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N-arylation method in aqueous phase system with substituted quinoline or isoquinoyl hydrazide pyridine-N-oxide as ligand

A quinoline hydrazide pyridine, arylation technology, applied in the chemical field, can solve problems such as complex ligand structure, cumbersome synthesis steps, and difficulty in obtaining it, and achieve the effects of broad application prospects, simple operation, and high yield

Active Publication Date: 2019-03-12
SHIHEZI UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the N-arylation reactions reported in these literatures usually need to be carried out in organic solvents, and most of the ligands used have complex structures, high prices or cumbersome synthesis steps, and are difficult to obtain.

Method used

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  • N-arylation method in aqueous phase system with substituted quinoline or isoquinoyl hydrazide pyridine-N-oxide as ligand
  • N-arylation method in aqueous phase system with substituted quinoline or isoquinoyl hydrazide pyridine-N-oxide as ligand
  • N-arylation method in aqueous phase system with substituted quinoline or isoquinoyl hydrazide pyridine-N-oxide as ligand

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Experimental program
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Effect test

preparation example Construction

[0039] The preparation method of ligand in the present invention is as figure 1 As shown, the specific operation steps are as follows:

[0040] The process of reaction i is: take 2-quinoline formic acid (1.732g, 10mmol) in a 100mL round bottom flask, add 3mL of ethanol to dissolve, and add 6mL of thionyl chloride dropwise within 15 minutes under ice-water bath conditions. Subsequently, it was heated under reflux for 8 hours, and TLC detected that the reaction was complete. After the reaction was completed, the ethanol was distilled off, and saturated NaHCO was added 3 The solution was adjusted to pH 7. After extraction with ethyl acetate, anhydrous Na 2 SO 4 The organic layer was dried, and the solvent was spin-dried to obtain the crude product of compound I. The product was then separated by column chromatography (eluent: petroleum ether-ethyl acetate) to obtain compound I (1.80 g, 90%) as a colorless oil.

[0041] The process of reaction ii was as follows: compound I (...

Embodiment 1

[0050] Embodiment 1: the synthesis of N-p-methoxyphenylimidazole

[0051] Its reaction formula is as follows:

[0052]

[0053] 8mg (0.05mmol) Cu 2 O, 21.7mg (0.1mmol) ligand, 119.4mg (0.5mmol) p-methoxyiodobenzene, 51mg (0.75mmol) imidazole, 40mg (1.0mmol) NaOH, 32.3mg (0.1mol) TBAB, 1.0ml EtOH: h 2 O(v / v)=1:1 was added into a 10ml Schlenk reaction tube, stirred and reacted by heating with a heating plate, and reacted at 120°C for 12 hours. After the reaction stopped, add 10ml of water, extract with ethyl acetate (3×20ml), combine the organic phases, wash with saturated brine, dry over anhydrous sodium sulfate, filter, distill off the solvent under reduced pressure, and pass the obtained reaction mixture through a silica gel column Separation and purification by column chromatography [eluent: petroleum ether / ethyl acetate (2:1)] gave 84 mg of N-p-methoxyphenylimidazole with a yield of 96%.

[0054] N-p-methoxyphenylimidazole: 1 H NMR (400MHz, CDCl 3 ): δ7.80(s, 1H), ...

Embodiment 2

[0055] Embodiment 2: the synthesis of N-p-methoxyphenylpyrrole

[0056] Its reaction formula is as follows:

[0057]

[0058] 4.4mg (0.05mmol) CuO, 21.7mg (0.1mmol) ligand, 119.4mg (0.5mmol) p-methoxyiodobenzene, 100mg (1.5mmol) pyrrole, 40mg (1.0mmol) NaOH, 32.3mg (0.1mmol) )TBAB, 1.0ml EtOH:H 2 O(v / v)=1:1 was added into a 10ml Schlenk reaction tube, stirred and reacted by heating with a heating plate, and reacted at 100°C for 14 hours. After the reaction stopped, add 10ml of water, extract with ethyl acetate (3×20ml), combine the organic phases, wash with saturated brine, dry over anhydrous sodium sulfate, filter, distill off the solvent under reduced pressure, and pass the obtained reaction mixture through a silica gel column Separation and purification by column chromatography [eluent: petroleum ether / ethyl acetate (10:1)] gave 81 mg of N-p-methoxyphenylpyrrole with a yield of 93%.

[0059] N-p-methoxyphenylpyrrole: 1 H NMR (400MHz, CDCl 3 ): δ7.34–7.32(m, 1H), 7.3...

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Abstract

The invention relates to an N-arylation method in an aqueous phase system with substituted quinoline or isoquinoyl hydrazide pyridine-N-oxide as a ligand. The N-arylation method in the aqueous phase system with the substituted quinoline or isoquinoyl hydrazide pyridine-N-oxide as the ligand comprises the following steps of: adding a catalyst, the ligand, a raw material, alkali, a phase transferring catalyst and a solvent into a reactor, heating and stirring, after the reaction is ended, separating and purifying a reaction solution to obtain an N-arylation product, wherein the raw material is aryl halide and a nitrogen-containing nucleophilic reagent, the solvent is a mixed solution of water and ethanol, and the catalyst is metal copper, or a copper oxide, or monovalent copper salt, or bivalent copper salt. The N-arylation method in the aqueous phase system with substituted quinoline or isoquinoyl hydrazide pyridine-N-oxide as the ligand has the characteristics of simplicity in operation, wide substrate application range, simplicity and easiness in separating products, high yield, economical process, environmental protection and the like.

Description

technical field [0001] The invention belongs to the technical field of chemistry, and specifically relates to an N-arylation method in an aqueous phase system using substituted quinoline or isoquinoline hydrazide pyridine-N-oxide as a ligand. Background technique [0002] Arylamines are an important class of compounds that widely exist in natural and non-natural products with physiological activities. The study of C-N bond formation reactions has always been an important research field in organic chemistry and has attracted widespread attention. [0003] The transition metal-catalyzed cross-coupling reaction of aromatic halides and amines is one of the most important methods for efficient and specific construction of C-N bonds, and has been widely studied and applied. Among them, the use of copper-catalyzed Ullmann reaction to achieve C–N bond cross-coupling is one of the most commonly used and effective methods in organic chemistry, and great progress has been made in indus...

Claims

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Application Information

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IPC IPC(8): C07C213/04C07D207/325C07D233/64C07D401/04C07D405/04C07D487/04C07C217/84C07C215/08C07B43/04
CPCC07B43/04C07C213/04C07D207/325C07D233/64C07D401/04C07D405/04C07D487/04C07C217/84C07C215/08
Inventor 谢建伟姚珍斌汪小创张洁
Owner SHIHEZI UNIVERSITY
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