-phenyl-4-pentyl-1, 3-enyne, and the other procedures were repeated in the same manner as in example 1 to give 34.2mg of 1, 4-diphenyl-3- (2-pyridyl) -2-hexylpyrrole as a yellow oil in a yield of 90%.
Characterization data for the synthesized 1, 4-diphenyl-3- (2-pyridyl) -2-hexylpyrrole are as follows:
the nuclear magnetic data are: 1 HNMR(300MHz,CDCl 3 )δ8.64(d,J＝4.1Hz,1H),7.53–7.47(m,1H),7.23(s,1H),7.21(d,J＝2.6Hz,3H),7.19–7.17(m,1H),7.15(s,1H),7.12(s,1H),7.08(dd,J＝6.3,2.6Hz,2H),7.02(dd,J＝4.9,3.0Hz,1H),6.89(d,J＝8.9Hz,2H),6.83(s,1H),6.51(dd,J＝4.9,1.0Hz,1H),6.45(d,J＝1.8Hz,1H),4.16(s,2H),3.85(s,3H)； 13 C NMR(75MHz,CDCl 3 )δ159.0,155.8,149.4,140.5,135.6,135.5,132.6,132.2,128.2,128.1,128.1,128.0,125.6,125.5,124.7,123.9,120.9,120.7,120.5,114.8,114.0,55.5,26.0。
the high resolution data is: HRMS (ESI) M/z 423.1523 (M + H) + ),calc.for C 27 H 22 N 2 OS 423.1526。
Example 18
The visible light catalytic synthesis process of N- (4-methoxyphenyl) -3- (2-pyridyl) -2- (3-thiophen methylene) -4- (2-furan) pyrrole has the following reaction formula:
the preparation method comprises the following specific steps: in this example, N-phenylglycine in example 1 was replaced with N- (p-methoxyphenyl) glycine, and 2- (2-pyridine) -1, 4-diphenyl-1, 3-enyne was replaced with 2- (2-pyridine) -1- (2-furan) -4- (3-thiophene) -1, 3-enyne, and otherwise the same as in example 1 was conducted to obtain 28mg of N- (4-methoxyphenyl) -3- (2-pyridyl) -2- (3-thienylmethylene) -4- (2-furan) pyrrole as a black solid, a melting point of 127.0 to 129.0 ℃ and a yield of 83%.
Characterization data for the synthesized N- (4-methoxyphenyl) -3- (2-pyridyl) -2- (3-thienylmethylene) -4- (2-furan) pyrrole are as follows:
the nuclear magnetic data are: 1 HNMR(300MHz,CDCl 3 )δ8.68(d,J＝5.0Hz,1H),7.66(td,J＝7.7,1.6Hz,1H),7.35(d,J＝7.9Hz,1H),7.28(d,J＝1.1Hz,1H),7.19(s,1H),7.11(d,J＝8.8Hz,2H),7.04(s,1H),7.04–7.01(m,1H),6.88(t,J＝5.9Hz,2H),6.54(d,J＝4.8Hz,1H),6.49(s,1H),6.28(dd,J＝3.2,1.9Hz,1H),5.90(d,J＝3.2Hz,1H),4.04(s,2H),3.83(s,3H)； 13 C NMR(75MHz,CDCl 3 )δ159.1,150.0,140.1,132.3,128.0,127.9,125.4,124.9,121.2,120.9,120.4,114.3,114.1,110.8,104.6,55.5,25.6。
the high resolution data is: HRMS (ESI) M/z 413.1315 (M + H) + ),calc.for C 25 H 20 N 2 O 2 S 413.1318。
Example 19
The visible light catalytic synthesis process of N-phenyl-3- (2-pyridyl) -2-benzyl-4- (3-fluorophenyl) pyrrole has the following reaction formula:
the preparation method comprises the following specific steps: in this example, the 2- (2-pyridine) -1, 4-diphenyl-1, 3-enyne in example 1 was replaced with 2- (2-pyridine) -1- (3-fluorophenyl) -4-phenyl-1, 3-enyne, and the same procedure as in example 1 was repeated except for using 30.3mg of N-phenyl-3- (2-pyridyl) -2-benzyl-4- (3-fluorophenyl) pyrrole as a yellow oily liquid in a yield of 75%.
Characterization data for the synthesized N-phenyl-3- (2-pyridyl) -2-benzyl-4- (3-fluorophenyl) pyrrole are as follows:
the nuclear magnetic data are: 1 H NMR(300MHz,CDCl 3 )δ8.66(dd,J＝5.2,1.9Hz,1H),7.53(td,J＝7.7,1.8Hz,1H),7.36–7.33(m,3H),7.21–7.16(m,3H),7.14–7.11(m,2H),7.03(dd,J＝5.9,4.5Hz,3H),6.99(d,J＝7.8Hz,1H),6.95–6.90(m,2H),6.85(dd,J＝8.4,6.1Hz,1H),6.72(dd,J＝7.2,2.0Hz,2H),4.21(s,2H)； 13 C NMR(75MHz,CDCl 3 )δ164.4,161.1,155.2,149.4,139.9,139.5,137.8,137.6,135.9,132.2,129.5,129.4,129.00,128.1,127.9,127.7,126.7,125.6,123.8,123.8,123.2,123.2,121.0,120.9,114.9,114.6,112.5,112.2,30.5。
the high resolution data is: HRMS (ESI) M/z 405.1756 (M + H) + ),calc.for C 28 H 21 FN 2 405.1762。
Example 20
The visible light catalytic synthesis process of N-phenyl-3- (2-pyridyl) -2-hexyl-4- (2-thiophene) pyrrole has the following reaction formula:
the preparation method comprises the following specific steps: in this example, the 2- (2-pyridine) -1, 4-diphenyl-1, 3-enyne in example 1 was replaced with 2- (2-pyridine) -1- (2-thiophene) -4-pentyl-1, 3-enyne, and the other procedures were repeated in the same manner as in example 1 to obtain 31.3mg of N-phenyl-3- (2-pyridyl) -2-hexyl-4- (2-thiophene) pyrrole as a yellow oil in a yield of 81%.
Characterization data for the synthesized N-phenyl-3- (2-pyridyl) -2-hexyl-4- (2-thiophene) pyrrole are as follows:
the nuclear magnetic data are: 1 HNMR(300MHz,CDCl 3 )δ8.69(d,J＝4.1Hz,1H),7.61(td,J＝7.7,1.8Hz,1H),7.49(dd,J＝7.3,1.5Hz,1H),7.45(s,1H),7.43–7.37(m,3H),7.28–7.24(m,1H),7.20–7.15(m,1H),7.06(dd,J＝5.1,1.0Hz,1H),6.92(s,1H),6.88(dd,J＝5.1,3.6Hz,1H),6.67(dd,J＝3.5,0.9Hz,1H),2.79–2.71(m,2H),1.19–1.12(m,2H),1.05(dd,J＝13.3,6.6Hz,2H),0.99–0.92(m,4H),0.72(t,J＝7.0Hz,3H)； 13 C NMR(75MHz,CDCl 3 )δ155.3,148.9,139.8,137.6,135.9,134.4,129.2,127.7,127.1,126.5,125.8,123.9,122.8,120.9,120.3,117.2,31.0,29.4,28.6,24.4,22.3,13.9。
the high resolution data is: HRMS (ESI) M/z 387.1883 (M + H) + ),calc.for C 25 H 26 N 2 S 387.1889。
Claims (7)
1. A method for synthesizing 3- (2-pyridine) substituted pyrrole compounds by visible light catalysis is characterized in that N-aryl substituted glycine shown in a formula I, beta- (2-pyridine) -1, 3-eneyne shown in a formula II, a visible light catalyst DPZ and additive sodium dihydrogen phosphate are uniformly mixed in a solvent under the protection of inert gas, and after reaction under the irradiation of visible light, the substituted pyrrole compounds shown in a formula III are obtained by separation and purification;
in the formula I, the formula II and the formula III, ar and R 1 Represents aryl, R and R 2 Represents H, alkyl or aryl.
2. The visible-light catalytic synthesis method of 3- (2-pyridine) substituted pyrrole compounds according to claim 1, wherein the reaction temperature is 20-30 ℃ and the reaction time is 24-72h.
3. The visible-light catalytic synthesis method of 3- (2-pyridine) substituted pyrrole compounds according to claim 1, wherein the solvent is a mixed solvent of 1, 2-dichloroethane and tetrahydrofuran, and the volume ratio of 1, 2-dichloroethane to tetrahydrofuran is (0.5-1.5): (0.5-1.5).
4. The visible-light catalytic synthesis method of 3- (2-pyridine) substituted pyrrole compounds according to claim 1, wherein the molar ratio of the N-aryl substituted glycine to the beta- (2-pyridine) -1, 3-eneyne is (1-2) to (0.5-1.5).
5. The visible-light catalytic synthesis method of 3- (2-pyridine) substituted pyrrole compounds according to claim 1, characterized in that the molar ratio of the visible-light catalyst DPZ to the beta- (2-pyridine) -1, 3-eneyne is (0.001-0.01): 1.
6. The process for the visible-light catalytic synthesis of 3- (2-pyridine) substituted pyrroles according to claim 1 wherein the additive sodium dihydrogen phosphate is present in a molar ratio to β - (2-pyridine) -1, 3-enyne of (0.5-1.5) to (0.5-1.5).
7. The visible-light catalytic synthesis method of 3- (2-pyridine) substituted pyrrole compounds according to claim 1, wherein the ratio of the volume of the solvent to the amount of beta- (2-pyridine) -1, 3-enyne substances is 30-501mmol.
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