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Palladium complex containing ortho-position carborane based benzimidazole structure, preparation method and application thereof

A technology for carborane benzimidazole and palladium complexes, which is applied in the field of complex synthesis, can solve the problems of high price and high reaction conditions, and achieves the effects of low use equivalents, easily available raw materials and green synthesis process

Active Publication Date: 2020-09-08
SHANGHAI INST OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0004] However, the above methods all need to use expensive raw materials such as enynes or alkynoic acids, and the reaction conditions are also relatively high, usually requiring heating

Method used

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  • Palladium complex containing ortho-position carborane based benzimidazole structure, preparation method and application thereof
  • Palladium complex containing ortho-position carborane based benzimidazole structure, preparation method and application thereof
  • Palladium complex containing ortho-position carborane based benzimidazole structure, preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0028] Embodiment 1: Synthesis of palladium complex and its catalytic synthesis of α-methylene-γ-butyrolactone compound C 17 h 14 o 2 Applications

[0029] At -78°C, n-BuLi in n-hexane (1.00 mL, 1.6 mmol) was slowly added dropwise to the ortho-carborane o-C 2 B 10 h 12 (92.0mg, 0.64mmol) in tetrahydrofuran solution, stirred at this temperature for 30 minutes, slowly rose to room temperature and continued to react for 1 hour, then added bromobenzimidazole (126.7mg, 0.64mmol), and continued to react at room temperature for 6 Hour. Then PdCl 2 (113.3 mg, 0.64 mmol) was added to the reaction system for an additional 3 hours. After the reaction is over, let it stand and filter, and dry the solvent under reduced pressure. The obtained crude product is separated by column chromatography (volume ratio of petroleum ether / tetrahydrofuran=6:1), and the brown target product containing ortho-carboryl benzo The palladium complex (254.4mg, yield 75%) of imidazole structure, reaction ...

Embodiment 2

[0036] Embodiment 2: Catalytic synthesis of α-methylene-γ-butyrolactone compound C in the palladium complex 18 h 16 o 2 Applications

[0037] Using the palladium complex prepared in Example 1 as a catalyst, palladium complex (0.0015mmol, 2.7mg), phenylacetylene (1mmol, 102mg), formic acid (1mmol, 46mg) and 4-methylstyrene (1mmol, 118mg) Dissolve in 5mL toluene, react at room temperature for 60 minutes, concentrate the reaction solution after completion, separate directly through silica gel column chromatography, dry until the mass remains unchanged, and obtain the corresponding product C 18 h 16 o 2 (productive rate 86%), reaction formula is:

[0038]

[0039] 1 H NMR (400MHz, CDCl 3 ):δ=7.55~7.49(m,2H),7.47~7.41(m,3H),7.26~7.18(m,4H),5.71(s,1H),5.39(t,J=7.2Hz,1H), 3.44 (dd, J = 16.4, 7.2Hz, 1H), 3.07 (dd, J = 16.4, 6.8Hz, 1H), 2.37 (s, 3H), elemental analysis: C 81.79, H 6.10 (theoretical); C 81.69, H 6.02 (actual).

Embodiment 3

[0040] Embodiment 3: Catalytic synthesis of α-methylene-γ-butyrolactone compound C in the palladium complex 18 h 16 o 3 Applications

[0041]Using the palladium complex prepared in Example 1 as a catalyst, palladium complex (0.002mmol, 3.6mg), phenylacetylene (1mmol, 102mg), formic acid (1mmol, 46mg) and 4-methoxystyrene (1mmol, 134mg ) was dissolved in 5mL toluene (toluene), and reacted at room temperature for 240 minutes. After the end, the concentrated reaction solution was directly separated by silica gel column chromatography, dried to the same quality, and the corresponding product C was obtained. 18 h 16 o 3 (productive rate 95%), reaction formula is:

[0042]

[0043] 1 H NMR (400MHz, CDCl 3 ):δ=7.56~7.49(m,2H),7.48~7.41(m,3H),7.25(d,J=8.0Hz,2H),6.92(d,J=8.0Hz,2H),5.70(s, 1H), 5.36(t, J=7.2Hz, 1H), 3.82(s, 3H), 3.41(dd, J=16.4, 7.2Hz, 1H), 3.08(dd, J=16.4, 7.2Hz, 1H), Elemental analysis: C 77.12, H 5.75 (theoretical); C 77.17, H 5.78 (actual).

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Abstract

The invention relates to a palladium complex containing an ortho-position carborane based benzimidazole structure, a preparation method and application thereof. The palladium complex is prepared by the following method of: dropwise adding an n-BuLi solution into a carborane solution and carrying out stirring reaction, then adding bromo-benzimidazole for continuous reaction, then adding PdCl2 intoa reaction system for continuous reaction, performing separation at the end of the reaction to obtain a palladium complex containing an ortho-position carborane based benzimidazole structure, and applying the complex to catalyzing the reaction of alkyne, carboxylic acid and olefin to prepare the alpha-methylene-gamma-butyrolactone compounds by a one-pot method. Compared with the prior art, the palladium complex disclosed by the invention is high in catalytic efficiency, and the lactone compound can be synthesized by utilizing simple and cheap raw materials under mild conditions.

Description

technical field [0001] The invention relates to the field of complex synthesis, in particular to a palladium complex containing an ortho carboryl benzimidazole structure and a preparation method and application thereof. Background technique [0002] α-methylene-γ-butyrolactone is a very important structural unit that widely exists in many natural products, bioactive molecules and drug molecules. Derivatives containing this structural skeleton have anti-tumor, anti-cytotoxicity, Antibacterial and other physiological and pharmacological activities. Therefore, the synthesis of α-methylene-γ-butyrolactone is favored by those skilled in the art. [0003] At present, the transition metal-catalyzed cyclization reaction of intramolecular enynes is the most commonly used and effective method to construct this structural skeleton. A series of functionalized α-methylene-γ-butyrolactone derivatives can also be constructed through the Rh-catalyzed cyclization reaction of 1,6-enynes, an...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F15/00B01J31/22C07D307/58
CPCC07F15/006B01J31/183C07D307/58B01J2231/328B01J2531/824Y02P20/584
Inventor 姚子健邓维高永红
Owner SHANGHAI INST OF TECH
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