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Palladium complex containing meta-position carborane triazole ligand and preparation method and application of palladium complex

A technology for meta-carborane and dipropargyl meta-carborane, which is applied in the field of complex synthesis, can solve the problems of harsh reaction conditions, long reaction time and the like, and achieves mild reaction conditions, simple preparation method, and wide industrial application. The effect of the application foreground

Active Publication Date: 2020-07-28
SHANGHAI INST OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Most of the traditional thioether synthesis methods are prepared by the oxidation reaction of mercaptan or thiophenol, which has the disadvantages of harsh reaction conditions and long reaction time.

Method used

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  • Palladium complex containing meta-position carborane triazole ligand and preparation method and application of palladium complex
  • Palladium complex containing meta-position carborane triazole ligand and preparation method and application of palladium complex
  • Palladium complex containing meta-position carborane triazole ligand and preparation method and application of palladium complex

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0034] Embodiment 1: Synthesis of palladium complex 1 and its application in the coupling reaction of catalyzed mercaptans and halogenated hydrocarbons

[0035] (1) At 0°C, add n-BuLi (22.0mmol) n-hexane solution dropwise to m-C containing m-carborane 2 B 10 h 12 (10.0mmol) in ether solution, continue to stir for 30 minutes after the dropwise addition, slowly rise to room temperature and continue to react for 30 minutes, then add 3-bromopropyne (21.0mmol), continue to react at room temperature for 3 hours, after the reaction ends The solvent was drained, and the product was recrystallized from n-hexane to obtain 1,3-dipropargyl m-carborane C 8 B 10 h 16 (productive rate 85%), reaction equation is:

[0036]

[0037] 1 H NMR (400MHz, CDCl 3 ,25°C): δ=3.55(s,2H),2.63(s,4H).Theoretical value of elemental analysis C 8 B 10 h 16 : C 43.61, H 7.32; Found: C 43.55, H 7.30.

[0038] (2) CuI (0.05mmol), 1,3-dipropargyl m-carborane (1.0mmol) and benzene azide (1.2mmol) were...

Embodiment 2

[0044] Embodiment 2: the synthesis of palladium complex 2

[0045] (1) At 0°C, add n-BuLi (22.0mmol) n-hexane solution dropwise to m-C containing m-carborane 2 B 10 h 12 (10.0mmol) in ether solution, continue to stir for 30 minutes after the dropwise addition, slowly rise to room temperature and continue to react for 30 minutes, then add 3-bromopropyne (21.0mmol), continue to react at room temperature for 3 hours, after the reaction ends The solvent was drained, and the product was recrystallized from n-hexane to obtain 1,3-dipropargyl m-carborane C 8 B 10 h 16 (productive rate 85%), reaction equation is:

[0046]

[0047] 1 H NMR (400MHz, CDCl 3 ,25°C): δ=3.55(s,2H),2.63(s,4H).Theoretical value of elemental analysis C 8 B 10 h 16 : C 43.61, H 7.32; Found: C 43.55, H 7.30.

[0048] (2) Dissolve CuI (0.05mmol), 1,3-dipropargyl m-carborane (1.0mmol) and 4-methoxyazidebenzene (1.5mmol) in THF at room temperature, and at this temperature React for 5 hours, then PdCl...

Embodiment 3

[0051] Embodiment 3: the synthesis of palladium complex 3

[0052] (1) At 0°C, add n-BuLi (22.0mmol) n-hexane solution dropwise to m-C containing m-carborane 2 B 10 h 12 (10.0mmol) in ether solution, continue to stir for 30 minutes after the dropwise addition, slowly rise to room temperature and continue to react for 30 minutes, then add 3-bromopropyne (21.0mmol), continue to react at room temperature for 3 hours, after the reaction ends The solvent was drained, and the product was recrystallized from n-hexane to obtain 1,3-dipropargyl m-carborane C 8 B 10 h 16 (productive rate 85%), reaction equation is:

[0053]

[0054] 1 H NMR (400MHz, CDCl 3 ,25°C): δ=3.55(s,2H),2.63(s,4H).Theoretical value of elemental analysis C 8 B 10 h 16 : C 43.61, H 7.32; Found: C 43.55, H 7.30.

[0055] (2) Dissolve CuI (0.05mmol), 1,3-dipropargyl m-carborane (1.0mmol) and 4-nitroazidobenzene (1.3mmol) in THF at room temperature, and react at this temperature 5 hours, then PdCl 2 (1...

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Abstract

The invention relates to a palladium complex containing a meta-position carborane triazole ligand and a preparation method and application of the palladium complex. The palladium complex is prepared by the following steps: (1) dropwise adding an n-BuLi solution into a meta-position carborane m-C2B10H12 solution, carrying out stirring and reacting, then adding 3-propargyl bromide for a reaction again, and after the reaction is finished, carrying out separating to obtain 1,3-dipropargyl meta-carborane; and (2) under the catalytic condition of a catalyst CuI, carrying out a reaction on 1,3-dipropargyl meta-carborane and aryl azide, then adding PdCl2 into a reaction system, continuing the reaction, and after the reaction is finished, carrying out separation to obtain the palladium complex containing the meta-carborane triazole ligand. Compared with the prior art, the preparation method provided by the invention is simple and green; the complex can efficiently catalyze a coupling reaction of mercaptan and halogenated hydrocarbon to synthesize thioether compounds; reaction conditions are mild, substrate universality is good, catalytic efficiency is high, and few byproducts are produced;and the catalyst has high stability and is not sensitive to air and water.

Description

technical field [0001] The invention relates to the field of complex synthesis, in particular to a palladium complex containing meta-carboranetriazole ligands, a preparation method and application thereof. Background technique [0002] Since carborane was synthesized in the 1960s, the chemistry of this stable carborane has aroused great interest and has gradually become an active field in modern chemical research. Due to their special physical and chemical properties, carborane derivatives are widely used in the synthesis of molecular recognition, liquid crystal materials, nonlinear optical materials and polymer materials. Carborane-based metal complexes have also been widely used as catalysts in organic synthesis. [0003] Thioether widely exists in natural product medicines, and its unique molecular structure makes it exhibit high pharmacological and biological activities, and is often used in the synthesis of medicines, electrochemical materials and fragrances. Most of ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F15/00B01J31/22C07C319/14C07C321/28C07C323/20C07C323/09C07C321/30
CPCC07F15/006B01J31/182C07C319/14B01J2531/824B01J2231/4294C07C321/28C07C323/20C07C323/09C07C321/30
Inventor 姚子健欧惠丹蒋晨妍张佳蔚马文江汪叶帆
Owner SHANGHAI INST OF TECH
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