Catalytic carbonylation method for synthesis of alpha-keto amide

A technology of ketamides and compounds, which is applied in the field of catalytic carbonylation to synthesize α-ketoamides, can solve the problems of insufficient application range, increased production costs, and strict reaction conditions, and achieve easy operation, stable reaction raw materials, and selectivity high effect

Inactive Publication Date: 2015-09-09
NANJING NORMAL UNIVERSITY
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  • Description
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  • Application Information

AI Technical Summary

Problems solved by technology

However, the introduction of ligands causes difficulties in the post-processing of the reaction, and also increases the production cost
Moreover, the reaction conditions of this type of method are strict, and the reaction generally needs to be carried out smoothly under a relatively large pressure (> 2MPa), and the temperature needs to be higher than 80 ° C.
In addition, such methods are only suitable for secondary amines, and the application range of the method is not wide enough
Compared with the reaction that can take place under high pressure, although there are constantly double carbonylation reactions under normal pressure being reported (V.dela Fuente, C.Godard, E.Zangrando, C.Claver and S.Castillón, Chem .Commun., 2012, 48, 1695-1697; Nozomi Saito, Takahisa Taniguchi, Naoyuki Hoshiya, Satoshi Shuto, Mitsuhiro Arisawa, and Yoshihiro Sato., Green Chem.2015, 17, 2358-2361), but these research protocols all require Only by adding special additives can the reaction proceed smoothly

Method used

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  • Catalytic carbonylation method for synthesis of alpha-keto amide
  • Catalytic carbonylation method for synthesis of alpha-keto amide
  • Catalytic carbonylation method for synthesis of alpha-keto amide

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0028]

[0029]Add palladium acetate (0.01mmol), 1-chloro-4-iodobenzene (0.5mmol), morpholine (0.5mmol), sodium carbonate (1.0mmol) and polyethylene glycol-400 (2.0g) to the 25mL reaction flask in sequence , and introduce one atmosphere of carbon monoxide. The mixture was stirred and reacted at room temperature for 6 hours, 15 mL of saturated brine was added, and extracted three times with ethyl acetate. Finally, the organic solvent was distilled off under reduced pressure and separated by column chromatography to obtain a white solid product with a yield of 80%.

[0030] 1 H NMR (400MHz, CDCl 3 ): δ7.89(d, J=8.0Hz, 2H), 7.48(d, J=8Hz, 2H), 3.79-3.73(m, 4H), 3.64(t, J=4Hz, 2H), 3.36ppm ( t, J = 4Hz, 2H); 13 C NMR (100MHz, CDCl 3 ): δ189.7, 164.9, 141.6, 131.5, 131.1, 129.5, 66.7, 66.6, 46.3, 41.7ppm; mp: 116.0-116.5°C.

Embodiment 2

[0032]

[0033] Add palladium acetate (0.01mmol), 1-methyl-2-iodobenzene (0.5mmol), morpholine (0.5mmol), sodium carbonate (1.0mmol) and polyethylene glycol-400 (2.0g ), and introduce one atmosphere of carbon monoxide. The mixture was stirred and reacted at room temperature for 9 hours, 15 mL of saturated brine was added, and extracted three times with ethyl acetate. Finally, the organic solvent was distilled off under reduced pressure and separated by column chromatography to obtain a yellow solid product with a yield of 93%.

[0034] 1 H NMR (400MHz, CDCl 3 ): δ7.70(d, J=8Hz, 1H), 7.47(td, J=8, 1.2Hz, 1H), 7.33-7.28(m, 2H), 3.78-3.74(m, 4H), 3.65(t , J=8Hz, 2H), 3.37(t, J=8Hz, 2H), 2.64ppm(s, 3H); 13 C NMR (100MHz, CDCl 3 ): δ193.1, 166.2, 141.6, 133.9, 132.7, 132.7, 131.5, 126.2, 66.7, 66.6, 46.3, 41.6, 21.8ppm.

Embodiment 3

[0036]

[0037] Add palladium acetate (0.01mmol), 1,3-dimethyl-5-iodobenzene (0.5mmol), morpholine (0.5mmol), sodium carbonate (1.0mmol) and polyethylene glycol-400 successively into 25mL reaction flask (2.0g), and introduce one atmosphere of carbon monoxide. The mixture was stirred and reacted at room temperature for 9 hours, 15 mL of saturated brine was added, and extracted three times with ethyl acetate. Finally, the organic solvent was distilled off under reduced pressure and separated by column chromatography to obtain a white solid product with a yield of 84%.

[0038] 1 H NMR (400MHz, CDCl 3 ): δ7.53(s, 2H), 7.26(s, 1H), 3.79-3.74(m, 4H), 3.63(t, J=4.8Hz, 2H), 3.34(t, J=4.8Hz, 2H) , 2.35ppm (d, J=0.5Hz, 6H). 13 C NMR (100MHz, CDCl 3 ): δ191.6, 165.7, 138.9, 136.8, 133.1, 127.3, 66.7, 66.7, 46.2, 41.6, 21.1ppm. HRMS (ESI) calcd for C 14 h 17 NO 3 [M+Na] m / z 270.110065, found m / z 270.111397; IR: ν max (KBr)=3458, 2965, 2921, 2893, 2850, 1755, 1675, 1653, 1592,...

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Abstract

The invention discloses a catalytic carbonylation method for synthesis of alpha-keto amide. A palladium source in an aqueous solution of polyethylene glycol or polyethylene glycol is used for in-situ formation of a highly active palladium nano-catalyst; and the palladium nano-catalyst can efficiently catalyze bis-carbonylation reaction of aryl halide and aliphatic amine for one-step synthesis of an alpha-keto amide compound by using carbon monoxide as a dicarbonyl source in the presence of alkali or without alkali, and does not require ligand. The synthesis method of alpha-keto amide uses the palladium nano-catalyst formed in situ, the reaction does not require ligand promotion and can achieve conversion with high efficiency and high selectivity; the substrate is stable, cheap and readily available, has good universality of functional groups; and the operation is safe and simple.

Description

technical field [0001] The present invention relates to a method for α-ketoamide compounds, in particular to a method for catalyzing carbonylation to synthesize α-ketoamide compounds. The method directly uses palladium nanoparticles formed in situ as a catalyst without ligands , to efficiently catalyze the preparation of α-ketoamides from double carbonylation of aromatic halides and aliphatic amines. Background technique [0002] The α-ketoamide skeleton structure widely exists in natural products and medicines, and is an important structure in some medicines; at the same time, it is also an important raw material for the synthesis of some heterocyclic compounds; its synthesis method has attracted widespread attention and has achieved certain results. Progress. Since 1982 Yamamoto (F.Ozawa, H.Soyama, T.Yamamoto, A.Yamamoto, Tetrahedron Lett., 1982, 23, 3383-3386) and Tanaka (T.Kobayashi and M.Tanaka, J.Organomet.Chem. , 1982, 233, C64-C66) created a palladium-catalyzed dou...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D295/185C07D333/24C07D261/08C07D211/58C07C231/10C07C235/80C07D213/40C07D209/18C07H15/26C07H1/00C07D295/108
CPCC07C231/10C07D209/18C07D211/58C07D213/40C07D261/08C07D295/108C07D295/185C07D333/24C07H1/00C07H15/26C07C235/80
Inventor 韩维杜宏艳阮晴
Owner NANJING NORMAL UNIVERSITY
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