Isolongifolia alkanoylquinazoline compound, synthesis method and application thereof

Abstract

The present invention discloses an isolongifolia alkanoyl quinazoline compound, a synthesis method, and its application. The target compound obtained by combining a quinazoline structure with a triphenylamine structure has an alkyl functional group that increases solubility, and a nitrogen heterocyclic structure containing triphenylamine and quinazoline that significantly improves its electron transport capacity. The target compound has electrochromic and electrochemical properties. As an electrode material for an organic supercapacitor, the target compound prepared by the present invention exhibits excellent n-doped electrochemical properties compared to existing electrode materials, showing a high area specific capacitance and excellent charge-discharge performance during n-type doped electrochemical redox processes. As an electrochromic material, the target compound exhibits excellent electrochromic properties.

Description

Technical Field

[0001] The present invention belongs to the technical field of organic compounds, and particularly relates to a method and application of preparing quinazoline compounds by activating the ortho-CH bond of a heterocyclic aldehyde using isolongifolia ketone as a substrate. Background Art

[0002] Organic electrode materials hold great promise for application in flexible organic devices due to their low cost and ease of modification. However, common polymer semiconductors are difficult to purify, have poor solubility, and their molecular weight is difficult to control. These drawbacks inhibit device performance and reproducibility. Small molecule organic electrode materials can effectively circumvent these drawbacks by eliminating molecular weight variations, facilitating purification, and increasing material reproducibility. Summary of the Invention

[0003] The main technical problem to be solved by the present invention is to provide a quinazoline derivative with a green substrate, low price and easy access, so that it can meet the needs of organic electrode materials. Another object of the present invention is to provide a method for synthesizing the above-mentioned compound. Another object of the present invention is to provide the application of the above-mentioned compound as an electrode material and an electrochromic material.

[0004] In order to achieve the above-mentioned object of the invention, the technical solution adopted by the present invention is: to provide an isolongifolia alkanoyl quinazoline compound having the following structure:

[0005]

[0006] The synthesis method of the above-mentioned isolongifolia alkanoyl quinazoline compound comprises:

[0007] (1) Using heterocyclic isolongifolia ketone as a substrate, a nucleophilic substitution reaction is carried out with benzaldehyde or 4-(N,N-diphenylamino)benzaldehyde in the presence of a basic catalyst to obtain intermediate IIa or intermediate IIb.

[0008]

[0009]

[0010] (2) a step of subjecting the intermediate IIa or the intermediate IIb to a cyclization reaction with guanidine hydrochloride in the presence of a basic catalyst to obtain the intermediate IIIa or the intermediate IIIb,

[0011]

[0012] (3) a step of reacting the intermediate IIIa or the intermediate IIIb with 4-diphenylaminobenzaldehyde to obtain an isolongifolia alkanoylquinazoline compound TPAB or TPANB.

[0013]

[0014] Furthermore, in step 1), the molar ratio of isolongiol to benzaldehyde or 4-(N,N-diphenylamino)benzaldehyde is 1:1-6.

[0015] Furthermore, in step 1), the nucleophilic substitution reaction is carried out in the presence of an organic solvent, the nucleophilic substitution reaction temperature is 80-120° C., and the reaction time is 6-72 h.

[0016] Specifically, the organic solvent is selected from any one of methanol, ethanol, isopropanol, dichloromethane, chloroform, 1,4-dioxane and 1,2-dichloroethane.

[0017] Furthermore, in step 1), the alkaline catalyst is selected from any one of sodium ethoxide, potassium ethoxide, potassium hydroxide, and sodium hydroxide, and the amount of the alkaline catalyst is 1.5-5.5% of the molar amount of benzaldehyde or 4-(N,N-diphenylamino)benzaldehyde.

[0018] Furthermore, in step 2), the molar ratio of intermediate IIa or intermediate IIb to guanidine hydrochloride is 1:3-9.

[0019] Furthermore, in step 2), the cyclization reaction is carried out in the presence of a solvent, the cyclization reaction temperature is 80 to 120° C., and the reaction time is 12 to 72 hours.

[0020] Specifically, the solvent is selected from any one of methanol, ethanol, tert-butanol, isopropanol, dichloromethane, chloroform, 1,4-dioxane and 1,2-dichloroethane.

[0021] Furthermore, in step 2), the alkaline catalyst is selected from any one of sodium ethoxide, potassium ethoxide, potassium hydroxide, sodium hydroxide, sodium tert-butoxide and potassium tert-butoxide, and the amount of the alkaline catalyst is 3.5-7.5% of the molar amount of intermediate IIa or intermediate IIb.

[0022] Furthermore, in step 3), the molar ratio of intermediate IIIa or intermediate IIIb to 4-diphenylaminobenzaldehyde is 1:1-7.

[0023] Furthermore, in step 3), the Schiff base reaction is carried out in the presence of a solvent, the Schiff base reaction temperature is 80 to 120° C., and the reaction time is 48 to 96 hours.

[0024] Specifically, the solvent is selected from any one of methanol, ethanol, tert-butanol and isopropanol.

[0025] The present invention also provides use of the isolongifolia alkanoylquinazoline compound as an electrode material for an organic supercapacitor.

[0026] The present invention also provides use of the isolongifolia alkanoyl quinazoline compound as an electrochromic material.

[0027] Compared with the prior art, the present invention has the following beneficial effects:

[0028] (1) The present invention provides a method for synthesizing quinazoline compounds with strong substrate universality, cheap and readily available materials, and green and renewable properties. The method uses cheap, readily available and green and renewable isolongol and aromatic aldehyde as starting materials, and carries out C-H bond activation and functional group construction under the catalysis of an alkaline catalyst. The reaction conditions are mild and the conversion is efficient (the yield of the nucleophilic substitution reaction reaches 80-89% in a short reaction time, the yield of the cyclization reaction reaches about 80%, and the yield of the Schiff base reaction reaches 70-88%). The method overcomes the shortcomings of the prior art of using aromatic compounds in terms of relatively stringent reaction substrate requirements and poor product solubility.

[0029] (2) This invention combines a quinazoline structure with a triphenylamine structure to prepare a novel isolongifolia alkylquinazoline compound. The alkyl functional group increases solubility, and the nitrogen heterocyclic structure containing triphenylamine and quinazoline significantly enhances its electron transport capacity, resulting in electrochromic and electrochemical properties. This invention is a novel multifunctional material with promising industrialization prospects and commercialization potential for multifunctional electrode materials.

[0030] (3) The isolongifolia alkanoyl quinazoline compound prepared by the present invention as an electrode material exhibits excellent n-doping electrochemical characteristics compared with existing electrode materials, and exhibits higher area specific capacitance and excellent charge and discharge performance in the n-type doping electrochemical redox process. -2 At this current density, the area specific capacitance of TPAB is 2.38mFcm -2 The capacitance retention rate is 93%. The area specific capacitance of TPANB is 2.13mF cm -2 , the capacitance retention rate is 90%.

[0031] (4) The isolongifolia alkanoyl quinazoline compound prepared by the present invention exhibits excellent electrochromic properties as an electrochromic material compared with existing electrochromic materials. By changing the applied potential from 0 to 1 V, the color of the film can be changed from colorless to blue. The coloring time of the TPAB film is 7.03 s, and the fading time is 6.49 s. The coloring and fading times of the TPANB film are 4.00 s and 3.00 s, respectively. The color rendering efficiency values ​​of TPAB and TPANB are 41.81 and 36.19 cm C, respectively. -1 .

[0032] It should be understood that all combinations of the aforementioned concepts and the additional concepts described in more detail below, as long as such concepts are not mutually inconsistent, can be considered as part of the inventive subject matter of the present application. In addition, all combinations of the claimed subject matter are considered as part of the inventive subject matter of the present application.

[0033] The foregoing and other aspects, embodiments, and features of the present invention will be more fully understood from the following description in conjunction with the accompanying drawings. Other additional aspects of the present invention, such as features and / or beneficial effects of the exemplary embodiments, will become apparent from the following description or through practice of specific embodiments according to the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] The accompanying drawings are not intended to be drawn to scale. In the accompanying drawings, corresponding operational steps in each figure are labeled with text in the figure. For the sake of clarity, not every step is described in every figure. Now, embodiments of various aspects of the present invention will be described by way of example and with reference to the accompanying drawings, in which:

[0035] Figure 1 CV curves of TPAB (a) and TPANB (b) in 0.5 M PC-LiClO4, GCD curves of TPAB (c) and TPANB (d) at different current densities during n-doping, and capacitance curves of TPAB (e) and TPANB (f) at different current densities.

[0036] Figure 2 Nyquist curves of TPAB (a) and TPANB (b), as well as cyclic stability curves of TPAB (c) and TPANB (d).

[0037] Figure 3 UV-visible absorption spectra of TPAB (a) and TPANB (b) films under different voltages, the inset is a local magnified image of the electrochromic structure, and the electrochromic-light absorption conversion curves of TPAB (c) and TPANB (d) films at a fixed wavelength. DETAILED DESCRIPTION

[0038] In order to better understand the technical content of the present invention, specific embodiments are given below in conjunction with the accompanying drawings.

[0039] Various aspects of the present invention are described herein with reference to the accompanying drawings, in which a number of illustrative embodiments are shown. The embodiments of the present invention are not necessarily intended to encompass all aspects of the present invention. It should be understood that the various concepts and embodiments described above, as well as those described in more detail below, may be implemented in any of a number of ways, as the concepts and embodiments disclosed herein are not limited to any particular implementation. In addition, some aspects disclosed herein may be used alone or in any appropriate combination with other aspects disclosed herein.

[0040] The present invention uses isolongifolia alkane I as the starting material. Its ortho-CH bond is activated under the catalytic action of an alkaline catalyst, and then undergoes a nucleophilic substitution reaction with an aromatic aldehyde to obtain the intermediate II shown. Intermediate II then undergoes a cyclization reaction with guanidine hydrochloride to obtain intermediate III. Intermediate III then reacts with 4-diphenylaminobenzaldehyde to obtain a quinazoline derivative. The present invention combines the nitrogen heterocycle and triphenylamine groups with excellent photoelectric activity, effectively enhancing the photoelectric properties of the compound. The synthetic route is as follows:

[0041]

[0042] The present invention is illustrated by the following examples, which are provided for illustrative purposes only and are not intended to limit the scope of the invention or its application. Unless otherwise specified, all raw materials used in the present invention are commercially available.

[0043] Example 1

[0044] The complete route for the synthesis of compound TPAB is as follows:

[0045]

[0046] The specific synthesis steps are:

[0047] 10 g (0.045 mol) of isolongifolia alkane, 6.35 g (0.060 mol) of benzaldehyde, 2.2 g (0.020 mol) of potassium tert-butoxide, and 50 mL of tert-butanol were added sequentially to a 100 mL single-necked flask and reacted at 70°C for 2 h. After completion, the reaction solution was cooled to room temperature. The solvent was removed by rotary evaporation, and the insoluble matter was collected. The insoluble matter was dissolved in a large amount of ethyl acetate, washed with water, dried over anhydrous sodium sulfate, and the filtrate was filtered and rotary evaporated until the solvent was completely evaporated to obtain crude product IIa. The crude product IIa was recrystallized, filtered, and dried to obtain compound IIa, (E)-7-benzylidene-1,1,5,5-tetramethyl-hexahydropyridine-1H-2,4a-methylene-8(2H)-naphthalenone (12.5 g, light yellow solid, yield 89.0%). 1H NMR(600MHz, CDCl3)δ7.53(s,1H),7.48-7.48(d,2H),7.41-7.39(t,2H),7.34-7.32 (t,1H),2.85-2.84(d,1H),2.64(s,1H),1.99(s,1H),1.85-1.87(m,1H),1.82(s,1H ),1.80-1.81(d,1H),1.77-1.78(d,1H),1.65-1.66(d,1H),1.51-1.55(m,1H),1.30 -1.32(d,1H),1.25(s,3H),1.06(s,3H),0.88(s,3H),0.86(s,3H).HRMS(ESI)m / z:C 22 H 28 O, theoretical value: 308.21; found value: 309.22 [M+H] + .

[0048] Compound IIa (2.8 g), guanidine hydrochloride (3.8 g, 0.040 mol), potassium tert-butoxide (2.2 g, 0.020 mol), and tert-butanol (50 mL) were added to a 100 mL three-necked flask and reacted at 70°C for 6 h. After completion of the reaction, the reaction mixture was cooled to room temperature. The reaction mixture was dissolved in a large amount of ethyl acetate, washed with water, dried over anhydrous sodium sulfate, and the filtrate was collected by filtration and rotary evaporation until the solvent was completely evaporated to obtain crude product IIIa. The crude product IIIa was recrystallized, filtered, and dried to obtain compound IIIa, 6,6,10,10-tetramethyl-4-phenyl-6,7,8,9,10,10a-hexahydro-5H-6a,9-methylbenz[H]quinazolin-2-amine (1.89 g, 60.0% yield). 1 HNMR(600MHz, CDCl3)δ7.53(s,1H),7.49(d,1H),7.48(s,1H),7.41-7.43(t,2H),7.40(s,1H),1.26(s,1H),1.24(s,3H), 1.20(s,1H),1.06(s,3H),0.98(s,2H),0.97(s,1H),0.96(s,2H),0.92(s,2H),0.88(s,3H),0.85(s,3H).HRMS(ESI)m / z:C 23 H 29 N3, theoretical value: 347.24; measured value: 348.24 [M+H] + .

[0049] Compound IIIa (0.400 g), 0.273 g (0.1 mmol g) of 4-(N,N-diphenylamino)benzaldehyde and 30 mL of ethanol were mixed evenly and poured into a 100 mL three-necked flask. The mixture was refluxed at 78°C for 12 h under nitrogen protection. After the reaction, the solvent was removed by rotary evaporation to obtain a solid crude product. The crude product was purified by recrystallization to obtain compound TPAB, namely ((E)-N-(4-(diphenylamino)benzylidene)-6,6,10,10-tetramethyl-4-phenyl-6,7,8,9,10,10a-hexahydro-5H-6a,9-methylbenz[H]quinazolin-2-amine). 1 H NMR (600MHz, CDCl3, δ, ppm): 9.808 (s, 1H, CH), 7.681-7.684 (d, J = 1.8Hz, 1H, A r-H),7.670-7.673(d,J=1.8Hz,1H,Ar-H),7.528(s,1H,Ar-H),7.489(s,1H,Ar -H),7.477(s,1H,Ar-H),7.387-7.413(t,J=15.6Hz,2H,Ar-H),7.354(s,1H,A r-H),7.342(s,2H,Ar-H),7.328(s,2H,Ar-H),7.181(s,3H,Ar-H),7.170(s,1H ,Ar-H),7.168(s,2H,Ar-H),7.022(s,1H,Ar-H),7.008(s,1H,CH),1.989-1.9 92(d,J=1.8Hz,1H,CH),1.775-1.782(d,J=2.7Hz,1H,CH),1.586(s,3H,CH),1. 317-1.319(d,1H,J=1.2Hz,CH),1.303(s,1H,CH),1.257(s,2H,CH),1.246(s, 3H,CH),1.062(s,3H,CH),0.883(s,3H,CH),0.855(s,3H,CH).HRMS(ESI)m / z:C 42 H 42 N4, theoretical value: 603.34; measured value: 603.35[M+] + .

[0050] Example 2

[0051] The complete route for the synthesis of compound TPANB is as follows:

[0052]

[0053] The specific synthesis steps are:

[0054] Isolongifolia alkane (10 g), 0.273 g (0.001 mol) of 4-(N,N-diphenylamino)benzaldehyde, potassium tert-butoxide (2.2 g), and tert-butanol (50 mL) were added sequentially to a 100 mL single-necked flask and reacted at 70°C for 2 h. After completion, the reaction solution was cooled to room temperature. The solvent was removed by rotary evaporation, and the insoluble matter was collected. The insoluble matter was dissolved in a large amount of ethyl acetate, washed with water, dried over anhydrous sodium sulfate, and the filtrate was filtered and rotary evaporated until the solvent was completely evaporated to obtain crude product IIb. The crude product IIb was recrystallized, filtered, and dried to obtain compound IIb, (E)-7-(4-(diphenylamino)benzylidene)-1,1,5,5-tetramethylhexahydro-1H-2,4a-methylene-8(2H)-naphthalenone. 1 H NMR(600MHz,CDCl3,δ,ppm):7.395(s,1H,Ar-H),7.381(s,1H,Ar-H),7.293-7 .296(d,J=1.8Hz,1H,Ar-H),7.283(s,2H,Ar-H),7.270(s,1H,Ar-H),7.144(s ,1H,Ar-H),7.136(s,1H,Ar-H),7.124(s,1H,Ar-H),7.088(s,1H,Ar-H),7.07 6(s,1H,Ar-H),7.063-7.065(d,J=1.2Hz,1H,Ar-H),7.046(s,1H,Ar-H),7.038 (s,1H,Ar-H),7.023(s,1H,CH),1.973-1.976(d,J=1.8Hz,2H,CH),1.860(s,1 H,CH),1.755-1.762(d,J=4.2Hz,1H,CH),1.294-1.298(d,J=2.4Hz,1H,CH),1. 255-1.259(d,J=2.4Hz,1H,CH),1.235(s,3H,CH),1.058(s,3H,CH),0.955(s, 2H,CH),0.874(s,3H,CH),0.860(s,3H,CH),0.847(s,2H,CH).HRMS(ESI)m / z:C 34 H 37 NO, theoretical value: 475.29; measured value: 476.30 [M+H] + .

[0055] Compound IIb (2.8 g), guanidine hydrochloride (3.8 g), 2.2 g (0.020 mol) of potassium tert-butoxide, and 50 mL of tert-butanol were added to a 100 mL three-necked flask and reacted at 70°C for 6 h. After completion of the reaction, the reaction solution was cooled to room temperature. The reaction solution was dissolved in a large amount of ethyl acetate, washed with water, dried over anhydrous sodium sulfate, and the filtrate was collected by filtration and rotary evaporation until the solvent was completely evaporated to obtain crude product IIIb. The crude product IIIb was recrystallized, filtered, and dried to obtain compound IIIb, namely 4-(4-(diphenylamino)phenyl)-6,6,10,10-tetramethyl-6,7,8,9,10,10a-hexahydro-5H-6a,9-methylbenz[H]quinazolin-2-amine. 1 H NMR (600MHz, CHCl3, δ, ppm): 7.451 (s, 1H, Ar-H), 7.436 (s, 1H, Ar-H), 7.290-7.294 (d, J = 2.4Hz, 2H, Ar-H), 7.276 (s, 2H, Ar-H ),7.155(s,2H,Ar-H),7.142(s,2H,Ar-H),7.106(s,1H,Ar-H),7.092(s,1H,Ar-H),7.069(s,1H,Ar-H),7.056(s,2H,CH),7. 045-7.046(d,J=0.6Hz,1H,Ar-H),4,816(s,2H,NH),2.313(s,1H,CH),1.747(s,2H,CH),1.372(s,3H,CH),1.275(s,1H,CH), 1.255(s,2H,CH),1.236(s,1H,CH),1.215(s,1H,CH),1.010(s,3H,CH),0.770(s,3H,CH),0.679(s,3H,CH).HRMS(ESI)m / z: C 35 H 38 N4, theoretical value: 514.31; measured value: 515.32 [M+H] + .

[0056] Compound IIIb (0.400 g), 0.273 g (0.001 mol) of 4-(N,N-diphenylamino)benzaldehyde and 30 mL of ethanol were mixed evenly and poured into a 100 mL three-necked flask. The mixture was refluxed at 78°C for 12 h under nitrogen protection. After the reaction, the solvent was removed by rotary evaporation to obtain a solid crude product. The crude product was purified by recrystallization to obtain compound TPANB, namely (E)-N-(4-(diphenylamino)benzylidene)-4-(4-(diphenylamino)phenyl)-6,6,10,10-tetramethyl-6,7,8,9,10,10a-hexahydro-5H-6a,9-methylbenz[H]quinazolin-2-amine (TPANB).1 H NMR (600MHz, CDCl3, δ, ppm): 9.806 (s, 1H, Ar-H), 7.668-7.682 (s, J = 8.4Hz, 1H, Ar-H), 7.457 (s, 2H ,Ar-H),7.395(s,2H,Ar-H),7.381(s,2H,Ar-H),7.351(s,1H,Ar-H),7.338(s,1H,Ar-H),7.325(s ,1H,Ar-H),7.295(s,2H,Ar-H),7.282(s,2H,Ar-H),7.269(s,2H,Ar-H),7.179(s,1H,Ar-H),7.16 7(s,1H,Ar-H),7.136(s,2H,Ar-H),7.123(s,2H,Ar-H),7.087(s,1H,Ar-H),7.075(s,1H,Ar-H),7 .063(s,1H,Ar-H),7.037(s,1H,Ar-H),7.023(s,1H,Ar-H),7.005(s,1H,CH),1.973-1.976(d,J=1 .8Hz,2H,CH),1.839-1.844(d,J=3.0Hz,1H,CH),1.794-1.797(d,J=1.8Hz,1H,CH),1.778-1.780( d,J=1.2Hz,1H,CH),1.755-1.761(d,J=3.6Hz,2H,CH),1.298(s,1H,CH),1.282(s,1H,CH),1.259( s,1H,CH),1.235(s,3H,CH),1.058(s,3H,CH),0.873(s,3H,CH),0.860(s,3H,CH).HRMS(ESI)m / z:C 54 H 51 N5, theoretical value: 769.41; measured value: 770.43 [M+H] + .

[0057] Application Example 1

[0058] TPAB obtained in Example 1 and TPANB obtained in Example 2 were dissolved in chloroform (10 mg mL -1), the above solution was filtered twice using a 0.22 μm organic filter, and the filtered solution was sprayed on the ITO glass to prepare organic compound electrodes, which were named TPAB electrode and TPANB electrode respectively. The spraying conditions are as follows: the pretreated ITO glass (indium tin oxide-plated glass, 10 mm wide, 20 mm long, 0.7 mm thick, surface resistivity: 8 Ω) was fixed on a heating plate at a temperature of 50°C, an airflow pressure of 150 Pa, and a spray angle of 45°. At the same time, the spraying distance was fixed at 10 cm, and 4 consecutive layers were deposited, with an interval of 100 s between each spraying. After the spraying was completed, post-curing was carried out for 20 minutes. In a 0.5 M LiClO4 / PC solution, a three-electrode electrolytic cell: TPAB electrode / TPANB electrode was the working electrode, platinum wire was the counter electrode, and Ag / Ag + The electrochemical properties of the two compounds were studied by cyclic voltammetry (CV) using an electrochemical workstation with a scan rate of 10–100 mV s -1 , the CV curves of TPAB and TPANB are as follows Figure 1 As shown in (a) and (b), scan rates were 10, 20, 50, and 100 mV s⁻¹, respectively. The results show that the peak currents of both compounds in the n-doped state are proportional to the scan rate. The CV curves reveal that both compounds exhibit reversible redox peaks. TPAB exhibits a higher peak current than TPANB, thus enabling higher n-doped capacitance.

[0059] The constant current charge and discharge (GCD) technique was used to further study the capacitance performance of TPAB electrode and TPANB electrode at different current densities. The GCD curves are shown in Figure 2. Figure 1 As shown in (c) and (d) of Figure 2, the area specific capacitance of the two compounds can be calculated from the GCD curves at different current densities. -2 At this current density, the area specific capacitance of TPAB is 2.38 mF cm -2 Importantly, even at 0.25 mA cm -2 At high current density, the area specific capacitance of TPAB remains at 2.23 mF cm -2 , the capacitance retention rate is 93% ( Figure 1 (e) in the figure). At a current density of 0.05 mA cm -2 When the area specific capacitance of TPANB is about 2.13mF cm -2 , at 0.25mAcm -2 At high current density, the area specific capacitance of TPAB remains at 2.00 mF cm -2 , the capacitance retention rate is 90% ( Figure 1(f) in the figure). Both compounds have high capacitance retention values ​​and good charge-discharge rate performance.

[0060] The conductivity and charge transfer properties of TPAB and TPANB on ITO were characterized by electrochemical impedance spectroscopy. Figure 2 As shown in (a) and (b), the linear part of the low field region represents the Weber impedance. The curves of the two compounds in the low field region are basically the same, and the slope of the EIS straight line part of TPANB is slightly higher than that of TPAB. The semicircle at the bottom of the curve belongs to the high field region, and the value of the intersection of the semicircle and the real axis is approximately the equivalent series resistance of the electrode material. Figure 2 As can be seen from (a) and (b), the real axis intersection value of TPANB is smaller than that of TPAB. Therefore, the resistance of TPANB is smaller than that of TPAB, indicating that TPANB has faster charge transfer and electrolyte ion diffusion rates.

[0061] The electrochemical stability of electrode materials is one of the important properties for their practical applications, such as Figure 2 TPAB and TPANB in ​​0.5M LiClO4 / PC solution, scan rate 100mA s -1 , the CV stability of the material was tested after 300 cycles. After 100 cycles, the CV areas of TPAB and TPANB increased to 149.24% and 149.28% of the initial areas, respectively, due to the continuous increase of dipoles during the cycle. At the same time, the redox peak potentials of the two compounds shifted. After 200 CV cycles, the CV areas of TPAB and TPANB were 78.07% and 82.76% of the CV areas of the first cycle, respectively. But after 300 cycles, the CV areas of TPAB and TPANB were 78.51% and 78.66% of the initial areas, respectively. The CV curve cycle test shows that the two compounds have good electrochemical stability.

[0062] Application Example 2

[0063] The TPAB electrode and TPANB electrode prepared in Application Example 1 were used to test the electrochromic (EC) properties of the two compounds using an electrochemical workstation and a UV-visible spectrometer. Figure 3 As shown ( Figure 3 The inset in (a) is a partial magnification. The color of the TPAB film does not change significantly within the applied voltage range of 0 to 0.8 V. However, when the applied voltage increases from 1.0 V to 1.5 V, the absorption peak intensity at 654 nm gradually increases. For the TPANB electrode, when the applied voltage increases from 0 V to 0.2 V, the absorption peak at 680 nm in the UV-visible absorption spectrum increases ( Figure 3(b) The inset is a partial magnification. When the applied potential reaches 1 V, the UV-visible absorption peak at 680 nm reaches its maximum intensity. Both compounds undergo a color change from colorless to blue. This phenomenon is likely due to the generation of TPA cation radicals under the action of the electric field, and the delocalization of electrons between the two nitrogen atoms, leading to charge transfer.

[0064] In addition, the electrochromic performance of TPAB was tested at a wavelength of 654 nm using a square wave potential of 0 to 1.5 V. Figure 3 It can be clearly seen in (c) that the coloring time of the TPAB film is 7.03s and the fading time is 6.49s. When an external voltage of 0.0-1.0V is applied, the coloring and fading times of the TPANB film at 680nm are 4.00s and 3.00s, respectively. The loose porous structure of the film can accelerate ion diffusion, so the color change response time of the material will be faster. The TPA unit replaces the 4-active site of the quinazoline ring. Its volume is larger than that of the benzene ring and its structure is more distorted, which can also be supported by theoretical calculations of the molecule. The fast response time of TPANB is mainly attributed to the conjugated π group of TPA in the TPANB molecule. The optical contrast of TPAB and TPANB is 9% and 10%, respectively. The color rendering efficiency (CE) value is one of the important performance indicators of EC materials and is calculated using Formula 1 and Formula 2. As Figure 3 As shown in (c) and (d), the CE values ​​of TPAB and TPANB are 41.81 and 36.19 cm C, respectively. -1 .

[0065] CE=ΔOD / Q d (1)

[0066] ΔOD=log(T b / T c ) (2)

[0067] While the present invention has been disclosed above with reference to preferred embodiments, this is not intended to limit the present invention. Persons skilled in the art will readily appreciate that various modifications and variations can be made without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention shall be determined by the claims.

Claims

1. An isolongifolia quinazoline compound, characterized in that It has the following structure:

2. The method for synthesizing the isolongifolia quinazoline compound according to claim 1, wherein include: (1) Using heterocyclic isolongifolia ketone as a substrate, a nucleophilic substitution reaction is carried out with benzaldehyde or 4-(N,N-diphenylamino)benzaldehyde in the presence of a basic catalyst to obtain intermediate IIa or intermediate IIb. (2) a step of subjecting the intermediate IIa or the intermediate IIb to a cyclization reaction with guanidine hydrochloride in the presence of a basic catalyst to obtain the intermediate IIIa or the intermediate IIIb, (3) a step of reacting the intermediate IIIa or the intermediate IIIb with 4-diphenylaminobenzaldehyde to obtain an isolongifolia alkanoylquinazoline compound TPAB or TPANB.

3. The method according to claim 2, wherein In step 1), the nucleophilic substitution reaction is carried out in the presence of an organic solvent, and the organic solvent is selected from any one of methanol, ethanol, isopropanol, dichloromethane, chloroform, 1,4-dioxane and 1,2-dichloroethane; the nucleophilic substitution reaction temperature is 80-120° C., and the reaction time is 6-72 h.

4. The method according to claim 2, wherein In step 1), the alkaline catalyst is selected from any one of sodium ethoxide, potassium ethoxide, potassium hydroxide, and sodium hydroxide, and the amount of the alkaline catalyst is 1.5-5.5% of the molar amount of benzaldehyde or 4-(N,N-diphenylamino)benzaldehyde; the molar ratio of isolongifolone to benzaldehyde or 4-(N,N-diphenylamino)benzaldehyde is 1:1-6.

5. The method according to claim 2, wherein In step 2), the cyclization reaction is carried out in the presence of a solvent, and the solvent is selected from any one of methanol, ethanol, tert-butanol, isopropanol, dichloromethane, chloroform, 1,4-dioxane and 1,2-dichloroethane; the cyclization reaction temperature is 80-120° C., and the reaction time is 12-72 h.

6. The method according to claim 2, wherein In step 2), the alkaline catalyst is selected from any one of sodium ethoxide, potassium ethoxide, potassium hydroxide, sodium hydroxide, sodium tert-butoxide and potassium tert-butoxide, and the amount of the alkaline catalyst is 3.5-7.5% of the molar amount of intermediate IIa or intermediate IIb; the molar ratio of intermediate IIa or intermediate IIb to guanidine hydrochloride is 1:3-9.

7. The method according to claim 2, wherein In step 3), the molar ratio of intermediate IIIa or intermediate IIIb to 4-diphenylaminobenzaldehyde is 1:1-7.

8. The method according to claim 2, wherein In step 3), the Schiff base reaction is carried out in the presence of a solvent, and the solvent is selected from any one of methanol, ethanol, tert-butanol and isopropanol; the Schiff base reaction temperature is 80-120° C., and the reaction time is 48-96 h.

9. Use of the isolongifolia alkanoylquinazoline compound according to claim 1 as an electrode material for an organic supercapacitor.

10. Use of the isolongifolia lantonyl quinazoline compound according to claim 1 as an electrochromic material.

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