Preparation method of aminated aromatic imide compound single crystal based on hydrothermal method
The water-hydrogen peroxide method synthesizes amino-substituted aromatic amides as single crystals efficiently and environmentally friendly, addressing solvent-intensive and complex operations in traditional methods.
Patent Information
- Application Number
- CN202510426215.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-04-07
- Publication Date
- 2025-07-15
AI Technical Summary
Existing methods for preparing aromatic amides suffer from high solvent usage, complex operations, and difficulty in obtaining pure single crystals, failing to align with the principles of green chemistry.
A water-hydrogen peroxide method is employed to synthesize amino-substituted aromatic amides, using hydrazine hydrate as both a reactant and solvent, under controlled conditions to produce high-purity single crystals.
The method achieves high yield and purity of single crystals with reduced environmental impact, simplifying operations and aligning with green chemistry principles.
Smart Images
Figure CN120309537A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the field of organic synthesis, and particularly relates to a method for preparing single crystals of amino-functionalized aromatic imide compounds based on the hydrothermal method. Background Art
[0002] The development of energy and materials is crucial for social development. However, the current preparation processes generally suffer from insufficient environmental compatibility, leading to excessive resource consumption and waste emissions. In order to develop advanced functional materials both in large quantities and in an environmentally friendly manner, people have turned their attention to green chemistry and technology. The core scientific issue in the development of green chemistry is to study new reaction systems, including new synthesis methods and routes, seek new chemical raw materials, explore new reaction conditions, and design and develop green products.
[0003] Aromatic imide compounds are prepared by the synthesis of aromatic anhydrides. This process has defects such as a large amount of organic solvents used, difficult treatment of by-products, cumbersome operation, and the products not being single crystals and requiring sublimation crystallization or recrystallization, which shows a significant gap from the requirements of the development of green chemistry. Although environmentally friendly synthesis technologies have become a research hotspot in recent years, there has been no breakthrough in the field of imide compounds from the traditional process framework, and it is difficult to achieve efficient and clean production. Summary of the Invention
[0004] In order to overcome the shortcomings and deficiencies of the prior art, the purpose of the present invention is to provide a method for preparing single crystals of amino-functionalized aromatic imide compounds based on the hydrothermal method. The present invention uses the hydrothermal method of hydrazine hydrate to successfully prepare single crystals of amino-functionalized aromatic imide compounds. The method of the present invention has mild reaction conditions, simple operation, high yield, and pure products, all of which are single crystals.
[0005] The present invention is achieved through the following technical solutions:
[0006] A method for preparing single crystals of amino-functionalized aromatic imide compounds based on the hydrothermal method, comprising the following steps:
[0007] Aromatic imide compounds and hydrazine hydrate are subjected to a hydrothermal reaction to obtain single crystals of amino-functionalized aromatic imide compounds; hydrazine hydrate serves as both a reaction medium and a reactant;
[0008] The structure of the aromatic imide compounds is:
[0009]
[0010] In the formula: R and R1 are each independently at least one of H, alkyl, primary amino group, secondary amino group, carboxyl group, hydroxyl group, and pyridyl group;
[0011] X1-X6 are each independently H, alkyl, NH2 group, F, Cl, Br, CN, and NO2 group.
[0012] The alkyl group is a C1-C10 alkyl group, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, etc.; the primary amino group and secondary amino group are -NHR2, where R2 is H, alkyl, phenyl, acetylphenyl, vinylphenyl.
[0013] The pyridyl group is 2-substituted pyridine, 3-substituted pyridine, or 4-substituted pyridine.
[0014] The structure of the aminated aromatic imide compound is
[0015]
[0016] In the formula: X1-X6 are each independently H, alkyl, NH2 group, F, Cl, Br, CN, NO2.
[0017] The temperature of the reaction is 90-160°C, preferably 100-120°C; the reaction time is 8-24 hours. The reaction is carried out in a closed reaction kettle, preferably in a high-pressure closed reaction kettle.
[0018] The molar ratio of hydrazine hydrate to the aromatic imide compound is 50:1 - 5000:1 (since hydrazine hydrate serves as both a solvent and a reactant, it needs to be in a large excess). The molar ratio is preferably (300-900):1.
[0019] Compared with the prior art, the present invention has the following beneficial effects and advantages:
[0020] (1) The reaction conditions of the present invention are mild, and the product is obtained in one step, reducing the labor intensity.
[0021] (2) The use of green chemical reagents in the present invention is beneficial to environmental protection.
[0022] (3) The products generated by the present invention are all single crystals with high purity and high yield. BRIEF DESCRIPTION OF THE DRAWINGS
[0023] Figure 1 Optical diagrams of single crystals of the products (Compound 3a and Compound 2b) in Examples 1 and 2;
[0024] Figure 2 Scanning electron microscope diagrams of single crystals of the products (Compound 3a and Compound 2b) in Examples 1 and 2;
[0025] Figure 3 Single crystal structures of the products (Compound 3a and Compound 2b) in Examples 1 and 2 (white: hydrogen; red: oxygen; gray: carbon; blue: nitrogen);
[0026] Figure 4 1H NMR spectrum of the product (Compound 3a) in Example 1. DETAILED DESCRIPTION OF THE INVENTION
[0027] The present invention will be further described in detail below in conjunction with embodiments and the accompanying drawings. However, the implementation modes and protection scope of the present invention are not limited thereto.
[0028] Example 1
[0029]
[0030] Using aromatic imide 1a (0.1 mmol) and hydrazine hydrate 2a (40 mmol) as starting materials, they were added to a sealed high-pressure reactor and heated at 100 °C for 12 hours in a forced-air oven (hydrothermal reaction) to obtain compound 3a. The solvent was evaporated to dryness at 80 °C to obtain single crystals of 3a (precipitated from the solution), and the yield was 97%.
[0031] Structure of compound 1a: Structure of compound 3a:
[0032] Example 2
[0033]
[0034] Using aromatic imide 1b (0.1 mmol) and hydrazine hydrate 2a (40 mmol) as starting materials, they were added to a sealed high-pressure reactor and heated at 100 °C for 12 hours in a forced-air oven (hydrothermal reaction) to obtain compound 2b. The solvent was evaporated to dryness at 80 °C to obtain single crystals of 2b (precipitated from the solution), and the yield was 97%.
[0035] Structural formula of compound 1b:
[0036] Structure of compound 2b:
[0037] Comparative Example 1 (stirring at room temperature)
[0038] Using aromatic imide 1a (0.1 mmol) and hydrazine hydrate 2a (40 mmol) as starting materials, they were added to a glass bottle and stirred for 12 hours. It was found that aromatic imide 1a was insoluble in hydrazine hydrate at room temperature, and compound 3a could not be obtained, and the yield was 0%.
[0039] Comparative Example 2 (heating and stirring)
[0040] Using aromatic imide 1a (0.1 mmol) and hydrazine hydrate 2a (40 mmol) as starting materials, they were added to a glass bottle and heated and stirred at 80 °C on a heating plate for 12 hours to obtain compound 3a, and the yield was 23%.
[0041] Figure 1 Optical diagrams of single crystals of the products (compound 3a and compound 2b) in Examples 1 and 2;
[0042] Figure 2 SEM images of single crystals of the products (Compound 3a and Compound 2b) in Examples 1 and 2;
[0043] Figure 3 Single crystal structures of the products (Compound 3a and Compound 2b) in Examples 1 and 2 (white: hydrogen; red: oxygen; gray: carbon; blue: nitrogen);
[0044] Figure 4 1H NMR spectrum of the product (Compound 3a) in Example 1.
[0045] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications made without departing from the spirit and principle of the present invention shall be equivalent replacement methods and are all included in the protection scope of the present invention.
Claims
1. A preparation method of single crystals of amino-functionalized aromatic imide compounds based on the hydrothermal method, characterized in that: Comprising the following steps: The aromatic imide compound and hydrazine hydrate undergo a hydrothermal reaction to obtain single crystals of amino-functionalized aromatic imide compounds; hydrazine hydrate serves as both a reaction medium and a reactant. The structure of the aromatic imide compound is: In the formula: R and R1 are each independently at least one of H, alkyl, secondary amino group, carboxyl group, hydroxyl group, pyridyl group; X1-X6 are each independently H, alkyl, amino group, F, Cl, Br, CN, NO2 group. The temperature of the reaction is 90-160 °C.
2. The method for preparing single crystals of amino-functionalized aromatic imide compounds based on hydrothermal method according to claim 1, wherein: The alkyl groups in R and R1 are C 1～10 alkyl groups; the primary amine group and secondary amine group are -NHR2, where R2 is H, an alkyl group, a phenyl group, an acetylphenyl group, or a vinylphenyl group; The pyridyl group is 2-substituted pyridine, 3-substituted pyridine, 4-substituted pyridine. The alkyl group described in X is C 1～10 alkyl group; The structure of the amino-functionalized aromatic imide compound is In the formula: X1-X6 are each independently H, alkyl, -NH2, F, Cl, Br, CN, -NO2.
3. The preparation method of the amino-functionalized aromatic imide compound single crystal based on the hydrothermal method according to claim 1, wherein: The temperature of the reaction is 100-120 °C.
4. The method for preparing single crystals of amino-functionalized aromatic imide compounds based on hydrothermal method according to claim 1, wherein: The molar ratio of hydrazine hydrate to the aromatic imide compound is (50-5000):
1.
5. The preparation method of the amino-functionalized aromatic imide compound single crystal based on the hydrothermal method according to claim 4, characterized in that: The molar ratio of hydrazine hydrate to the aromatic imide compound is (300-900):
1.
6. The preparation method of the single crystal of the amino-functionalized aromatic imide compound based on the hydrothermal method according to claim 1, characterized in that: The reaction time is 8-24 hours; the reaction is carried out in a high-pressure sealed reactor.
7. Single crystals of amino-functionalized aromatic imide compounds based on hydrothermal method obtained by the preparation method according to any one of claims 1-6.