Preparation method of N-allyl arylamine

Abstract

The invention relates to a preparation method of N-allyl arylamine. The method comprises the following steps: firstly, sequentially adding allyl alcohol compounds, aromatic amine compounds, a promoter and a catalyst into a reaction solvent; and after the obtained mixture is reacted for 5-14 hours under the reflux temperature condition of 50-100 DEG C, evaporating partial solvent under reduced pressure, thereby obtaining crude reaction liquid; carrying out extraction on the rough reaction liquid by using diethyl ether so as to obtain extract liquor; and finally, drying the extract liquor until the extract liquor is constant in weight, and then carrying out column chromatography isolation on the obtained product. According to the invention, a catalyst system is simple, and no ligand is required, and N-allyl arylamine is cheap and easy to take; and the method is mild in reaction conditions, short in reaction time, simple in post-treatment, high in yield and good in selectivity, and therefore, the method is an environment-friendly green synthesis technology, and has a good industrial application prospect.

Description

technical field [0001] The invention relates to N-allyl arylamine in the field of organic synthetic chemistry, in particular to a preparation method of N-allyl arylamine. Background technique [0002] As an important class of organic synthesis intermediates, N-allyl arylamines are intermediates in medicine, agrochemical industry, dyes and plastics. [0003] The preparation of traditional N-allyl aryl amine is to use acid or alkali as catalyst in solution, and allyl halide is used as alkylating agent to react with aromatic amine, but its yield and selectivity are relatively poor, will There are two products of monoallyl substituted arylamine and diallyl substituted arylamine, and even over-alkylated products such as quaternary ammonium salts. [0004] At present, using allyl alcohols as alkylating reagents and reacting with aromatic amines catalyzed by noble metals is one of the main methods for synthesizing N-allyl arylamines. Because the allyl alcohol compound is cheap, e...

AI Technical Summary

Problems solved by technology

In 1999, Shyh-Chyun Yang used Pd(OAc)2-PPh3 as a catalyst, Ti(OPr-i)4 is an additive, allyl alcohol and arylamine compounds are used to synthesize N-allyl arylamine. Although the catalyst is relatively simple and relatively cheap in this method, there are still more diallyl substituted arylamines in the reaction product , while the selectivity of monosubstituted products is poor (Synthesis (Synthesis), No. 10, 1999, pages 1747–1752)

In 2011, Hidemasa Hikawa used palladium acetate as a catalyst, sodium m-triphenylphosphine monosulfonate (TPPMS) as a ligand, and reacted allyl alcohol and anthranilic acid compounds to synthesize allylaniline at room temperature. Although this method has mild conditions , high yield, but long reaction time (48 hours required) and expensive ligand TPPMS (Jouranl of Organic Chemistry, Vol. 76, 2011, pp. 8433–8439)

In 2011, Amitabha Sarkar used the complex [(η3-allyl)PdCl]2 to catalyze allyl alcohol compounds and aromatic amines to synthesize allylamines. This method is applicable to a wide range of substrate aromatic amines and produces The rate is high, but the catalyst is expensive and the preparation process is complicated (Jouranl of Organic Chemistry, Vol. 76, 2011, pp. 8508–8512)

It can be seen that there are still many problems in the above-mentioned methods: (1) expensive catalyst or additive; (2) long reaction time; (3) poor selectivity of reaction product; (4) the scope of application of the reaction substrate is limited