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Ligand-free and non-solvent synthesis method for preparing secondary amine under catalysis of ruthenium trichloride

A ruthenium trichloride-catalyzed, synthetic method technology, applied in the field of catalytic chemistry, can solve environmental hazards and other problems, and achieve the effect of avoiding the use of phosphine-containing ligands and organic solvents

Inactive Publication Date: 2016-04-27
SUZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0002]Secondary amine compounds are widely used in medicine, pesticide and other industries. The main synthesis methods include alkylation of halogenated aromatic hydrocarbons and amines, ketones or Reductive amination of aldehydes and hydroamination of unsaturated hydrocarbons and amines, etc., but these synthesis methods often require the use of environmentally harmful organic solvents, halogenated hydrocarbons, and reducing agents
However, so far, there are few reports in the literature on the use of glycerol as a hydrogen source to reduce nitro compounds to prepare N-substituted amino compounds.
Among them, Shi Feng's research group at Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences once used RuCl3 and triphenylphosphine (PPh3) as the catalytic system, and trifluorotoluene (CF3 -Ph) as a solvent to catalyze the reaction of nitro compounds, alcohols and glycerol to obtain secondary and tertiary amines respectively (see X.J.Cui, Y.Q.Deng, F.Shi, ACSCatal., 2013,3(5):808;), but this method also uses toxic phosphine-containing ligands and organic solvents

Method used

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  • Ligand-free and non-solvent synthesis method for preparing secondary amine under catalysis of ruthenium trichloride
  • Ligand-free and non-solvent synthesis method for preparing secondary amine under catalysis of ruthenium trichloride
  • Ligand-free and non-solvent synthesis method for preparing secondary amine under catalysis of ruthenium trichloride

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025] Example 1: RuCl 3 The catalytic system catalyzes the reaction of nitrobenzene and benzyl alcohol.

[0026]

[0027] Nitrobenzene (1mmol), benzyl alcohol (1.5mmol), K 2 CO 3 (1 mmol), RuCl 3 (3mol%) and glycerol (10mmol) were added to a dry reaction tube with a magnetic stirrer, and then the reaction tube was washed with N 2 Replaced 3 times, stirred and reacted at 130°C for 24h. After the reaction, the solution was cooled to room temperature, 5 mL of water was added, and then extracted with 3×5 mL of chloroform, the organic phase was combined, and the organic phase was dried with anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by rotary evaporation and separated by silica gel column chromatography. , to obtain the target product (yield 80%).

[0028] 1 H-NMR (400MHz, DMSO- d 6 ):δ4.26(d, J =4.0Hz,2H),6.22(t, J =8.0Hz,1H),6.50(t, J =8.0Hz,1H),6.57(d, J =8.0Hz,2H),7.03(t, J =8.0Hz,2H),7.22(t, J =8.0Hz,1H),7.31(t, J =8.0Hz,2H),7.3...

Embodiment 2

[0030] Example 2: RuCl 3 The catalytic system catalyzes the reaction of nitrobenzene and p-methylbenzyl alcohol.

[0031] Nitrobenzene (1mmol), p-methylbenzyl alcohol (1.5mmol), K 2 CO 3 (1 mmol), RuCl 3 (3mol%) and glycerol (10mmol) were added to a dry reaction tube with a magnetic stirrer, and then the reaction tube was washed with N 2 Replaced 3 times, stirred and reacted at 130°C for 24h. After the reaction, the solution was cooled to room temperature, 5 mL of water was added, and then extracted with 3×5 mL of chloroform, the organic phase was combined, and the organic phase was dried with anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by rotary evaporation and separated by silica gel column chromatography. , to obtain the target product (yield 84%, the structural formula is shown below).

[0032]

[0033] 1 H-NMR (400MHz, DMSO- d 6 ):δ2.27(s,3H),4.20(d, J =8.0Hz,2H),6.15(t, J =8.0Hz,1H),6.50(t, J =8.0Hz,1H),6.55(d, J =8.0Hz,2H),7.02(...

Embodiment 3

[0035] Example 3: RuCl 3 The catalytic system catalyzes the reaction of nitrobenzene and p-methoxybenzyl alcohol.

[0036] Nitrobenzene (1mmol), p-methoxybenzyl alcohol (1.5mmol), K 2 CO 3 (1 mmol), RuCl 3 (3mol%) and glycerol (10mmol) were added to a dry reaction tube with a magnetic stirrer, and then the reaction tube was washed with N 2 Replaced 3 times, stirred and reacted at 130°C for 24h. After the reaction, the solution was cooled to room temperature, 5 mL of water was added, and then extracted with 3×5 mL of chloroform, the organic phase was combined, and the organic phase was dried with anhydrous magnesium sulfate, filtered, and the filtrate was concentrated by rotary evaporation and separated by silica gel column chromatography. , to obtain the target product (yield 85%, the structural formula is shown below).

[0037]

[0038] 1 H-NMR (400MHz, DMSO- d 6 ):δ3.71(s,3H),4.17(d, J =4.0Hz,2H),6.12(t, J =8.0Hz,1H),6.49(t, J =8.0Hz,1H),6.55(d, J =8.0Hz,2H),6...

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Abstract

The invention discloses a ligand-free and non-solvent synthesis method for preparing secondary amine under catalysis of ruthenium trichloride. The method comprises steps as follows: reactants including nitrobenzene compounds, alcohol compounds, an alkaline compound, ruthenium trichloride and glycerin in the mole ratio being 1:(1-2):(1-2):(0.02-0.05):(5-15) are added to a reaction container provided with a stirring device under the protection of inert gases, the mixture is stirred at the temperature of 100-150 DEG C and reacts for 20-30 hours, and secondary amine compounds are obtained. RuCl3 is directly used as a catalyst under the condition that no auxiliary ligand or solvent is added, toxic phosphine-containing ligands are avoided, and consumption of alcohol is reduced to a great extent. Besides, according to the method, secondary amine is selectively generated by adding glycerin serving as a hydrogen source, the whole process is environment-friendly, efficient and easy to operate, and the ligand-free and non-solvent synthesis method is a good method for synthesis of secondary amine.

Description

technical field [0001] The invention belongs to the technical field of catalytic chemistry, in particular to a 3 ) is a method for synthesizing secondary amines through catalysis, which can be carried out under the conditions of no ligand and no solvent. Background technique [0002] Secondary amine compounds are widely used in medicine, pesticide and other industries. The main synthesis methods include the alkylation reaction of halogenated aromatic hydrocarbons and amines, the reductive amination reaction of ketones or aldehydes, and the hydrogen amine reaction of unsaturated hydrocarbons and amines. However, these synthetic methods often require the use of environmentally harmful organic solvents, halogenated hydrocarbons, and reducing agents. [0003] In order to overcome the above shortcomings, more and more researches focus on the use of cheap and less toxic alcohols to react with aniline derivatives and use the "hydrogen transfer" strategy to prepare N-substituted am...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C209/00C07C211/48C07C213/02C07C217/58C07C217/84C07D307/52C07D213/38C07D317/58B01J27/13
CPCB01J27/13C07C209/00C07C213/02C07D213/38C07D307/52C07D317/58C07C211/48C07C217/58C07C217/84
Inventor 李红喜谭大伟郎建平
Owner SUZHOU UNIV
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