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A kind of ru complex catalyzes the method of acceptor-free dehydrogenation of primary amine to generate nitrile
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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, medium selectivity, etc., and achieve good catalytic effect, The effect of single catalytic system and good dehydrogenation performance
Active Publication Date: 2021-11-30
SICHUAN UNIV
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However, these reported systems still have disadvantages such as low reaction efficiency, limited substrate range, moderate selectivity, and low TON.
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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 anhydrousmagnesiumsulfate, 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 .
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Abstract
The invention discloses a method for Ru complexes to catalyze the dehydrogenation of primary amines to generate nitriles without acceptors. According to the molar ratio of 1:100:(100-500):1000-3000, Ru complexes, alkali, Primary amine and organic solvent, stirred and reacted at 80‑120°C, stopped the reaction to collect the reaction solution after the gas chromatography monitored the complete disappearance of the raw materials, centrifuged the reaction solution, took the supernatant, and extracted it with dichloromethane The organic phases were combined, dried and filtered, and the organic solvent was evaporated under reduced pressure to obtain a filtrate, which was purified by column chromatography to obtain the target product nitrile. The catalyst of the present invention has good activity, and after the reaction is finished, the catalytic system is single, the product selectivity is good, the follow-up treatment is simple, the system is universal, and it has good performance on primary amines substituted by various aryl groups, alkyl groups and heteroaryl groups. Catalytic effect, which also has good dehydrogenation performance for 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
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