N-arylating method using pyrrole-2-hydrazide compound as ligand in aqueous phase system

A technology of hydrazides and compounds, applied in the field of chemistry, can solve problems such as long reaction time and narrow substrate adaptability, and achieve the effects of simple operation, high yield and wide application range of substrates

Active Publication Date: 2010-07-14
SUN YAT SEN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Aqueous copper-catalyzed C-N coupling reactions have also received increasing attention (Pellón, R.F.; Estévez-Braun, A. Docampo, M.L.; Martín, A.; Ravelo, A.G. Synlett 2005, 1606; Lu, Z.; Twieg , R.J.Tetrahedron Lett.2005, 46, 2997), but there are also disadvantages such as narrow substrate adaptability, need for inert gas protection, and long reaction time, which limit its popularization and use

Method used

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  • N-arylating method using pyrrole-2-hydrazide compound as ligand in aqueous phase system
  • N-arylating method using pyrrole-2-hydrazide compound as ligand in aqueous phase system
  • N-arylating method using pyrrole-2-hydrazide compound as ligand in aqueous phase system

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0026] Embodiment 1: the synthesis of N-p-methoxyphenylaniline

[0027]

[0028] 9.5mg (0.05mmol) CuI, 50mg (0.25mmol) ligand, 187mg (1.0mmol) p-methoxybromobenzene, 372mg (4.0mmol) aniline, 112mg (2.0mmol) KOH, 161mg (0.5mmol) TBAB, 2.0mlH 2 O was added into a 10ml microwave reaction tube and reacted at 130°C (100W) for 5 minutes. After the reaction stopped, add 10ml of water, extract with ethyl acetate (3×20ml), combine the organic phases, wash with saturated brine, dry over anhydrous sodium sulfate, filter, distill off the solvent under reduced pressure, and pass the obtained reaction mixture through a silica gel column Separation and purification by column chromatography [eluent: petroleum ether / ethyl acetate (20:1)] gave 156 mg of N-p-methoxyphenylaniline with a yield of 78%.

[0029] N-p-methoxyphenylaniline: 1 H NMR (300MHz, CDCl 3 ): δ7.20-7.25(m, 2H), 7.08(d, J=7.8Hz, 2H), 6.82-6.93(m, 5H), 5.49(br s, 1H), 3.82(s, 3H). 13 C NMR (75MHz, CDCl 3 ): δ155.0, 144.9...

Embodiment 2

[0031] Embodiment 2: the synthesis of 4-methoxy-N-p-methylaniline

[0032]

[0033] 4.0mg (0.05mmol) CuO, 31mg (0.25mmol) ligand, 187mg (1.0mmol) p-methoxybromobenzene, 428mg (4.0mmol) p-methylaniline, 112mg (2.0mmol) KOH, 161mg (0.5mmol) )TBAB, 2.0ml H 2 O was added into a 10ml microwave reaction tube and reacted at 130°C (100W) for 5 minutes. After the reaction stopped, add 10ml of water, extract with ethyl acetate (3×20ml), combine the organic phases, wash with saturated brine, dry over anhydrous sodium sulfate, filter, distill off the solvent under reduced pressure, and pass the obtained reaction mixture through a silica gel column Separation and purification by column chromatography [eluent: petroleum ether / ethyl acetate (20:1)] gave 119 mg of 4-methoxy-N-p-methylaniline with a yield of 56%.

[0034] 4-Methoxy-N-p-methylaniline: 1 H NMR (300MHz, CDCl 3 ): δ7.05(m, 4H), 6.86(m, 4H), 5.41(brs, 1H), 3.81(s, 3H), 2.31(s, 3H). 13 C NMR (75MHz, CDCl 3 ): δ154.5, 142.2,...

Embodiment 3

[0036] Embodiment 3: the synthesis of N-benzylaniline

[0037]

[0038] 95mg (0.5mmol) CuI, 35mg (0.25mmol) ligand, 157mg (1.0mmol) bromobenzene, 214mg (2.0mmol) benzylamine, 80mg (2.0mmol) NaOH, 161mg (0.5mmol) TBAB, 2.0ml H 2 O was added into a 10ml microwave reaction tube and reacted at 130°C (100W) for 5 minutes. After the reaction stopped, add 10ml of water, extract with ethyl acetate (3×20ml), combine the organic phases, wash with saturated brine, dry over anhydrous sodium sulfate, filter, distill off the solvent under reduced pressure, and pass the obtained reaction mixture through a silica gel column Separation and purification by column chromatography [eluent: petroleum ether / ethyl acetate (20:1)] gave 119 mg of N-benzylaniline with a yield of 65%.

[0039] N-Benzylaniline: 1 H NMR (300MHz, CDCl 3 ): δ7.17-7.41(m, 7H), 6.65-6.77(m, 3H), 4.36(s, 2H), 4.06(br s, 1H). 13 C NMR (75MHz, CDCl 3 ): δ147.9, 139.3, 129.1, 128.4, 127.3, 127.0, 117.4, 112.7, 48.2. ESI-MS...

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Abstract

The invention provides an N-arylating method with convenience, mild reaction condition, friendly environment and economical process in an aqueous phase system. An aryl bromide or iodide and amine are used as raw materials, water is used as a solvent, metallic copper or a copper oxide or cuprous salt or cupric salt is used as a catalyst, and a pyrrole-2-hydrazide compound is used as a ligand to produce a C-N coupled reaction; the N-arylating method comprises the following reaction processes: adding the catalyst, the ligand, an aryl halide, the amine, a surfactant and the water into a microwavereactor or a reaction vessel, and carrying out a stirring reaction by adopting a microwave auxiliary heating or ordinary heat bath heating mode; after the reaction is finished, separating a reaction mixed liquid and purifying to obtain an N-arylating product. The method of the invention has the characteristics of simple operation, wide application range of substrates, simple and easy separation of products, high yield, economical process, friendly environment and the like. The water is used as a reaction solvent, the substrates have wide application ranges, and the N-arylating method has broad application prospect in the aspect of preparing natural products, medicaments and pesticides.

Description

technical field [0001] The invention relates to the technical field of chemistry, in particular to an N-arylation method. technical background [0002] Arylamines are an important class of compounds that widely exist in natural and non-natural products with physiological activities. The study of C-N bond formation reactions has been widely valued. [0003] The Ullmann reaction is currently one of the most effective methods for constructing C-N bonds in organic synthetic chemistry, and has a wide range of applications in industry. The early Ullmann reaction required relatively harsh conditions, such as high temperature, strong base, equivalent copper catalyst and long reaction time, and the yield was not high, and toxic polar solvents were often used, which limited its large-scale application. . In recent years, the use of palladium catalysts has enabled this reaction to be carried out under relatively mild conditions (Hartwig, J.F.Synlett2006,1283; Hartwig, J.F.Acc.Chem.Re...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07B43/04B01J31/30B01J31/28B01J31/22C07C213/02C07C217/92C07C217/84C07C209/10C07C211/48C07C211/52C07D295/096C07C221/00C07C225/22C07D317/66
Inventor 万一千谢建伟朱新海孟飞黄漫娜
Owner SUN YAT SEN UNIV
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