CN115044922A - Preparation method of pyridino-imidazole skeleton fused ring compound under electrocatalysis - Google Patents
Preparation method of pyridino-imidazole skeleton fused ring compound under electrocatalysis Download PDFInfo
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 22
- GAMYYCRTACQSBR-UHFFFAOYSA-N 4-azabenzimidazole Chemical group C1=CC=C2NC=NC2=N1 GAMYYCRTACQSBR-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 12
- -1 phenyl alkynes Chemical class 0.000 claims abstract description 11
- 239000012043 crude product Substances 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 239000012973 diazabicyclooctane Chemical class 0.000 claims abstract description 6
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical class C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000047 product Substances 0.000 claims abstract description 5
- 238000010898 silica gel chromatography Methods 0.000 claims abstract description 3
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical group CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 150000001345 alkine derivatives Chemical class 0.000 claims description 5
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 4
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical group FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- CMWTZPSULFXXJA-UHFFFAOYSA-N Naproxen Natural products C1=C(C(C)C(O)=O)C=CC2=CC(OC)=CC=C21 CMWTZPSULFXXJA-UHFFFAOYSA-N 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- 229960002009 naproxen Drugs 0.000 claims description 2
- JTTWNTXHFYNETH-UHFFFAOYSA-N propyl 4-methylbenzenesulfonate Chemical group CCCOS(=O)(=O)C1=CC=C(C)C=C1 JTTWNTXHFYNETH-UHFFFAOYSA-N 0.000 claims description 2
- SBPIDKODQVLBGV-UHFFFAOYSA-N 1h-imidazole;pyridine Chemical group C1=CNC=N1.C1=CC=NC=C1 SBPIDKODQVLBGV-UHFFFAOYSA-N 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 239000000654 additive Substances 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract description 2
- 125000000524 functional group Chemical group 0.000 abstract description 2
- 239000007800 oxidant agent Substances 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 8
- 230000002194 synthesizing effect Effects 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 125000002883 imidazolyl group Chemical group 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 150000003222 pyridines Chemical class 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000010183 spectrum analysis Methods 0.000 description 2
- VNHBYKHXBCYPBJ-UHFFFAOYSA-N 5-ethynylimidazo[1,2-a]pyridine Chemical compound C#CC1=CC=CC2=NC=CN12 VNHBYKHXBCYPBJ-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ORDDGAKVEOTVKV-UHFFFAOYSA-N N1C=CC2=CC=CC=C12.NN Chemical compound N1C=CC2=CC=CC=C12.NN ORDDGAKVEOTVKV-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000006254 arylation reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 150000002537 isoquinolines Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/05—Heterocyclic compounds
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/07—Oxygen containing compounds
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/09—Nitrogen containing compounds
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/11—Halogen containing compounds
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- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
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- Chemical Kinetics & Catalysis (AREA)
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- Nitrogen Condensed Heterocyclic Rings (AREA)
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Abstract
The invention discloses a preparation method of a polysubstituted pyridine imidazole skeleton fused ring compound under electrocatalysis, belonging to the technical field of organic synthesis. The method comprises the following steps: to the reactor, substituted pyridoimidazoles, substituted phenyl alkynes, tetraethylammonium tetrafluoroborate, DABCO were added. After the reaction is promoted in the solvent by electrocatalysis, a crude product is obtained by concentrating the solvent by using a rotary evaporator, and the crude product is separated by using silica gel column chromatography to obtain a target product. The synthesis method of the polysubstituted pyridine imidazole skeleton condensed ring compound under electrocatalysis provided by the invention is scientific and reasonable, and the synthesis methodThe method has the characteristics of green and environment-friendly approach, mild condition, simple and convenient operation, no need of adding an oxidant and an additive, low price, wide functional group universality and the like. The reaction equation is as follows:
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a preparation method of a pyridine-imidazole skeleton fused ring compound under electrocatalysis.
Background
Pyridoimidazoles are widely found in nature. The condensed ring compound has photophysical properties and can be widely applied to luminescent materials: ((a) New J.chem.2014,38,189-197.(b) Eur.J.org.chem.2017,40, 5975-5985.(c) J.org.chem.2010,75, 2776-2784.)
In view of the application value of the pyridoimidazole skeleton fused ring compound, the development of a novel method for practically and effectively synthesizing the pyridoimidazole skeleton fused ring compound is of great significance.
The method for synthesizing the pyridine imidazole skeleton fused ring compound comprises the following steps:
in 2016, a Lee subject group reports an effective method for synthesizing imidazole [5,1,2-cd ] indole hydrazine through a double-hydrocarbon functional direct arylation reaction of 2-alkyl imidazole [1,2-a ] pyridine and alkyne under the catalysis of palladium. (Eur.J.Org.chem.2016,34, 5722-5731.) the reaction is represented by formula I:
significant disadvantages in the above-described process for preparing a pyridoimidazole skeleton fused ring compound: the reaction temperature is higher and the reaction time is longer.
Disclosure of Invention
In order to overcome the defects of the prior art for synthesizing the pyridine and imidazole skeleton condensed ring compound, the invention provides a method for preparing a polysubstituted pyridine and imidazole skeleton condensed ring compound under the promotion of electrocatalysis.
Electrocatalytic synthesis reactions have many significant advantages: the method can avoid using toxic or difficultly-treated catalysts, electrons are green reaction reagents, reaction products have high purity and are easy to separate, and the method almost has no pollution to the environment; in the electrocatalytic reaction, the electrode voltage or current can be changed to regulate and control the reaction rate so as to avoid side reaction, thereby improving the selectivity and yield of the target product.
A preparation method of a polysubstituted pyridine imidazole skeleton fused ring compound under an electrocatalysis strategy, wherein the pyridine imidazole skeleton fused ring compound has a structure shown as a formula II:
the R substituent group is selected from phenyl, methyl, cyclohexyl, 4-methyl benzene sulfonic acid propyl ester group, methyl cyanide chrysanthemate propyl ester group, kungfu chrysanthemate propyl ester group, isobutyl phenylpropionic acid propyl ester group, isoxofenac propyl ester group, 2- (4- (cyclopentyl methyl) phenyl) propyl ester group and naproxen propyl ester group; is characterized in that substituted pyridylimidazole, substituted phenyl internal alkyne, tetraethylammonium tetrafluoroborate and DABCO are added into a reactor, and the molar ratio of the substituted pyridylimidazole to the substituted phenyl internal alkyne to the tetraethylammonium tetrafluoroborate to the DABCO is 1: 1.2: 2: 0.005. the solvent is hexafluoroisopropanol: tetrahydrofuran (4mL:1 mL). After the reaction is promoted in the solvent by electrocatalysis, concentrating by using a rotary evaporator to obtain a crude product, and separating the crude product by using silica gel column chromatography to obtain a target product, wherein the chemical reaction process is shown as a formula III:
the preparation method is characterized by comprising the following steps: the cathode and the anode adopt graphite felt electrodes, and the reaction is promoted by electrocatalysis under the condition of constant current of 8mA, the reaction temperature is 60 ℃, and N is 2 The reaction time is 2-3 h.
The beneficial effects of the invention are as follows: the method for synthesizing the polysubstituted pyridine and imidazole skeleton condensed ring compound under the electrocatalysis is scientific and reasonable, provides a new way for synthesizing the polysubstituted pyridine and imidazole derivative, obtains the pyridine and imidazole skeleton condensed ring compound with various substituents, and is characterized in that: the method has the advantages of mild conditions, simple and convenient operation, no need of additional oxidant and additive, safety, greenness, low price and wide functional group universality.
Drawings
FIG. 1 is an NMR spectrum of compound 3ae prepared in example 5;
FIG. 2 is an NMR spectrum of compound 3af prepared in example 6;
FIG. 3 is an NMR spectrum of compound 3ag prepared in example 7.
Detailed Description
The invention is described in further detail below with reference to the following figures and specific examples:
the test methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1
Preparation of pyridoimidazole skeleton fused ring compound 3aa
A10 mL three-necked flask was charged with pyridoimidazole 1a (0.1mmol,23.6mg), diphenyleneyne 2a (0.12mmol,42.2mg), tetraethylammonium tetrafluoroborate (0.2mmol, 43.4mg), and DABCO (0.005mmol, 0.6 mg). The system was sealed with a rubber stopper, and graphite felt electrodes (2cm x 1cm x 0.5cm) were used for both the cathode and anode electrodes. And (3) filling nitrogen into the system, and adding hexafluoroisopropanol: tetrahydrofuran (4mL:1 mL). The reaction was carried out at 60 ℃ under a current of 8mA for 2 h. After the reaction is finished, the solvent is removed by using a rotary evaporator to obtain a crude product, the crude product is separated by column chromatography (200-mesh silica gel 300) (petroleum ether/ethyl acetate: 8/1), and the solvent is removed by using the rotary evaporator to obtain the target product, namely the unsubstituted isoquinoline salt derivative 3aa, wherein the yield is 88%.
Spectrum analysis data 3aa:
1 H NMR(500MHz,CDCl 3 ):δ8.05(t,J＝4.25Hz,1H),7.97(d,J＝4.25Hz,2H),7.58(d,J＝7.49Hz,2H),7.44(t,J＝7.46Hz,2H),7.37(t,J＝7.28Hz,1H),7.18(d,J＝7.87Hz,3H),7.04(t,J＝7.53Hz,2H),6.89(s,2H),2.35(s,3H),1.99(s,6H). 13 C NMR(125MHz,CDCl 3 ):δ150.7,139.9,138.1,137.1,134.3,133.1,132.2,131.1,131.0,130.2,129.9,128.9,128.2,128.1,127.7,127.2,126.4,125.6,125.4,112.4,111.3,21.2,20.4.
example 2
2a in example 1 was replaced by 2b, and the experimental results are shown in Table 1, except that the conditions were the same as in example 1.
Spectrum analysis data 3ab:
1 H NMR(500MHz,CDCl3):δ7.99(dd,J＝6.8,1.8Hz,1H),7.96–7.88(m,2H),7.70–7.65(m,2H),7.55(t,J＝7.7Hz,2H),7.44–7.37(m,1H),7.02(s,2H),2.54(s,3H),2.38(s,3H),2.18(s,6H). 13 C NMR(125MHz,CDCl3):δ149.8,139.7,138.1,137.2,134.3,131.9,130.8,129.6,128.9,128.3,127.4,127.3,127.1,127.0,126.2,111.4,110.7,21.3,20.5,12.2.
example 3
2a in example 1 was replaced with 2c, and the experimental results were shown in Table 1, except that the conditions were the same as in example 1.
Spectrogram analysis data 3ac:
1 H NMR(500MHz,CDCl3):δ7.99–7.92(m,2H),7.87(d,J＝7.21Hz,1H),7.83(d,J＝7.53Hz,2H),7.58(t,J＝7.61Hz,2H),7.45(t,J＝7.34Hz,1H),7.03(s,2H),2.42(s,3H),2.29(td,J＝8.52,4.31Hz,1H),2.11(s,6H),0.92–0.83(m,2H),0.64(q,J＝5.24,4.71Hz,2H). 13 C NMR(125MHz,CDCl3):δ149.5,140.0,138.2,137.1,134.5,132.2,132.0,130.0,128.7,128.1,127.8,127.0,126.1,124.7,110.6,110.3,21.3,20.4,10.4,10.0.
example 4
2a in example 1 was replaced with 2d, and the experimental results are shown in Table 1, except that the conditions were the same as in example 1.
Spectrogram analysis data 3ad:
1 H NMR(500MHz,CDCl3):δ8.01(d,J＝8.0Hz,1H),7.94(t,J＝7.8Hz,1H),7.87(d,J＝7.5Hz,1H),7.62(d,J＝7.3Hz,2H),7.53(t,J＝7.6Hz,2H),7.42(t,J＝7.5Hz,1H),7.00(s,2H),6.85(d,J＝9.4Hz,1H),3.78(t,J＝6.2Hz,2H),3.06–2.97(m,2H),2.13(s,3H),2.05(t,J＝8.9Hz,6H),1.68(m,1H),1.23(s,3H),1.17(s,3H). 13 C NMR(125MHz,CDCl 3 ):δ149.7,144.6,140.0,138.4,136.9,133.7,133.0,131.9,131.1,130.4,129.9,129.7,129.0,128.4,128.0,127.7,127.4,126.3,126.2,111.8,111.1,69.4,29.3,22.9,21.6,21.3,20.4.
example 5
2a in example 1 was replaced with 2e, and the experimental results are shown in Table 1, except that the conditions were the same as in example 1.
Spectrogram analysis data 3ae:
1 H NMR(500MHz,CDCl 3 ):δ8.00(d,J＝7.92Hz,1H),7.93(t,J＝7.78Hz,1H),7.86(d,J＝7.56Hz,1H),7.63(d,J＝7.58Hz,2H),7.53(t,J＝7.52Hz,2H),7.42(t,J＝7.42Hz,1H),7.00(s,2H),3.76(t,J＝6.34Hz,2H),3.03(t,J＝7.69Hz,2H),2.37(s,3H),2.13(s,6H),1.68(m,,2H),1.25(d,J＝6.50Hz,1H),1.14(d,J＝6.47Hz,12H). 13 C NMR(125MHz,CDCl 3 ):δ172.2,149.9,140.0,138.3,137.0,134.2,132.1,131.8,131.4,130.0,129.0,128.4,127.9,127.3,126.5,126.3,111.7,111.0,62.9,35.7,29.9,29.3,23.7,23.6,21.4,20.5,16.7.
example 6
2a in example 1 was replaced with 2f, and the experimental results were shown in Table 1, except that the conditions were the same as in example 1.
Spectrogram analysis data 3af:
1 H NMR(500MHz,CDCl 3 ):δ8.05(d,J＝7.96Hz,1H),7.97(t,J＝7.78Hz,1H),7.90(d,J＝7.56Hz,1H),7.65(d,J＝7.39Hz,2H),7.57(t,J＝7.63Hz,2H),7.46(t,J＝7.39Hz,1H),7.03(s,2H),6.88(d,J＝9.47Hz,1H),3.81(t,J＝6.20Hz,2H),3.07(t,J＝7.38Hz,2H),2.41(s,3H),2.16(s,6H),2.08(d,J＝8.92Hz,1H),1.71(dd,J＝13.71,7.48Hz,3H),1.27(s,3H),1.20(s,3H). 13 C NMR(125MHz,CDCl 3 ):δ170.0,149.8,140.0,138.2,137.0,136.9,134.0,132.0,131.3,131.2,130.1,130.1,129.9,128.9,128.3,127.9,127.3,126.4,126.3,111.7,111.0,63.7,32.7,30.7,29.1,28.4,28.4,23.2,21.3,20.4,14.8.
example 7
The same conditions as in example 1 were used except that 2g was used instead of 2a in example 1, and the results of the experiment are shown in Table 1.
Spectrogram analysis data 3ag:
1 H NMR(500MHz,CDCl 3 ):δ8.01(d,J＝7.91Hz,1H),7.94(t,J＝7.78Hz,1H),7.87(d,J＝7.53Hz,1H),7.60(d,J＝7.57Hz,2H),7.54(t,J＝7.55Hz,2H),7.43(t,J＝7.39Hz,1H),7.10–7.00(m,4H),6.99(s,2H),3.79(m,2H),3.46(q,J＝7.22Hz,1H),2.95(m,2H),2.41(d,J＝7.10Hz,2H),2.36(s,3H),2.10(s,6H),1.81(m,1H),1.64(m,2H),1.35(d,J＝7.20Hz,3H),0.87(d,J＝6.54Hz,6H). 13 C NMR(125MHz,CDCl 3 ):δ174.6,149.9,140.6,140.0,138.4,137.8,137.0,134.1,132.1,131.6,131.4,130.0,129.4,129.0,128.4,127.9,127.4,127.2,126.4,126.4,111.7,111.1,64.0,45.1,30.3,29.8,29.4,23.3,22.5,21.4,20.5,18.4.
example 8
2h is used for replacing 2a in the example 1, the other conditions are the same as the example 1, and the experimental results are shown in the table 1.
Spectrogram analysis data 3ah:
1 H NMR(500MHz,CDCl 3 ):δ8.04–8.00(m,2H),7.94(t,J＝7.77Hz,1H),7.87(d,J＝7.41Hz,2H),7.63(d,J＝7.55Hz,2H),7.55(t,J＝7.58Hz,3H),7.48–7.41(m,2H),7.35(d,J＝7.43Hz,1H),7.28(s,1H),7.02–6.94(m,3H),5.17(s,2H),3.82(t,J＝6.19Hz,2H),3.39(s,2H),3.02(t,J＝7.54Hz,2H),2.36(s,3H),2.12(s,6H),1.69(m,2H). 13 CNMR(125MHz,CDCl 3 ):δ190.9,171.3,160.5,149.9,140.6,140.1,138.4,137.1,136.4,135.6,134.1,132.9,132.5,132.1,131.4,131.3,130.0,129.6,129.4,129.0,128.4,128.0,127.9,127.8,127.4,126.4,126.4,125.2,121.1,111.8,111.1,73.7,64.0,39.9,29.3,23.2,21.4,20.5.
example 9
2a in example 1 was replaced with 2i, and the experimental results are shown in Table 1, except that the conditions were the same as in example 1.
Spectrogram analysis data 3ai:
1 H NMR(500MHz,CDCl 3 ):δ8.01(d,J＝7.87Hz,1H),7.93(t,J＝7.76Hz,1H),7.87(d,J＝7.55Hz,1H),7.60(d,J＝7.44Hz,2H),7.54(t,J＝7.50Hz,2H),7.43(t,J＝7.40Hz,1H),7.06(q,J＝8.03Hz,4H),6.98(d,J＝3.08Hz,2H),3.79(m,2H),3.46(q,J＝7.11Hz,1H),3.10(dd,J＝13.92,4.08Hz,1H),2.95(m,2H),2.47(dd,J＝13.94,9.49Hz,1H),2.36(s,3H),2.33(d,J＝7.43Hz,2H),2.10(s,6H),2.08–1.99(m,2H),1.89(s,1H),1.66(m,3H),1.55–1.46(m,1H),1.35(d,J＝7.13Hz,3H). 13 C NMR(125MHz,CDCl 3 ):δ220.0,174.4,149.9,140.1,138.9,138.4,138.4,137.0,134.1,132.1,131.5,131.4,130.0,129.1,129.0,128.4,127.9,127.6,127.4,126.5,126.3,111.7,111.1,64.0,51.0,45.1,38.2,35.3,29.4,29.3,23.4,21.4,20.6,20.5,18.4.
example 10
2j is used to replace 2a in example 1, the other conditions are the same as example 1, and the experimental results are shown in Table 1.
Spectrogram analysis data 3aj:
1 H NMR(500MHz,CDCl 3 ):δ8.03(d,J＝7.97Hz,1H),7.94(t,J＝7.80Hz,1H),7.86(d,J＝7.58Hz,1H),7.64(t,J＝9.58Hz,2H),7.59(d,J＝7.63Hz,2H),7.52(q,6.45Hz,3H),7.42(t,J＝7.45Hz,1H),7.25(d,J＝4.41Hz,1H),7.15–7.07(m,2H),6.95(d,J＝6.58Hz,2H),3.89(s,3H),3.84(m,1H),3.77(m,1H),3.61(q,J＝7.13Hz,1H),2.96(m,2H),2.34(s,3H),2.08(s,6H),1.64(m,2H),1.44(d,J＝7.14Hz,3H). 13 CNMR(125MHz,CDCl 3 ):δ173.5,156.7,148.6,138.8,137.5,136.0,134.7,133.0,132.8,131.1,130.7,130.1,129.0,128.3,128.0,127.4,127.1,126.4,126.1,125.5,125.4,125.3,124.9,118.1,110.8,110.1,104.7,76.4,76.2,75.9,63.0,54.4,44.4,28.3,22.3,20.4,19.5,17.4.
TABLE 1
Claims (2)
1. A method for preparing a polysubstituted pyridoimidazole skeleton fused ring compound under an electrocatalytic strategy, wherein the pyridoimidazole skeleton fused ring compound has a structure shown as a formula I:
the R substituent group is selected from phenyl, methyl, cyclohexyl, 4-methyl benzene sulfonic acid propyl ester group, methyl cyanide chrysanthemate propyl ester group, methyl gongfruite propyl ester group, isobutyl phenylpropionic acid propyl ester group, isoxofenate propyl ester group, 2- (4- (cyclopentyl methyl) phenyl) propyl ester group and naproxen propyl ester group; is characterized in that substituted pyridylimidazole, substituted phenyl internal alkyne, tetraethylammonium tetrafluoroborate and DABCO are added into a reactor, and the molar ratio of the substituted pyridylimidazole to the substituted phenyl internal alkyne to the tetraethylammonium tetrafluoroborate to the DABCO is 1: 1.2: 2: 0.005. the solvent is hexafluoroisopropanol: tetrahydrofuran (4mL:1 mL). After the reaction is promoted in a solvent by electrocatalysis, concentrating by using a rotary evaporator to obtain a crude product, and separating the crude product by using silica gel column chromatography to obtain a target product, wherein the chemical reaction process is shown as a formula II:
2. the method of claim 1, wherein: the cathode and the anode adopt graphite felt electrodes, and the reaction is promoted by electrocatalysis under the condition of constant current of 8mA at the reaction temperature of 60 ℃ under N 2 The reaction time is 2-3 h.
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