Method for preparing aromatic primary amine by taking ammonia water as ammonia source in water phase system

Abstract

The invention provides a method for preparing aromatic primary amine by taking ammonia water as an ammonia source in a water phase system. In the method, aromatic halogenate and the ammonia water are used as raw materials, water is used as a solvent, at room temperature or under the heating condition of common oil bath, carbonates, fluorides, phosphates and hydroxides of alkali metals or alkaline-earth metals are taken as alkalis, and a catalytic reaction is preformed through adding a surfactant and using a temary catalysis system composed of copper catalyst, hydrazide and ketone. The method has the characteristics that the operation is simple, wide substrate application range is wide, the product is simple and easy to separate, the yield is high, the process is economic and is environment-friendly and the like; and reaction conditions are flexible, thus corresponding room temperature or heating mode can be selected according to practical requirements. In addition, the environment friendliness of the reaction is effectively improved by using water as a reaction solvent, thereby better conforming to the development requirements of green chemistry. Especially, the substrate is wide in application range and has wide application prospects in the aspects of preparing natural products, medicines and pesticides.

Description

technical field [0001] The invention relates to the technical field of chemistry, in particular to a method for preparing aromatic primary amines by reacting copper-catalyzed aromatic halides with ammonia water in an aqueous system. technical background [0002] Aromatic primary amines are important intermediates in organic synthesis, and are also important intermediates in the manufacture of agricultural chemicals, dyes, pharmaceuticals and some other chemical materials. They are widely used in pesticides, medicines and materials science ((a)K .Weissermel, H.J. Arpe, Industry Organic Chemistry, Wiley-VCH, Weinheim, 1997; (b) S.A. Lawrence, Amines: Synthesis Properties, and Application, Cambridge University Press, Cambridge, 2004.). Therefore, how to prepare aromatic primary amines more conveniently and quickly has attracted extensive attention. At present, the method of catalytic hydrogenation of nitroaromatic hydrocarbons is mainly used in domestic and foreign industries ...

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Problems solved by technology

Because these methods generally require severe reaction conditions of high temperature and high pressure, there are problems such as high equipment requirements and inconvenient operation, and high temperature and high pressure conditions limit the tolerance of some functional groups

Chinese patent CN 1555921A discloses a transition metal catalyzed method for preparing aniline from benzene at normal pressure and lower temperature with ammonia as amination agent and hydrogen peroxide as oxidant, but the conversion rate of benzene is not ideal

Chinese patent CN 1807397 discloses a method for synthesizing aniline in one step with benzene and hydroxylamine hydrochloride in acetic acid medium with soluble vanadium salt as a catalyst under relatively mild conditions. The reaction process is easy to operate and low in cost, but the yield of aniline is still low. Low

Wan et al. reported that N 2 , N 2 '-Diisopropyl oxalyl hydrazide as ligand copper-catalyzed coupling method of halogenated aromatics and ammonia (F.Meng, X.Zhu, Y.Wan, et al., Eur.J.Org.Chem. 2010, 6149.), but the reaction time is longer at lower temperatures, and there are certain substrate limitations

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