Rapid synthesis method for biomass-based amine

Patent metadata

Field	Value
Publication number	US-12187693-B2
Application number	US-201917266824-A
Country	US
Kind code	B2
Filing date	Jul 31, 2019
Priority date	Aug 6, 2018
Publication date	Jan 7, 2025
Grant date	Jan 7, 2025

Abstract

A rapid synthesis method for a biomass-based amine, including: using formamide as an amine source, formic acid as a hydrogen source, and biomass aldehyde or ketone as a raw material, conduct rapid heating promoting direct addition of formamide and aldehyde or ketone compound through microwave-assisted heating and without a solvent and catalyst, and carrying out formic acid reduction preparing and obtaining a corresponding formamide derivative; selectively converting the formamide derivative under the action of a base into a corresponding primary amine through alcoholysis. The microwave-assisted heating reaction system has a significantly higher catalytic efficiency than a corresponding oil bath system, greatly shortens a reaction time, and significantly improves selectivity, where a conversion rate of a biomass aldehyde or ketone compound may reach at least 99%, and a formamide derivative yield may reach 85-99%; the formamide derivative is synthesized to a primary amine through alcoholysis, where a yield may reach 92-99%.

First claim

What is claimed is:

1. A rapid synthesis method for an amine, comprising: by using formamide as an amine source, using formic acid as a hydrogen source, and using an aldehyde or ketone compound as a raw material, carrying out a direct addition reaction on the formamide and the aldehyde or ketone compound through microwave-assisted heating and in the absence of a solvent and a catalyst, and then carrying out formic acid reduction to obtain a corresponding formamide derivative; dissolving the formamide derivative in methanol, and under the action of a base, carrying out a reaction at 60 to 100° C. for 2 to 8 h to obtain the amine, wherein
the formamide derivative is prepared in a microwave reactor, a reaction system is an airtight system, nitrogen is introduced before a reaction until pressure is 1 to 3 MPa, a reaction temperature is 160 to 200° C., and a reaction time is 2 to 15 min,
a ratio of amounts of substance of the formamide, the formic acid, and the aldehyde or ketone is 6-15:6-15:2, and
the aldehyde or ketone compound is furfural, 5-methylfurfural, benzaldehyde, veratraldehyde, cinnamaldehyde, glycolaldehyde, propionaldehyde, methyl isobutyl ketone, cyclopentanone, cyclohexanone, or acetophenone.

2. The rapid synthesis method for an amine according to claim 1 , wherein the formamide derivative is N-furylmethyl formamide, N-5-methylfurfuryl formamide, N-benzylformamide, N-3,4-dimethoxybenzyl formamide, N-phenylacrylformamide, N-2-hydroxyethyl formamide, N-propylformamide, N-methyl isobutyl formamide, N-cyclopentylformamide, N-cyclohexylformamide, or N-benzyl methyl formamide.

3. The rapid synthesis method for an amine according to claim 1 , wherein a ratio of an amount of substance of the formamide derivative to an amount of substance of the base is 1:1-5, and a ratio of the formamide derivative to the methanol is 1 mol: 1-3 L.

4. The rapid synthesis method for an amine according to claim 1 , wherein the base is sodium hydroxide, cesium carbonate, or sodium ethoxide.

5. The rapid synthesis method for an amine according to claim 1 , wherein the amine is 2-furfurylamine, 5-methylfuranethylamine, benzylamine, 3,4-dimethoxybenzylamine, cinnamamide, 2-aminoethanol, propylamine, methylisobutylamine, cyclopentylamine, cyclohexylamine, or benzylmethylamine.

Assignees

• Univ Nanjing Agricultural

Inventors

• Li Hu
• Fang Zhen
• Smith Richard Lee

Classifications

• C07C231/08

  from amides by reaction at nitrogen atoms of carboxamide groups · CPC title

• C07C213/02

  by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups · CPC title

• C07C2601/08

  the ring being saturated · CPC title

• C07C209/62

  by cleaving carbon-to-nitrogen, sulfur-to-nitrogen, or phosphorus-to-nitrogen bonds, e.g. hydrolysis of amides, N-dealkylation of amines or quaternary ammonium compounds (C07C209/24 takes precedence) · CPC title

• C07D307/52 Primary

  Radicals substituted by nitrogen atoms not forming part of a nitro radical · CPC title