Preparation method of N-allyl arylamine

A technology of allyl aryl amine and allyl alcohol, which is applied in the field of preparation of N-allyl aryl amine, which can solve the limitation of the scope of application of the reaction substrate, long reaction time (requires 48 hours, ligand TPPMS Expensive and other problems, to achieve good industrial application prospects, cheap and easy to use, avoid the use of toxic organic solvents

Inactive Publication Date: 2013-06-12
NORTHWEST NORMAL UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0018] Example 1 A kind of preparation method of N-allyl aryl amine, first 2 mmol allyl alcohol, 1 mmol 2,5-dichloroaniline, 0.1 mmol trifluoroacetic acid, 0.01 mmol palladium nitrate are added in the reaction solvent successively, then in 50 After reacting at reflux temperature for 12 hours, part of the solvent was distilled off under reduced pressure to obtain a crude reaction solution; the crude reaction solution was extracted three times with diethyl ether (3mL x 3) to obtain an extract; the final extract was passed through a vacuum box at 50°C After drying to constant weight, N-allyl-2,5-dichloroaniline was obtained by conventional separation method of column chromatography with a yield of 40.2%.

[0019] Among them: the mass volume ratio (g / ml) of the aromatic amine compound to the reaction solvent is 1:19.

[0020] The reaction solvent was a mixture of 2 ml dioxane and 1 ml water.

Embodiment 2

[0021] Example 2 A kind of preparation method of N-allyl aromatic amine, first 3 mmol allyl alcohol, 1 mmol 2-methoxy-4-nitroaniline, 0.15 mmol trifluoromethanesulfonic acid, 0.02 mmol palladium nitrate are added successively In the reaction solvent, react at reflux temperature of 80°C for 10h, and evaporate part of the solvent under reduced pressure to obtain a crude reaction solution; the crude reaction solution is extracted three times with diethyl ether (3mL x 3) to obtain an extract; finally The extract was dried in a vacuum oven at 50°C to constant weight and then separated by conventional column chromatography to obtain N-allyl-2-methoxy-4-nitroaniline with a yield of 84.6%.

[0022] Among them: the mass volume ratio (g / ml) of the aromatic amine compound to the reaction solvent is 1:18.

[0023] The reaction solvent was a mixture of 2 ml dioxane and 1 ml water.

Embodiment 3

[0024] Example 3 A preparation method of N-allyl arylamine, first 3 mmol allyl alcohol, 1 mmol 1-naphthylamine, 0.2 mmol trifluoroacetic acid, 0.0212 g palladium carbon (wherein the content of palladium is 5wt%) is sequentially added to the reaction solvent , then reacted at reflux temperature of 90°C for 5 hours, and then evaporated part of the solvent under reduced pressure to obtain a crude reaction solution; the crude reaction solution was extracted three times with diethyl ether (3mL x 3) to obtain an extract; the final extract After drying in a vacuum oven at 50°C to constant weight, N-allyl-1-naphthylamine was obtained by conventional column chromatography with a yield of 84.2%.

[0025] Among them: the mass volume ratio (g / ml) of the aromatic amine compound to the reaction solvent is 1:21.

[0026] The reaction solvent was a mixture of 2 ml dioxane and 1 ml water.

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PUM

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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...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C209/18C07C211/52C07C213/08C07C217/84C07C211/58
Inventor 杜正银鄢余飞车富寿
Owner NORTHWEST NORMAL UNIVERSITY
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