Unlock instant, AI-driven research and patent intelligence for your innovation.

Method for catalyzing receptor-free dehydrogenation of primary amine to generate nitrile by Ru coordination compound

A technology for catalyzing primary amines and complexes, applied in chemical instruments and methods, preparation of organic compounds, organic chemistry, etc., can solve the problems of limited substrate range, low reaction efficiency, moderate selectivity, etc. The effect of single catalytic system and good dehydrogenation performance

Active Publication Date: 2020-09-08
SICHUAN UNIV
View PDF3 Cites 3 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, these reported systems still have disadvantages such as low reaction efficiency, limited substrate range, moderate selectivity, and low TON.

Method used

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
View more

Image

Smart Image Click on the blue labels to locate them in the text.
Viewing Examples
Smart Image
  • Method for catalyzing receptor-free dehydrogenation of primary amine to generate nitrile by Ru coordination compound
  • Method for catalyzing receptor-free dehydrogenation of primary amine to generate nitrile by Ru coordination compound
  • Method for catalyzing receptor-free dehydrogenation of primary amine to generate nitrile by Ru coordination compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0034] Embodiment 1: the preparation of benzonitrile:

[0035]

[0036] After synthesizing the Ru complex according to the method shown in A, add the Ru complex, base, primary amine and organic solvent into the reaction test tube according to the molar ratio of 1:100:200:1000. The reaction system was stirred and reacted at 100° C. for 24 h. The complete disappearance of raw materials was monitored by gas chromatography, and the reaction was stopped. Centrifuge, take the supernatant and add 5ml of water, extract with dichloromethane (5ml×3), combine the organic phases, dry with anhydrous magnesium sulfate, filter, evaporate the filtrate to remove the organic solvent under reduced pressure, and purify by column chromatography to obtain Colorless liquid, yield 95.4%.

[0037] In the Ru complex, the ligand of the double CNP structure used is:

[0038]

[0039] The product detection data is as follows: Benzonitrile(1). 1 H NMR (400MHz, CDCl 3 )δ (ppm) 7.66-7.59 (m, 3H), ...

Embodiment 2

[0040] Embodiment 2: the preparation of compound 4-methylbenzonitrile:

[0041]

[0042] After preparing and synthesizing the Ru complex according to the method in Example 1, add the Ru complex, alkali, primary amine and organic solvent into the reaction test tube according to the molar ratio of 1:100:100:1000, and stir the reaction at 100°C for 24 hours. In the Ru complex, the ligand of the double CNP structure used is:

[0043]

[0044] Using 4-methoxybenzylamine as the substrate, a white solid was obtained with a yield of 95.0%.

[0045] The product detection data is as follows: 4-methylbenzonitrile(2). 1 H NMR (600MHz, CDCl 3 )δ (ppm) 7.51 (d, J = 8.2Hz, 2H), 7.26 (d, J = 8.0Hz, 2H), 2.40 (s, 3H);13 C NMR (150MHz, CDCl 3 )δ (ppm) 143.7, 132.0, 129.9, 119.1, 109.2, 21.8cm -1 .

Embodiment 3

[0046] Embodiment 3: the preparation of compound 4-methoxybenzonitrile:

[0047]

[0048] After preparing and synthesizing the Ru complex according to the method in Example 1, add the Ru complex, alkali, primary amine and organic solvent into the reaction test tube according to the molar ratio of 1:100:200:1500, and stir the reaction at 100°C for 24 hours. In the Ru complex, the ligand of the double CNP structure used is:

[0049]

[0050] 4-methoxybenzylamine was selected as the substrate to obtain a white solid with a yield of 96.9%.

[0051] The product detection data is as follows: 4-methoxybenzonitrile(3). 1 H NMR (CDCl 3 ,400MHz): δ(ppm)7.59(d,J=8.9Hz,2H),6.95(d,J=9.0Hz,2H),3.86(s,3H); 13 C NMR (CDCl 3 ,100MHz): δ(ppm)162.9,134.0,119.2,114.8,104.0,55.6cm -1 .

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

PUM

No PUM Login to View More

Abstract

The invention discloses a method for catalyzing receptor-free dehydrogenation of primary amine to generate nitrile by a Ru coordination compound. The method comprises: adding a Ru coordination compound, an alkali, a primary amine and an organic solvent into a reaction test tube according to a mol ratio of 1:100:(100-500):1000-3000, and carrying out a stirring reaction under the condition of 80 to120 DEG C; and when gas chromatography monitors that the raw materials completely disappear, stopping the reaction, collecting the reaction solution, centrifuging the reaction solution, taking the supernatant, extracting with dichloromethane, merging the organic phases, drying, filtering, evaporating the organic solvent under reduced pressure to obtain a filtrate, and carrying out column chromatography purification on the filtrate to obtain the target product nitrile. According to the invention, the catalyst is good in activity, single in catalytic system, good in product selectivity, simple in subsequent treatment and good in system universality after the reaction is finished, has a good catalytic effect on various aryl, alkyl and heteroaryl substituted primary amines, and also has a gooddehydrogenation performance on secondary amines.

Description

technical field [0001] The invention relates to the field of chemical reaction synthesis, in particular to a method for Ru complexes to catalyze the dehydrogenation of primary amines to generate nitriles without acceptors. Background technique [0002] Cyano groups are present in many biologically active natural products, pharmaceuticals, and functional materials. As an important intermediate in organic synthesis, nitriles can be easily transformed into various fine and useful complex molecules after simple treatment. Methods for preparing nitrile compounds have been reported, such as Sandmeyer reaction, Rosenmond-Von Braun reaction, conversion of alcohols and other compounds, and oxidative dehydration of primary amines. However, the above-mentioned methods are usually carried out under relatively harsh high-temperature conditions, need to add highly toxic metal cyanides, metal catalysts, strong oxidants, etc., and always produce stoichiometric by-products, which have a lar...

Claims

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

Application Information

Patent Timeline
no application Login to View More
IPC IPC(8): C07C253/00C07C255/50C07C255/54C07C255/58C07C255/52C07D317/68C07D213/84C07D333/38C07D307/68C07D209/42C07C255/57C07C255/03C07C255/46C07C255/33C07C255/47C07D209/04
CPCC07C253/00C07D209/04C07D209/42C07D213/84C07D307/68C07D317/68C07D333/38C07C2601/14C07C2603/74C07C255/50C07C255/54C07C255/58C07C255/52C07C255/57C07C255/03C07C255/46C07C255/33C07C255/47
Inventor 李瑞祥聂旭凤付海燕陈华
Owner SICHUAN UNIV