Synthesis method of a quick recovery type photo-induced phase change imine compound

Abstract

The application discloses a synthesis method of a quick recovery photo-induced phase change imine compound, which is synthesized by a two-step method: in the first step, 4-amino phenol and 4-hydroxy-3-methyl benzaldehyde are used as raw materials, and a product obtained by a reductive amination reaction is used as a raw material for a second step reaction; in the second step, the reductive amination reaction product and 1-chloro undecane are used as reactants, and an alkyl substitution reaction is carried out to obtain 4-undecyloxy-N-[(3-methyl-4'-undecyloxyphenyl) methylene] aniline. The imine compound can realize a quick liquid-solid recovery process without any auxiliary means after photo-induced solid-liquid phase change, and the response capacity of the material is significantly improved.

Description

Technical Field

[0001] This invention belongs to the field of photofunctional materials and relates to a method for synthesizing a fast-recovery photoinduced phase transition imine compound. Background Technology

[0002] Stimulus-responsive materials are a class of materials that respond specifically to stimuli such as light, electricity, heat, and magnetism from the external environment. They are an important category of materials developed for the design and manufacture of smart materials. Among them, photofunctional materials utilize clean, remotely controllable, and non-contact regulated light stimulation as an energy source, causing specific changes in the material to achieve certain functions. Photochromic molecules are a widely studied class of molecular materials within photofunctional materials, such as azobenzene, spiropyran, and their derivatives.

[0003] Photoinduced phase change materials (PCTs) are a class of photofunctional materials that have been developing rapidly in recent years. Their defining characteristic is the transformation of a material from one phase to another under light irradiation. In particular, room-temperature photoinduced solid-liquid transition materials (PLTs) can directly transform from a solid to an isotropic liquid under room-temperature ultraviolet light without the need for heating. During the phase transition, various physicochemical properties of the material, such as volume, internal energy, viscosity, and solubility, change significantly, either individually or simultaneously. Utilizing these property changes, PCTs can be applied to micro-photomechanical systems, reversible adhesives, and solar thermal fuels, making them a very promising class of functional materials. However, PCTs often need to remain in a liquid state for hours or even days after transforming from a solid to a liquid. If the material needs to revert from a liquid to a solid state, it requires the assistance of light of other wavelengths or heating, affecting the speed and reversibility of the material's use.

[0004] Therefore, it is essential to design and synthesize a fast-recovery photoinduced phase transition compound. Summary of the Invention

[0005] The purpose of this invention is to provide a method for synthesizing a fast-recovery photoinduced phase transition imine compound, thereby shortening the recovery time of the material after photoinduced solid-liquid phase transition and improving the material's response speed without the need for auxiliary means such as the introduction of other wavelengths of light or heating.

[0006] The present invention adopts the following technical solution:

[0007] This invention relates to a method for synthesizing a fast-recovery photoinduced phase transition imine compound, the synthesis steps of which are as follows:

[0008] 1) A two-step method was used to synthesize a fast-recovery photoinduced phase transition imine compound. The first step was a reduction amination reaction: 15 mmol of 4-aminophenol and 15 mmol of 4-hydroxy-3-methylbenzaldehyde were dissolved in 10 ml of ethanol solvent and heated to 60 °C for 10 h under magnetic stirring.

[0009] 2) Processing to obtain the crude product of the first step: Pour the mixture after the reaction in step 1) into 100 ml of water and then filter it under vacuum. Place the filter cake in a vacuum oven for 24 h to obtain the crude product of 4-hydroxy-N-[(3-methyl-4'-hydroxyphenyl)methylene]aniline;

[0010] 3) Second step alkyl substitution reaction: 5 mmol of crude 4-hydroxy-N-[(3-methyl-4'-hydroxyphenyl)methylene]aniline and 12 mmol of 1-chloroundecane were dissolved in 15 ml of DMF solvent, and then 1 g of potassium carbonate and 2 mg of potassium iodide were added. The reaction solution was kept at 120 °C and refluxed for 16 h.

[0011] 4) Processing the crude product from the second step: Pour the mixture from the reaction in step 3) into 100 ml of water, filter to obtain a precipitate, keep the precipitate in a 60 °C oven for 24 h, and then perform column chromatography using ethyl acetate as the eluent. After rotary evaporation, the final product of the fast-reversing photoinduced phase transition imine compound 4-undecyloxy-N-[(3-methyl-4'-undecyloxyphenyl)methylene]aniline is obtained. The product is a nearly colorless crystal with a yield of 65%.

[0012] Preferably, the reactants in step 1) of the reductive amination reaction are 4-aminophenol and 4-hydroxy-3-methylbenzaldehyde.

[0013] Preferably, the reactants for the alkyl substitution reaction in step 3) are crude 4-hydroxy-N-[(3-methyl-4'-hydroxyphenyl)methylene]aniline and 1-chloroundecane.

[0014] Preferably, in step 3), the alkyl substitution reaction is carried out using DMF as the reaction solvent.

[0015] Preferably, in step 4), ethyl acetate is used as the eluent for column chromatography.

[0016] The fast-recovery photoinduced phase transition imine compound of the present invention is characterized in that 4-undecoxy-N-[(3-methyl-4'-undecoxyphenyl)methylene]aniline changes from a solid to a liquid under ultraviolet light irradiation and immediately returns to a solid state after the light irradiation is stopped, without the need for other light irradiation assistance or light-assisted treatment. Attached Figure Description

[0017] Figure 1 The molecular formula is 4-undecyloxy-N-[(3-methyl-4'-undecyloxyphenyl)methylene]aniline;

[0018] Figure 2 The nuclear magnetic resonance spectrum of 4-undecyloxy-N-[(3-methyl-4'-undecyloxyphenyl)methylene]aniline prepared according to the present invention. Detailed Implementation

[0019] To further illustrate the technical means and effects of the present invention, the following detailed description is provided in conjunction with the preferred embodiments of the present invention and their accompanying drawings.

[0020] Example 1

[0021] 1) A two-step method was used to synthesize a fast-recovery photoinduced phase transition imine compound. The first step was a reduction amination reaction: 15 mmol of 4-aminophenol and 15 mmol of 4-hydroxy-3-methylbenzaldehyde were dissolved in 10 ml of ethanol solvent and heated to 60 °C for 10 h under magnetic stirring.

[0022] 2) Processing to obtain the crude product of the first step: Pour the mixture after the reaction in step 1) into 100 ml of water and then filter it under vacuum. Place the filter cake in a vacuum oven for 24 h to obtain the crude product of 4-hydroxy-N-[(3-methyl-4'-hydroxyphenyl)methylene]aniline;

[0023] 3) Second step alkyl substitution reaction: 5 mmol of crude 4-hydroxy-N-[(3-methyl-4'-hydroxyphenyl)methylene]aniline and 12 mmol of 1-chloroundecane were dissolved in 15 ml of DMF solvent, and then 1 g of potassium carbonate and 2 mg of potassium iodide were added. The reaction solution was kept at 120 °C and refluxed for 16 h.

[0024] 4) Processing the crude product of the second step: Pour the mixture after the reaction in step 3) into 100 ml of water, filter to obtain a precipitate, keep the precipitate in an oven at 60 °C for 24 h, and then perform column chromatography with ethyl acetate as eluent. After rotary evaporation, the final product of the fast-reversing photoinduced phase change imine compound 4-undecyloxy-N-[(3-methyl-4'-undecyloxyphenyl)methylene]aniline is obtained.

[0025] Example 2

[0026] 1) A two-step method was used to synthesize a fast-recovery photoinduced phase transition imine compound. The first step was a reduction amination reaction: 15 mmol of 4-aminophenol and 15 mmol of 4-hydroxy-3-methylbenzaldehyde were dissolved in 10 ml of ethanol solvent and heated to 60 °C for 10 h under magnetic stirring.

[0027] 2) Processing to obtain the crude product of the first step: Pour the mixture after the reaction in step 1) into 100 ml of water and then filter it under vacuum. Place the filter cake in a vacuum oven for 24 h to obtain the crude product of 4-hydroxy-N-[(3-methyl-4'-hydroxyphenyl)methylene]aniline;

[0028] 3) Second step alkyl substitution reaction: 5 mmol of crude 4-hydroxy-N-[(3-methyl-4'-hydroxyphenyl)methylene]aniline and 12 mmol of 1-chloroundecane were dissolved in 15 ml of DMF solvent, and then 1 g of potassium carbonate and 2 mg of potassium iodide were added. The reaction solution was kept at 130 °C and refluxed for 12 h.

[0029] 4) Processing the crude product of the second step: Pour the mixture after the reaction in step 3) into 100 ml of water, filter to obtain a precipitate, keep the precipitate in an oven at 60 °C for 24 h, and then perform column chromatography with ethyl acetate as eluent. After rotary evaporation, the final product of the fast-reversing photoinduced phase change imine compound 4-undecyloxy-N-[(3-methyl-4'-undecyloxyphenyl)methylene]aniline is obtained.

[0030] Example 3

[0031] 1) A two-step method was used to synthesize a fast-recovery photoinduced phase transition imine compound. The first step was a reduction amination reaction: 15 mmol of 4-aminophenol and 15 mmol of 4-hydroxy-3-methylbenzaldehyde were dissolved in 10 ml of ethanol solvent and heated to 60 °C for 10 h under magnetic stirring.

[0032] 2) Processing to obtain the crude product of the first step: Pour the mixture after the reaction in step 1) into 100 ml of water and then filter it under vacuum. Place the filter cake in a vacuum oven for 24 h to obtain the crude product of 4-hydroxy-N-[(3-methyl-4'-hydroxyphenyl)methylene]aniline;

[0033] 3) Second step alkyl substitution reaction: 5 mmol of crude 4-hydroxy-N-[(3-methyl-4'-hydroxyphenyl)methylene]aniline and 12 mmol of 1-chloroundecane were dissolved in 15 ml of DMF solvent, and then 1 g of potassium carbonate and 2 mg of potassium iodide were added. The reaction solution was kept at 140 °C and refluxed for 10 h.

[0034] 4) Processing the crude product of the second step: Pour the mixture after the reaction in step 3) into 100 ml of water, filter to obtain a precipitate, keep the precipitate in an oven at 60 °C for 24 h, and then perform column chromatography with ethyl acetate as eluent. After rotary evaporation, the final product of the fast-reversing photoinduced phase change imine compound 4-undecyloxy-N-[(3-methyl-4'-undecyloxyphenyl)methylene]aniline is obtained.

[0035] Example 4

[0036] 1) A two-step method was used to synthesize a fast-recovery photoinduced phase transition imine compound. The first step was a reduction amination reaction: 15 mmol of 4-aminophenol and 15 mmol of 4-hydroxy-3-methylbenzaldehyde were dissolved in 10 ml of ethanol solvent and heated to 80 °C for 6 h under magnetic stirring.

[0037] 2) Processing to obtain the crude product of the first step: Pour the mixture after the reaction in step 1) into 100 ml of water and then filter it under vacuum. Place the filter cake in a vacuum oven for 24 h to obtain the crude product of 4-hydroxy-N-[(3-methyl-4'-hydroxyphenyl)methylene]aniline;

[0038] 3) Second step alkyl substitution reaction: 5 mmol of crude 4-hydroxy-N-[(3-methyl-4'-hydroxyphenyl)methylene]aniline and 12 mmol of 1-chloroundecane were dissolved in 15 ml of DMF solvent, and then 1 g of potassium carbonate and 2 mg of potassium iodide were added. The reaction solution was kept at 120 °C and refluxed for 16 h.

[0039] 4) Processing the crude product of the second step: Pour the mixture after the reaction in step 3) into 100 ml of water, filter to obtain a precipitate, keep the precipitate in an oven at 60 °C for 24 h, and then perform column chromatography with ethyl acetate as eluent. After rotary evaporation, the final product of the fast-reversing photoinduced phase change imine compound 4-undecyloxy-N-[(3-methyl-4'-undecyloxyphenyl)methylene]aniline is obtained.

[0040] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any other way. Any person skilled in the art may make changes or modifications to the above-disclosed technical content to create equivalent embodiments. However, any simple modifications, equivalent changes, and modifications made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the protection scope of the present invention.

Claims

1. A method for synthesizing a fast-recovery photoinduced phase transition imine compound, characterized in that: The synthesis steps are as follows: 1) A two-step method was used to synthesize a fast-recovery photoinduced phase transition imine compound. The first step was a reduction amination reaction: 15 mmol of 4-aminophenol and 15 mmol of 4-hydroxy-3-methylbenzaldehyde were dissolved in 10 ml of ethanol solvent and heated to 60 °C for 10 h under magnetic stirring. 2) Processing to obtain the crude product of the first step: Pour the mixture after the reaction in step 1) into 100 ml of water and then filter it under vacuum. Place the filter cake in a vacuum oven for 24 h to obtain the crude product of 4-hydroxy-N-[(3-methyl-4'-hydroxyphenyl)methylene]aniline; 3) Second step alkyl substitution reaction: 5 mmol of crude 4-hydroxy-N-[(3-methyl-4'-hydroxyphenyl)methylene]aniline and 12 mmol of 1-chloroundecane were dissolved in 15 ml of DMF solvent, and then 1 g of potassium carbonate and 2 mg of potassium iodide were added. The reaction solution was kept at 120 °C and refluxed for 16 h. 4) Processing the crude product of the second step: Pour the mixture after the reaction in step 3) into 100 ml of water, filter to obtain a precipitate, keep the precipitate in an oven at 60 °C for 24 h, and then perform column chromatography with ethyl acetate as eluent. After rotary evaporation, the final product of the fast-reversing photoinduced phase change imine compound 4-undecyloxy-N-[(3-methyl-4'-undecyloxyphenyl)methylene]aniline is obtained.

2. The method for synthesizing the fast-recovery photoinduced phase transition imine compound as described in claim 1, characterized in that, 4-Undecyloxy-N-[(3-methyl-4'-undecyloxyphenyl)methylene]aniline changes from a solid to a liquid under ultraviolet light, and immediately returns to a solid state after the light is removed, without the need for other light or heating assistance.

Images