CN113930791B - Electric synthesis method of pyrido-bipyrimidine tetraketone compound - Google Patents
Electric synthesis method of pyrido-bipyrimidine tetraketone compound Download PDFInfo
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 28
- 238000001308 synthesis method Methods 0.000 title description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 23
- SMUQFGGVLNAIOZ-UHFFFAOYSA-N methylquinoline Natural products C1=CC=CC2=NC(C)=CC=C21 SMUQFGGVLNAIOZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 19
- -1 2-methylquinoline compound Chemical class 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 239000003792 electrolyte Substances 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical group CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 claims description 7
- 229940107816 ammonium iodide Drugs 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 238000004440 column chromatography Methods 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 239000007772 electrode material Substances 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 238000004811 liquid chromatography Methods 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 239000000047 product Substances 0.000 description 37
- 238000005481 NMR spectroscopy Methods 0.000 description 28
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- 239000003480 eluent Substances 0.000 description 10
- 238000001228 spectrum Methods 0.000 description 10
- 239000003208 petroleum Substances 0.000 description 7
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 5
- 238000004587 chromatography analysis Methods 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000012916 structural analysis Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- JJPSZKIOGBRMHK-UHFFFAOYSA-N 2,6-dimethylquinoline Chemical compound N1=C(C)C=CC2=CC(C)=CC=C21 JJPSZKIOGBRMHK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- SQRYQSKJZVQJAY-UHFFFAOYSA-N 6-bromo-2-methylquinoline Chemical compound C1=C(Br)C=CC2=NC(C)=CC=C21 SQRYQSKJZVQJAY-UHFFFAOYSA-N 0.000 description 1
- OCCIBGIEIBQGAJ-UHFFFAOYSA-N 6-chloro-2-methylquinoline Chemical compound C1=C(Cl)C=CC2=NC(C)=CC=C21 OCCIBGIEIBQGAJ-UHFFFAOYSA-N 0.000 description 1
- NAGJQQFMJKMXJQ-UHFFFAOYSA-N 6-methoxy-2-methylquinoline Chemical compound N1=C(C)C=CC2=CC(OC)=CC=C21 NAGJQQFMJKMXJQ-UHFFFAOYSA-N 0.000 description 1
- 102100028292 Aladin Human genes 0.000 description 1
- 101710065039 Aladin Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012822 chemical development Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 1
- RXMRGBVLCSYIBO-UHFFFAOYSA-M tetramethylazanium;iodide Chemical compound [I-].C[N+](C)(C)C RXMRGBVLCSYIBO-UHFFFAOYSA-M 0.000 description 1
- 239000002699 waste material Substances 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
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains three hetero rings
- C07D471/14—Ortho-condensed systems
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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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- 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
- C25B3/09—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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- 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
- C25B3/20—Processes
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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
- C25B3/20—Processes
- C25B3/29—Coupling reactions
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Pyridine Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The application discloses an electrosynthesis method of a pyrido-bipyrimidine tetraketone compound, which relates to the technical field of organic synthesis, and comprises the following steps: (1) Respectively adding an electrolyte, a 2-methylquinoline compound, a 1, 3-dimethyl-6-semicarbazide compound, a solvent and an electrode into an electrolytic tank which is not separated, and electrifying and stirring for reaction; (2) And (3) separating and purifying the solution after the reaction is finished to obtain the pyridine [2,3-d:6,5-d' ] bipyrimidine-2, 4,6,8 (1H, 3H,7H, 9H) -tetraketone compound.
Description
Technical field:
the application relates to the technical field of organic synthesis, in particular to an electric synthesis method of pyridine [2,3-d:6,5-d' ] bipyrimidine-2, 4,6,8 (1H, 3H,7H, 9H) -tetraketone compounds.
The background technology is as follows:
polysubstituted pyridine compounds are important nitrogen-containing heterocycles and widely exist in bioactive molecules and photoelectric materials. In particular to a pyridine [2,3-d:6,5-d' ] bipyrimidine-2, 4,6,8 (1H, 3H,7H, 9H) -tetraketone compound, the molecular structure of which consists of one pyridine and two pyrimidine rings, which is an important potential functional active molecule. Thus, research on the synthetic methods thereof has been an important point of research by organic chemists. However, since the reaction involves the formation of two carbon-carbon bonds and one carbon-nitrogen bond, little research is currently being done on the synthesis of pyridine [2,3-d:6,5-d' ] bipyrimidines-2, 4,6,8 (1H, 3H,7H, 9H) -tetraones.
In 2021, the Zhu group synthesized pyridine [2,3-d:6,5-d' ] bipyrimidine-2, 4,6,8 (1H, 3H,7H, 9H) -tetranes (R-J.Xie, J-H.Liu, Q-Y, zhang, Y-J.yang, L-Q.Song, T-Q, shao, K-X, liu and Y-P.Zhu, org.Chem.Front,2021,8,2274.) in tandem with 1, 3-dimethyl-6-semicarbazide using copper salts as catalyst. Although the method can well realize the synthesis, the metal residues often affect the utility of the synthesized drug molecules and functional molecules and require multiple steps to remove the metal residues, the steps are complicated, and a large amount of waste liquid is discharged.
The application comprises the following steps:
the application aims to solve the technical problem of providing a synthesis method of pyridine [2,3-d:6,5-d '] bipyrimidine-2, 4,6,8 (1H, 3H,7H, 9H) -tetraketone compounds, which adopts a green electromechanical chemical synthesis method to prepare the pyridine [2,3-d:6,5-d' ] bipyrimidine-2, 4,6,8 (1H, 3H,7H, 9H) -tetraketone compounds under a reaction environment without adding metal and chemical oxidant so as to overcome the defects of the prior art.
The technical problems to be solved by the application are realized by adopting the following technical scheme:
an electrosynthesis method of pyridine [2,3-d:6,5-d' ] bipyrimidine-2, 4,6,8 (1H, 3H,7H, 9H) -tetraketone compound, comprising the following steps:
(1) Electrocatalytic reaction: respectively adding an electrolyte, a 2-methylquinoline compound, a 1, 3-dimethyl-6-semicarbazide compound and a solvent into a reaction tank, installing a catalytic electrode, and electrifying and stirring for reaction;
(2) And (3) separating and purifying: and (3) separating and purifying the solution after the electrocatalytic reaction is finished to obtain the pyridine [2,3-d:6,5-d' ] bipyrimidine-2, 4,6,8 (1H, 3H,7H, 9H) -tetraketone compound.
The pyridine [2,3-d:6,5-d' ] bipyrimidine-2, 4,6,8 (1H, 3H,7H, 9H) -tetraketone compound has the structure shown as follows:
wherein R is 1 Is hydrogen, C 1 ~C 5 Alkyl, C 1 ~C 5 One or more of alkoxy, halogen; r is R 2 Is C 1 ~C 5 An alkyl group; r is R 3 Is C 1 ~C 5 An alkyl group.
Optionally, the 2-methylquinoline compound has a structure as shown below:
wherein R is 1 Is hydrogen, C 1 ~C 5 Alkyl, C 1 ~C 5 Alkoxy, halogen.
Optionally, the 1, 3-dimethyl-6-semicarbazide compound has a structure as shown below:
wherein R is 2 Is C 1 ~C 5 An alkyl group; r is R 3 Is C 1 ~C 5 An alkyl group.
Optionally, the mass ratio of the 2-methylquinoline compound to the 1, 3-dimethyl-6-semicarbazide compound is 1:1-1:4.
Optionally, the initial concentration of the 2-methylquinoline compound is 0.05-0.2 mol/L.
Optionally, the electrolyte is one of tetrabutylammonium tetrafluoroborate, lithium perchlorate, ammonium iodide, potassium iodide, sodium iodide, tetramethyl ammonium iodide and tetrabutyl ammonium iodide, and the mass of the electrolyte is 30-120% of that of the 2-methylquinoline compound.
Optionally, the temperature of the stirring reaction is 0-140 ℃.
Optionally, the solvent is one of dimethyl sulfoxide, N-dimethylformamide, N-methylpyrrolidone, N-dimethylacetamide, acetonitrile, water and 1, 2-dichloroethane.
Alternatively, the catalytic electrode is a conventional electrode material.
Optionally, the separation and purification method is one of column chromatography, liquid chromatography, distillation and recrystallization separation.
More optionally, the separation and purification method is column chromatography.
Optionally, the eluent of the column chromatography is petroleum ether/ethyl acetate. This is not a requirement of the present application to say that other eluent systems are not required, as long as reagents meeting the elution objectives can be used.
The beneficial effects of the application are as follows: the application provides an electric synthesis method of pyridine [2,3-d:6,5-d '] bipyrimidine-2, 4,6,8 (1H, 3H,7H, 9H) -tetraketone compounds, which is characterized in that the pyridine [2,3-d:6,5-d' ] bipyrimidine-2, 4,6,8 (1H, 3H,7H, 9H) -tetraketone compounds are synthesized by a one-pot method under electrochemical conditions through 2-methylquinoline compounds and 1, 3-dimethyl-6-semicarbazide compounds, and the method does not need the use of metal and chemical oxidants, has high economy of reaction atoms, and meets the requirements of green chemical development.
Description of the drawings:
FIG. 1 shows the product of example 1 of the present application 1 H NMR;
FIG. 2 shows the product of example 1 of the present application 13 C NMR;
FIG. 3 shows the product obtained in example 2 of the present application 1 H NMR;
FIG. 4 shows the product obtained in example 2 of the present application 13 C NMR;
FIG. 5 shows the product of example 3 of the present application 1 H NMR;
FIG. 6 shows the product of example 3 of the present application 13 C NMR;
FIG. 7 shows the product obtained in example 4 of the present application 1 H NMR;
FIG. 8 shows the product obtained in example 4 of the present application 13 C NMR;
FIG. 9 shows the product obtained in example 5 of the present application 13 C NMR;
FIG. 10 shows the product obtained in example 5 of the present application 1 H NMR;
The specific embodiment is as follows:
the application is further described below with reference to specific embodiments and illustrations in order to make the technical means, the creation features, the achievement of the purpose and the effect of the implementation of the application easy to understand.
An electrosynthesis method of pyridine [2,3-d:6,5-d' ] bipyrimidine-2, 4,6,8 (1H, 3H,7H, 9H) -tetraketone compound, comprising the following steps:
(1) Electrocatalytic reaction: respectively adding an electrolyte, a 2-methylquinoline compound, a 1, 3-dimethyl-6-semicarbazide compound and a solvent into a reaction tank, installing a catalytic electrode, and electrifying and stirring for reaction;
(2) And (3) separating and purifying: separating and purifying the solution after the electrocatalytic reaction is completed to obtain pyridine [2,3-d:6,5-d' ] bipyrimidine-2, 4,6,8 (1H, 3H,7H, 9H) -tetraketone compounds;
the pyridine [2,3-d:6,5-d' ] bipyrimidine-2, 4,6,8 (1H, 3H,7H, 9H) -tetraketone compound synthesized by the application has the structure shown as follows:
wherein R is 1 Is hydrogen, C 1 ~C 5 Alkyl, C 1 ~C 5 One or more of alkoxy, halogen; r is R 2 Is C 1 ~C 5 An alkyl group; r is R 3 Is C 1 ~C 5 An alkyl group.
Specifically, in a 10mL undivided electrolytic tank, an electrode, a 2-methylquinoline compound, a 1, 3-dimethyl-6-semicarbazide compound, an electrolyte and a solvent are respectively added into the undivided electrolytic tank, and the mixture is electrified and stirred for reaction; the amount of the electrolyte is 30-120% of the amount of the 2-methylquinoline compound. The mass ratio of the 2-methylquinoline compound to the 1, 3-dimethyl-6-semicarbazide compound is 1:1-1:4. The initial concentration of the 2-methylquinoline compound is 0.05-0.2 mol/L, and the temperature of the stirring reaction is 0-140 ℃. The electrode is selected from conventional commercial electrode materials such as platinum electrode, carbon electrode, nickel electrode, copper electrode, etc.
The solution after the reaction was dried under reduced pressure, and the residue was separated by column chromatography on a silica gel column and passed through the column using a petroleum ether/ethyl acetate system as eluent. This is not a requirement of the present application to say that other eluent systems are not required, as long as reagents meeting the elution objectives can be used.
The reaction formula is:
the embodiment of the application realizes the reaction of the 2-methylquinoline compound and the 1, 3-dimethyl-6-semicarbazide compound under electrochemical conditions for the first time, and the pyridine [2,3-d:6,5-d' ] bipyrimidine-2, 4,6,8 (1H, 3H,7H, 9H) -tetraketone compound is obtained with high selectivity. The method is a green and efficient method for synthesizing pyridine [2,3-d:6,5-d' ] bipyrimidine-2, 4,6,8 (1H, 3H,7H, 9H) -tetraketone compounds.
In the examples, the 2-methylquinoline and 1, 3-dimethyl-6-semicarbazide compounds used were analytically pure reagents purchased directly from Yu Annai Ji chemical, jiu Ding chemical, aladin and Aldamasc, and the solvents or eluents used were purchased from Guo nationality without any additional treatment.
Example 1
In a 10mL undivided cell were placed 2-methylquinoline (0.3 mmoL,42.9 mg), 1, 3-dimethyl-6-semicarbazide (0.6 mmol,93.1 mg), ammonium iodide (0.3 mmol,43.5 mg), and N, N-dimethylformamide (3.0 mL), and a platinum sheet electrode as both anode and cathode, and the reaction was stirred under energization (I=10mA) at 120 ℃. After the completion of the reaction (TLC trace detection), the residue obtained by spin-drying was purified by chromatography using an ethyl acetate/petroleum ether system as an eluent to give the product 1,3,7, 9-tetramethyl-5- (quinolin-2-yl) -pyridine [2,3-d:6,5-d' ] bipyrimidin-2, 4,6,8 (1H, 3H,7H, 9H) -tetraone in 81% yield.
The obtained product 1,3,7, 9-tetramethyl-5- (quinolin-2-yl) -pyridine [2,3-d:6,5-d ]']The structural analysis of the bipyrimidine-2, 4,6,8 (1H, 3H,7H, 9H) -tetraone product is shown in FIGS. 1-2. FIG. 1 is a schematic illustration of 1,3,7, 9-tetramethyl-5- (quinolin-2-yl) -pyridine [2,3-d:6,5-d ]']Bipyrimidine-2, 4,6,8 (1H, 3H,7H, 9H) -tetraone products 1 H nuclear magnetic resonance [ ] 1 H-NMR) spectra; FIG. 2 is a schematic illustration of 1,3,7, 9-tetramethyl-5- (quinolin-2-yl) -pyridine [2,3-d:6,5-d ]']Bipyrimidine-2, 4,6,8 (1H, 3H,7H, 9H) -tetraone products 13 C nuclear magnetic resonance 13 C-NMR) spectrum.
Characterization data is 1 H NMR(CDCl 3 ,400MHz,ppm):δ=8.29(d,J=8.0Hz,1H),8.02(d,J=8.4Hz,1H),7.93(d,J=6.8Hz,1H),7.73–7.69(m,1H),7.60–7.56(m,1H),7.43(d,J=8.8Hz,1H),3.81(s,6H),3.27(s,6H); 13 C NMR(CDCl 3 ,100MHz,ppm):δ=159.0,157.0,156.7,153.5,150.7,147.5,135.1,129.5,129.0,128.1,127.1,126.4,120.1,105.1,30.4,28.4。
The 1,3,7, 9-tetramethyl-5- (quinolin-2-yl) -pyridine [2,3-d:6,5-d' ] bipyrimidin-2, 4,6,8 (1H, 3H,7H, 9H) -tetraone compound prepared in example 1 has the structural formula:
example 2
2, 6-dimethylquinoline (0.3 mmoL,47.1 mg), 1, 3-dimethyl-6-semicarbazide (0.6 mmoL,93.1 mg), ammonium iodide (0.3 mmoL,43.5 mg), and N, N-dimethylformamide (3.0 mL) were placed in a 10mL undivided electrolytic cell, and a platinum sheet electrode was used as both an anode and a cathode, and the reaction was performed by stirring (I=10mA) with electricity at 120 ℃. After the completion of the reaction (TLC trace detection), the residue obtained by spin-drying was purified by chromatography using an ethyl acetate/petroleum ether system as an eluent to give the product 1,3,7, 9-tetramethyl-5- (6-methylquinolin-2-yl) -pyridine [2,3-d:6,5-d' ] bipyrimidin-2, 4,6,8 (1H, 3H,7H, 9H) -tetraone in 83% yield.
The obtained product 1,3,7, 9-tetramethyl-5- (6-methylquinolin-2-yl) -pyridine [2,3-d:6,5-d ]']The structural analysis of the bipyrimidine-2, 4,6,8 (1H, 3H,7H, 9H) -tetraone product is shown in FIGS. 3-4. FIG. 3 is a schematic illustration of 1,3,7, 9-tetramethyl-5- (6-methylquinolin-2-yl) -pyridine [2,3-d:6,5-d 'provided in example 2 of the present application']Bipyrimidine-2, 4,6,8 (1H, 3H,7H, 9H) -tetraone products 1 H nuclear magnetic resonance [ ] 1 H-NMR) spectra; FIG. 4 is a schematic illustration of 1,3,7, 9-tetramethyl-5- (6-methylquinolin-2-yl) -pyridine [2,3-d:6,5-d 'provided in example 2 of the present application']Bipyrimidine-2, 4,6,8 (1H, 3H,7H, 9H) -tetraone products 13 C nuclear magnetic resonance 13 C-NMR) spectrum.
Characterization data is 1 H NMR(CDCl 3 ,400MHz,ppm):δ=8.20(d,J=7.6Hz,1H),7.91(d,J=8.4Hz,1H),7.69–7.68(m,1H),7.54(d,J=8.4Hz,J=2.0Hz,1H),7.39(d,J=8.4Hz,1H),3.80(s,6H),3.26(s,6H),2.56(s,3H);13C NMR(CDCl3,100MHz,ppm):δ=159.1,157.2,155.8,153.6,150.9,146.2,136.4,134.6,131.8,128.7,127.3,127.1,120.2,105.2,30.4,28.5,21.6。
The 1,3,7, 9-tetramethyl-5- (6-methylquinolin-2-yl) -pyridine [2,3-d:6,5-d' ] bipyrimidin-2, 4,6,8 (1H, 3H,7H, 9H) -tetraone compound prepared in example 2 has the structural formula:
example 3
6-methoxy-2-methylquinoline (0.3 mmoL,51.9 mg), 1, 3-dimethyl-6-semicarbazide (0.6 mmoles, 93.1 mg), ammonium iodide (0.3 mmoles, 43.5 mg), and N, N-dimethylformamide (3.0 mL) were placed in a 10mL undivided electrolytic cell, and a platinum sheet electrode was used as both an anode and a cathode, and the reaction was performed with stirring (I=10mA) at 120 ℃. After the completion of the reaction (TLC trace detection), the residue obtained by spin-drying was purified by chromatography using an ethyl acetate/petroleum ether system as an eluent to give the product 1,3,7, 9-tetramethyl-5- (6-methoxyquinolin-2-yl) -pyridine [2,3-d:6,5-d' ] bipyrimidin-2, 4,6,8 (1H, 3H,7H, 9H) -tetraone in 76% yield.
The obtained product 1,3,7, 9-tetramethyl-5- (6-methoxyquinolin-2-yl) -pyridine [2,3-d:6,5-d ]']The structure analysis of the bipyrimidine-2, 4,6,8 (1H, 3H,7H, 9H) -tetraone product is shown in fig. 5-6, and the result is shown in fig. 5, which is 1,3,7, 9-tetramethyl-5- (6-methoxyquinolin-2-yl) -pyridine [2,3-d:6,5-d ]']Bipyrimidine-2, 4,6,8 (1H, 3H,7H, 9H) -tetraone products 1 H nuclear magnetic resonance [ ] 1 H-NMR) spectra; FIG. 6 is a diagram of 1,3,7, 9-tetramethyl-5- (6-methoxyquinolin-2-yl) -pyridine [2,3-d:6,5-d 'provided in example 3 of the present application']Bipyrimidine-2, 4,6,8 (1H, 3H,7H, 9H) -tetraone products 13 C nuclear magnetic resonance 13 C-NMR) spectrum.
Characterization data is 1 H NMR(CDCl 3 ,400MHz,ppm):δ=8.18(d,J=8.0Hz,1H),7.91(d,J=9.2Hz,1H),7.39–7.34(m,2H),7.20–7.19(m,1H),3.95(s,3H),3.79(s,6H),3.26(s,6H); 13 C NMR(CDCl 3 ,100MHz,ppm):δ=159.1,157.8,157.3,154.1,153.6,150.9,143.6,134.1,130.4,128.2,122.1,120.4,106.0,105.2,55.6,30.4,28.5。
The 1,3,7, 9-tetramethyl-5- (6-methoxyquinolin-2-yl) -pyridine [2,3-d:6,5-d' ] bipyrimidin-2, 4,6,8 (1H, 3H,7H, 9H) -tetraone compound prepared in example 3 has the structural formula:
example 4
6-chloro-2-methylquinoline (0.3 mmoL,53.1 mg), 1, 3-dimethyl-6-semicarbazide (0.6 mmoles, 93.1 mg), ammonium iodide (0.3 mmoles, 43.5 mg), and N, N-dimethylformamide (3.0 mL) were placed in a 10mL undivided electrolytic cell, and a platinum sheet electrode was used as both an anode and a cathode, and the reaction was performed with stirring (I=10mA) at 120 ℃. After the completion of the reaction (TLC trace detection), the residue obtained by spin-drying was purified by chromatography using an ethyl acetate/petroleum ether system as an eluent to give the product 1,3,7, 9-tetramethyl-5- (6-chloroquinolin-2-yl) -pyridine [2,3-d:6,5-d' ] bipyrimidin-2, 4,6,8 (1H, 3H,7H, 9H) -tetraone in 43% yield.
The obtained product 1,3,7, 9-tetramethyl-5- (6-chloroquinolin-2-yl) -pyridine [2,3-d:6,5-d ]']The structural analysis of the bipyrimidine-2, 4,6,8 (1H, 3H,7H, 9H) -tetraone product is shown in FIGS. 7-8. FIG. 7 is a schematic illustration of 1,3,7, 9-tetramethyl-5- (6-chloroquinolin-2-yl) -pyridine [2,3-d:6,5-d 'provided in example 4 of the present application']Bipyrimidine-2, 4,6,8 (1H, 3H,7H, 9H) -tetraone products 1 H nuclear magnetic resonance [ ] 1 H-NMR) spectra; FIG. 8 is a schematic diagram of 1,3,7, 9-tetramethyl-5- (6-chloroquinolin-2-yl) -pyridine [2,3-d:6,5-d ] provided in example 4 of the present application']Bipyrimidine-2, 4,6,8 (1H, 3H,7H, 9H) -tetraone products 13 C nuclear magnetic resonance 13 C-NMR) spectrum.
Characterization data is 1 HNMR(CDCl 3 ,400MHz,ppm):δ=8.20(d,J=8.8Hz,1H),7.95–7.91(m,2H),7.66–7.63(m,1H),7.44(d,J=8.4Hz,1H),3.80(s,6H),3.26(s,6H); 13 C NMR(CDCl 3 ,100MHz,ppm):δ=159.2,157.2,156.6,153.7,150.8,145.9,134.3,132.3,130.7,130.5,127.9,126.9,121.2,105.1,30.5,28.6。
The 1,3,7, 9-tetramethyl-5- (6-chloroquinolin-2-yl) -pyridine [2,3-d:6,5-d' ] bipyrimidin-2, 4,6,8 (1H, 3H,7H, 9H) -tetraone compound prepared in example 4 has the structural formula:
example 5
6-bromo-2-methylquinoline (0.3 mmoL,66.3 mg), 1, 3-dimethyl-6-semicarbazide (0.6 mmoles, 93.1 mg), ammonium iodide (0.3 mmoles, 43.5 mg), and N, N-dimethylformamide (3.0 mL) were placed in a 10mL undivided electrolytic cell, and the platinum sheet electrode was reacted as both an anode and a cathode with stirring (I=10mA) at 120 ℃. After the completion of the reaction (TLC trace detection), the residue obtained by spin-drying was purified by chromatography using an ethyl acetate/petroleum ether system as an eluent to give the product 1,3,7, 9-tetramethyl-5- (6-bromoquinolin-2-yl) -pyridine [2,3-d:6,5-d' ] bipyrimidin-2, 4,6,8 (1H, 3H,7H, 9H) -tetraone in 60% yield.
The obtained product 1,3,7, 9-tetramethyl-5- (6-bromoquinolin-2-yl) -pyridine [2,3-d:6,5-d ]']The structural analysis of the bipyrimidine-2, 4,6,8 (1H, 3H,7H, 9H) -tetraone product is shown in FIGS. 9-10. FIG. 9 is a schematic illustration of 1,3,7, 9-tetramethyl-5- (6-bromoquinolin-2-yl) -pyridine [2,3-d:6,5-d 'provided in example 5 of the present application']Bipyrimidine-2, 4,6,8 (1H, 3H,7H, 9H) -tetraone products 1 H nuclear magnetic resonance [ ] 1 H-NMR) spectra; FIG. 10 is a schematic illustration of 1,3,7, 9-tetramethyl-5- (6-bromoquinolin-2-yl) -pyridine [2,3-d:6,5-d 'provided in example 5 of the present application']Bipyrimidine-2, 4,6,8 (1H, 3H,7H, 9H) -tetraone products 13 C nuclear magnetic resonance 13 C-NMR) spectrum.
Characterization data is 1 H NMR(CDCl 3 ,400MHz,ppm):δ=8.19(d,J=8.0Hz,1H),8.09–8.08(m,1H),7.88(d,J=8.8Hz,1H),7.79–7.76(m,1H),7.44(d,J=8.4Hz,1H),3.80(s,6H),3.26(s,6H); 13 C NMR(CDCl 3 ,100MHz,ppm):δ=159.2,157.4,156.5,153.7,150.8,146.1,134.2,133.1,130.8,130.2,128.4,121.2,120.4,105.1,30.5,28.6。
The 1,3,7, 9-tetramethyl-5- (6-bromoquinolin-2-yl) -pyridine [2,3-d:6,5-d' ] bipyrimidin-2, 4,6,8 (1H, 3H,7H, 9H) -tetraone compound prepared in example 5 has the structural formula:
the energizing stirring reaction time in the embodiment of the application can be arbitrary, and pyridine [2,3-d:6,5-d' ] bipyrimidine-2, 4,6,8 (1H, 3H,7H, 9H) -tetraketone compounds can be prepared only by energizing, the optimal energizing time is about 18h, and the yield of the obtained product is highest. Any other time can prepare pyridine [2,3-d:6,5-d' ] bipyrimidin-2, 4,6,8 (1H, 3H,7H, 9H) -tetraketone compound, but the yield is changed, the yield is gradually increased from the beginning of electrifying to 18h, and when the yield exceeds 18h, the yield is reduced, possibly due to the overlong electrifying catalysis time, the generated product is converted into other byproducts.
The foregoing has shown and described the basic principles and main features of the present application and the advantages of the present application. It will be understood by those skilled in the art that the present application is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present application, and various changes and modifications may be made without departing from the spirit and scope of the application, which is defined in the appended claims. The scope of the application is defined by the appended claims and equivalents thereof.
Claims (7)
1. An electrosynthesis method of pyridine [2,3-d:6,5-d' ] bipyrimidin-2, 4,6,8 (1H, 3H,7H, 9H) -tetraketone compound is characterized by comprising the following steps:
(1) Electrocatalytic reaction: respectively adding an electrolyte, a 2-methylquinoline compound, a 1, 3-dimethyl-6-semicarbazide compound and a solvent into a reaction tank, installing a catalytic electrode, and electrifying and stirring for reaction;
(2) And (3) separating and purifying: separating and purifying the solution after the electrocatalytic reaction is completed to obtain pyridine [2,3-d:6,5-d' ] bipyrimidine-2, 4,6,8 (1H, 3H,7H, 9H) -tetraketone compounds;
the pyridine [2,3-d:6,5-d' ] bipyrimidine-2, 4,6,8 (1H, 3H,7H, 9H) -tetraketone compound has the structure shown as follows:
wherein R is 1 Is hydrogen, C 1 ~C 5 Alkyl, C 1 ~C 5 One or more of alkoxy, halogen; r is R 2 Is C 1 ~C 5 An alkyl group; r is R 3 Is C 1 ~C 5 An alkyl group;
the electrolyte is ammonium iodide;
the temperature of the electrified stirring reaction is 120 ℃, and the current is 10mA;
the mass ratio of the 2-methylquinoline compound to the 1, 3-dimethyl-6-semicarbazide compound is 1:2.
2. The electrosynthesis method of claim 1, wherein: the 2-methylquinoline compound has a structure shown as follows:
wherein R is 1 Is hydrogen, C 1 ~C 5 Alkyl, C 1 ~C 5 Alkoxy, halogen.
3. The electrosynthesis method of claim 1, wherein: the 1, 3-dimethyl-6-semicarbazide compound has a structure shown as follows:
wherein R is 2 Is C 1 ~C 5 An alkyl group; r is R 3 Is C 1 ~C 5 An alkyl group.
4. The electrosynthesis method of claim 1, wherein: the initial concentration of the 2-methylquinoline compound is 0.05-0.2 mol/L.
5. The electrosynthesis method of claim 1, wherein: the solvent is one of dimethyl sulfoxide, N-dimethylformamide, N-methylpyrrolidone, N-dimethylacetamide, acetonitrile, water and 1, 2-dichloroethane.
6. The electrosynthesis method of claim 1, wherein: the catalytic electrode is a conventional electrode material.
7. The electrosynthesis method of claim 1, wherein: the separation and purification method is one of column chromatography, liquid chromatography, distillation and recrystallization separation.
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009001214A2 (en) * | 2007-06-28 | 2008-12-31 | Pfizer Products Inc. | Thieno[2,3-d]pyrimidin-4(3h)-one, isoxazolo[5,4-d]pyrimidin-4(5h)-one and isothiazolo[5,4-d]pyrimidin-4(5h)-one derivatives as calcium receptor antagonists |
CN110790763A (en) * | 2019-11-24 | 2020-02-14 | 烟台大学 | Process for preparing pyridobipyrimidine and pyridobipyrazole derivatives |
CN111910206A (en) * | 2019-05-07 | 2020-11-10 | 中国科学技术大学 | Method for synthesizing 3-cyano-substituted imidazo [1,5-a ] quinoline compound |
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Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2009001214A2 (en) * | 2007-06-28 | 2008-12-31 | Pfizer Products Inc. | Thieno[2,3-d]pyrimidin-4(3h)-one, isoxazolo[5,4-d]pyrimidin-4(5h)-one and isothiazolo[5,4-d]pyrimidin-4(5h)-one derivatives as calcium receptor antagonists |
CN111910206A (en) * | 2019-05-07 | 2020-11-10 | 中国科学技术大学 | Method for synthesizing 3-cyano-substituted imidazo [1,5-a ] quinoline compound |
CN110790763A (en) * | 2019-11-24 | 2020-02-14 | 烟台大学 | Process for preparing pyridobipyrimidine and pyridobipyrazole derivatives |
Non-Patent Citations (3)
Title |
---|
Electrochemical synthesis of dipyrazolo/ dipyrimidine-fused pyridines via oxidative domino cyclization of C(sp 3 )–H bonds;Peng Qian et al.;《Org. Chem. Front.》;第9卷;第1662–1667页 * |
Iodine-Promoted Synthesis of Dipyrazolo/Diuracil-Fused Pyridines and o-Amino Diheteroaryl ketones via Oxidative Domino Annulation of 2/4-Methylazaarenes;Xin-Ke Zhang et al.;《Adv. Synth. Catal.》;第363卷;第4632 – 4638页 * |
Organic photocatalysis for the radical couplings of boronic acid derivatives in batch and flow;Fabio Lima et al.;《Chem. Commun.》;第54卷;第5606--5609页 * |
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