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N,N-coordinated palladium complex with meta-carborane ligand and preparation and application of palladium complex

A technology of m-carborane and palladium complexes, applied in the field of synthetic chemistry, can solve problems such as mild reaction conditions, small substrate adaptability, use of toxic reagents, etc., and achieve easy separation, low-cost, low-toxicity separation, and high yield Effect

Active Publication Date: 2019-10-25
SHANGHAI APPLIED TECHNOLOGIES COLLEGE
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, many of these methods have disadvantages such as the use of toxic reagents, mild reaction conditions, and limited scope of substrate adaptation.

Method used

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  • N,N-coordinated palladium complex with meta-carborane ligand and preparation and application of palladium complex
  • N,N-coordinated palladium complex with meta-carborane ligand and preparation and application of palladium complex
  • N,N-coordinated palladium complex with meta-carborane ligand and preparation and application of palladium complex

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0032] Synthesis of N,N-coordinated divalent palladium complexes Pd containing m-carborane ligands:

[0033]

[0034] At -78°C, n-BuLi (1.6M) in n-hexane (1.00 mL, 1.6 mmol) was slowly added dropwise to m-C containing ortho carborane 2 B 10 h 10 (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 3-chloromethylpyridine (162.3mg, 1.28mmol), continued to react at room temperature 5 hours. Then PdCl 2 (112.0 mg, 0.64 mmol) was added to the reaction system for an additional 2 hours. After the reaction is over, let it sit and filter, and dry the solvent under reduced pressure. The obtained crude product is separated by column chromatography (petroleum ether / ethyl acetate=8:1), and the brown target product palladium complex Pd (231.8 mg, produced rate of 72%).

[0035] 1 H NMR (400MHz, CDCl 3 ,25℃):δ=7.89(d,J=7.0Hz,2H),7.58(s,2H),7.42(d,J=6.5Hz,2H),7.30(t,...

Embodiment 2

[0038] Palladium complexes catalyze the formylation of anilines:

[0039]

[0040] The palladium complex Pd prepared in Example 1 was used as a catalyst to catalyze the formylation of aniline: aniline (1mmol, 93mg) and divalent palladium complex Pd (0.01mmol, 5.0mg) were dissolved in 4mL DMF, at 60°C The reaction was carried out for 6 hours. After the end, the concentrated reaction solution was directly separated by silica gel column chromatography, and dried until the quality remained unchanged to obtain the corresponding product C 7 h 7 NO (92% yield), 1 H NMR (400MHz, CDCl 3 , 25°C): δ=9.82(s, 1H), 7.76(d, J=7.2Hz, 2H), 7.60-752(m, 3H), 6.52(s, 1H). Elemental analysis: C 69.41, H 5.82, N 11.56 (theoretical); C 69.51, H 5.88, N 11.49 (actual).

Embodiment 3

[0042] Palladium complexes catalyze the formylation of 4-methylanilide:

[0043]

[0044] The palladium complex Pd prepared in Example 1 was used as a catalyst to catalyze the formyl reaction of 4-methylaniline: 4-methylaniline (1mmol, 107mg) and divalent palladium complex Pd (0.002mmol, 1.0mg) were dissolved In 4mL DMF, react at 90°C for 8 hours. After the end, the concentrated reaction solution is directly separated by silica gel column chromatography, dried until the mass remains constant, and the corresponding product C is obtained. 8h 9 NO (82% yield), 1 H NMR (400MHz, CDCl 3 ,25℃):δ=9.85(s,1H),7.79(d,J=7.2Hz,2H),7.52(d,J=7.2Hz,2H),6.57(s,1H),2.23(s,3H ). Elemental analysis: C 71.09, H 6.71, N 10.36 (theoretical); C71.01, H 6.78, N 10.40 (actual).

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Abstract

The invention relates to an N,N-coordinated palladium complex with a meta-carborane ligand and preparation and application of the palladium complex. A preparation method of the palladium complex comprises the following steps that (1) an n-BuLi solution is added into a meta-carborane solution and then a reaction is performed at a room temperature for 30-60 min; (2) 3-chloromethylpyridine is added and reacts at the room temperature for 3-5 h; (3) PdCl2 is added and reacts at the room temperature for 2-5 h, and the palladium complex is obtained through post-treatment; and the palladium complex isused for catalyzing an arylamine formylation reaction to prepare an arylamine formamide compound. Compared with the prior art, the synthesis process of the palladium complex is simple and green, andhas excellent selectivity and a high yield; and the palladium complex has the characteristics such as stable physicochemical properties and thermal stability, and exhibits excellent catalytic activityin the arylamine formylation reaction.

Description

technical field [0001] The invention belongs to the technical field of synthetic chemistry and relates to an N,N-coordinated divalent palladium complex containing meta-carborane ligands and its preparation and application. Background technique [0002] Formamide widely exists in natural products and is often used as a pharmacodynamic functional group of drugs, and most of its derivatives have significant biological activity. In organic synthesis reactions, formyl is one of the most effective protecting groups for amino groups in amine compounds, and the formed formamide is also an important precursor for the synthesis of isocyanates and formamidines. In addition, formamide can also be used as a Lewis base catalyst to catalyze alkylation and hydrosilylation reactions. As early as the 1950s, Fieser et al. successfully used formic acid as a raw material to realize the formylation of aniline. Subsequently, various formylating reagents were reported correspondingly, such as chl...

Claims

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Application Information

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IPC IPC(8): C07F15/00B01J31/18C07C231/08C07C233/03C07C233/25C07C233/15
CPCB01J31/1815B01J2531/0213B01J2531/824C07C231/08C07F15/0066C07C233/03C07C233/25C07C233/15
Inventor 姚子健李荣建吕文瑞高永红邓维
Owner SHANGHAI APPLIED TECHNOLOGIES COLLEGE
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