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Application of palladium complex to fatty amine formylation reaction

The technology of fatty amine formyl and fatty amine formamide is applied in the application field of palladium complexes in fatty amine formylation reaction, and can solve the problems of mild reaction conditions, small adaptability of substrates, use of toxic reagents, and the like, Achieve the effect of easy separation, cheap and low toxicity separation, and high yield

Active Publication Date: 2019-10-25
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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  • Application of palladium complex to fatty amine formylation reaction
  • Application of palladium complex to fatty amine formylation reaction
  • Application of palladium complex to fatty amine formylation reaction

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 complex catalyzed ethyl carbamylation reaction:

[0039]

[0040] The palladium complex Pd prepared in Example 1 was used as a catalyst to catalyze the formyl reaction of ethylamine: ethylamine (1mmol, 45mg) and divalent palladium complex Pd (0.01mmol, 5.0mg) were dissolved in 4mL of DMF, at 60 The reaction was carried out at ℃ for 10 hours. After the end, the concentrated reaction solution was directly separated by silica gel column chromatography, and dried until the mass remained unchanged to obtain the corresponding product C 3 h 7 NO (90% yield), 1 H NMR (400MHz, CDCl 3 , 25°C): δ=9.93 (s, 1H), 4.56 (s, 1H), 3.32-3.21 (m, 2H), 1.65 (t, J=7.5Hz, 3H). Elemental analysis: C 49.30, H9.65, N 19.16 (theoretical); C 49.33, H 9.68, N 19.19 (actual).

Embodiment 3

[0042] Palladium complexes catalyze the formylation of n-propylcarbamate:

[0043]

[0044]The palladium complex Pd prepared in Example 1 was used as a catalyst to catalyze the formyl reaction of n-propylamine: n-propylamine (1mmol, 59mg) and divalent palladium complex Pd (0.002mmol, 1.0mg) were dissolved in 4mL DMF, at 100 The reaction was carried out at ℃ for 8 hours, and after the end, the concentrated reaction solution was directly separated by silica gel column chromatography, dried until the mass remained constant, and the corresponding product C was obtained. 4 h 9 NO (96% yield), 1 H NMR (400MHz, CDCl 3 ,25℃):δ=9.95(s,1H),4.59(s,1H),3.36-3.25(m,2H),1.65-1.60(m,2H),1.09(t,J=7.2Hz,3H) . Elemental analysis: C 55.15, H 10.41, N 16.08 (theoretical); C 55.11, H 10.48, N 16.04 (actual).

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Abstract

The invention relates to application of a palladium complex to a fatty amine formylation reaction. A N,N-coordinated palladium complex containing a meta-carbobane ligand is used as a catalyst, N,N-dimethyl formamide is used as a formylating reagent and a solvent to catalyze the fatty amine formylation reaction to prepare a fatty amine carboxamide compound. Compared with the prior art, the N,N-coordinated divalent palladium complex containing the metacarbanyl ligand in the application is high in catalytic activity under mild conditions and can catalyze the formylation reaction of a fatty amine.DMF is further used as a formylating reagent and a solvent, and is inexpensive, low in toxicity, easy to separate and high in yield (88-96%).

Description

technical field [0001] The invention belongs to the technical field of synthetic chemistry and relates to the application of a palladium complex in fatty carbamylation reaction. 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 chloral, ammonium formate, formate ester, etc. ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/18C07F15/00C07C231/08C07C233/03
CPCB01J31/1815C07F15/0066C07C231/08B01J2531/824B01J2531/0213C07C233/03
Inventor 姚子健吕文瑞李荣建高永红邓维
Owner SHANGHAI INST OF TECH
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