CN118223050A - Electrochemical synthesis method of triazole compound - Google Patents
Electrochemical synthesis method of triazole compound Download PDFInfo
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- CN118223050A CN118223050A CN202211639786.2A CN202211639786A CN118223050A CN 118223050 A CN118223050 A CN 118223050A CN 202211639786 A CN202211639786 A CN 202211639786A CN 118223050 A CN118223050 A CN 118223050A
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- -1 triazole compound Chemical class 0.000 title claims abstract description 16
- 238000001308 synthesis method Methods 0.000 title claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 29
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000005859 coupling reaction Methods 0.000 claims abstract description 24
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 10
- 230000001105 regulatory effect Effects 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 47
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 32
- 229910052736 halogen Inorganic materials 0.000 claims description 28
- 150000002367 halogens Chemical class 0.000 claims description 28
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 27
- 125000003118 aryl group Chemical group 0.000 claims description 24
- 239000012295 chemical reaction liquid Substances 0.000 claims description 23
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 238000003786 synthesis reaction Methods 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 230000015572 biosynthetic process Effects 0.000 claims description 17
- 229910002804 graphite Inorganic materials 0.000 claims description 16
- 239000010439 graphite Substances 0.000 claims description 16
- 229910052697 platinum Inorganic materials 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 125000006570 (C5-C6) heteroaryl group Chemical group 0.000 claims description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 9
- 229910052801 chlorine Inorganic materials 0.000 claims description 9
- 239000000460 chlorine Substances 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 claims description 8
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 7
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims description 5
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 claims description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000005842 heteroatom Chemical group 0.000 claims description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 229920002530 polyetherether ketone Polymers 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000000010 aprotic solvent Substances 0.000 claims description 2
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- MCZDHTKJGDCTAE-UHFFFAOYSA-M tetrabutylazanium;acetate Chemical compound CC([O-])=O.CCCC[N+](CCCC)(CCCC)CCCC MCZDHTKJGDCTAE-UHFFFAOYSA-M 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 21
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 14
- 230000008569 process Effects 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 7
- 239000000741 silica gel Substances 0.000 description 7
- 229910002027 silica gel Inorganic materials 0.000 description 7
- 238000003487 electrochemical reaction Methods 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 238000012546 transfer Methods 0.000 description 4
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 description 3
- 230000003321 amplification Effects 0.000 description 3
- YTAIULCXHWIZQI-UHFFFAOYSA-N n'-pyridin-2-ylbenzenecarboximidamide Chemical compound C=1C=CC=CC=1C(/N)=N/C1=CC=CC=N1 YTAIULCXHWIZQI-UHFFFAOYSA-N 0.000 description 3
- 238000003199 nucleic acid amplification method Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- PTSGSAZNUXYIGA-UHFFFAOYSA-N 4-fluoro-N'-pyridin-2-ylbenzenecarboximidamide Chemical compound N\C(=N/c1ccccn1)c1ccc(F)cc1 PTSGSAZNUXYIGA-UHFFFAOYSA-N 0.000 description 2
- FJIWCUKMCRMDBW-UHFFFAOYSA-N N'-(5-chloropyridin-2-yl)benzenecarboximidamide Chemical compound ClC=1C=CC(=NC=1)NC(C1=CC=CC=C1)=N FJIWCUKMCRMDBW-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- KNXKVYCVGXFLES-UHFFFAOYSA-N pyridine-2-carboximidamide Chemical class NC(=N)C1=CC=CC=N1 KNXKVYCVGXFLES-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001540 azides Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 238000003402 intramolecular cyclocondensation reaction Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention provides an electrochemical synthesis method of triazole compounds. The invention discloses an electrochemical synthesis method of a compound shown in a formula I, which comprises the following steps: in an organic solvent, in the presence of quaternary ammonium salt, regulating the current density to be 0.4-1.0 mA/cm 2 in a flowing electrochemical reactor, and carrying out nitrogen-nitrogen coupling reaction on a compound shown in a formula II to obtain the compound shown in the formula I; wherein m, R 1 and R 2 are defined. The method has strong operability, safety and better industrial application prospect.
Description
Technical Field
The invention relates to an electrochemical synthesis process suitable for triazole compounds, in particular to an electrochemical N-N coupled ring-closing reaction taking amidinopyridine compounds as substrates, and more particularly relates to an electrochemical flow synthesis process.
Background
The triazole pyridine nucleus is an important intermediate compound widely applied in the field of biological medicine because of the specific nitrogen-containing heterocyclic ring motif. The traditional synthetic route is usually synthesized by reaction under the action of a strong oxidant by taking hydrazine compounds such as hydrazine hydrate as a substrate source, and the improved synthetic route is synthesized by reaction by utilizing azide under the catalysis of copper, so that the whole process route has the defects of high operation risk, serious environmental pollution and the like. In recent years, an electrochemical anodic oxidation process driven by electrons has become a widely accepted environment-friendly synthesis method for constructing N-N, and a new way for synthesizing triazole compounds is realized by taking amidinopyridine compounds as a substrate and through an electrochemical reaction of intramolecular ring closure.
However, electrochemical reactions are often accompanied by electrode reactions of hydrogen evolution, oxygen evolution and chlorine evolution on the electrode surface, which are liable to cause electrode polarization and electrode passivation deactivation. Electrochemical reactions, on the other hand, are limited by the low conductivity of organic solutions, are prone to arcing hazards at high battery operating voltages, present a safety risk in the presence of flammable and potentially explosive organic solvents, and increase process energy consumption.
When the scale-up capability of electrochemical synthesis is designed, even if electrolyte is introduced to enhance the conductivity of the solution, the high current and high voltage required by the reaction inevitably bring about certain potential safety hazards due to the fact that the organic solvent with lower conductivity is used as a reaction solvent. In addition, because the site of the electrochemical reaction is the interface reaction between the first type conductor and the second type conductor, in the kettle-type reactor, the inter-phase transfer resistance of reaction molecules and electrons can be greatly increased, and the electrode polarization phenomenon is very easy to generate, for example, in CN101407923A, succinic acid is produced by rod-shaped electrode catalysis in a water system, and the electrochemical reaction is limited by the electron transfer and material mass transfer efficiency between electrodes, and the expansion reaction scale is limited, so that the combination of fluid chemistry and electrochemistry is an effective strategy for realizing the scale expansion of electrochemical synthesis. The amplification mode of the serpentine micro-channel is taken as a typical electrochemical flow amplification mode, and comprises two types, wherein one type is designed into the serpentine micro-channel for the electrode, the design and processing difficulties are high, and the cost of the lost electrode is quite high; one is that the drainage plate is a serpentine microchannel, and the effective utilization rate of the electrode area by the design is low.
In addition, the low current density of electrochemical reactions limits the scale application of electrochemical synthesis, resulting in the most currently reported electrochemical synthesis reactions being milligram scale reactions.
Disclosure of Invention
The invention aims to overcome the defects of small scale and difficult amplification of the existing electrocatalytic synthesis of triazole compounds. Therefore, the invention provides an electrochemical synthesis method of triazole compounds. The method provided by the invention has the advantages of simple and safe process and strong operability, is suitable for electrochemical large-scale production of triazole compounds, and has kilogram-level production and delivery capacity.
The invention provides an electrochemical synthesis method of a compound shown in a formula I, which comprises the following steps: in an organic solvent, in the presence of quaternary ammonium salt, regulating the current density to be 0.4-1.0 mA/cm 2 in a flowing electrochemical reactor, and carrying out nitrogen-nitrogen coupling reaction on a compound shown in a formula II to obtain the compound shown in the formula I;
Wherein m is 0, 1, 2, 3 or 4;
r 1 is independently halogen, C 1～C6 alkyl, C 1～C6 alkyl substituted with one or more halogens, C 6～C10 aryl, C 6～C10 aryl substituted with one or more C 1～C6 alkyl, or 5-to 6-membered heteroaryl;
R 2 is independently C 1～C6 alkyl, C 6～C10 aryl, C 6～C10 aryl substituted with one or more halogens, a 5-to 6-membered heteroaryl, or a 5-to 6-membered heteroaryl substituted with one or more halogens;
Wherein the hetero atom in each of the 5-6 membered heteroaryl groups is independently selected from 1,2 or 3 of N, S and O, and the hetero atom number is independently 1,2 or 3.
In one embodiment, in R 1, the halogen in the halogen and the C 1～C6 alkyl substituted with one or more halogens may be independently fluorine, chlorine or bromine, for example chlorine.
In one embodiment, in R 1, the C 1～C6 alkyl, the C 1～C6 alkyl substituted with one or more halogens, and the C 1～C6 alkyl substituted with one or more C 1～C6 alkyl groups may independently be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl.
In one embodiment, in R 1, the C 6～C10 aryl and the C 6～C10 aryl of C 6～C10 aryl substituted with one or more C 1～C6 alkyl groups may independently be phenyl.
In one embodiment, in R 2, the C 1～C6 alkyl group may independently be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl.
In one embodiment, in R 2, the halogen in the phenyl substituted with one or more halogens and the 5-to 6-membered heteroaryl substituted with one or more halogens may be independently fluorine, chlorine or bromine, for example fluorine.
In one embodiment, in R 2, the C 6～C10 aryl and the C 6～C10 aryl in the C 6～C10 aryl substituted with one or more halogens may be independently phenyl.
In one embodiment, m is 0 or 1.
In one embodiment, R 1 is independently halogen, such as chlorine.
In one embodiment, R 2 is independently C 6～C10 aryl or C 6～C10 aryl substituted with one or more halogens, such as phenyl or p-fluorophenyl.
In one embodiment, the compound of formula II is any one of the following compounds:
In one embodiment, the electrode of the flow electrochemical reactor is a plate electrode.
In one aspect, the flow electrochemical reactor may be a diaphragm-free, spaced-apart flow electrochemical reactor, preferably comprising a housing (e.g., a rigid stainless steel plate housing), an inlet, an outlet, an insulating plate, a cathode plate, an electrolytic cell, and an anode plate, preferably with the reaction solution flowing in from the inlet of the electrolytic cell and out from the outlet, the cathode plate and the anode plate being connected to a DC power source via current collectors.
In one embodiment, the number of the flow electrochemical reactors is 1 or n, n is 2, 3, 4, 5, 6, 7, 8, 9 or 10, for example, 5, and when the number of the flow electrochemical reactors is n, the flow electrochemical reactors are stacked in parallel.
In one embodiment, in the flow electrochemical reactor, the insulating plate is made of a material conventional in the reaction in the field, for example, polyetheretherketone or polytetrafluoroethylene.
In a certain scheme, in the flowing electrochemical reactor, the insulating plate is of a hollow structure and can be connected with a temperature control system, and the temperature control system can be used for controlling the temperature of the flowing electrochemical reactor.
In one aspect, the anode plate of the flow electrochemical reactor is an anode plate conventional in such reactions in the art, for example, the anode plate is a platinum anode plate, a graphite anode plate, a stainless steel anode plate, or a Reticulated Vitreous Carbon (RVC) anode plate, preferably a graphite anode plate.
In one aspect, the cathode plate of the flow electrochemical reactor is a cathode plate conventional in the art for such reactions, for example, the cathode plate is a platinum cathode plate or a graphite cathode plate, preferably a platinum cathode plate.
In one embodiment, in the flow electrochemical reactor, the electrolytic cell is made of materials conventional in the reaction field, such as polyetheretherketone or polytetrafluoroethylene.
In one embodiment, the volume of the electrolytic cell may be 10-500 mL, and the volume of the electrolytic cell is the volume of a single electrolytic cell reactor, specifically the product of the effective area and the electrode spacing.
In a certain scheme, the electrode spacing of the flow electrochemical reactor is 1-20 mm, preferably 1-10 mm, for example 1-5 mm, and another example is 5mm or 2mm, and the electrode spacing of the flow electrochemical reactor is the mass transfer distance of electrons from the electrode surface to the solution body.
In one aspect, the flow electrochemical reactor has an effective area of 20cm 2～500cm2, for example 25cm 2 or 450cm 2; the effective area refers to the corresponding areas of the cathode plate and the anode plate.
In one embodiment, the flow electrochemical reactor is provided with a diversion trench and a sink trench at the inlet and the outlet.
In one aspect, the flow electrochemical reactor contains a screen and/or liquid diversion channels that enhance turbulence of the reaction liquid flow.
In one embodiment, the organic solvent is an organic solvent conventional in such reactions in the art, such as an aprotic solvent, and further such as a nitrile solvent, preferably acetonitrile.
In one embodiment, the quaternary ammonium salt is a quaternary ammonium salt conventional in such reactions in the art, such as one or more of tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium acetate and tetrabutylammonium chloride, preferably tetrabutylammonium bromide or tetrabutylammonium iodide.
In one embodiment, the ratio of the amount of the compound of formula II to the amount of quaternary ammonium material may be 1: (2 to 4), preferably 1:3.
In one embodiment, the mass to volume ratio of the compound of formula II to the organic solvent is conventional in the art for such reactions, e.g., 1: (20-200) g/mL, preferably 1:100g/mL.
In one embodiment, the temperature of the nitrogen-nitrogen coupling reaction is a reaction temperature conventional in such reactions in the art, e.g., 15-25 ℃, preferably 20 ℃.
In one embodiment, the nitrogen-nitrogen coupling reaction is performed under a shielding gas, for example, the shielding gas is nitrogen.
In one embodiment, the nitrogen-nitrogen coupling reaction is performed under the action of a direct current power supply, and preferably, the direct current power supply comprises a constant current mode and a constant voltage mode.
In one embodiment, when the nitrogen-nitrogen coupling reaction is performed at a constant voltage, the voltage is set according to the current density, and the voltage is, without limitation, 1 to 300V.
In one embodiment, the nitrogen-nitrogen coupling reaction is performed under constant current, which is set according to current density, but not limited to, 5mA to 5000mA, preferably 10mA to 2000mA, and more preferably 16mA to 1800mA, for example 1800mA, 1350mA, 360mA or 16mA.
In one embodiment, the current density may be 0.5 to 1mA/cm 2, preferably 0.64 to 1mA/cm 2, for example 0.64mA/cm 2、0.8mA/cm2、1mA/cm2 or 0.6mA/cm 2.
In a certain scheme, in the flowing electrochemical reactor, the flowing mode of the reaction liquid is a single-channel flowing mode or a circulating flowing mode; the circulating flow mode means that the reaction liquid obtains enough electrons to fully react with the substrate in the continuous flowing circulation process; the single-channel flow mode is that the reaction liquid obtains enough electrons in the flowing electrochemical reactor to meet the requirement of complete substrate reaction.
Preferably, in the flow electrochemical reactor, the flow mode of the reaction liquid is a circulating flow reaction.
In a certain scheme, when the reaction solution of the nitrogen-nitrogen coupling reaction is reacted in a circulating flow mode, the flow rate of the reaction solution is conventional in the art, and the flow rate of the reaction solution can be, without limitation, 20mL/min to 500mL/min, preferably 28 to 450mL/min, for example 28mL/min, 81mL/min or 450mL/min.
In one embodiment, when the reaction solution of the nitrogen-nitrogen coupling reaction is reacted in a single-channel flow mode, the flow rate of the reaction solution is conventional in the art, and the flow rate of the reaction solution may be 1-10 mL/min, preferably 4mL/min, without limitation.
In one embodiment, the progress of the nitrogen-nitrogen coupling reaction can be detected by methods conventional in the art for monitoring such reactions (e.g., LCMS, TLC, HPLC or NMR), typically using the compound of formula II as starting material as an endpoint when the compound is lost or no longer reacted. The reaction time may be 15h to 30h, for example 17h, 26h, 28h or 30h. Preferably, the nitrogen-nitrogen coupling reaction is completed to 3-10F/mol.
In one embodiment, the nitrogen-nitrogen coupling reaction preferably includes a post-treatment step, and after the reaction is completed, the reaction solution is concentrated and passed through a column to obtain the compound shown in the formula I.
In a certain scheme, the nitrogen-nitrogen coupling reaction comprises the following steps of mixing a compound shown in a formula II, quaternary ammonium salt and an organic solvent under a protective gas to obtain a reaction solution, adding the reaction solution into a flowing electrochemical reactor at a flow rate of 28-450 mL/min (circulating flow mode) or a flow rate of 1-10 mL/min (single-channel flow mode), reacting under a direct current power supply and constant current, wherein the current intensity is 10 mA-2000 mA, the current density is 0.4-1.0 mA/cm 2, the electrode is a graphite anode plate and a platinum cathode plate, and concentrating the reaction solution through a column after the reaction is finished to obtain the compound shown in the formula I.
In a certain scheme, the nitrogen-nitrogen coupling reaction comprises the following steps of mixing a compound shown in a formula II, quaternary ammonium salt and an organic solvent in a raw material tank to obtain a reaction liquid under the protection of nitrogen at the temperature of 10-30 ℃, adding the reaction liquid into a flowing electrochemical reactor at the flow rate of 28-450 mL/min (circulating flow mode) or the flow rate of 1-10 mL/min (single-channel flow mode) by a conveying metering pump, carrying out the reaction under the condition of direct current power supply and constant current, wherein the current intensity is 10 mA-2000 mA, the current density is 0.4-1.0 mA/cm 2, the electrode is a graphite anode plate and a platinum cathode plate, and concentrating the reaction liquid to pass through a column after the reaction is finished to obtain the compound shown in the formula I.
Term interpretation:
Unless otherwise indicated, all terms used in the description and claims of the present invention have the following meanings:
Current density = current/flow electrochemical reactor active area N, where N is the number of electrochemical reactors;
The above preferred conditions can be arbitrarily combined on the basis of not deviating from the common knowledge in the art, and thus, each preferred embodiment of the present invention can be obtained.
The reagents and materials used in the present invention are commercially available.
The invention has the positive progress effects that: the method for synthesizing the triazole compound by electrochemical flow provided by the invention can be used for producing the triazole compound in an amplified manner, has high utilization rate of electrons, is green and efficient, has low processing cost and strong universality, is convenient to maintain, can enhance the mass transfer effect by adopting the liquid diversion groove and the screen, has intrinsic safety, and has good industrialized prospect.
Drawings
Fig. 1 is a schematic diagram of a flow electrochemical reactor.
FIG. 2 is a schematic illustration of an electrochemical flow synthesis process flow.
Reference numerals: 1-raw material tank, 2-delivery metering pump, 3-DC power supply, 4-flow electrochemical reactor, 11-rigid stainless steel base plate, 12-insulating plate, 13-cathode plate, 14-anode plate, 15-electrolytic cell, 16-inlet, 17-outlet and 18-current collector.
Detailed Description
The invention is further illustrated by means of the following examples, which are not intended to limit the scope of the invention. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.
The following examples can be carried out on an electrochemical flow synthesis process flow as shown in fig. 2, comprising a feed tank (1), a delivery metering pump (2), a direct current power supply (3) and a flow electrochemical reactor (4); in the following examples, as shown in fig. 1, the electrochemical reactor comprises an electrochemical reactor unit consisting of a rigid stainless steel base plate (11), an insulating plate (12), a cathode plate (13), an electrolytic cell (15) and an anode plate (14), wherein the reaction solution flows in from an inlet (16) of the electrolytic cell, flows out from an outlet (17), and the electrode is connected with a direct current power supply through a current collector (18).
In the embodiment, the outlet and the inlet of the electrochemical reactor are provided with the diversion trench and the sink.
The electrochemical reactor used in this example contains screens and/or liquid shunt channels.
Example 1
N- (pyridin-2-yl) benzamidine (0.5 g,2.53mmol,1.0 eq.) and tetrabutylammonium bromide (2.5 g,3 eq.) were dissolved in 50mL (100V) acetonitrile under nitrogen. The anode of the selected electrochemical reactor is graphite, the cathode is a platinum sheet, the volume of the electrolytic cell is 12.5mL, the effective area of the electrolytic cell is 25cm 2, and the electrode spacing is 5mm. The direct current power supply is set to be in a constant current mode, the current is 16mA, the reaction liquid is reacted in a circulating flow mode at the flow rate of 28mL/min, the temperature of the electrochemical reactor is controlled to be 15-25 ℃, the flow is stopped after the reaction is carried out for 17 hours, and the power supply is disconnected. The product was concentrated and passed through a column (silica gel column, mobile phase: ethyl acetate/n-heptane=2/1) to give 0.45g of 2-phenyl- [1,2,4] triazolo [1,5, a ] pyridine as a product in 92% yield.
Example 2
N- (pyridin-2-yl) benzamidine (10.0 g,0.051mol,1.0 eq.) and tetrabutylammonium bromide (49.0 g,3 eq.) were dissolved in 1000mL (100V) acetonitrile under nitrogen. The anode of the selected electrochemical reactor is graphite, the cathode is a platinum sheet, the volume of the electrolytic cell is 225mL, the effective area of the electrolytic cell is 450cm 2, and the electrode spacing is 5mm. The direct current power supply is set to be in a constant current mode, the current is 360mA, the reaction liquid is reacted in a circulating flow mode at the flow rate of 81mL/min, the temperature of the electrochemical reactor is controlled to be 15-25 ℃, the flow is stopped after the reaction is carried out for 15h, and the power supply is disconnected. The product was concentrated and passed through a column (silica gel column, mobile phase: ethyl acetate/n-heptane=2/1) to give 9.2g of 2-phenyl- [1,2,4] triazolo [1,5, a ] pyridine as a product in 93% yield.
Example 3
N- (pyridin-2-yl) benzamidine (100.0 g,0.51mol,1.0 eq.) and tetrabutylammonium bromide (490 g,3 eq.) were dissolved in 10L (100V) acetonitrile under nitrogen. The anode of the selected electrochemical reactor is graphite, the cathode is a platinum sheet, the volume of a single electrolytic cell is 225mL, the effective area of the electrolytic cell is 450cm 2, the electrode spacing is 5mm, and 5 electric reactor units are overlapped in parallel. The direct current power supply is set to be in a constant current mode, the current is 1800mA, the reaction liquid is reacted in a circulating flow mode at the flow rate of 450mL/min, the temperature of the electrochemical reactor is controlled to be 15-25 ℃, the flow is stopped after the reaction is carried out for 30 hours, and the power supply is disconnected. The product was concentrated and purified by column chromatography (silica gel column, mobile phase: ethyl acetate/n-heptane=2/1) to give 92g of 2-phenyl- [1,2,4] triazolo [1,5, a ] pyridine as a product in 93% yield.
Example 4
N- (5-chloropyridin-2-yl) benzamidine (100.0 g,0.43mol,1.0 eq.) and tetrabutylammonium iodide (480 g,3 eq.) were dissolved in 10L (100V) acetonitrile under nitrogen. The anode of the selected electrochemical reactor is graphite, the cathode is a platinum sheet, the volume of a single electrolytic cell is 225mL, the effective area of the electrolytic cell is 450cm 2, the electrode spacing is 5mm, and 5 electric reactor units are overlapped in parallel. The direct current power supply is set to be in a constant current mode, the current is 1800mA, the reaction liquid is reacted in a circulating flow mode at the flow rate of 450mL/min, the temperature of the electrochemical reactor is controlled to be 15-25 ℃, the flow is stopped after the reaction is carried out for 26 hours, and the power supply is disconnected. The product solution was concentrated and subjected to column chromatography (silica gel column, mobile phase: ethyl acetate/n-heptane=2/1) to give 83g of 6-chloro-2-phenyl- [1,2,4] triazolo [1,5, a ] pyridine as a product in a yield of 84%.
Example 5
N- (5-chloropyridin-2-yl) benzamidine (100.0 g,0.43mol,1.0 eq.) and tetrabutylammonium iodide (480 g,3 eq.) were dissolved in 10L (100V) acetonitrile under nitrogen. The anode of the selected electrochemical reactor is graphite, the cathode is a platinum sheet, the volume of a single electrolytic cell is 90mL, the effective area of the electrolytic cell is 450cm 2, the electrode spacing is 2mm, and 5 electric reactor units are stacked in series. The direct current power supply is set to be in a constant current mode, the current is 1350mA, the reaction liquid is reacted in a single-channel flow mode at the flow rate of 4mL/min, the temperature of the electrochemical reactor is controlled at 15-25 ℃, the flow of the reaction liquid in the raw material tank is stopped after the consumption of the reaction liquid, and the power supply is disconnected. The product solution was concentrated and subjected to column chromatography (silica gel column, mobile phase: ethyl acetate/n-heptane=2/1) to give 76g of 6-chloro-2-phenyl- [1,2,4] triazolo [1,5, a ] pyridine as a product in 77% yield.
Example 6
4-Fluoro-N- (pyridin-2-yl) benzamidine (100.0 g,0.46mol,1.0 eq.) and tetrabutylammonium iodide (515 g,3 eq.) were dissolved in 10L (100V) acetonitrile under nitrogen. The anode of the selected electrochemical reactor is graphite, the cathode is a platinum sheet, the volume of a single electrolytic cell is 225mL, the effective area of the electrolytic cell is 450cm 2, the electrode spacing is 5mm, and 5 electric reactor units are overlapped in parallel. The direct current power supply is set to be in a constant current mode, the current is 1800mA, the reaction liquid is reacted in a circulating flow mode at the flow rate of 450mL/min, the temperature of the electrochemical reactor is controlled to be 15-25 ℃, the flow is stopped after the reaction is carried out for 28h, and the power supply is disconnected. The product liquid was concentrated and subjected to column chromatography (silica gel column, mobile phase: ethyl acetate/n-heptane=2/1) to give 69g of 2- (4-fluorophenyl) - [1,2,4] triazolo [1,5, a ] pyridine as a product in a yield of 70%.
Example 7
4-Fluoro-N- (pyridin-2-yl) benzamidine (100.0 g,0.46mol,1.0 eq.) and tetrabutylammonium iodide (515 g,3 eq.) were dissolved in 10L (100V) acetonitrile under nitrogen. The anode of the selected electrochemical reactor is graphite, the cathode is a platinum sheet, the volume of a single electrolytic cell is 225mL, the effective area of the electrolytic cell is 450cm 2, the electrode spacing is 5mm, and 5 electric reactor units are overlapped in parallel. The direct current power supply is set to be in a constant current mode, the current is 2700mA, the reaction liquid is reacted in a circulating flow mode at the flow rate of 450mL/min, the temperature of the electrochemical reactor is controlled to be 15-25 ℃, the flow is stopped after the reaction is carried out for 18 hours, and the power supply is disconnected. The product liquid was concentrated and subjected to column chromatography (silica gel column, mobile phase: ethyl acetate/n-heptane=2/1) to give 38g of 2- (4-fluorophenyl) - [1,2,4] triazolo [1,5, a ] pyridine as a product in 40% yield.
Claims (10)
1. An electrochemical synthesis method of a compound shown in a formula I, which is characterized by comprising the following steps:
In an organic solvent, in the presence of quaternary ammonium salt, regulating the current density to be 0.4-1.0 mA/cm 2 in a flowing electrochemical reactor, and carrying out nitrogen-nitrogen coupling reaction on a compound shown in a formula II to obtain the compound shown in the formula I;
Wherein,
M is 0, 1,2, 3 or 4;
r 1 is independently halogen, C 1～C6 alkyl, C 1～C6 alkyl substituted with one or more halogens, C 6～C10 aryl, C 6～C10 aryl substituted with one or more C 1～C6 alkyl, or 5-to 6-membered heteroaryl;
R 2 is independently C 1～C6 alkyl, C 6～C10 aryl, C 6～C10 aryl substituted with one or more halogens, a 5-to 6-membered heteroaryl, or a 5-to 6-membered heteroaryl substituted with one or more halogens;
The hetero atom in each of the 5-6 membered heteroaryl groups is independently selected from 1, 2 or 3 of N, S and O, and the number of hetero atoms is independently 1, 2 or 3.
2. A method for the electrochemical synthesis of a compound of formula I according to claim 1, wherein the method satisfies one or more of the following conditions:
(1) In R 1, the halogen and the halogen in the C 1～C6 alkyl substituted with one or more halogens are independently fluorine, chlorine or bromine, for example chlorine;
(2) In R 1, the C 1～C6 alkyl, the C 1～C6 alkyl substituted with one or more halogens, and the C 1～C6 alkyl in the phenyl substituted with one or more C 1～C6 alkyl are independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl;
(3) In R 1, the C 6～C10 aryl and C 6～C10 aryl in C 6～C10 aryl substituted with one or more C 1～C6 alkyl groups are independently phenyl;
(4) In R 2, the C 1～C6 alkyl is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or tert-butyl;
(5) In R 2, the halogen in the phenyl substituted with one or more halogens and the 5-to 6-membered heteroaryl substituted with one or more halogens is independently fluorine, chlorine or bromine, for example fluorine;
(6) In R 2, the C 6～C10 aryl and C 6～C10 aryl of C 6～C10 aryl substituted with one or more halogens are independently phenyl;
(7) m is 0 or 1;
And (8) the current density is from 0.5 to 1mA/cm 2, preferably from 0.64 to 1mA/cm 2, for example 0.64mA/cm 2、0.8mA/cm2、1mA/cm2 or 0.6mA/cm 2.
3. A method for the electrochemical synthesis of a compound of formula I according to claim 2, wherein the method satisfies one or more of the following conditions:
(1) R 1 is independently halogen, for example, chlorine;
and (2) R 2 is independently C 6～C10 aryl or C 6～C10 aryl substituted with one or more halogens, for example phenyl or p-fluorophenyl.
4. The method for electrochemical synthesis of a compound of formula I according to claim 3, wherein the compound of formula II is any one of the following compounds:
5. A method for the electrochemical synthesis of a compound of formula I according to claim 1, wherein the method satisfies one or more of the following conditions:
(1) The organic solvent is an aprotic solvent, for example a nitrile solvent, preferably acetonitrile;
(2) The quaternary ammonium salt is one or more of tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium acetate and tetrabutylammonium chloride, preferably tetrabutylammonium bromide or tetrabutylammonium iodide;
(3) The ratio of the amount of the compound represented by formula II to the amount of the quaternary ammonium salt substance is 1: (2 to 4), preferably 1:3, a step of;
(4) The mass volume ratio of the compound shown in the formula II to the organic solvent is 1: (20-200) g/mL, preferably 1:100g/mL;
(5) The temperature of the nitrogen-nitrogen coupling reaction is 15-25 ℃, preferably 20 ℃;
(6) The nitrogen-nitrogen coupling reaction is carried out under a shielding gas, for example, the shielding gas is nitrogen;
(7) The nitrogen-nitrogen coupling reaction is carried out under the action of a direct current power supply, and preferably, the direct current power supply comprises a constant current mode and a constant voltage mode;
And (8) the flow pattern of the reaction liquid in the flow electrochemical reactor is a single-channel flow pattern or a circulating flow pattern, preferably a circulating flow pattern.
6. A method for the electrochemical synthesis of a compound of formula I according to claim 5, wherein the method satisfies one or more of the following conditions:
(1) When the nitrogen-nitrogen coupling reaction is carried out under constant voltage, the voltage is 1-300V;
(2) When the nitrogen-nitrogen coupling reaction is carried out under constant current, the current is 5mA to 5000mA, preferably 10mA to 2000mA, further preferably 16mA to 1800mA, for example 1800mA, 1350mA, 360mA or 16mA;
(3) When the reaction liquid of the nitrogen-nitrogen coupling reaction is reacted in a circulating flow mode, the flow rate of the reaction liquid is 20 mL/min-500 mL/min, preferably 28-450 mL/min, for example 28mL/min, 81mL/min or 450mL/min;
(4) When the reaction liquid of the nitrogen-nitrogen coupling reaction is reacted in a single-channel flow mode, the flow rate of the reaction liquid is 1-10 mL/min, preferably 4mL/min;
and (5) the nitrogen-nitrogen coupling reaction comprises the following post-treatment steps, and after the reaction is finished, the reaction solution is concentrated and passes through a column to obtain the compound shown in the formula I.
7. The method for electrochemical synthesis of a compound of formula I according to claim 6, wherein the nitrogen-nitrogen coupling reaction comprises the steps of: under the protection gas, mixing the compound shown in the formula II, quaternary ammonium salt and the organic solvent to obtain a reaction solution, adding the reaction solution into the flowing electrochemical reactor at a flow rate of 28-450 mL/min or a flow rate of 1-10 mL/min, reacting under a direct current power supply and constant current, wherein the current intensity is 10 mA-2000 mA, the current density is 0.4-1.0 mA/cm 2, the electrode is a graphite anode plate and a platinum cathode plate, and concentrating the reaction solution to pass through a column after the reaction is finished to obtain the compound shown in the formula I.
8. A method for the electrochemical synthesis of a compound of formula I according to claim 1, wherein the method satisfies one or more of the following conditions:
(1) The electrode of the flow electrochemical reactor is a plate electrode;
(2) The flow electrochemical reactor is a diaphragm-free flow electrochemical reactor, preferably comprises a shell, an inlet, an outlet, an insulating plate, a cathode plate, an electrolytic cell and an anode plate, and preferably, the reaction liquid flows in from the inlet of the electrolytic cell and flows out from the outlet, and the cathode plate and the anode plate are connected with a direct current power supply through a current collector;
And (3) the number of the flow electrochemical reactors is 1 or n, n is 2,3, 4,5, 6,7, 8, 9 or 10, for example, 5, and when the number of the flow electrochemical reactors is n, the flow electrochemical reactors are overlapped in parallel.
9. A method for the electrochemical synthesis of a compound of formula I according to claim 8, wherein the method satisfies one or more of the following conditions:
(1) In the flow electrochemical reactor, the insulating plate is made of polyether-ether-ketone or polytetrafluoroethylene;
(2) In the flow electrochemical reactor, the insulating plate is of a hollow structure;
(3) The anode plate of the flow electrochemical reactor is a platinum anode plate, a graphite anode plate, a stainless steel anode plate or a netlike glassy carbon anode plate, and is preferably a graphite anode plate;
(4) The cathode plate of the flowing electrochemical reactor is a platinum cathode plate or a graphite cathode plate, preferably a platinum cathode plate;
(5) In the flow electrochemical reactor, the electrolytic cell is made of polyether-ether-ketone or polytetrafluoroethylene;
(6) The flow electrochemical reactor is provided with a diversion channel and a converging channel at the inlet and the outlet;
(7) The flow electrochemical reactor contains a screen and/or a liquid shunt tank;
And (8) the electrolytic cell volume is 10-500 mL.
10. A method for the electrochemical synthesis of a compound of formula I according to claim 1, wherein the method satisfies one or more of the following conditions:
(1) The electrode spacing of the flow electrochemical reactor is 1 to 20mm, preferably 1 to 10mm, for example 1 to 5mm, and for example 5mm or 2mm;
And (2) the flow electrochemical reactor has an effective area of 20cm 2～500cm2, for example 25cm 2 or 450cm 2.
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