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A method for preparing formamide and n-methylamines by selective reduction of carbon dioxide and amines regulated by ligands

A technology of carbon dioxide and methylamine, applied in chemical instruments and methods, preparation of reductive alkylation, preparation of carboxylic acid amide, etc., can solve the problems of complex factors affecting reaction conditions, changing temperature, etc., and achieve wide application range of substrates, Reduction of reaction cost, reduction of reaction risk factor and effect of reaction cost

Active Publication Date: 2021-03-16
NANKAI UNIV
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  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0007] For existing CO 2 In the method for preparing formamide and N-methylamines by selective reduction of amines, the reaction conditions have complex factors and need to change the temperature. The present invention provides a selective reduction of carbon dioxide and amines regulated by ligands to prepare formamide and N-methylamine methods, which use cheap copper salts as catalysts, and realize CO under mild conditions only by regulating the ligands of the reaction. 2 Preparation of Formamide and N-Methylamines by Selective Reduction of Amines

Method used

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  • A method for preparing formamide and n-methylamines by selective reduction of carbon dioxide and amines regulated by ligands
  • A method for preparing formamide and n-methylamines by selective reduction of carbon dioxide and amines regulated by ligands
  • A method for preparing formamide and n-methylamines by selective reduction of carbon dioxide and amines regulated by ligands

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preparation example Construction

[0033] The specific steps of the preparation method are:

[0034] Step 1 Add amines, hydrosilanes, catalysts, ligands and solvents into the reactor, wherein the molar ratio of catalysts to ligands is 1:2-1:4, and the molar ratio of catalysts to amines is 2.5%-5 %, the molar ratio of amines to hydrosilane is 1:2-3. After mixing, fill the reactor with 0.1-8.0MPa of CO 2 ;

[0035] Step 2: control the reaction temperature to 20-80°C, and react for 10-48h;

[0036] After the reaction in Step 3 is completed, the reaction system is cooled to room temperature and separated by column chromatography to obtain formamide and N-methylated products.

[0037] The raw material amines can be selected as secondary amines. Wherein the ligand can be o-phenanthroline, three (4-methoxyphenyl) phosphine, three (4-trifluoromethylphenyl) phosphine, three (4-methylphenyl) phosphine, three (4- Chlorophenyl)phosphine, tricyclohexylphosphine, diphenylcyclohexylphosphine, 1,4-bis(diphenylphosphine)bu...

Embodiment 1

[0041] The influence of embodiment 1 catalyst on formamide and N-methylamines yield

[0042] A ligand-regulated CO 2 The method for preparing formamide and N-methylamines through selective reduction of amines, the steps are as follows:

[0043] 1) Add catalyst, 4.5mg (5mol%) o-phenanthroline, acetonitrile 2mL, 54 μL (0.5mmol) N-methylaniline, 0.2mL (1.5mmol) phenylsilane into a 10mL Schlenk tube, and then add connected to a CO filled 2 the balloon;

[0044] 2) The reaction temperature is controlled at 50°C, and the reaction time is 12 hours;

[0045] 3) After the reaction was completed and the reaction system was cooled to room temperature, 5 mL of ethyl acetate was added and stirred at room temperature for 3 h;

[0046] 4) Add internal standard 1,3,5-trimethoxybenzene, take a small amount of sample for gas chromatography analysis, and the yield is the gas spectrum yield.

[0047] Table 1 Effect of different catalysts on the yield of N-methyl-N-formylaniline and N,N-dimet...

Embodiment 2

[0051] The influence of embodiment 2 ligand on the yield of formamide and N-methylamines

[0052] A ligand-regulated CO 2 The method for preparing formamide and N-methylamines through selective reduction of amines, the steps are as follows:

[0053] 1) 2.5mol% catalyst Cu 2 (OH) 2 CO 3 , ligand, acetonitrile 2mL, 54μL (0.5mmol) N-methylaniline, 0.2mL (1.5mmol) phenylsilane were added to a 10mL Schlenk tube, and then a CO 2 the balloon;

[0054] 2) The reaction temperature is controlled at 50°C, and the reaction time is 12h;

[0055] 3) After the reaction was completed and the reaction system was cooled to room temperature, 5 mL of ethyl acetate was added and stirred at room temperature for 3 h;

[0056] 4) Add internal standard 1,3,5-trimethoxybenzene, take a small amount of sample for gas chromatography analysis, and the yield is the gas spectrum yield.

[0057] The influence of table 2 ligand on the yield of N-methyl-N-formylaniline and N,N-dimethylaniline

[0058] ...

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Abstract

The invention relates to a method for preparing formamide and N-methylamines by carrying out selective reduction on carbon dioxide and amines regulated by a ligand. According to the method, copper salt is used as a catalyst, organic amine or organic phosphorus is used as the ligand, CO2 and a hydrosilane are respectively used as a C1 resource and a reducing agent, and amines are used as a nucleophilic reagent; a reaction is carried out in an organic solvent, the consumption of the catalyst is 1-5mol%, and the consumption of the ligand is 1-20 mol%, the reaction temperature is 20-80 DEG C, theCO2 pressure is 0.1-8.0 MPa, the reaction time is 10-48h, the highest yield of the formamide is up to 98%, and the highest yield of the N-methylamine is up to 95%. The method provided by the inventionhas the advantages that the ligand is used for a regulation method for selective reduction preparation of the formamide and the N-methylamines for the first time; the catalyst is low in price, easy to obtain and simple in composition; the renewable CO2 is used as a raw material, so that the use of the traditional toxic formylation and methylation reagents is avoided; the substrate is wide in application scope and is suitable for a variety of secondary amines.

Description

technical field [0001] The invention belongs to the field of preparation of formamide and N-methylamines, in particular to a method for preparing formamide and N-methylamines through selective reduction of carbon dioxide and amines regulated by ligands. Background technique [0002] C and N are two important components of nature and life, so the C-N bond construction reaction has long been valued by chemists. Amides are important intermediates and products in organic synthesis, and are also important substances in living organisms. Proteins contain multiple amide units. Among them, formamide, as a relatively simple structure among amides, plays an important role in the fields of medicine and pesticides. N-methylamines are structural units of various alkaloids, intermediates of various dyes and natural products in organic synthesis, and can also be used as protective groups for amines. In the traditional method, CO or HCOOH is used as the starting material in the synthesis ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C231/10C07C233/03C07C233/15C07C233/25C07C209/28C07C211/48C07C211/27C07C211/52C07C213/08C07C217/84C07D295/185C07D295/03C07D295/023
CPCC07C209/28C07C213/08C07C231/10C07D295/023C07D295/03C07D295/185C07C233/03C07C211/48C07C211/52C07C211/27C07C217/84C07C233/15C07C233/25
Inventor 李雪冬李红茹夏书梅何良年
Owner NANKAI UNIV
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