CN110590784B - Derivative based on pyrrolopyrroledione and preparation method and application thereof - Google Patents

Derivative based on pyrrolopyrroledione and preparation method and application thereof Download PDF

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CN110590784B
CN110590784B CN201910876234.5A CN201910876234A CN110590784B CN 110590784 B CN110590784 B CN 110590784B CN 201910876234 A CN201910876234 A CN 201910876234A CN 110590784 B CN110590784 B CN 110590784B
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王利民
何玉龙
王峰
王桂峰
李俊
覃志忠
田禾
陈立荣
韩建伟
黄卓
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Lily Group Co ltd
East China University of Science and Technology
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Abstract

The invention discloses a derivative based on pyrrolopyrroledione, which has the following structural general formula:
Figure DDA0002204442180000011
wherein R is a substituted or unsubstituted alkyl, heterocyclyl, aryl or heteroaryl group. The invention provides a pyrrolopyrroledione-based derivative as Fe3+The probe has good solubility in various common organic solvents, and can conveniently identify and sense ferric ions in different media.

Description

Derivative based on pyrrolopyrroledione and preparation method and application thereof
Technical Field
The invention belongs to the technical field of preparation and application of sensing materials, and particularly relates to a derivative based on pyrrolo-pyrrole-Dione (DPP) and a preparation method and application thereof.
Background
As a transition metal element, iron is widely found in nature. Iron is important for human production and life, history records exist, and iron is utilized in spring, autumn and warring countries as early as the time. Iron exists in nature primarily as iron ore and ions, primarily involving two valence states, divalent and trivalent. The detection of iron ions is crucial in the fields of life health, environmental protection and industrial production. Iron plays an important role in the synthesis of hemoglobin in living systems, and in some redox reaction systems in the human body, iron also serves as a carrier for some enzymes and electron transfer, and is also an important component of catalase, cytochrome and the like. The deficiency of iron will lead to a decrease in hemoglobin content and a decrease in physiological activity, causing a significant decrease in the amount of oxygen carried by hemoglobin, thereby affecting the supply of nutrients and oxygen in the brain. If a human body is lack of iron for a long time, iron deficiency anemia can be caused. However, excessive iron intake also poses a health risk, for example, if high concentrations of iron are ingested, the risk of hemochromatosis, heart disease and certain cancers increases. The excessive existence of iron ions in water also brings huge pressure to environmental protection, and with the expansion of human activity areas and the diversification of water source development forms, the causes of water source pollution in nature include not only artificial discarded wastes, but also chemical changes of minerals in water sources and other factors. Iron ions in the water source are deposited through complex chemical reactions and can enter the water source again in the form of ions under an acidic condition, so that the water source is polluted newly. Iron ions also present a certain hazard in industrial production, for example, in beer production, even if very small amounts of iron ions are present, they accelerate the aging process of beer, thereby reducing the quality of beer. In the aquaculture industry, if iron ion deposits are attached to the surfaces of crab eggs, the oxygen and sunlight intake of the crab eggs is insufficient, so that the vitality of embryos is reduced. In view of the great influence of iron ions on a plurality of fields, it is important to develop a method capable of rapidly identifying, accurately detecting and monitoring iron ions in real time.
Until now, a series of methods for detecting the content of metal ions, such as instrumental analysis methods of inductively coupled plasma atomic emission spectrometry, high performance liquid chromatography, capillary electrophoresis, polarography, etc., have been developed. These methods have a low detection limit for metal ions, can identify metal ions having a very low concentration, and can accurately quantify the content of each metal ion. However, these methods usually require expensive instruments, specialized technical operators, and are difficult to implement in field detection, real-time monitoring, etc. Fluorescent probes have received much attention in recent years due to their advantages of high sensitivity, low detection limit, high specificity, and low cost. In general, a fluorescent probe molecule is composed of a chromophoric group and a recognition group, the chromophoric group determines the luminescent property and sensitivity of the fluorescent probe, and the recognition group determines the specificity and selectivity of the fluorescent probe. Compared with the traditional instrument analysis method, the method for identifying and detecting the existence and the content of the metal ions by using the fluorescent probe has the advantages of high sensitivity, strong selectivity, short response time, low cost, real-time monitoring, simplicity in operation, capability of realizing outdoor operation and the like. At present, some methods for detecting Cu have been developed2+、Pb2+、Hg2+Fluorescent probes for heavy metal ions. pyrrolopyrrole-Dione (DPP), a bright red high performance pigment, has received much attention due to its superior light stability, thermal stability, and strong absorption and emission in the visible region. Due to these excellent optical properties, DPP plays an important role in research and development in the fields of solar cells, organic field effect transistors, organic light emitting diodes, and the like. For fluorescent probes, DPP is a chromophore with superior properties. Long wavelength excitation and emission are critical to reduce scattering and ensure that background emission is minimized, while DPP excites and emits in the very long wavelength region. Because of these excellent properties of DPP, it has been studied by many groups to use DPP as a chromophore to attach different recognition groups to accomplish detection of different analytes. For example: a mercury ion probe in which a thioether chain is linked to DPP, a citric acid probe in which a pyridine ring is linked to DPP, and a hydrogen sulfide probe in which a nitroethylene chain is linked to DPP.
Disclosure of Invention
The invention aims to provide a derivative based on pyrrolo-pyrrole-Dione (DPP).
The second purpose of the invention is to provide a preparation method of the derivative based on the pyrrolopyrrole-Dione (DPP).
The third purpose of the invention is to provide the application of the derivative based on the pyrrolopyrrole-Dione (DPP) as a fluorescent probe.
The fourth purpose of the invention is to provide an application of the derivative based on pyrrolopyrrole-Dione (DPP) as a fluorescent probe in a ferric ion detection material.
The fifth purpose of the invention is to provide the application of the derivative based on the pyrrolopyrrole-Dione (DPP) as a fluorescent probe in a fluorescent sensor.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
in a first aspect, the present invention provides a pyrrolopyrroledione-based derivative having the following general structural formula:
Figure BDA0002204442160000021
wherein R is a substituted or unsubstituted alkyl, heterocyclyl, aryl or heteroaryl group.
More preferably, in the pyrrolopyrroledione-based derivative, R is a C1-18 substituted or unsubstituted alkyl group.
More preferably, in the pyrrolopyrroledione-based derivative, R is methyl, ethyl, isopropyl, n-propyl, tert-butyl, n-butyl, isobutyl
Figure BDA0002204442160000031
N-octyl (- (CH)2)7CH3) Iso-octyl radical
Figure BDA0002204442160000032
1-bromobutyl (- (CH)2)4Br), 1-bromo-n-hexyl (- (CH)2)6Br), 1-bromo-n-octyl (- (CH)2)8Br), C12 alkyl, C18 alkyl.
Most preferably, the pyrrolopyrroledione-based derivative is one of the following structures:
Figure BDA0002204442160000033
Figure BDA0002204442160000041
the second aspect of the present invention provides a method for preparing the pyrrolopyrroledione-based derivative, comprising the steps of:
Figure BDA0002204442160000042
dissolving a compound 2 in a solvent, adding alkali, reacting for 0.1-12 h at 110-140 ℃, cooling to room temperature, adding bromoalkane, wherein the molar ratio of the compound 2 to the alkali to the bromoalkane is 1 (5-10) to (5-10), and reacting for 0.1-12 h at 70-100 ℃ to obtain a compound 3;
Figure BDA0002204442160000051
dissolving a compound 3 in a solvent, adding hydrochloric acid, wherein the molar ratio of the compound 3 to the hydrochloric acid is 1 (20-40), and reacting at 50-80 ℃ for 1-24 hours to obtain a compound 4;
Figure BDA0002204442160000052
dissolving a compound 4 and malononitrile with a molar ratio of 1 (3-8) in a solvent, adding a catalytic amount of catalyst neutral alumina, and reacting at room temperature for 1-24 h to obtain a compound 5.
The alkali is anhydrous potassium carbonate or potassium tert-butoxide.
The brominated alkane is one of bromoethane, bromo-n-propane, bromo-isobutane, bromo-n-octane, bromo-isooctane, 1, 4-dibromobutane, 1, 6-dibromohexane and 1, 8-dibromooctane.
The solvent is N, N-dimethylformamide, N-dimethylpyrrolidone, acetonitrile, dichloromethane, tetrahydrofuran, deionized water, tertiary amyl alcohol, methanol, toluene and glycol.
The preparation method of the compound 2 comprises the following steps:
Figure BDA0002204442160000053
dissolving p-cyanobenzaldehyde in a solvent, adding ethylene glycol and p-methylbenzenesulfonic acid, wherein the molar ratio of the p-cyanobenzaldehyde to the ethylene glycol is 1: (1.5-3), reacting p-toluenesulfonic acid accounting for 0.0001-0.01% of the molar percentage of p-cyanobenzaldehyde at the temperature of 110-140 ℃ to obtain a compound 1;
Figure BDA0002204442160000061
putting metal sodium particles into a solvent, adding a catalytic amount of catalyst ferric trichloride, heating to 100-120 ℃, keeping for 1-10 h, cooling to room temperature, adding a compound 1, heating to 100-120 ℃, dropwise adding diisopropyl succinate, wherein the molar ratio of sodium to the compound 1 to the diisopropyl succinate is (3-8): 1.5-4): 1, keeping for 1-24 h after dropwise adding, cooling, adjusting the pH value to be neutral, performing suction filtration, and drying to obtain a compound 2.
The solvent is N, N-dimethylformamide, N-dimethylpyrrolidone, acetonitrile, dichloromethane, tetrahydrofuran, deionized water, tertiary amyl alcohol, methanol, toluene and glycol.
The third aspect of the invention provides an application of the derivative based on the pyrrolopyrroledione as a fluorescent probe.
The fourth aspect of the invention provides an application of the pyrrolopyrroledione-based derivative as a fluorescent probe in a ferric ion detection material.
The derivative based on the pyrrolopyrrole-dione has high sensitivity to ferric ions, specific identification capability to the ferric ions and long-wave emission characteristic when being used as a fluorescent probe.
The fifth aspect of the invention provides an application of the pyrrolopyrroledione-based derivative as a fluorescent probe in a fluorescent sensor. When the derivative based on the pyrrolopyrroledione is used as a fluorescent probe, the invention uses DPP as a chromophore and uses dicyano-substituted vinyl as a recognition group.
Due to the adoption of the technical scheme, the invention has the following advantages and beneficial effects:
the derivative based on the pyrrolopyrroledione (DPP) provided by the invention is used as a ferric ion sensing material, the pyrrolopyrroledione (DPP) is used as a fluorescent chromophore, and malononitrile is grafted through simple Schiff base reactionTo DPP precursors as recognition groups. The invention provides a pyrrolopyrroledione (DPP) -based derivative as Fe3+The probe has good solubility in various common organic solvents, and can conveniently identify and sense ferric ions in different media. The fluorescent probe taking the pyrrolopyrroledione (DPP) as the chromophore has excellent photophysical properties, such as better light resistance, higher heat resistance and stronger photobleaching resistance. By introducing the DPP chromophore in the probe molecule, long-wavelength excitation and emission is achieved, which effectively reduces scattering and minimizes background emission, effectively reducing interference. The derivative based on the pyrrolopyrroledione (DPP) provided by the invention is used as Fe3+The probe molecule can carry out rapid and sensitive qualitative identification and quantitative detection on ferric ions in various media.
The invention provides a pyrrolopyrroledione (DPP) -based derivative as Fe3+A probe molecule which is found to have higher sensitivity and better selectivity to ferric ions (the probe can effectively convert Fe even3+With Fe2+Distinguished), and the probe has better solubility in various common organic solvents, which makes the identification and detection application of ferric ions possible in practice.
The use of the pyrrolopyrroledione (DPP-based derivative as Fe) provided by the present invention3+The probe can carry out rapid and sensitive qualitative identification and quantitative detection on ferric ions in the sewage.
Drawings
FIG. 1 is a fluorescence titration curve in which a compound 5-1 is used as a ferric ion probe, and the compound 5-1 is dissolved in ethanol and titrated with an aqueous solution of ferric trichloride.
FIG. 2 is a photograph of an ethanol solution of compound 5-1, compound 5-1 dissolved in ethanol and exposed to ferric ion under a 365nm ultraviolet lamp.
FIG. 3 is a fluorescence spectrum of compound 5-1 as a ferric ion probe, after compound 5-1 is dissolved in ethanol and exposed to different metal ions.
FIG. 4 is a bar graph comparing fluorescence intensity of compound 5-1 after exposure to different metal ions dissolved in ethanol with compound 5-1 as a ferric ion probe.
FIG. 5 is a diagram showing the ultraviolet absorption spectrum of compound 5-1 after exposure to different metal ions dissolved in ethanol, with compound 5-1 as a ferric ion probe.
FIG. 6 is a diagram showing the quantitative relationship between the fluorescence intensity of compound 5-1 dissolved in ethanol and the concentration of ferric ion, with compound 5-1 as the ferric ion probe.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
4-Cyanobenzaldehyde was purchased from Shanghai Michelin Biochemical technology Ltd, 100g, 98%; ethylene glycol was purchased from Shanghai Aladdin Biotechnology, Inc., 100mL, 99.8%; the p-toluenesulfonic acid is purchased from Shanghai Xiandong biological technology limited, 100g, 98%; acetic acid was purchased from Shanghai Michelin Biotechnology Ltd, 500mL, 99.5%; diisopropyl succinate was purchased from 100g, 98% of Shanghai Michelle chemical technology, Inc.; t-amyl alcohol was purchased from Shanghai Aladdin Biotechnology, Inc., 100mL, 99%; metal sodium was purchased from shanghai Linfeng Chemicals, ltd, 250g, 98%; ferric chloride was purchased from Beijing Georgi Xue Xin scientific Co., Ltd, 99%, 500 g; toluene was purchased from national pharmaceutical group chemical reagents, ltd, 500mL, CP grade; tetrahydrofuran was purchased from Shanghai Bailingwei chemical technology, Inc., 250mL, 99.9%; sodium bicarbonate was purchased from Shanghai Aladdin Biotechnology, Inc., 500g, 99.8%; n, N-dimethylformamide was purchased from 99%, 1L of Shanghai Tantake Technique, Inc.; anhydrous potassium carbonate was purchased from beijing yinaoka technologies ltd, 100g, 99.995%; bromoethane was purchased from Shanghai Bailingwei chemical technology, Inc., 99%, 2.5L; hydrochloric acid is purchased from chemical reagent of national medicine group, Inc., 36-38% and 500 mL; methylene chloride was purchased from Shanghai Lingfeng Chemicals Co., Ltd, 99.5%, 25 kg; neutral alumina was purchased from Shanghai Aladdin Biotechnology GmbH, 99.99%, 25 g; malononitrile was purchased from Shanghai Bailingwei chemical technology Co., Ltd, 99%, 25 g.
Example 1
Figure BDA0002204442160000081
P-cyanobenzaldehyde (30g, 228.8mmol), ethylene glycol (23mL, 412mmol) and p-toluenesulfonic acid (0.5g, 0.003mmol) were charged into a reaction flask containing 300mL of toluene, and the reaction was allowed to proceed overnight at 130 ℃ by connecting to a water separator, after completion of the reaction, the reaction solution was cooled to room temperature, and a saturated aqueous sodium bicarbonate solution was added to the reaction solution to conduct extraction to remove p-toluenesulfonic acid. The organic phase was collected and dried over anhydrous magnesium sulfate. Compound 1 was further refined by column chromatography on silica gel eluting with dichloromethane to give 37.06g of Compound 1 in 92% yield.1H-NMR(400MHz,CDCl3):δ7.69(d,2H),7.60(d,2H),5.86(s,1H),4.14-4.05(m,4H).13CNMR(100MHz,CDCl3):δ143.48,132.62,127.58,119.01,113.27,102.83,65.85。
Figure BDA0002204442160000082
Adding 30mL of tertiary amyl alcohol into a three-neck flask, adding 4g of sodium particles under stirring, adding 5mg of ferric trichloride with a catalytic amount, heating to 110 ℃ and keeping for 2 hours, cooling the mixed solution to room temperature, adding 1(13g, 0.074mol) of a compound, heating to 110 ℃, dropwise adding a 30mL of tertiary amyl alcohol solution of diisopropyl succinate (7.5g, 0.037mol) into the three-neck flask, keeping the dropping speed at 3-4 seconds per drop, reacting for 4 hours after the dropping is finished, cooling the reaction solution to room temperature after the reaction is finished, adding acetic acid to adjust the pH to be neutral, and performing suction filtration and drying. Refluxing the solid crude product with water, filtering, and drying; and refluxing the solid crude product with N, N-dimethylformamide, performing suction filtration, drying and repeating the steps twice in a circulating manner to obtain a red solid compound 2, wherein the compound 2 is not used for a common deuteration reagent, so that the composition of the compound is represented by element analysis, and the analysis result is a theoretical value: 66.66% of C, 4.66% of H and 6.48% of N; measurement values: c66.31%, H4.19%, N6.27%.
Figure BDA0002204442160000091
Compound 2(500mg, 1.16mmol), anhydrous potassium carbonate (1.4g, 10.2mmol), and N, N-dimethylformamide (30mL) were added to a reaction flask, and the reaction was carried out at 120 ℃ for half an hour, then the reaction solution was cooled to room temperature after half an hour, ethyl bromide (1.1g, 10.2mmol) was added, the temperature was raised to 80 ℃ and the reaction was carried out for 4 hours, and the solvent was removed after completion of the reaction. Compound 3-1 was isolated by column chromatography on silica gel with an eluent composition of petroleum ether and dichloromethane of 1:3 to give 243mg of compound 3-1 with a yield of 43%.1HNMR(400MHz,CDCl3)δ：7.83(d,4H),7.60(d,4H),5.86(s,2H),4.11–4.06(m,8H),3.73–3.71(m,4H),1.17(t,6H)；13C NMR(100MHz,CDCl3)δ：162.5,148.0,140.9,128.8,128.7,126.9,109.9,102.9,65.3,41.6,13.5。
Figure BDA0002204442160000092
Compound 3-1(300mg, 0.62mmol), tetrahydrofuran (50mL), and 2mol/L hydrochloric acid 10mL were added to a reaction flask, and the mixture was stirred at 60 ℃ for reaction for 2 hours, after the reaction was completed, the solvent was removed, and compound 4-1 was isolated by silica gel column chromatography, the eluent composition was petroleum ether and dichloromethane was 1:4, to give 213mg of compound 4-1, with a yield of 86%.1H NMR(400MHz,CDCl3)δ：10.06(s,2H),8.01–7.94(m,8H),3.96(t,4H),1.14(t,6H)；13C NMR(100MHz,CDCl3)δ：191.2,162.2,147.6,137.6,133.2,129.8,129.1,111.3,35.4,13.2。
Figure BDA0002204442160000101
Compound 4-1(200mg, 0.5mmol), malononitrile (132mg, 2mmol), dichloromethane 50mL, and neutral alumina 25mg were added to a reaction flask, and the mixture was stirred at room temperature for 4 hours, after the reaction was completed, the alumina was filtered off, the solvent was removed by rotary evaporation under reduced pressure, and compound 5-1 was isolated by silica gel column chromatography, the eluent composition was petroleum ether, dichloromethane 1:5, to give 203mg of compound 5-1, with a yield of 82%.1HNMR(400MHz,CDCl3)δ：8.03(d,4H),7.96(d,4H),7.82(s,2H),3.97(t,4H),1.02(t,6H)；13C NMR(100MHz,CDCl3)δ：162.4,158.1,147.3,133.3,133.1,131.3,129.8,113.5,112.5,111.9,84.2,36.4,13.3。
Example 2
Figure BDA0002204442160000102
The procedure for the synthesis of compound 3-2 was the same as that for the synthesis of compound 3-1 in example 1, except that ethyl bromide in the step for the synthesis of compound 3-1 in example 1 was replaced with n-propyl bromide (10.2mmol), and the other reaction steps were the same as in example 1, and the amounts of the respective substances were the same in terms of moles as in example 1. The nuclear magnetic data for compound 3-2 are as follows:1HNMR(400MHz,CDCl3)δ：7.80(d,4H),7.62(d,4H),5.84(s,2H),4.11–4.06(m,8H),3.50–3.46(m,4H),1.56-1.52(m,4H),0.78(t,6H)；13C NMR(100MHz,CDCl3)δ：163.4,144.6,142.1,129.1,127.8,126.5,108.7,103.2,65.2,42.8,21.2,12.1。
Figure BDA0002204442160000111
the nuclear magnetic data for compound 4-2 are as follows:1HNMR(400MHz,CDCl3)δ:10.02(s,2H),8.03–7.91(m,8H),3.98(t,4H),1.75(t,4H),0.76(t,6H)；13C NMR(100MHz,CDCl3)δ：191.4,164.2,144.3,142.8,135.8,130.1,127.2,107.4,49.1,22.7,11.8。
Figure BDA0002204442160000112
the nuclear magnetic data for compound 5-2 are as follows:1HNMR(400MHz,CDCl3)δ：8.02(d,4H),7.94(d,4H),7.85(s,2H),3.69(t,4H),1.71(t,4H),0.64(t,6H)；13C NMR(100MHz,CDCl3)δ：163.1,158.4,141.5,136.9,129.7,129.4,126.1,112.8,106.3,80.5,48.7,22.4,11.2。
example 3
Figure BDA0002204442160000121
The procedure for the synthesis of compound 3-3 was the same as that for the synthesis of compound 3-1 in example 1, except that bromoethane was replaced with bromoisobutane (10.2mmol) in the step for the synthesis of compound 3-1 in example 1, and the other reaction steps were the same as those in example 1, and the amounts of the respective substances were the same in terms of moles as those in example 1. The nuclear magnetic data for compounds 3-3 are as follows:1HNMR(400MHz,CDCl3)δ:7.73(d,4H),7.58(d,4H),5.84(s,2H),4.13–4.07(m,8H),3.52–3.48(m,4H),2.46-2.31(m,2H),0.87-0.83(t,12H)；13C NMR(100MHz,CDCl3)δ:163.1,144.3,142.2,136.5,127.6,127.2,108.7,104.6,65.4,54.6,29.2,20.4。
Figure BDA0002204442160000122
the nuclear magnetic data for compounds 4-3 are as follows:1HNMR(400MHz,CDCl3)δ：10.05(s,2H),8.01–7.95(m,8H),2.97(t,4H),2.42-2.35(m,2H),0.85-0.81(t,12H)；13C NMR(100MHz,CDCl3)δ：191.3,163.2,144.7,142.5,136.8,130.4,127.6,107.3,54.8,30.2,21.1。
Figure BDA0002204442160000131
compound 5Nuclear magnetic data for-3 are as follows:1HNMR(400MHz,CDCl3)δ：8.01(d,4H),7.97(d,4H),7.83(s,2H),3.47(t,4H),2.36-2.33(t,2H),0.84-0.82(t,12H)；13C NMR(100MHz,CDCl3)δ：163.2,161.7,142.2,137.4,130.2,129.6,126.8,113.2,107.4,81.1,54.5,29.3,21.3。
example 4
Figure BDA0002204442160000132
The procedure for the synthesis of compound 3-4 was the same as that for the synthesis of compound 3-1 in example 1, except that ethyl bromide in the step for the synthesis of compound 3-1 in example 1 was replaced with N-octane bromide (10.2mmol), anhydrous potassium carbonate was replaced with potassium tert-butoxide, and N, N-dimethylformamide was replaced with N, N-dimethylpyrrolidone, and other reaction procedures were the same as in example 1, using the same amount of each substance as in example 1 in terms of moles. The nuclear magnetic data for compounds 3-4 are as follows:1HNMR(400MHz,CDCl3)δ：7.75(d,4H),7.60(d,4H),5.87(s,2H),4.10–4.07(m,8H),3.52–3.47(m,4H),1.65-1.61(m,4H),1.30-1.24(m,20H),0.85(t,6H)；13C NMR(100MHz,CDCl3)δ：163.6,141.8,136.7,136.3,129.6,127.2,107.3,105.4,65.1,45.2,32.3,31.1,30.2,26.9,22.8,14,5。
Figure BDA0002204442160000141
the nuclear magnetic data for compounds 4-4 are as follows:1HNMR(400MHz,CDCl3)δ：10.03(s,2H),7.96–7.83(m,8H),3.67(t,4H),1.65(t,4H),1,31-1.24(m,20H),0.91(t,6H)；13C NMR(100MHz,CDCl3)δ：191.4,163.8,144.0,142.3,136.4,130.2,127.2,107.6,45.2,32.1,31.4,29.3,29.1,27.4,22.9,14.5。
Figure BDA0002204442160000142
the nuclear magnetic data for compounds 5-4 are as follows:1HNMR(400MHz,CDCl3)δ：8.05(d,4H),7.93(d,4H),7.81(s,2H),3.46(t,4H),1.58(t,4H),1.31-1.24(m,20H),0.89(t,6H)；13C NMR(100MHz,CDCl3)δ：163.7,158.2,141.9,137.5,130.2,129.1,126.7,113.8,108.5,82.1,45.3,31.8,31.1,29.1,29.4,27.3,22.6,13.8。
example 5
Figure BDA0002204442160000143
The procedure for the synthesis of compound 3-5 was the same as that for the synthesis of compound 3-1 in example 1, except that ethyl bromide in the step for the synthesis of compound 3-1 in example 1 was replaced with bromoisooctane (10.2mmol), anhydrous potassium carbonate was replaced with potassium tert-butoxide, and N, N-dimethylformamide was replaced with N, N-dimethylpyrrolidone, and other reaction procedures were the same as in example 1, and the amounts of the respective substances were the same in terms of moles as those in example 1. The nuclear magnetic data for compounds 3-5 are as follows:1HNMR(400MHz,CDCl3)δ：7.72(d,4H),7.58(d,4H),5.88(s,2H),4.13–4.09(m,8H),3.48–3.45(m,4H),1.93-1.91(t,2H),1.56-1.53(m,4H),1.31-1.29(m,4H),1.26-1.24(m,4H),1.21-1.18(m,4H),1.01-0.98(m,6H),0.89-0.86(m,6H)；13C NMR(100MHz,CDCl3)δ：163.8,158.8,137.6,136.2,129.7,127.1,107.2,105.4,65.3,49.7,38.4,32.2,29.1,26.4,23.4,14.2,11.5。
Figure BDA0002204442160000151
the nuclear magnetic data for compounds 4-5 are as follows:1HNMR(400MHz,CDCl3)δ：10.02(s,2H),7.80-7.67(m,8H),3.43–3.38(m,4H),1.94-1.91(t,2H),1.57-1.55(m,4H),1.33-1.30(m,4H),1.27-1.25(m,4H),1.20-1.17(m,4H),1.02-0.97(m,6H),0.88-0.85(m,6H)；13C NMR(100MHz,CDCl3)δ：191.2,163.8,144.2,142.1,136.3,129.6,126.4,107.1,49.2,38.4,32.6,29.7,26.5,23.4,14.6,11.3。
Figure BDA0002204442160000152
the nuclear magnetic data for compounds 5-5 are as follows:1HNMR(400MHz,CDCl3)δ：8.01(d,4H),7.96(d,4H),7.83(s,2H),3.41–3.39(m,4H),1.96-1.93(t,2H),1.56-1.53(m,4H),1.34-1.31(m,4H),1.26-1.23(m,4H),1.21-1.18(m,4H),1.03-0.99(m,6H),0.89-0.86(m,6H)；13C NMR(100MHz,CDCl3)δ：163.6,158.4,142.1,137.2,130.3,130.6,126.1,113.4,107.5,81.2,49.3,38.2,32.6,29.5,26.1,23.4,14.5,11.2。
example 6
Figure BDA0002204442160000161
The procedure for the synthesis of Compound 3-6 was the same as that for Compound 3-1 in example 1, except that ethyl bromide in the procedure for the synthesis of Compound 3-1 in example 1 was replaced with 1, 4-dibromobutane (10.2mmol), anhydrous potassium carbonate was replaced with potassium tert-butoxide, and N, N-dimethylformamide was replaced with acetonitrile, and the other reaction procedures were the same as in example 1, using the same amount of each substance as in example 1 in terms of moles. The nuclear magnetic data for compounds 3-6 are as follows:1HNMR(400MHz,CDCl3)δ：7.75(d,4H),7.57(d,4H),5.84(s,2H),4.12–4.08(m,8H),3.54-3.51(m,4H),3.47–3.44(m,4H),1.83-1.81(m,4H),1.54-1.52(m,4H)；13C NMR(100MHz,CDCl3)δ：164.7,141.3,137.2,136.2,129.3,127.5,107.2,105.4,65.3,44.7,33.2,28.2,27.6。
Figure BDA0002204442160000162
the nuclear magnetic data for compounds 4-6 are as follows:1HNMR(400MHz,CDCl3)δ：10.07(s,2H),7.84-7.76(m,8H),3.53-3.49(m,4H),3.44–3.38(m,4H),1.82-1.79(m,4H),1.61-1.58(m,4H)；13C NMR(100MHz,CDCl3)δ：191.2,164.5,144.3,141.5,136.8,129.7,126.5,107.6,44.5,33.7,28.4,27.2。
Figure BDA0002204442160000171
the nuclear magnetic data for compounds 5-6 are as follows:1HNMR(400MHz,CDCl3)δ：8.04(d,4H),7.95(d,4H),7.81(s,2H),3.53-3.47(m,8H),1.82-1.79(m,4H),1.54-1.51(m,4H)；13C NMR(100MHz,CDCl3)δ：164.3,158.7,142.3,137.2,130.1,129.4,126.1,113.2,107.5,81.1,44.0,33.2,28.3,27.2。
example 7
Figure BDA0002204442160000172
Synthesis procedure of Compound 3-7 was the same as that of Compound 3-1 in example 1, except that ethyl bromide in the step of synthesizing Compound 3-1 in example 1 was replaced with 1, 6-dibromohexane (10.2mmol), anhydrous potassium carbonate was replaced with potassium tert-butoxide, N-dimethylformamide was replaced with acetonitrile, and other reaction procedures were the same as in example 1, and the amounts of each substance were the same in terms of moles as those in example 1. The nuclear magnetic data for compounds 3-7 are as follows:1HNMR(400MHz,CDCl3)δ：7.71(d,4H),7.53(d,4H),5.82(s,2H),4.11–4.09(m,8H),3.53-3.50(m,4H),3.45–3.43(m,4H),1.85-1.82(m,4H),1.58-1.55(m,4H),1.35-1.31(m,8H)；13C NMR(100MHz,CDCl3)δ：164.2,141.6,137.7,136.9,129.1,127.2,107.6,105.1,65.8,45.2,33.4,32.5,31.4,27.2,26.5。
Figure BDA0002204442160000181
the nuclear magnetic data for compounds 4-7 are as follows:1HNMR(400MHz,CDCl3)δ：10.07(s,2H),7.81-7.73(m,8H),3.55-3.51(m,4H),3.46–3.41(m,4H),1.84-1.80(m,4H),1.65-1.63(m,4H),1.31-1.28(m,8H)；13C NMR(100MHz,CDCl3)δ：191.4,164.2,144.1,141.7,136.4,130.1,127.3,107.6,45.2,33.2,32.1,31.5,27.4,26.8。
Figure BDA0002204442160000182
the nuclear magnetic data for compounds 5-7 are as follows:1HNMR(400MHz,CDCl3)δ：8.02(d,4H),7.93(d,4H),7.84(s,2H),3.51-3.46(m,8H),1.79-1.76(m,4H),1.64-1.61(m,4H),1.32-1.27(m,8H)；13C NMR(100MHz,CDCl3)δ：164.7,158.5,142.8,137.4,130.8,129.6,126.3,113.7,107.1,81.2,44.8,33.5,32.6,31.8,27.3,26.2。
example 8
Figure BDA0002204442160000191
The procedure for the synthesis of the compound 3-8 was the same as that for the synthesis of the compound 3-1 in example 1, except that ethyl bromide in the step for the synthesis of the compound 3-1 in example 1 was replaced with 1, 8-dibromooctane (10.2mmol), anhydrous potassium carbonate was replaced with potassium tert-butoxide, and N, N-dimethylformamide was replaced with acetonitrile, and the other reaction procedures were the same as those in example 1, and the amounts of the respective substances were the same in terms of moles as those in example 1. The nuclear magnetic data for compounds 3-8 are as follows:1HNMR(400MHz,CDCl3)δ：7.74(d,4H),7.52(d,4H),5.86(s,2H),4.13–4.09(m,8H),3.54-3.51(m,4H),3.47–3.44(m,4H),1.87-1.84(m,4H),1.67-1.54(m,4H),1.32-1.25(m,16H)；13C NMR(100MHz,CDCl3)δ：164.8,141.7,137.4,136.3,129.5,127.7,107.2,105.6,65.4,45.6,33.8,32.6,31.2,29.1,28.5,28.0,27.2。
the nuclear magnetic data for compounds 4-8 are as follows:1HNMR(400MHz,CDCl3)δ：10.02(s,2H),7.79-7.72(m,4H),7.67-7.64(m,4H),3.57-3.55(m,4H),3.49–3.45(m,4H),1.89-1.85(m,4H),1.66-1.52(m,4H),1.31-1.26(m,16H)；13C NMR(100MHz,CDCl3)δ：191.6,164.8,144.3,142.1,136.5,130.4,127.6,107.3,45.4,33.6,32.5,31.7,29.2,28.5,28.1,27.1。
the nuclear magnetic data for compounds 5-8 are as follows:1HNMR(400MHz,CDCl3)δ：8.05(d,4H),7.94(d,4H),7.86(s,2H),3.53-3.48(m,8H),1.81-1.79(m,4H),1.65-1.62(m,4H),1.33-1.28(m,16H)；13C NMR(100MHz,CDCl3)δ：164.5,158.9,142.4,137.2,130.6,129.3,126.4,113.5,107.4,81.6,44.9,33.7,32.8,31.2,29.4,28.5,28.1,27.3。
application example 1
An ethanol solution of the compound 5-1 with the concentration of 2 mu mol/L (containing 5% DMSO as a dispersing agent) is prepared, and the specific operation steps are as follows: weighing 10mg of compound 5-1, placing the compound 5-1 in a 100mL volumetric flask, diluting the compound 5-1 to a scale with DMSO, measuring 1mL of the compound with a pipette, placing the compound in another 100mL volumetric flask, adding 4mLDMSO, and finally diluting the compound with ethanol to a scale, thereby obtaining an ethanol solution of the compound 5-1 with 2 mu mol/L.
Preparing a ferric trichloride aqueous solution with the solubility of 10 mmol/L: 2mL of the ethanol solution of the compound 5-1 with the concentration of 2. mu. mol/L is placed in a quartz cuvette, and 10mmol/L of an aqueous solution of ferric trichloride is gradually added dropwise into the cuvette by using a pipette gun, wherein 2. mu.L of the aqueous solution of ferric trichloride is added dropwise each time. And (3) recording the fluorescence intensity of the ethanol solution of the compound 5-1 after the ferric trichloride aqueous solution is added in each time by using a fluorescence spectrophotometer. The result shows that the compound 5-1 used as the ferric ion probe in the invention has high sensitivity to ferric ions, and when the concentration of ferric ions in the cuvette reaches only 190 mu mmol/L, the fluorescence is almost completely quenched, as shown in figure 1, the figure 1 is a fluorescence titration curve in which the compound 5-1 is used as the ferric ion probe, and the compound 5-1 is dissolved in ethanol and titrated with ferric trichloride aqueous solution. The probe solutions before and after exposure to ferric ion showed a large visual difference as observed under a 365nm uv lamp, as shown in fig. 2, which is a photograph of compound 5-1 in ethanol, compound 5-1 dissolved in ethanol and exposed to ferric ion under a 365nm uv lamp.
Application example 2
2mL of an ethanol solution of compound 5-1 at a concentration of 2. mu. mol/L was added to a cuvette, and 40. mu.L of 10mmol/L aqueous solutions of different metal ions (metal ions: K, respectively) were added thereto+,Na+，Mg2+，Ca2+,Fe2+，Co2 +，Ni2+，Mn2+，Zn2+，Pb2+，Cu2+，Hg2+，Cr3+，Fe3+) The metal ions are derived from their sulfate, nitrate or chloride salts, respectively. The result shows that only ferric ions can significantly quench the fluorescence of the compound 5-1 ethanol solution, and other metal ions have no obvious influence on the fluorescence of the compound 5-1 ethanol solution. The molecular structure of the compound 5-1 is used as a fluorescent probe to have specific recognition capability on ferric ions.
FIG. 3 is a fluorescence spectrum of compound 5-1 as a ferric ion probe, after compound 5-1 is dissolved in ethanol and exposed to different metal ions. The results in the figure show that only ferric ions can effectively quench the fluorescence of the fluorescent probe in the invention.
FIG. 4 is a histogram comparing the fluorescence intensity of compound 5-1 as ferric ion probe after compound 5-1 is dissolved in ethanol and exposed to different metal ions, and FIG. 4 shows that compound 5-1 prepared by the present invention has specific recognition ability for ferric ion as fluorescent probe relative to other metal ions.
Application example 3
2mL of a 2. mu. mol/L ethanol solution of compound 5-1 was added to a cuvette, and 40. mu.L of 10mmol/L aqueous solutions of different metal ions (metal ions: K, respectively) were added thereto+,Na+，Mg2+，Ca2+,Fe2+，Co2+，Ni2+，Mn2+，Zn2+，Pb2+，Cu2+，Hg2+，Cr3+，Fe3+) The metal ions are derived from their sulfate, nitrate or chloride salts, respectively. And recording the ultraviolet absorption curve characteristics of the ethanol solution of the compound 5-1 after different metal ions are respectively added by using an ultraviolet-visible absorption spectrometer. The results show that for the addition of K+,Na+，Mg2+，Ca2+,Fe2+，Co2+，Ni2+，Mn2+，Zn2+，Pb2+，Cu2+，Hg2+，Cr3+The plasma is generated by the plasma generation device,the ultraviolet absorption curve of the ethanol solution of the compound 5-1 is not obviously changed relative to that of a blank solution, and Fe is added3+The absorption band is then enhanced with a slight blue shift (FIG. 5, FIG. 5 is a graph of the UV absorption spectrum of compound 5-1 dissolved in ethanol and exposed to different metal ions with compound 5-1 as a ferric ion probe), which can be attributed to the interaction of ferric ions with probe molecule 5-1, destroying the hyperconjugation of probe molecule 5-1. For the other ions, no similar phenomena occurred, indicating that there was no significant interaction of the other ions with the probe molecule 5-1. The specific recognition capability of the probe molecule 5-1 on ferric ions is further verified.
Application example 4
According to the fluorescence titration curve of the probe molecule 5-1 in application example 1, it can be found that at low Fe3+At the concentration, the fluorescence intensity of the ethanol solution of the probe molecule 5-1 and Fe3+The concentration exhibited a good linear relationship. According to the Stern-Volmer equation and the equation DL ═ 3d/k, the quantitative relationship between the fluorescence intensity of the probe molecule 5-1 in ethanol solution and the concentration of ferric ions in aqueous solution was determined (as shown in FIG. 6, FIG. 6 is a schematic diagram showing the quantitative relationship between the fluorescence intensity of the compound 5-1 in ethanol and the concentration of ferric ions, with the compound 5-1 as ferric ion probe), as follows:
fluorescence intensity of-50.31 x +7749.6
And x is the molar concentration of ferric ions in the solution to be detected.
The detection limit of the probe molecule 5-1 to the ferric ions is determined to be 6 x 10-8mol/L。
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (2)

1. An application of a pyrrolopyrrole dione derivative in preparation of a ferric ion detection material;
wherein the pyrrolopyrroledione derivative is a compound represented by formula 5:
Figure FDA0003348399260000011
in the formula, R is C1～C18Alkyl, 1-bromobutyl, 1-bromo-n-hexyl or 1-bromo-n-octyl.
2. The use according to claim 1, wherein the pyrrolopyrroledione derivative is one of the following compounds:
Figure FDA0003348399260000012
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