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N-arylation process with hydrazone as ligand in aqueous phase system

A technology of arylation and ligands, which is applied in chemical instruments and methods, preparation of amino compounds, organic chemistry, etc., can solve the problems that cannot be popularized and used, and achieve the effects of improving environmental friendliness, low temperature, and broad application prospects

Inactive Publication Date: 2006-07-19
SUN YAT SEN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the above-mentioned reactions can only be carried out for specific compounds, so they cannot be widely used.

Method used

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  • N-arylation process with hydrazone as ligand in aqueous phase system
  • N-arylation process with hydrazone as ligand in aqueous phase system
  • N-arylation process with hydrazone as ligand in aqueous phase system

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0026] Embodiment 1: the synthesis of N-phenylbenzylamine

[0027]

[0028] 8mg (0.1mmol) CuO, 55mg (0.2mmol) dicyclohexanone oxalyldihydrazone, 102mg (0.5mmol) iodobenzene, 160mg (1.5mmol) benzylamine, 56mg (1.0mmol) KOH, 8.1mg (0.025mmol) TBAB, 1.5ml H 2 O was added to an 8ml microwave reaction tube, and reacted at 100W and 130°C for 2min. After the reaction stopped, it was extracted with ethyl acetate, washed with water, washed with saturated brine, dried over anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure, separated and purified by silica gel column chromatography [eluent: petroleum ether / ethyl acetate ( 50:1)] to obtain 82 mg of N-phenylbenzylamine, with a yield of 90%.

[0029] MS (ESI source, m / z): 184 (M + +1); 1 H NMR (CDCl 3 , 300MHz) δ7.32(dd, J=7.2, 6.6Hz, 4H), 7.24-7.26(m, 1H), 7.15(t, J=7.8, 2H), 6.69(t, J=7.2Hz, 1H) , 6.61 (d, J=7.8, 2H), 4.31 (s, 2H), 3.97 (brs, 1H).

Embodiment 2

[0030] Embodiment 2: the synthesis of N-p-nitrophenylbenzylamine

[0031]

[0032] 37mg (0.25mmol) FeSO 4, 70mg (0.25mmol) dicyclohexanone oxalyldihydrazone, 102mg (0.5mmol) p-nitrobromobenzene, 54mg (0.5mmol) benzylamine, 228mg (1.5mmol) CsF, 68mg (0.25mmol) SDS-Na, 1.5 m H 2 O was added to an 8ml microwave reaction tube and reacted at 100W at 80°C for 10min. After the reaction stopped, it was extracted with ethyl acetate, washed with water, washed with saturated brine, dried over anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure, separated and purified by silica gel column chromatography [eluent: petroleum ether / ethyl acetate ( 5:1)] to obtain 51 mg of N-p-nitrophenylbenzylamine with a yield of 45%.

[0033] MS (ESI source, m / z): 229 (M + +1); 1 H NMR (CDCl 3 , 300MHz) δ8.07(d, J=9Hz, 2H), 7.31-7.39(m, 5H), 6.56(d, J=9Hz, 2H), 4.85(brs, 1H), 4.42(s, 2H).

Embodiment 3

[0034] Embodiment 3: the synthesis of N-p-methoxyphenylbenzylamine

[0035]

[0036] 13mg (0.05mmol) CuSO 4 .5H 2 O, 20mg (0.1mmol) diacetonyl oxalyldihydrazone, 94mg (0.5mmol) p-methoxybromobenzene, 214mg (2.0mmol) benzylamine, 69mg (0.5mmol) K 2 CO 3 , 161mg (0.5mmol) TBAB, 1.5ml H 2 O was added to an 8ml microwave reaction tube, and reacted at 100W and 130°C for 5min. After the reaction stopped, it was extracted with ethyl acetate, washed with water, washed with saturated brine, dried over anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure, separated and purified by silica gel column chromatography [eluent: petroleum ether / ethyl acetate ( 30:1)] to obtain 98 mg of N-p-methoxyphenylbenzylamine with a yield of 92%.

[0037] MS (ESI source, m / z): 214 (M + +1); 1 H NMR (CDCl 3 , 300MHz) δ7.27-7.37 (m, 5H), 6.74-6.78 (m, 2H), 6.60-6.64 (m, 2H), 4.28 (s, 2H), 3.73 (s, 3H).

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Abstract

The provided N-arylation method in water phase system for C-N coupling reaction comprises: using aryl halide and amine or nitrogen-contained heteroaromatic compound as material and water as solvent, heating traditionally or with microwave; using the carbonate, fluoride, phosphate and hydrate of alkali metal or alkali earth metal as base; with transient metal catalysis, adding surfactant to promote the C-N coupling reaction with acylated hydrazone compound as ligand. This invention just needs mild reaction condition, and has wide application.

Description

technical field [0001] The invention relates to the field of chemical engineering, in particular to a method for N-arylation reaction. technical background [0002] Arylamines are an important class of compounds that widely exist in natural and non-natural products with physiological activities. The research on the C-N bond formation reaction has attracted widespread attention. [0003] The Ullmann reaction of carbon-nitrogen cross-coupling has a long history since it was first reported in 1903 (Ley, S.V.; Thomas, A.W. Angew. Chem. Int. Ed. 2003, 42, 5400 and related citations). Since this reaction is usually carried out in a polar solution with a high boiling point, under the condition of a high temperature, a catalytic amount or an equivalent amount of copper powder as a catalyst, there are long reaction times, difficult subsequent processing of the reaction, and complex reaction products. The disadvantages such as low reaction yield. In 1983, Migita et al. first discove...

Claims

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Application Information

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IPC IPC(8): C07C209/10C07C211/48C07D207/00C07D213/00C07D223/02
Inventor 万一千朱新海马彦陈功宋化灿苏丽
Owner SUN YAT SEN UNIV
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