Preparation and application of α-carbonyl amide derivatives

Abstract

The invention discloses the preparation and application of an α-carbonylamide derivative, wherein 4-(1,2,2-triphenylvinyl)acetophenone and an aniline derivative are placed in dimethyl sulfoxide, potassium persulfate is used as an oxidant, anhydrous ferric chloride is used as a catalyst, the reaction requires nitrogen protection, the reaction is carried out at a heating temperature of 120°C for 12 hours, and after the reaction is completed, the compound molecule is separated and purified to obtain the compound molecule. The molecules synthesized according to the above method have a large conjugated system and have significant pressure-induced color change properties. The compound of the present invention has low preparation cost, simple operation, simple method, and the compound exhibits significant pressure-induced color change properties, and can be applied to the fields of pressure-induced color change, luminescent materials, color packaging printing, printing and dyeing, and anti-counterfeiting technology. At the same time, the synthesis method can be used for the synthesis of fine organic chemical fields such as pesticides and medicines.

Description

Technical Field

[0001] The present invention belongs to the field of organic synthesis, and specifically relates to the preparation and application of an α-carbonyl amide derivative Background Art

[0002] α-Carboxylamide derivatives are important active intermediates in the synthesis of medicines and pesticides. (Chem. Eur. J. 2015, 21, 8033-8037; Tetrahedron Letters, 2017, 58, 546-551;), therefore, the synthesis of α-carbonyl amide derivatives has attracted widespread attention and interest from scientists. In addition, many literatures have reported the synthesis of α-carbonyl amide derivatives (Angewandte Chemie-International Edition 2016, 55, 5327; Angewandte Chemie-International Edition 2008, 47, 947; Journal of the American Chemical Society 1985, 107, 3235-3245; Journal of the American Chemical Society 2010, 132, 28; Journal of the American Chemical Society 2010, 132, 28; Organic Letters 2014, 16, 5772... etc.).

[0003] In 2007, Xu Bin et al. (CN101121692) disclosed that substituted aromatic acetamide was used as raw material, and methylene was oxidized under catalysis to obtain α-carbonyl amide; in 2009, Jiao Ning et al. (CN101735095) disclosed that aryl acetylene was coupled with amine compounds in the presence of relevant auxiliary agents using copper as catalyst under the action of oxidant to obtain α-carbonyl amide derivatives. In addition, they also tried another method to synthesize α-carbonyl amide, namely: α-carbonyl aldehyde and amine compounds were condensed under copper catalysis to prepare the corresponding α-carbonyl amide (Organic Letters, 2012, 14, 3280-3284); Li et al. also prepared α-carbonyl derivatives by coupling N-substituted formamide with α-carbonyl formic acid under CuBr2 catalysis (Chem. Commun., 2013, 49 ,3640); Wu Jian et al. (CN109096139) disclosed a relatively novel method for synthesizing α-carbonyl amides, in which a novel pyridine imidazole amine compound reacts with water to prepare α-carbonyl amide derivatives by ring opening without metal catalysis. The above-mentioned methods for synthesizing α-carbonyl amide derivatives have their own advantages and disadvantages, and play an important role in the synthesis of α-carbonyl amide derivatives.

[0004] This paper invented a new method to synthesize α-carbonyl amide, that is, using highly conjugated reactants 4-(1,2,2-triphenylvinyl)acetophenone and p-cyanoaniline or p-nitroaniline, as well as an oxidant and a catalyst, to react under nitrogen protection and temperature to obtain α-carbonyl amide. Compared with the previous synthesis of α-carbonyl amide, this method has obvious advantages: the raw materials are easily available, the price is low, and the operation is simple. Summary of the invention

[0005] The object of the present invention is to provide a novel α-carbonyl amide derivative which is easy to synthesize and has remarkable pressure-induced color change properties.

[0006] The purpose of the present invention is achieved through the following technical solutions:

[0007] Pressure-induced chromic fluorescent material, the specific molecular structure is as follows:

[0008]

[0009] The pressure-induced chromic fluorescent material comprises the following steps:

[0010] 4-(1,2,2-triphenylvinyl)acetophenone and aniline derivatives are placed in a solvent, and heated to react under the action of an oxidant, a catalyst and a solvent. After the reaction is completed, an α-carbonylamide derivative is obtained. The specific synthesis process is as follows:

[0011]

[0012] The oxidant is selected from any one of potassium persulfate and triethylenediamine (TDEA).

[0013] The catalyst is selected from any one of anhydrous ferric chloride and anhydrous ferric sulfate.

[0014] The molar ratio of the 4-(1,2,2-triphenylvinyl)acetophenone, the aniline derivative and potassium persulfate is 1:1-1.5:3-5.

[0015] The heating reaction temperature is 100-150°C and the reaction time is 10-15h.

[0016] The reaction solvent is any one of dimethyl sulfoxide and N,N-dimethylformamide.

[0017] The core key condition of the present invention is to use 4-(1,2,2-triphenylvinyl)acetophenone and aniline derivatives as substrates, place them in dimethyl sulfoxide, use potassium persulfate as an oxidant and anhydrous ferric chloride as a catalyst to react, and after the reaction is completed, separate and purify to obtain the compound molecule.

[0018] The compound synthesized by the present invention has a large conjugated system, and the molecules all have significant pressure-induced color change. The preparation method of the α-carbonyl amide derivative of the present invention is simple, easy to operate, and low in cost. It can be applied to luminescent materials, pressure-induced color change materials, fluorescent inks and anti-counterfeiting fields. At the same time, the synthesis method can be used for the synthesis of fine organic chemical fields such as pesticides and medicines. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 This is the hydrogen NMR spectrum of the A-1 molecule.

[0020] Figure 2 This is the carbon NMR spectrum of the A-1 molecule.

[0021] Figure 3 This is the high-resolution mass spectrum of the A-1 molecule.

[0022] Figure 4 This is the single crystal structure diagram of the A-1 molecule.

[0023] Figure 5 This is the hydrogen nuclear magnetic resonance spectrum of the A-2 molecule.

[0024] Figure 6 This is the carbon NMR spectrum of the A-2 molecule.

[0025] Figure 7 This is the high-resolution mass spectrum of the A-2 molecule.

[0026] Figure 8 This is the single crystal structure diagram of the A-2 molecule.

[0027] Fig. 9 The fluorescence spectra of A-1 before and after grinding.

[0028] Fig.10 This is the color change of A-1 before and after grinding.

[0029] Fig.11 The fluorescence spectra of A-2 before and after grinding.

[0030] Fig.12 And the color change diagram of A-2 before and after grinding.

[0031] Fig.13 Powder XRD patterns of A-2 before and after grinding.

[0032] Fig.14 Application of functional organic material molecule A-1.

[0033] Fig.15 Application of functional organic material molecule A-2. DETAILED DESCRIPTION

[0034] The present invention is further described below with reference to embodiments, but the scope of protection claimed by the present invention is not limited to the scope described in the embodiments.

[0035] Example 1: Synthesis of A-1 molecule

[0036] 4-(1,2,2-Triphenylvinyl)acetophenone (187.2 mg, 0.5 mmol), p-cyanoaniline (88.6 mg, 0.75 mmol), potassium persulfate (405.5 mg, 1.5 mmol), anhydrous ferric chloride (8.2 mg 0.05 mmol), and 4 mL of dimethyl sulfoxide were added sequentially into a 25 mL reaction bottle. The reaction was protected by nitrogen. After reacting at a heating temperature of 120 ° C for 12 h, water was added to quench the reaction, and the product was extracted with dichloromethane. After being spin-dried, the product was purified by column chromatography (PE:EA=25:1) to obtain the molecule as a solid (80.8 mg) with a yield of 13.4%.

[0037] The structural formula is as follows:

[0038]

[0039] A-1 Structural Formula

[0040] Example 2: Synthesis of A-1 molecule

[0041] 4-(1,2,2-Triphenylvinyl)acetophenone (187.2 mg, 0.5 mmol), p-cyanoaniline (88.6 mg, 0.75 mmol), potassium persulfate (405.5 mg, 1.5 mmol), anhydrous ferric sulfate (20.0 mg 0.05 mmol), and 4 mL of dimethyl sulfoxide were added sequentially into a 25 mL reaction bottle, and the reaction was protected by nitrogen. After reacting at a heating temperature of 120 ° C for 12 h, water was added to quench the reaction, and the product was extracted with dichloromethane. After being spin-dried, the molecule A-1 was obtained by column chromatography (PE:EA=15:1) as a solid (50.8 mg) with a yield of 8.4%.

[0042] It can be seen from Examples 1 and 2 that using anhydrous ferric chloride as a catalyst can greatly improve the reaction yield.

[0043] Example 3: Synthesis of A-2 molecule

[0044] 4-(1,2,2-Triphenylvinyl)acetophenone (187.2 mg, 0.5 mmol), 4-nitroaniline (103.6 mg, 0.75 mmol), potassium persulfate (405.5 mg, 1.5 mmol), anhydrous ferric chloride (8.2 mg 0.05 mmol), and 4 mL of dimethyl sulfoxide were added sequentially into a 25 mL reaction bottle, and the reaction was protected by nitrogen. After reacting at a heating temperature of 120 ° C for 12 h, water was added to quench, and the product was extracted with dichloromethane. After being spin-dried, the molecule A-2 was obtained by column chromatography (PE:EA=20:1) as a solid of 160.8 mg with a yield of 35.5%.

[0045] The structural formula is as follows:

[0046]

[0047] A-2 structure

[0048] Example 4: Synthesis of A-2 molecule

[0049] 4-(1,2,2-Triphenylvinyl)acetophenone (187.2 mg, 0.5 mmol), 4-nitroaniline (103.6 mg, 0.75 mmol), potassium persulfate (405.5 mg, 1.5 mmol), anhydrous ferric chloride (8.2 mg 0.05 mmol), and 4 mL of N,N-dimethylformamide were added sequentially into a 25 mL reaction bottle, and the reaction was protected by nitrogen. After reacting at a heating temperature of 120 ° C for 12 h, water was added to quench the reaction, and the product was extracted with dichloromethane. After being spin-dried, the product was purified by column chromatography (PE:EA=20:1) to obtain the molecule A-2 as a solid (60.8 mg) with a yield of 15.5%.

[0050] The structural formula is as follows:

[0051]

[0052] A-2 structure

[0053] It can be seen from Examples 3 and 4 that using dimethyl sulfoxide as a solvent can greatly increase the reaction yield.

[0054] Example 5

[0055] 4-(1,2,2-Triphenylvinyl)acetophenone (187.2 mg, 0.5 mmol), benzylamine (173.8 mg, 0.75 mmol), potassium persulfate (405.5 mg, 1.5 mmol), anhydrous ferric chloride (8.2 mg 0.05 mmol) and 4 mL of dimethyl sulfoxide were added sequentially into a 25 mL reaction bottle. The reaction was protected by nitrogen. After reacting for 12 h at a heating temperature of 120 °C, no target product was found to be generated.

[0056] Example 6

[0057] Weigh 10 mg of the yellow-green material molecule A-1 prepared in Example 1 and put it into a mortar. After grinding it with a pestle for 1 minute, irradiate it with a 365 ultraviolet lamp and find that the dye molecule changes from the previous yellow-green to yellow. The ground yellow dye is stirred and washed with n-hexane for 2 minutes to obtain a yellow-green molecule. The washed yellow-green fluorescent molecule can be ground to yellow again, and the yellow dye can also be washed to yellow-green. This process can be cycled infinitely.

[0058] Fig. 9 and Fig.10 The fluorescence spectrum and color change diagram of the yellow-green molecule A-1 before and after grinding are shown respectively. Fig. 9 Here, pristine refers to the original solid powder (solid before grinding), ground refers to the solid powder after grinding, and soaked refers to the solid powder washed with n-hexane after grinding. Fig.10 It can be seen that after grinding, the maximum emission wavelength of the dye molecule is red-shifted by 14 nm, and the fluorescence color changes from yellow-green to yellow. After washing the ground solid powder with n-hexane, the yellow-green color can be restored, indicating that the dye molecule has good pressure-induced color change properties and good reversibility.

[0059] Similarly, 10 mg of the yellow-green material molecule A-2 prepared in Example 3 was weighed and put into a mortar. After grinding with a pestle for 1 minute, it was irradiated with a 365 ultraviolet lamp and found that the dye molecule changed from the previous yellow-green to light yellow. The ground light yellow dye was stirred and washed with n-hexane for 2 minutes to obtain a yellow-green molecule. The washed yellow-green fluorescent molecule can be ground to yellow, and the yellow dye can also be washed to yellow-green. This process can be cycled infinitely.

[0060] Fig.11 and Fig.12 They are the fluorescence spectrum and color change diagram of the yellow material molecule A-2 before and after grinding. Fig.11 Here, pristine refers to the original solid powder (solid before grinding), ground refers to the solid powder after grinding, and soaked refers to the solid powder washed with n-hexane after grinding. Fig.11 It can be seen that after grinding, the maximum emission wavelength of the dye molecule blue-shifts by 9nm, and the fluorescence color changes from yellow-green to light yellow. After washing the ground solid powder with n-hexane, it can return to yellow, indicating that the dye molecule has good pressure-induced color change properties and good reversibility.

[0061] Fig.13 The XRD patterns of powder A-2 before and after grinding. Fig.13 Here, pristine refers to the original solid powder and the solid before grinding (top), ground refers to the solid powder after grinding (middle), and soaked refers to the solid powder washed with n-hexane after grinding (bottom); Fig.13 It can be seen that the dye molecules show clear and sharp diffraction peaks before grinding, indicating ordered crystalline properties, while the solid after grinding shows quite weak diffraction, indicating that the ground sample is amorphous in nature, and the force destroys or weakens the interaction between molecules. This transition from crystalline to amorphous state leads to a blue shift in the fluorescence color. However, washing with n-hexane greatly improves the crystallinity, and sharp diffraction peaks appear at the same time, which are in good agreement with the original diffraction peaks, and the fluorescence color also returns to the yellow-green color before grinding.

[0062] The specific implementation process of using the functional organic material molecule A-1 as a read-write device is as follows: spread the yellow-green dye molecule evenly on it, and then write an "A" on paper. Then, under a 365nm fluorescent light, it will be found that the "A" is yellow. This shows that this dye molecule can be well used as a read-write device and has significant anti-counterfeiting applications. Fig.14 Application of functional organic material molecule A-1.

[0063] The specific implementation process of using the functional organic material molecule A-2 as a read-write device is as follows: the yellow-green dye molecule is evenly spread on it, and then an "F" is written on paper. Then, under a 365nm fluorescent light, it is found that the "F" is yellow. It can be seen that this dye molecule can be well used as a read-write device and has significant anti-counterfeiting applications. Fig.15 Application of functional organic material molecule A-2.

[0064] The above embodiments of the present invention are described in detail in conjunction with the embodiments, but the present invention is not limited to the described embodiments. For those skilled in the art, various changes, modifications, substitutions and variations of these embodiments are made without departing from the principles and spirit of the present invention, and still fall within the scope of protection of the present invention.

Claims

1. An α-carbonyl amide derivative, characterized in that: Its structural formula is as follows: 。 2. The method for preparing an α-carbonylamide derivative according to claim 1, characterized in that: The following steps are involved: 4-(1,2,2-triphenylvinyl)acetophenone and aniline derivatives are placed in a solvent and heated to react under the action of an oxidant and a catalyst. After the reaction, an α-carbonylamide derivative is obtained. The specific synthesis process is as follows: ； The oxidant is selected from potassium persulfate; The catalyst is selected from any one of anhydrous ferric chloride and anhydrous ferric sulfate; The reaction solvent is any one of dimethyl sulfoxide and N,N-dimethylformamide.

3. The method for preparing the α-carbonyl amide derivative according to claim 2, characterized in that: The molar ratio of 4-(1,2,2-triphenylvinyl)acetophenone, aniline derivative and oxidant is 1:1-1.5:3-5.

4. The method for preparing an α-carbonyl amide derivative according to claim 2, characterized in that: The heating reaction temperature is 100-150°C and the reaction time is 10-15h.

5. Use of the α-carbonylamide derivative according to claim 1 as a pressed color-changing material.

6. Use of the α-carbonylamide derivative according to claim 1 as a fluorescent anti-counterfeiting material.

7. The use according to claim 6, characterized in that: The wavelength of the fluorescent light is 300-385nm.

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