CN110407718B - Benzoylimide derivative with triphenylamine as donor, and preparation and application thereof - Google Patents
Benzoylimide derivative with triphenylamine as donor, and preparation and application thereof Download PDFInfo
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- CN110407718B CN110407718B CN201910548735.0A CN201910548735A CN110407718B CN 110407718 B CN110407718 B CN 110407718B CN 201910548735 A CN201910548735 A CN 201910548735A CN 110407718 B CN110407718 B CN 110407718B
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Abstract
The invention provides a benzoyl imide derivative (I) taking triphenylamine as a donor, a preparation method thereof and application thereof in preparing a piezochromic material. The novel benzoyl imide derivative is used as a luminescent material, and the light color conversion from green to yellow and from blue to yellow can be respectively obtained by grinding two crystals of the novel benzoyl imide derivative, and the novel benzoyl imide derivative has the following beneficial effects: the preparation method is simple, and the material has excellent piezochromic property.
Description
(I) the technical field
The invention relates to a benzamide derivative taking triphenylamine as a donor, a preparation method thereof and application thereof in preparing a piezochromic material.
(II) background of the invention
The organic stimuli-responsive material is an organic material whose physical properties (such as color, luminescence, etc.) change under the influence of external environmental factors (such as temperature, pressure, solvent, PH, etc.). Among them, piezochromic materials have been extensively studied in recent years. The piezochromism refers to the phenomenon that the fluorescence color of the material is converted under the action of external force. The material with piezochromic property has unprecedented application potential in the fields of anti-counterfeiting identification, chemical sensing and the like. Therefore, the method has important theoretical significance and practical application value for the research and development of the piezochromic material.
Triphenylamine is used as a strong electron-donating group and is often applied to the construction of luminescent molecules. Due to the existence of oxygen and nitrogen atoms, weak interactions such as hydrogen bonds are easily formed among molecules of the phenylimide derivative, so that the derivative has a variable aggregation state structure, and the derivative is just favorable for obtaining the piezochromic property. The novel benzoyl imide derivative constructed by taking triphenylamine as a donor has important significance for promoting the development of the piezochromic luminescent material.
Disclosure of the invention
The invention aims to provide a novel benzoyl imide derivative taking triphenylamine as a donor, a preparation method thereof and application thereof in preparing a piezochromic material.
The technical scheme adopted by the invention is as follows:
a benzene imide derivative taking triphenylamine as a donor has a structure shown in a formula (I):
the invention also relates to a method for preparing the benzamide derivative, which comprises the following steps: dissolving a compound shown in a formula (II) in dichloromethane, irradiating for 5-7 days by using a 365nm ultraviolet lamp, and separating and purifying reaction liquid to obtain the benzimide derivative; the amount of methylene chloride is at least such that all of the reactants are dissolved.
The separation and purification method comprises the following steps: extracting the reaction solution with dichloromethane and deionized water successively, combining the organic phases, adding MgSO 4 Drying, concentrating under reduced pressure, and separating and purifying by column chromatography to obtain a yellow solid target product, namely the phthalimide derivative;
during column chromatography separation, a stationary phase is 300-400 meshes of silica gel, and a mobile phase is petroleum ether: and ethyl acetate in a volume ratio of 3: 1.
The compound of formula (II) is prepared by the following method: under the protection of nitrogen, dissolving 4-fluoroaniline, benzil, diphenylamine benzaldehyde and amine acetate in an acetic acid solvent, heating and refluxing for 10-18 hours, and separating and purifying reaction liquid to obtain the compound shown in the formula (II).
The separation and purification method comprises the following steps: cooling the reaction solution, adding deionized water, precipitating white solid, filtering, extracting the filter residue with dichloromethane and deionized water, mixing the organic phases, and adding MgSO 4 Drying, concentrating under reduced pressure, and separating and purifying by column chromatography to obtain a white solid target product, namely the compound of the formula (II).
The amount ratio of the 4-fluoroaniline, the benzil, the diphenylamine-benzaldehyde and the amine acetate is 1-5: 1: 1-1.2: 1 to 4. The acetic acid is preferably added in an amount just enough to dissolve all of the reactants.
During column chromatography separation, the stationary phase is 300-400 mesh silica gel, and the mobile phase is ethyl acetate: and the volume ratio of the dichloromethane is 1: 200.
The invention also relates to application of the benzoyl imide derivative in preparing a piezochromic material.
Dissolving the obtained compound (I) in mixed solvents of ethanol and water in different proportions, and slowly volatilizing the solvents to grow crystals. Crystals emitting light in two colors, green and blue, 1a and 1b, respectively, were obtained.
Further grinding 1a and 1b with a mortar changed the color of the luminescence, 1a from green to yellow and 1b from blue to yellow.
The invention has the following beneficial effects: the invention provides a new benzoyl imide derivative which can be used as a piezochromic material, the preparation method is simple, and the material has excellent piezochromic performance.
Description of the drawings
FIG. 1 shows fluorescence emission spectrum of compound (I) according to the present invention.
FIG. 2 shows the emission spectra of the crystal 1a according to the invention with different degrees of grinding.
FIG. 3 is a graph showing the emission spectra of the crystal 1b of the present invention with different degrees of grinding.
(V) detailed description of the preferred embodiments
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto:
example 1: synthesis of Compound (II)
Under the protection of nitrogen, 4-fluoroaniline (111mg, 10mmol), benzil (420mg, 2mmol), diphenylaminobenzaldehyde (546.66mg, 2mmol) and ammonium acetate (617mg, 8mmol) were dissolved in acetic acid (15mL) solvent, and the reaction system was refluxed for 14 hours. Adding deionized water after the system is cooled, precipitating a large amount of white solid, filtering, extracting the obtained white solid with dichloromethane and deionized water, combining organic phases, adding anhydrous MgSO into the obtained organic phase 4 Drying, concentrating under reduced pressure, and separating and purifying by column chromatography, wherein the stationary phase is silica gel of 300-400 meshes, and the mobile phase is ethyl acetate: dichloromethane 1: 150-200 mixed solvent, finally obtaining 500mg of the target product (II) as white solid with 46% yield.
Compound (II) 1 H NMR data: (500MHz, DMSO) δ 7.50-7.46 (m,2H),7.36(dt, J ═ 9.0,3.5Hz,2H),7.32(dt, J ═ 5.2,2.2Hz,6H), 7.30-7.22 (m,6H), 7.22-7.15 (m,4H),7.09(t, J ═ 7.4Hz,2H),7.03(dd, J ═ 8.5,1.0Hz,4H), 6.85-6.80 (m,2H) ms (esi) theoretical value m/z: 557.23, found: 559.1 (M) + )。
Example 2: synthesis of Compound (I)
The compound (100mg, 0.18mmol) obtained in example 1 was dissolved in methylene chloride (100mL) solvent and irradiated under an ultraviolet lamp of 365nm for 7 days. Extracting with dichloromethane and deionized water after reaction, mixing organic phases, adding anhydrous MgSO into the obtained organic phase 4 Drying, concentrating under reduced pressure, and separating and purifying by column chromatography, wherein the stationary phase is silica gel of 300-400 meshes, and the mobile phase is petroleum ether: ethyl acetate 3:1 mixed solvent to give the target 42mg as a yellow solid in 42% yield.
Compound (I) 1 H NMR data: (500MHz, Tol) δ 7.89(d, J ═ 3.5Hz,1H),7.79(d, J ═ 74Hz,1H),7.55(dd, J ═ 11.2,8.3Hz,1H),7.10(s,5H), 7.05-6.95 (m,12H),6.92(dd, J ═ 8.9,5.6Hz,3H), 6.89-6.82 (m,3H),6.73(t, J ═ 5.8Hz,1H),6.42(t, J ═ 8.5Hz,1H), ms (esi) theoretical values m/z: 589.22, found: 591.5 (M) + )。
Example 3: crystal growth of crystals 1a, 1b
The compound obtained in example 2 was dissolved in a mixture of ethanol and water (1:1, 2:1, 3:1, 4:1, 5:1) at different ratios, respectively, and the solvent was slowly volatilized at room temperature, and crystals having green and blue fluorescence were grown as 1a and 1b, respectively.
Example 4: emission spectra of crystals 1a, 1b and piezochromic spectra of crystals
The crystals 1a and 1b obtained in example 3 were subjected to fluorescence emission spectroscopy of a solid to obtain characteristic fluorescence emission spectra thereof, and as shown in fig. 1, it was confirmed that they have photoluminescence properties. The emission peaks of the substances 1a and 1b are 448nm and 497nm respectively.
The crystals 1a and 1b obtained in example 3 were subjected to fluorescence emission spectra of different solids in a mortar to obtain characteristic fluorescence emission spectra thereof, which were confirmed to have piezochromic properties as shown in fig. 2. The emission peak ranges of the substances 1a and 1b are 495 nm-544 nm and 451 nm-547 nm respectively.
Claims (9)
1. A benzene imide derivative taking triphenylamine as a donor has a structure shown in a formula (I):
2. a process for the preparation of a phthalimide derivative according to claim 1, which comprises: dissolving a compound shown in a formula (II) in dichloromethane, irradiating for 5-7 days by using a 365nm ultraviolet lamp, and separating and purifying reaction liquid to obtain the benzimide derivative;
3. the method according to claim 2, wherein the separation and purification method comprises: extracting the reaction solution with dichloromethane and deionized water successively, combining organic phases, adding MgSO 4 Drying, concentrating under reduced pressure, and separating and purifying by column chromatography to obtain yellow solid target product, namely the benzamide derivative;
4. the method according to claim 3, wherein during the column chromatography separation, a stationary phase is silica gel with a size of 300-400 meshes, and a mobile phase is petroleum ether: and ethyl acetate in a volume ratio of 3: 1.
5. The process according to claim 2, characterized in that the compound of formula (II) is prepared by: under the protection of nitrogen, dissolving 4-fluoroaniline, benzil, diphenylamine benzaldehyde and amine acetate in an acetic acid solvent, heating and refluxing for 10-18 hours, and separating and purifying reaction liquid to obtain the compound shown in the formula (II).
6. The method according to claim 5, wherein the separation and purification method comprises the following steps: cooling the reaction solution, adding deionized water, precipitating white solid, filtering, extracting the filter residue with dichloromethane and deionized water, mixing the organic phases, adding MgSO 4 Drying, concentrating under reduced pressure, and separating and purifying by column chromatography to obtain a white solid target product, namely the compound of the formula (II).
7. The method according to claim 5, wherein the amount of the 4-fluoroaniline, benzil, diphenylaminobenzaldehyde, and amine acetate material is from 1 to 5: 1: 1-1.2: 1 to 4.
8. The method of claim 6, wherein during the column chromatography separation in the process of preparing the compound of formula (II), the stationary phase is 300-400 mesh silica gel, and the mobile phase is ethyl acetate: and the volume ratio of the dichloromethane is 1: 200.
9. Use of the phthalimide derivative of claim 1 in the preparation of piezochromic materials.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102079974A (en) * | 2009-11-26 | 2011-06-01 | 宁波大学 | Fluorinated triphenylamine derivative biological blue light materials and preparation method thereof |
| CN109761847A (en) * | 2018-12-26 | 2019-05-17 | 浙江工业大学 | A kind of saccharin derivative and the preparation method and application thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102079974A (en) * | 2009-11-26 | 2011-06-01 | 宁波大学 | Fluorinated triphenylamine derivative biological blue light materials and preparation method thereof |
| CN109761847A (en) * | 2018-12-26 | 2019-05-17 | 浙江工业大学 | A kind of saccharin derivative and the preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| Highly efficient luminescent benzoylimino derivative and fluorescent probe from a photochemical reaction of imidazole as an oxygen sensor;Yu, Yue 等;《 Chemical Communications 》;20181213;第55卷(第7期);977-980页 * |
| 三苯胺的压致变色机制研究;吴锦霞 等;《光谱学与光谱分析》;20141031;第34卷(第10期);273-274页 * |
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