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CN-122010931-A - Synthesis method and application of asymmetric 1, 10-phenanthroline

CN122010931ACN 122010931 ACN122010931 ACN 122010931ACN-122010931-A

Abstract

The invention relates to the technical field of chemical synthesis, in particular to a synthesis method and application of asymmetric 1, 10-phenanthroline. The synthesis method of the asymmetric 1, 10-phenanthroline comprises the following steps of reacting 8-aminoquinoline and crotonaldehyde under the catalysis of NaI under an acidic condition to obtain an intermediate 1, oxidizing the intermediate 1 under the acidic condition to obtain an intermediate 2, and reacting the intermediate 2 with phosphorus trioxyhalide to obtain the asymmetric 1, 10-phenanthroline. The synthesis method of the asymmetric 1, 10-phenanthroline provided by the invention has the advantages of short synthesis period, high production efficiency, available raw materials and low cost through three-step efficient reaction, provides a convenient and efficient synthesis means for scientific researchers, expands the modification method and substrate range of the asymmetric phenanthroline, is suitable for large-scale industrial production, and meets a great deal of requirements of markets on phenanthroline derivatives.

Inventors

  • WANG LI
  • KANG YU
  • XU ZEHUI

Assignees

  • 首都师范大学

Dates

Publication Date
20260512
Application Date
20251212

Claims (10)

  1. 1. The synthesis method of the asymmetric 1, 10-phenanthroline is characterized by comprising the following steps of: S1, 8-aminoquinoline and crotonaldehyde react under the catalysis of NaI under an acidic condition to obtain an intermediate 1; s2, performing oxidation reaction on the intermediate 1 in an acidic condition to obtain an intermediate 2; S3, reacting the intermediate 2 with phosphorus oxyhalide to obtain the asymmetric 1, 10-phenanthroline; The phosphorus oxyhalide comprises at least one of phosphorus oxychloride and phosphorus oxybromide.
  2. 2. The method for synthesizing the asymmetric 1, 10-phenanthroline according to claim 1, wherein S1 comprises the steps of mixing 8-aminoquinoline with NaI, sequentially adding inorganic acid and crotonaldehyde, reacting, quenching, adjusting pH, extracting, and performing column chromatography to obtain an intermediate 1; preferably, in S1, the inorganic acid is added dropwise; preferably, in S1, the pH is regulated by an alkaline agent, and the regulated pH is 7-8; Preferably, the alkaline agent comprises at least one of sodium carbonate, potassium carbonate and sodium bicarbonate.
  3. 3. The synthesis method of the asymmetric 1, 10-phenanthroline according to claim 1 or 2, wherein in S1, the molar ratio of the addition of the 8-aminoquinoline, the crotonaldehyde and the NaI is 10 (20-30) (0.1-0.15); preferably, in S1, the concentration of the 8-aminoquinoline in the inorganic acid is 2.5mol/L-3mol/L; preferably, in S1, the inorganic acid is aqueous concentrated sulfuric acid; Preferably, the concentration of the aqueous concentrated sulfuric acid is 65% -85%; Preferably, in S1, the temperature of the reaction is 100-120 ℃, and the reaction time is 1.5-2.5 h; Preferably, in S1, the solvent for extraction is at least one of dichloromethane or chloroform; preferably, in S1, the quenched solution is water; preferably, in S1, the eluent for column chromatography is dichloromethane: methanol= (20-30): 1.
  4. 4. The method for synthesizing asymmetric 1, 10-phenanthroline according to any one of claims 1-3, wherein S2 comprises the steps of dispersing intermediate 1 in organic acid, adding oxidant, reacting, quenching, adjusting pH, extracting, drying, concentrating to obtain intermediate 2; preferably, in S2, the quenched solvent is water; preferably, in S2, the pH is adjusted by an alkaline agent, and the adjusted pH is 7-8; Preferably, the alkaline agent comprises at least one of sodium carbonate, potassium carbonate and sodium bicarbonate.
  5. 5. The method for synthesizing asymmetric 1, 10-phenanthroline according to any one of claims 1-4, wherein in S2, the molar ratio of the intermediate 1 to the hydrogen peroxide is 1 (1-10); Preferably, in S2, the concentration of the intermediate 1 in the organic acid is 0.5mol/L to 1.0mol/L; Preferably, in S2, the solvent for extraction is at least one of dichloromethane or chloroform; Preferably, in S2, the organic acid is at least one selected from acetic acid and trifluoroacetic acid; preferably, in S2, the oxidizing agent includes at least one of hydrogen peroxide, ozone, and peracetic acid; preferably, in S2, the temperature of the oxidation reaction is 65-80 ℃, and the time of the oxidation reaction is 3-5 h.
  6. 6. The method for synthesizing the asymmetric 1, 10-phenanthroline according to any one of claims 1 to 5, wherein S3 comprises the steps of mixing an intermediate 2 with a solvent, adding phosphorus trihaloide and N, N-dimethylformamide in a protective atmosphere, and obtaining the asymmetric 1, 10-phenanthroline through reaction, quenching, pH adjustment, extraction and column chromatography; preferably, in S3, the pH is regulated by an alkaline agent, and the regulated pH is 7-8; Preferably, the alkaline agent comprises at least one of sodium carbonate, potassium carbonate and sodium bicarbonate; Preferably, in S3, the quenched solvent is water.
  7. 7. The method for synthesizing asymmetric 1, 10-phenanthroline according to any one of claims 1-6, wherein in S3, the extracted solvent is at least one of dichloromethane or chloroform; Preferably, in S3, the solvent includes at least one of dichloromethane, tetrahydrofuran, and acetonitrile; Preferably, in S3, the protective atmosphere includes at least one of nitrogen, argon and helium.
  8. 8. The method for synthesizing asymmetric 1, 10-phenanthroline according to any one of claims 1 to 7, wherein in S3, the addition temperature of phosphorus trihalide and N, N-dimethylformamide is-5 ℃ to 5 ℃; Preferably, in S3, the reaction temperature is 20-40 ℃ and the reaction time is 8-16 h.
  9. 9. The method for synthesizing asymmetric 1, 10-phenanthroline according to any one of claims 1-8, wherein in S3, the molar ratio of the addition of the intermediate 2, phosphorus trihalide and N, N-dimethylformamide is 1 (1.0-2.0): 0.5-1.5; Preferably, in S3, the concentration of the intermediate 2 in the solvent is 0.05mol/L to 0.4mol/L Preferably, in S3, the eluent for column chromatography is dichloromethane: methanol= (50-70): 1.
  10. 10. Use of asymmetric 1, 10-phenanthroline prepared by the synthesis method of asymmetric 1, 10-phenanthroline according to any one of claims 1-9 in lanthanide luminescent complexes, transition metal catalyzed organic reactions, rare earth element separations and lanthanides and actinides separations.

Description

Synthesis method and application of asymmetric 1, 10-phenanthroline Technical Field The invention relates to the technical field of chemical synthesis, in particular to a synthesis method and application of asymmetric 1, 10-phenanthroline. Background Phenanthroline (also called 1, 10-phenanthroline) is an important accessory ligand. The molecules of the fluorescent dye have a coplanar 14-pi electron structure, have good stability, and play a key functional ligand role in the fields of catalysis, material science, biomedicine, energy sources, sensors and the like as efficient electron donors. In addition, the phenanthroline has excellent modifiable property, and the modifier plays an important role in various fields. The asymmetric phenanthroline ligand has obvious advantages in various fields due to the unique structural characteristics and excellent coordination capability, namely, 1, the asymmetric phenanthroline ligand has high efficiency, good tolerance and excellent enantiomer and diastereomer selectivity in the catalysis field, 2, the asymmetric ligand can reduce energy loss, improve luminous intensity and service life through the unique structural characteristics of the ligand in the aspect of lanthanide luminescence, and 3, compared with the symmetric complex in the aspect of radiation de-excitation, the asymmetric complex has higher efficiency in the radiation de-excitation process, which is beneficial to improving the performance of a luminous material. 4. In the aspect of separation of lanthanum and actinium, the asymmetric ligand shows high extraction capacity for actinium ions with different valence states by virtue of the unique structural characteristics, and meanwhile, the extraction capacity for rare earth elements is extremely low. This selective extraction mechanism allows the asymmetric ligand to efficiently separate actinides from the mixture containing lanthanides, achieving good lanthanides and actinides separation. The characteristic not only improves the separation efficiency, but also reduces the separation cost, and has important practical application value in the fields of nuclear fuel post-treatment, radioactive waste treatment and the like. In addition, two nitrogen atoms of the 1, 10-phenanthroline have good coordination ability to transition metals, and researches show that if atoms with electron donating ability are introduced into the 2,9 positions of the atoms, the coordination ability of the whole ligand can be further obviously improved by the synergistic effect of the atoms and the nitrogen atoms. The modification strategy provides a new idea for developing high-performance asymmetric phenanthroline ligand. At present, most of the synthesis of asymmetric 1, 10-phenanthroline takes commercial 2, 9-dimethyl-1, 10-phenanthroline as a starting material, and mainly adopts two regulation strategies. One is to oxidize methyl groups to aldehyde groups by selenium dioxide, then to connect different groups by stepwise reaction, and the other is to oxidize aldehyde groups to carboxyl groups, and to connect different end groups by carboxyl activation, respectively. Although the synthetic method can obtain the asymmetric phenanthroline with different substituents, the synthetic process usually involves a plurality of intermediate steps and possible protection and deprotection steps, thereby not only prolonging the synthetic period and reducing the production efficiency, but also limiting the types of the functionalized asymmetric phenanthroline ligand due to the limitations of aldehyde group and carboxyl reaction types, and finally severely restricting the diversity research of the asymmetric 1, 10-phenanthroline ligand and the application prospect in mass production. Disclosure of Invention In view of the above, the invention aims to solve the problems of longer synthetic route, lower synthetic efficiency and limited substrate expansion of asymmetric 1, 10-phenanthroline in the prior art, thereby providing a synthetic method and application of the asymmetric 1, 10-phenanthroline. The invention provides a method for synthesizing asymmetric 1, 10-phenanthroline, which comprises the following steps of S1, 8-aminoquinoline and crotonaldehyde react under the catalysis of NaI under an acidic condition to obtain an intermediate 1, S2 and the intermediate 1 react under the acidic condition to obtain an intermediate 2 through oxidation reaction, S3 and the intermediate 2 react with phosphorus trioxyhalide to obtain the asymmetric 1, 10-phenanthroline, wherein the phosphorus trioxyhalide comprises at least one of phosphorus oxychloride and phosphorus tribromoxide. In some alternative embodiments, the synthetic route of the asymmetric 1, 10-phenanthroline synthesis method is as follows: 。 in some alternative embodiments, S1 comprises the steps of mixing 8-aminoquinoline with NaI, sequentially adding mineral acid and crotonaldehyde, reacting, quenching, adjusting pH, extracting, and performing