Method for preparing substituted primary aliphatic amine

Abstract

The invention belongs to the fields of medicinal and natural compound chemical intermediates and related chemical technologies, and relates to a preparation method of substituted primary amine. The method adopts benzonitrile and its derivative as raw materials, takes nanoporous palladium as a catalyst, takes hydrogen as a hydrogen source, and performs selective hydrogenation to prepare the substituted primary amine. The molar concentration of benzonitrile and its derivative in a solvent is 0.01-2 mmol / mL, and the molar ratio of benzonitrile and its derivative to the catalyst is 1:0.01-1:0.5; the size pore skeleton of the nanoporous palladium is 1 nm to 50 nm; and the pressure of hydrogen gas is 0.1 to 20.0 MPa. The method has the beneficial effects that the obtained product has high selectivity, the reaction condition is very mild, no additives is needed, the operation and the post-treatment are simple, the catalyst reproducibility is good, the multi-time catalytic effect with repeateduse is not significantly reduced, and the method provides possibility for industrialization.

Description

technical field [0001] The invention belongs to the field of chemical intermediates of medicine and natural compounds and related chemical technologies, and relates to a preparation method for substituting aliphatic primary amines. Background technique [0002] The selective reduction of nitriles to prepare aliphatic primary amines is a very important step in organic synthesis, especially in the synthesis of some important high-value compounds (such as bioactive molecules, natural products, and industrial materials of other important natural products). The synthesis of pure aliphatic primary amines is a key step. [0003] The traditional method for preparing aliphatic primary amines by selective reduction of nitriles is mainly divided into two categories, one is a homogeneous catalyst combined with ligands by Ru, Ir, Co, Fe and other transition metals, although the activity of this type of catalyst is relatively high High, but there are many disadvantages, such as poor sele...

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Problems solved by technology

[0003] The traditional method for preparing aliphatic primary amines by selective reduction of nitriles is mainly divided into two categories, one is a homogeneous catalyst combined with ligands by Ru, Ir, Co, Fe and other transition metals, although the activity of this type of catalyst is relatively high High, but there are many disadvantages, such as poor selectivity, and the formation of more by-product secondary and tertiary amines

Secondly, very high temperature and pressure are often required (T>120°C and H 2 >50bar), and the catalyst is expensive, difficult to separate and recover, and cannot be reused [REGUILLO R, GRELLIER M, VAUTRAVERS N, et al. J. Am. Chem. Soc. ,WERKMEISTER S,WENDT B,JIAO H,et al.Nat.Commun.2014,5,4111.; MUKHERJEE A,SRIMANI D,CHAKRABORTY S,MILSTEIN D,et al.J.Am.Chem.Soc.2015,137 ,8888–8891.]; the second is heterogeneous catalysts that have been studied more, such catalysts include Raney nickel, Raney cobalt, etc., but the catalysts are generally sensitive and extremely unstable, and there is a great danger, and the use of A large amount of additive alkali (NH 3 ) to improve the selectivity of the reaction, which limits industrial applications , 2001; p 254.; BLASER H U, MALAN C, PUGIN B, SPINDLER F, et al. Adv. Synth. Catal. 2003, 345, 103–151.]

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