n,n-Coordinated Palladium Complex Containing Meta-Carborane Ligand and Its Preparation and Application

A technology of meta-carborane and palladium complexes, applied in the field of synthetic chemistry, can solve the problems of using toxic reagents, small adaptability of substrates, unfriendly reaction conditions, etc., and achieves easy separation, cheap and low toxicity separation, high catalysis active effect

Active Publication Date: 2021-05-11
SHANGHAI INST OF TECH
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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 Containing Meta-Carborane Ligand and Its Preparation and Application
  • n,n-Coordinated Palladium Complex Containing Meta-Carborane Ligand and Its Preparation and Application
  • n,n-Coordinated Palladium Complex Containing Meta-Carborane Ligand and Its Preparation and Application

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 present invention relates to N,N-coordinated palladium complexes containing meta-carborane ligands and preparation and application thereof. The preparation method of palladium complexes comprises the following steps: 1) adding n-BuLi solution to meta-carbon In the borane solution, react at room temperature for 30-60min; 2) add 3-chloromethylpyridine, and react at room temperature for 3-5h; 3) add PdCl 2 , and reacted at room temperature for 2-5 h, and the palladium complex is obtained after post-treatment; the palladium complex is used to catalyze the arylamine formylation reaction to prepare the arylamine carboxamide compounds. Compared with the prior art, the synthesis process of the palladium complex in the present invention is simple and green, and has excellent selectivity and high yield; the palladium complex has the characteristics of stable physical and chemical properties, thermal stability, etc. It exhibits excellent catalytic activity in the acylation 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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Patent Type & Authority Patents(China)
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 INST OF TECH
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