CN108689963B - Diazosulfide malononitrile, synthetic method thereof and method for detecting CN < - > - Google Patents

Diazosulfide malononitrile, synthetic method thereof and method for detecting CN < - > Download PDF

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CN108689963B
CN108689963B CN201810721697.XA CN201810721697A CN108689963B CN 108689963 B CN108689963 B CN 108689963B CN 201810721697 A CN201810721697 A CN 201810721697A CN 108689963 B CN108689963 B CN 108689963B
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btd
tpa
malononitrile
benzothiadiazole
dichloromethane
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CN108689963A (en
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凡素华
张灵美
刘平平
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Fuyang Normal University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
    • C07D285/01—Five-membered rings
    • C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
    • C07D285/14—Thiadiazoles; Hydrogenated thiadiazoles condensed with carbocyclic rings or ring systems
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    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material

Abstract

The invention discloses diazosulfide malononitrile, a synthetic method thereof and CN detection‑The benzothiadiazole malononitrile of the formula:
Figure DDA0001718769350000011
the synthesis method of diazosulfide malononitrile comprises the following steps: (1) synthesizing an intermediate TPA-BTD-Br; (2) synthesizing an intermediate TPA-BTD-CHO; (3) and (3) synthesizing benzothiadiazole malononitrile TPA-BTD-BT. Diazosulfide malononitrile fluorescence detection CN‑Taking tetrahydrofuran THF as a solvent, adding benzothiadiazole malononitrile TPA-BTD-BT to prepare a tetrahydrofuran THF solution of the benzothiadiazole malononitrile TPA-BTD-BT; (2) adding a sample to be detected into a tetrahydrofuran THF solution of benzothiadiazole malononitrile TPA-BTD-BT; (3) identifying whether CN exists in the sample to be detected through naked eye observation, ultraviolet-visible absorption spectrum or fluorescence spectrum‑. The invention successfully constructs the pair CN‑The turn-on type fluorescent sensor has high selectivity and strong anti-interference capability.

Description

Diazosulfide malononitrile, synthetic method thereof and method for detecting CN < - >
Technical Field
The present invention relates to CN-The technical field of detection. In particular to diazosulfide malononitrile, a synthetic method thereof and CN detection-The method of (1).
Background
Cyanide is widely used in industrial production and daily life, and can be used for electroplating, plastic manufacturing, metallurgy, gold extraction, leather making and the like. However, cyanide is a very toxic substance and poisons very rapidly. They can enter the human body through many routes, such as skin absorption, wound entry, respiratory tract inhalation, etc., and after entering the human body, they can poison hemoglobin in blood, cause dyspnea, and suffocate cells due to hypoxia. Adult death may be caused by oral administration of 150-250 mg. Therefore, a fast and accurate detection of CN was developed-The ionic method is very interesting, since over decades chemosensor fluorescent probes have been used for CN-The excellent sensitivity and selectivity of ions has thus attracted considerable attention.
To date, scientists have developed a number of assays for CN-Methods include formation of cyanide complexes with transition metals, boron derivatives and CdSe quantum dots, titration, chromatography, electrochemical methods. But in phase with the chemical sensor fluorescent probe methodCompared with the prior art, the chemical sensor has the advantages of better selectivity, higher sensitivity, lower cost and convenient and simple operation. Chemical sensor fluorescent probe pair CN-The mechanisms of (a) include nucleophilic addition reactions, hydrogen bonding interactions, supramolecular self-assembly and deprotonation. CN based on nucleophilic addition reaction-The chemosensor fluorescent probe has more excellent selectivity and sensitivity. Based on the above mechanism, a series of probes such as oxazine, pyran, squarane, trifluoroacetylbenzene, acyltriazine, acridine, salicylaldehyde and carboxamide have been reported in the past several years. Therefore, a new CN is designed and synthesized-Chemical sensor fluorescent probes have become a hotspot of research. Under the funding of natural science fund (1708085MB43) in Anhui province, major project of education hall in Anhui province (KJ2018ZD035), excellent youth talents in colleges and universities support plan major project (gxyqZD2016192), and lateral cooperation major and major project (XDHX201704, XDHX201701) of Fuyang city government-Fuyang faculty college of teachers and schools, the applicant detects CN-The method of (1) was intensively studied.
Disclosure of Invention
Therefore, the technical problem to be solved by the present invention is to provide a method for CN-Chemical sensor fluorescent probe benzothiadiazole malononitrile for detection, synthetic method thereof and CN detection method-The method of (1).
In order to solve the technical problems, the invention provides the following technical scheme:
diazosulfide malononitrile, characterized by the formula (I):
Figure BDA0001718769330000021
the synthesis method of diazosulfide malononitrile is characterized by comprising the following steps:
(1) synthesizing an intermediate TPA-BTD-Br, wherein the intermediate TPA-BTD-Br is shown as a formula (II):
Figure BDA0001718769330000022
(2) synthesizing an intermediate TPA-BTD-CHO from the intermediate TPA-BTD-Br, wherein the intermediate TPA-BTD-CHO is represented by the formula (III):
Figure BDA0001718769330000023
(3) the synthesis of benzothiadiazole malononitrile TPA-BTD-BT, which is represented by formula (I):
Figure BDA0001718769330000031
in the synthesis method of the diazosulfide malononitrile, in the step (1), 4-diphenylaminobenzene boronic acid, 4, 7-dibromo-2, 1, 3-diazosulfide, 4- (triphenylphosphine) palladium and potassium carbonate are placed in a three-neck flask, and tetrahydrofuran THF, toluene and distilled water H are added into the mixture2O, dropwise adding methyl trioctyl ammonium chloride; adding magnetite, fully stirring, and reacting under nitrogen atmosphere; after the reaction is finished, adding distilled water into the reactant, extracting with dichloromethane to obtain an organic phase, carrying out vacuum distillation on the organic phase obtained by extraction to obtain a concentrate, and carrying out column chromatography separation, concentration and drying on the concentrate to obtain an intermediate TPA-BTD-Br; the eluent for column chromatography separation is a mixture of dichloromethane and petroleum ether.
In the synthesis method of the diazosulfide malononitrile, in the step (1), 2.7568g of 4-diphenylanilinobenzeneboronic acid, 2.3576g of 4, 7-dibromo-2, 1, 3-diazosulfide, 0.1342g of 4- (triphenylphosphine) palladium and 1.7880g of potassium carbonate are placed in a 250mL three-necked bottle, and 60mL of tetrahydrofuran THF, 45mL of toluene and 22mL of distilled water H are added into the mixture2O, then 0.1mL of methyl trioctyl ammonium chloride is added dropwise; adding a magnet, fully stirring, and carrying out reflux reaction for 16 hours under a nitrogen atmosphere, wherein the temperature of the reflux reaction is 85 ℃; after the reaction is finished, adding 200mL of distilled water into the reactant, extracting with dichloromethane to obtain an organic phase, carrying out vacuum distillation on the organic phase obtained by extraction to obtain a concentrate, and carrying out column chromatography separation, concentration and drying on the concentrate to obtain an intermediate TPA-BTD-Br; the eluent for column chromatography separation is a mixture of dichloromethane and petroleum ether, wherein the dichloromethane isAnd petroleum ether in a volume ratio of 1: 3.5.
In the step (2), the intermediate TPA-BTD-Br, 4-formylphenylboronic acid, 4- (triphenylphosphine) palladium and potassium carbonate are placed in a three-neck flask, methyl trioctyl ammonium chloride is dropwise added, and then tetrahydrofuran THF, toluene and distilled water H are added into the mixture2O; adding magnetite, fully stirring and dissolving, and carrying out reflux reaction under nitrogen atmosphere; after the reaction is finished, extracting with an extracting agent dichloromethane to obtain an organic phase, and performing rotary evaporation on the organic phase obtained by extraction to obtain a dry solid; and (3) separating, concentrating and drying the dried solid by column chromatography to obtain an intermediate TPA-BTD-CHO, wherein the eluent for column chromatography separation is a mixture of dichloromethane and petroleum ether.
In the synthesis method of the diazosulfide malononitrile, in the step (2), the intermediate TPA-BTD-Br2.2737g, the 4-formylphenylboronic acid 1.1100g, the 4- (triphenylphosphine) palladium 0.2588g and the potassium carbonate 1.5525g are placed in a 250mL three-neck flask, 0.1mL of methyl trioctyl ammonium chloride is added dropwise, and then 40mL of tetrahydrofuran THF, 60mL of toluene and 25mL of distilled water H are added into the mixture2O; adding a magnet, fully stirring and dissolving, and carrying out reflux reaction for 16 hours under a nitrogen atmosphere, wherein the temperature of the reflux reaction is 85 ℃; after the reaction is finished, extracting with an extracting agent dichloromethane to obtain an organic phase, and performing rotary evaporation on the organic phase obtained by extraction to obtain a dry solid; and (3) carrying out column chromatography separation, concentration and drying on the dried solid to obtain an intermediate TPA-BTD-CHO, wherein an eluent for column chromatography separation is a mixture of dichloromethane and petroleum ether, and the volume ratio of the dichloromethane to the petroleum ether is 1: 3.5.
In the step (3), putting intermediate TPA-BTD-CHO, malononitrile and ammonium acetate into a three-neck flask, adding glacial acetic acid into the mixture, adding a magnet, fully stirring, and reacting under nitrogen atmosphere; after the reaction is finished, extracting with an extracting agent dichloromethane to obtain an organic phase, performing rotary evaporation on the organic phase obtained by extraction to obtain a concentrate, performing column chromatography separation, concentration and drying on the concentrate to obtain benzothiadiazole malononitrile TPA-BTD-BT, wherein an eluent obtained by the column chromatography separation is a mixture of dichloromethane and petroleum ether.
In the step (3), the intermediate TPA-BTD-CHO1.5045g, the malononitrile 2.5219g and the ammonium acetate 4.7811g are placed in a 500mL three-neck flask, 200mL glacial acetic acid is added into the mixture, then the magnet is added, the mixture is fully stirred, and then the reaction is carried out for 8 hours under nitrogen atmosphere, and the reaction temperature is 117 ℃; after the reaction is finished, extracting an upper layer of organic matter by using an extracting agent dichloromethane, carrying out rotary evaporation on the upper layer of organic matter to obtain a concentrate, carrying out column chromatography separation, concentration and drying on the concentrate to obtain the benzothiadiazole malononitrile TPA-BTD-BT, wherein an eluent for the column chromatography separation is a mixture of dichloromethane and petroleum ether, and the volume ratio of the dichloromethane to the petroleum ether is 1: 1.
The method for detecting CN < - > by using benzothiadiazole malononitrile comprises the following steps: (1) adding benzothiadiazole malononitrile TPA-BTD-BT into tetrahydrofuran THF (tetrahydrofuran) serving as a solvent to prepare a tetrahydrofuran THF solution of the benzothiadiazole malononitrile TPA-BTD-BT; the benzothiadiazole malononitrile TPA-BTD-BT is shown below:
Figure BDA0001718769330000051
(2) adding a sample to be detected into a tetrahydrofuran THF solution of benzothiadiazole malononitrile TPA-BTD-BT; (3) identifying whether CN exists in the sample to be detected through naked eye observation, ultraviolet-visible absorption spectrum or fluorescence spectrum-。
Fluorescence detection of diazosulfide malononitrile CN-The visual observation and identification method comprises the following steps: the color of the solution changes from orange to yellow, which indicates that CN exists in the sample to be detected-(ii) a The identification method of the ultraviolet-visible absorption spectrum comprises the following steps: performing UV-vis spectrum test at 660nm of 200--(ii) a The fluorescence spectrum identification method comprises the following steps: generating an emission peak at 600nm under the excitation of 465nm, and showing that CN exists in the sample to be detected-Or under the irradiation of 365nm ultraviolet lamp, the solution shows bright orange fluorescence, which indicates CN in the sample to be detected-。
The technical scheme of the invention achieves the following beneficial technical effects:
the invention synthesizes benzothiadiazole malononitrile molecules (TPA-BDT-BT) containing electron deficiency groups by using 4-diphenylamino phenylboronic acid, 4-formylphenylboronic acid, 4, 7-dibromo-2, 1, 3-benzothiadiazole and malononitrile as raw materials under the fundation of a natural science fund (1708085MB43) in Anhui province, a major project (KJ2018ZD035) in Anhui province, a major project (gxyqZD2016192) for supporting plan of excellent youth talents in colleges and universities, and a major project (XDHX201704, XDHX 701) in Fuyang government-Fuyang-David colleges. The synthesized intermediate and product adopt infrared spectrum (IR), ultraviolet-visible absorption spectrum (UV-vis), Fluorescence Spectrum (FS) and nuclear magnetic resonance hydrogen spectrum (F: (R))1HNMR and NMR carbon Spectroscopy (C:)13CNMR) were characterized. The benzothiadiazole malononitrile TPA-BTD-BT contains electron-deficient groups, and CN is activated-The nucleophilic addition to the dicyano group breaks the electron-withdrawing ability of the dicyano group and hinders charge transfer. Diazosulfide malononitrile TPA-BTD-BT as fluorescent probe for CN-Detection of (2), the molecule being specific for CN only-Selective recognition, fluorescence enhancement factor of 16, other anions (F)-, Cl-,Br-,I-,CH3COO-,NO2 -,NO3 -,H2PO4 -,HCO3 -,CO3 2-,SO4 2-) Does not affect the sensor pair CN-Identification of (1). Successfully constructs the diazosulfide malononitrile TPA-BTD-BT to CN-The turn-on type fluorescent sensor has high selectivity and strong anti-interference capability.
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FIG. 1 is a scheme of the synthesis of benzothiadiazole malononitrile TPA-BTD-BT according to the invention;
FIG. 2 TPA-BTD-B (OH) 4-Dianilinophenylboronic acid of the present invention2And an infrared spectrum of intermediate TPA-BTD-Br;
FIG. 3 is an infrared spectrum of intermediate TPA-BTD-Br and intermediate TPA-BTD-CHO of the present invention;
FIG. 4 is an infrared spectrum of the intermediate TPA-BTD-CHO and benzothiadiazole malononitrile TPA-BTD-BT of the present invention.
FIG. 5 UV-VISIBLE ABSORPTION SPECTRUM OF TETRAHYDROFURAN SOLUTION OF BENZOTHIADIAZOTHIADIAZOLE MALONITRILE TPA-BTD-BT OF THE INVENTION, the concentration of TPA-BTD-BT being 2 × 10-5mol/L；
FIG. 6 shows the fluorescence spectrum of a tetrahydrofuran solution of benzothiadiazole malononitrile TPA-BTD-BT of the present invention at a concentration of TPA-BTD-BT 2 × 10-5mol/L；
FIG. 7 Process for preparing intermediate TPA-BTD-Br of the invention1HNMR (deuterium with chloroform CDCl)3Is a solvent);
FIG. 8 Process for preparing intermediate TPA-BTD-Br of the invention13CNMR (deuterium-doped chloroform CDCl)3Is a solvent);
FIG. 9 of the intermediate TPA-BTD-CHO of the invention1HNMR (deuterium with chloroform CDCl)3Is a solvent);
FIG. 10 of intermediate TPA-BTD-CHO of the invention13CNMR (deuterium-doped chloroform CDCl)3Is a solvent); FIG. 11 TPA-BTD-BT of benzothiadiazole malononitrile of the invention1HNMR (deuterium with chloroform CDCl)3Is a solvent);
FIG. 12 preparation of TPA-BTD-BT of benzothiadiazole malononitrile of the invention13CNMR (deuterium-doped chloroform CDCl)3Is a solvent);
FIG. 13 is a graph of nuclear magnetic shift analysis of intermediate TPA-BTD-CHO of the present invention;
FIG. 14 nuclear magnetic shift analysis chart of benzothiadiazole malononitrile TPA-BTD-BT of the present invention
FIG. 15 THF solution of benzothiadiazole malononitrile TPA-BTD-BT of the present invention (concentration of TPA-BTD-BT 2.0 × 10-5mol/L) adding CN-And ultraviolet-visible absorption spectrum of other anions (added CN)-And the concentration of other anions are 4.0 × 10-5mol/L)；
FIG. 16 THF solution of benzothiadiazole malononitrile TPA-BTD-BT of the present invention (concentration of TPA-BTD-BT 2.0 × 10-5mol/L) adding CN-And fluorescence spectra of other anions (added CN)-And the concentration of other anions are 4.0 × 10-5mol/L)
FIG. 17 THF solution of benzothiadiazole malononitrile TPA-BTD-BT of the present invention (concentration of TPA-BTD-BT 2.0 × 10-5mol/L) adding CN-And other anions, which change color under 365nm ultraviolet radiation, (Blank, CN from left to right-，F-,Cl-，Br-，I-,CH3COO-， NO2 -，NO3 -，H2PO4 -，HCO3 -，CO3 2-，SO4 2-)；
FIG. 18 THF solution of benzothiadiazole malononitrile TPA-BTD-BT of the present invention (concentration of TPA-BTD-BT 2.0 × 10-5mol/L), adding CN with different concentrations-Ultraviolet-visible absorption spectrum (CN)-The concentration increases from 0 to 4.0 × 10 in the direction of the arrow-5mol/L)；
FIG. 19 THF solution of benzothiadiazole malononitrile TPA-BTD-BT of the present invention (concentration of TPA-BTD-BT 2.0 × 10-5mol/L), adding CN with different concentrations-Fluorescence spectrum of (lambda)ex465nm, 5 slits; CN-The concentration increases from 0 to 4.0 × 10 in the direction of the arrow-5mol/L)；
FIG. 20 THF solution of benzothiadiazole malononitrile TPA-BTD-BT of the present invention (concentration of TPA-BTD-BT 2.0 × 10-5mol/L), adding various anions and CN-Ultraviolet-visible absorption spectrum of (CN added)-And the concentration of other anions are 4.0 × 10-5mol/L)；
FIG. 21 THF solution of benzothiadiazole malononitrile TPA-BTD-BT of the present invention (concentration of TPA-BTD-BT 2.0 × 10-5mol/L), adding various anions and CN-Histogram of fluorescence enhancement factor of (added CN)-And the concentration of other anions are 4.0 × 10-5mol/L)。
Detailed Description
1. Benzothiadiazole malononitrile, represented by the formula:
Figure BDA0001718769330000071
the Benzothiadiazole (BTD) has good electron carrier transfer performance and can form a D-A conjugated structure with an electron-donating group. The diazosulfide is introduced into molecules to enlarge the delocalization range of pi electrons of the molecules, so that ultraviolet light waves are subjected to red shift, and the conjugated hyperchromic effect is achieved. In the application, because the diazosulfide is introduced, the propionitrile-containing molecule pair CN can be led-The selectivity and the sensitivity of the method are greatly improved.
2. The synthesis method of diazosulfide malononitrile, the synthesis route diagram of which is shown in figure 1, comprises the following steps:
(1) synthesizing an intermediate TPA-BTD-Br;
in step (1), 2.7568g of 4-dianilinophenylboronic acid, 2.3576g of 4, 7-dibromo-2, 1, 3-benzothiadiazole, 0.1342g of 4- (triphenylphosphine) palladium and 1.7880g of potassium carbonate were placed in a 250mL three-necked flask, and 60mL of tetrahydrofuran THF, 45mL of toluene and 22mL of distilled water H were added to the mixture2O, then 0.1mL of methyl trioctyl ammonium chloride is added dropwise; adding a magnet, fully stirring, and carrying out reflux reaction for 16 hours under a nitrogen atmosphere, wherein the temperature of the reflux reaction is 85 ℃; after the reaction is finished, adding 200mL of distilled water into the reactant, extracting with dichloromethane to obtain an organic phase, carrying out vacuum distillation on the organic phase obtained by extraction to obtain a concentrate, and carrying out column chromatography separation, concentration and drying on the concentrate to obtain an intermediate TPA-BTD-Br; the eluent for column chromatography separation is a mixture of dichloromethane and petroleum ether, and the volume ratio of the dichloromethane to the petroleum ether is 1: 3.5.
The hydrogen nuclear magnetic resonance spectrum of intermediate TPA-BTD-Br is shown in FIG. 7:1HNMR/ppm: 7.82(d, J ═ 7.60Hz,1H), 7.73(d, J ═ 8.76Hz,2H), 7.49(d, J ═ 7.64Hz, 1H),7.18-7.24(m,5H),7.10-7.12(m,5H),6.98-7.02(m, 2H). Nuclear magnetic resonance carbon spectrum of intermediate TPA-BTD-Br, as shown in fig. 8:13CNMR/ppm:152.95.152.13, 147.42,146.31,132.55,131.34,128.87,128.81,128.37,126.29,124.01,122.49,121.59,111.16。
(2) synthesizing an intermediate TPA-BTD-CHO;
in step (2), intermediate TPA-BTD-Br2.2737g, 4-formylphenylboronic acid 1.1100g, 4- (triphenylphosphine) palladium 0.2588g and potassium carbonate 1.5525g were placed in a 250mL three-necked flask, 0.1mL methyltrioctylammonium chloride was added dropwise, and then 40mL tetrahydrofuran THF, 60mL toluene and 25mL distilled water H were added to the mixture2O; adding a magnet, fully stirring and dissolving, and carrying out reflux reaction for 16 hours under a nitrogen atmosphere, wherein the temperature of the reflux reaction is 85 ℃; after the reaction is finished, extracting with an extracting agent dichloromethane to obtain an organic phase, and performing rotary evaporation on the organic phase obtained by extraction to obtain a dry solid; and (3) carrying out column chromatography separation, concentration and drying on the dried solid to obtain an intermediate TPA-BTD-CHO, wherein an eluent for column chromatography separation is a mixture of dichloromethane and petroleum ether, and the volume ratio of the dichloromethane to the petroleum ether is 1: 3.5.
Nuclear magnetic resonance hydrogen spectra of intermediate TPA-BTD-CHO, as shown in fig. 9:1HNMR/ppm: 10.03(s, 1H),7.92(d, J ═ 8.16Hz,2H), 7.72(d, J ═ 8.12Hz,2H), 7.52(d, J ═ 8.60Hz,2H),7.26 to 7.31(m,5H), 7.05 to 7.15(m, 9H). Intermediate TPA-BTD-CHO NMR carbon spectrum, as shown in FIG. 10:13CNMR/ppm:191.90,148.45, 147.36,146.65,134.70,132.80,130.35,129.42,128.04,126.91, 124.90,123.50,123.13。
(3) and (3) synthesizing benzothiadiazole malononitrile TPA-BTD-BT.
In the step (3), putting the intermediate TPA-BTD-CHO1.5045g, the malononitrile 2.5219g and the ammonium acetate 4.7811g into a 500mL three-neck flask, adding 200mL of glacial acetic acid into the mixture, adding a magnet, fully stirring, and then reacting for 8 hours under a nitrogen atmosphere at the reaction temperature of 117 ℃; after the reaction is finished, extracting with an extractant dichloromethane to obtain an organic phase, performing rotary evaporation on the organic phase obtained by extraction to obtain a concentrate, performing column chromatography separation, concentration and drying on the concentrate to obtain benzothiadiazole malononitrile TPA-BTD-BT, wherein an eluent obtained by the column chromatography separation is a mixture of dichloromethane and petroleum ether, and the volume ratio of the dichloromethane to the petroleum ether is 1: 1.
Nuclear magnetic resonance hydrogen spectra of benzothiadiazole malononitrile TPA-BTD-BT, as shown in fig. 11:1HNMR/ppm：8.20(d,J＝8.40Hz,2H),8.07(d,J＝8.48Hz,2H), 7.86-7.90(m,3H),7.78-7.82(m,2H),7.28-7.32(m,4H),7.18-7.22 (m,6H),7.06-7.12(m,2H),0.87-0.90(m, 3H). Nuclear magnetic resonance carbon spectrum of benzothiadiazole malononitrile TPA-BTD-BT, as shown in fig. 12:13CNMR/ppm:176.81,159.06, 158.07,154.09,153.74,148.58,147.32,143.64,134.68,131.51, 131.09,130.41,130.11,129.98,129.46,129.20,128.28,126.93, 125.93,125.15,123.63,122.50,113.91,112.79。
3. characterization of the Compounds
3.1 Infrared Spectrum
Taking a proper amount of dry potassium bromide and a sample to be detected, uniformly grinding the mixture in an agate mortar, tabletting and detecting infrared rays. 4-Diphenylaminobenzeneboronic acid TPA-BTD-B (OH)2The IR spectra of intermediate TPA-BTD-Br, intermediate TPA-BTD-CHO and diazosulfide malononitrile TPA-BTD-BT are shown in FIG. 2, FIG. 3 and FIG. 4.
As can be seen from FIG. 2, 4-dianilinophenylboronic acid TPA-BTD-B (OH)2And intermediate TPA-BTD-Br at 1600cm-1And 1500cm-1The strong absorption peaks are all nearby and are 600cm at 900--1There is also a strong absorption peak in the range. Because the stretching vibration of the C ═ C double bond of the mononuclear aromatic hydrocarbon is 1600cm-1And 1500cm-1Has an absorption peak, and the bending vibration outside the C-H bond surface is 900-690cm-1And (4) a region. TPA-BTD-Br was known to contain a benzene ring. The expansion vibration of the C-N double bond is 1600-1690cm-1In the meantime, as shown in FIG. 2, the peak intensity of the intermediate TPA-BTD-Br is enhanced at each position; this is because the force constant of the bond of the benzothiadiazole is large, and the peak intensity is increased at each position. The 4-diphenylamine-phenylboronic acid TPA-B (OH) can be obtained by analysis2And 4, 7-dibromo-2, 1, 3-benzothiadiazole to generate intermediate TPA-BTD-Br.
As can be seen from FIG. 3, the intermediate TPA-BTD-Br and the intermediate TPA-BTD-CHO were at 1600cm-1And 1500cm-1The strong absorption peaks are all nearby and are 600cm at 900--1There is also a strong absorption peak in the range. Because the stretching vibration of the C ═ C double bond of the mononuclear aromatic hydrocarbon is 1600cm-1And 1500cm-1Has an absorption peak, and the bending vibration outside the C-H bond surface is 900-690cm-1And (4) a region. TPA-BTD-CHO is known to contain a benzene ring. The telescopic vibration of aldehyde group is 1750--1Region, it can be seen from FIG. 3 that the intermediate TPA-BTD-CHO is 1695cm-1There is an absorption peak, and the intermediate TPA-BTD-CHO contains-CHO. As can be seen from the analysis, the intermediate TPA-BTD-Br was reacted with p-formylphenylboronic acid to produce the intermediate TPA-BTD-CHO.
As can be seen from FIG. 4, the intermediate TPA-BTD-CHO and benzothiadiazole malononitrile TPA-BTD-BT were at 1600cm-1And 1500cm-1The strong absorption peaks are all nearby and are 600cm at 900--1There is also a strong absorption peak in the range. Because the stretching vibration of the C ═ C double bond of the mononuclear aromatic hydrocarbon is 1600cm-1And 1500cm-1Has an absorption peak, and the bending vibration outside the C-H bond surface is 900-690cm-1And (4) a region. Therefore, it was found that benzothiadiazole malononitrile TPA-BTD-BT contained benzene rings. The telescopic vibration of aldehyde group is 1750--1As can be seen from FIG. 3, no absorption peak is observed in this region by TPA-BTD-BT, indicating that benzothiadiazole malononitrile TPA-BTD-BT has no-CHO, and analysis shows that the reaction of TPA-BTD-CHO with malononitrile produces benzothiadiazole malononitrile TPA-BTD-BT.
3.2 UV-visible absorption and fluorescence Spectroscopy
The UV-visible absorption spectrum of the tetrahydrofuran solution of benzothiadiazole malononitrile TPA-BTD-BT, as shown in FIG. 5, shows two main absorption bands at 400nm of 200-367 nm, 317 nm and 367nm respectively. The visible region shows a broad absorption band at 465 nm.
The fluorescence spectrum of the tetrahydrofuran solution of benzothiadiazole malononitrile TPA-BTD-BT, as shown in FIG. 6, shows that the THF solution of TPA-BTD-BT generates an emission peak at 600nm under excitation of 465nm under the condition that the entrance slit and the exit slit are both 5, and shows larger stokes shift.
3.3 nuclear magnetic resonance spectrum
FIGS. 7 and 8 are NMR hydrogen and carbon spectra of intermediate TPA-BTD-Br;
FIGS. 9 and 10 are NMR hydrogen and carbon spectra of intermediate TPA-BTD-CHO;
FIGS. 11 and 12 are NMR hydrogen and carbon spectra of benzothiadiazole malononitrile TPA-BTD-BT.
From fig. 9, it can be seen that the chemical shift of aldehyde hydrogen is 10.03(s, 1H,) since the electron withdrawing effect of aldehyde group is greater than that of benzothiadiazole:
so as shown in fig. 11: 2. chemical shifts for hydrogen on carbon No. 4 are 7.92(d, J ═ 8.16Hz,2H), and for hydrogen on carbon No. 3, 5 are 7.52(d, J ═ 8.60Hz, 2H); 6. chemical shift of hydrogen on carbon 7 is 7.72(d, J ═ 8.12Hz, 2H); 8. chemical shifts of hydrogen on carbons No. 10, 13, 15, 17, 19 are 7.26 to 7.31(m,6H), and chemical shifts of hydrogen on carbons No. 9, 11, 12, 14, 16, 18, 19, 20 are 7.05 to 7.15(m, 8H).
Since the chemical shifts of the aldehyde groups shown in FIGS. 11 and 12 disappeared, it was judged that the intermediate TPA-BTD-CHO reacted with malononitrile to produce benzothiadiazole malononitrile TPA-BTD-BT. As shown in fig. 14, the chemical shift of the hydrogen on carbon No. 22 should be about 8.2, and since one hydrogen in the nmr hydrogen spectrum of benzothiadiazole malononitrile TPA-BTD-BT in fig. 11 has a chemical shift of 8.20 (d, J ═ 8.40Hz,2H), the intermediate TPA-BTD-CHO, which was obtained in summary, reacts with malononitrile to produce benzothiadiazole malononitrile TPA-BTD-BT.
4. Diazosulfide malononitrile fluorescence detection CN-The method comprises the following steps:
(1) adding benzothiadiazole malononitrile TPA-BTD-BT into tetrahydrofuran THF (tetrahydrofuran) serving as a solvent to prepare a tetrahydrofuran THF solution of the benzothiadiazole malononitrile TPA-BTD-BT; the benzothiadiazole malononitrile TPA-BTD-BT is shown below:
Figure BDA0001718769330000111
(2) adding a sample to be detected into a tetrahydrofuran THF solution of benzothiadiazole malononitrile TPA-BTD-BT;
(3) identifying whether CN exists in the sample to be detected through naked eye observation, ultraviolet-visible absorption spectrum or fluorescence spectrum-(ii) a The visual observation and identification method comprises the following steps: the color of the solution changes from orange to yellow, which indicates that CN exists in the sample to be detected-(ii) a The identification method of the ultraviolet-visible absorption spectrum comprises the following steps: the UV-vis spectrum test is carried out at 660nm of 200-Decrease or disappear, the absorption peak at 465nm is decreased and blue shift to 440nm occurs, and two equal absorption points appear at 430nm and 407nm, which indicates that CN exists in the sample to be detected-(ii) a The fluorescence spectrum identification method comprises the following steps: generating an emission peak at 600nm under the excitation of 465nm, and showing that CN exists in the sample to be detected-Or under the irradiation of 365nm ultraviolet lamp, the solution shows bright orange fluorescence, which indicates CN in the sample to be detected-。
Dissolving benzothiadiazole malononitrile TPA-BTD-BT in tetrahydrofuran THF, and respectively adding CN into the tetrahydrofuran THF solution of the benzothiadiazole malononitrile TPA-BTD-BT-And other anions, and then separately determining CN-Adding benzothiadiazole malononitrile TPA-BTD-BT into tetrahydrofuran THF solution, and adding other anions into the benzothiadiazole malononitrile TPA-BTD-BT into tetrahydrofuran THF solution, wherein the concentration of the benzothiadiazole malononitrile TPA-BTD-BT is 2 × 10-5mol/L, CN added-And other anions were all at a concentration of 4 × 10-5mol/L; the other anions include Cl-、SO4 2-、F-、Br-、I-、H2PO4 -、NO2 -、NO3 -、CO3 2-、HCO3 -And CH3COO-。
As can be seen in FIG. 15, the benzothiadiazole malononitrile TPA-BTD-BT was reacted with 2equiv of CN in THF solution-And other anions (F)-,Cl-,Br-,I-,CH3COO-,NO2 -,NO3 -,H2PO4 -,HCO3 -,CO3 2-, SO4 2-) UV-vis Spectroscopy at 660nm of 200--When the TPA-BTD-BT is added into a THF solution of TPA-BTD-BT, the absorption peak of the UV-vis absorption spectrum at 367nm is reduced until disappearance, and the absorption peak at 465nm is reduced and blue shift to 440nm occurs, which shows that the conjugation degree of TPA-BTD-BT is reduced, and the electron transition energy of the system is increased, thereby causing blue shift. The solution changes color from orange to yellowYellow.
As shown in fig. 16, in the case of 5 for both entrance and exit slits, the THF solution of benzothiadiazole malononitrile TPA-BTD-BT produced an emission peak at 600nm under 465nm excitation, showing a large stokes shift. When reacted with 2equiv of other anions (F)-,Cl-,Br-,I-,CH3COO-, NO2 -,NO3 -,H2PO4 -,HCO3 -,CO3 2-,SO4 2-) When FS fluorescence detection is carried out, the response of TPA-BTD-BT to other anions is not obviously changed, but to CN-Has larger change, which indicates that TPA-BTD-BT is opposite to CN-The selectivity of (A) is better. With CN-The fluorescence intensity is obviously enhanced by adding ions, i.e. the compound has very potential to be used for detecting CN-The chemical sensor of (1). Under UV irradiation (365nm), the solution color was clearly observed, as shown in FIG. 17, with the addition of CN-The rear solution shows bright orange fluorescence, and the fluorescence color is not changed after other ions are added, which also fully indicates that the TPA-BTD-BT is used for CN-Has better selectivity.
As can be seen from FIG. 18, with CN-Gradual increase in ion concentration (0-4 × 10)-5mol/L), the absorption peak of the UV-vis absorption spectrum at 367nm gradually decreases until disappears, the absorption peak at 465nm gradually decreases and undergoes blue shift (blue shift to 440nm), and two equal absorption points appear at 430nm and 407nm, which indicates CN-The TPA-BTD-BT reacts with the TPA-BTD-BT to generate new substances. At the same time, the solution changed color from orange to yellow (as shown in FIG. 18).
As can be seen from FIG. 19, with CN-The peak intensity at 600nm is obviously enhanced by continuously adding the fluorescent dye, and the fluorescence enhancement factor is 16. Description of CN-Reacts with TPA-BTD-BT to form a new substance. This is also under UV irradiation with CN-The reason why the fluorescence of the latter solution is significantly enhanced. The above results fully indicate that TPA-BTD-BT is on CN-Is a good "turn-on" type fluorescence sensor.
(2) Other yinIon-pair diazosulfide malononitrile TPA-BTD-BT fluorescence detection CN-The interference effect of (c).
In the method (2), the benzothiadiazole malononitrile TPA-BTD-BT is dissolved in tetrahydrofuran THF, then other anions are respectively added into the tetrahydrofuran THF solution of the benzothiadiazole malononitrile TPA-BTD-BT, and CN is respectively added into the tetrahydrofuran THF solution of the benzothiadiazole malononitrile TPA-BTD-BT added with other anions-After being mixed uniformly, the other anions and CN are added into tetrahydrofuran THF solution of diazosulfide malononitrile TPA-BTD-BT which is respectively measured-The concentration of the benzothiadiazole malononitrile TPA-BTD-BT is 2 × 10-5The concentration of the other anions added is 4 × 10-5mol/L; the added CN-Has a concentration of 4 × 10-5mol/L; the other anions include Cl-、SO4 2-、F-、Br-、I-、H2PO4 -、NO2 -、NO3 -、 CO3 2-、HCO3 -And CH3COO-。
As can be seen from FIG. 20, 4 × 10 was added-5When the other anions are added in mol/L, the absorption spectrum does not change obviously, and when 4 × 10 is further added-5mol/L of CN-When the absorption spectrum changes with the addition of CN only-The spectrum of (a) is similar in variation. This indicates that TPA-BTD-BT acts on CN in the presence of other ions-Still has excellent recognition function.
As can be seen from FIG. 21, in the absence of CN-In the presence of 4 × 10-5When the other anions are added to the solution containing the other anions, the fluorescence intensity does not change obviously, and when the solution containing the other anions is added to the solution, 4 × 10 is added-5mol/L of CN-When the fluorescence intensity was increased significantly.
As can be seen from the histogram of FIG. 21 for the fluorescence enhancement factor at 596nm from the emission band, although the presence of other anions had a slight effect on their enhancement factor, the presence of other ions did not affect the TPA-BTD-BT on CN-"turn-on" type fluorescence recognition of (1). From this, we can see that we successfully constructed "TPA-BTD-BT" to CN-The turn-on type fluorescent sensor has high selectivity and strong anti-interference capability.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications are possible which remain within the scope of the appended claims.

Claims (6)

1. Diazosulfide malononitrile, characterized by the formula (I):
Figure FDA0002449301290000011
2. the synthesis method of diazosulfide malononitrile is characterized by comprising the following steps:
(1) synthesizing an intermediate TPA-BTD-Br, wherein the intermediate TPA-BTD-Br is shown as a formula (II):
Figure FDA0002449301290000012
placing 4-diphenylanilinophenylboronic acid, 4, 7-dibromo-2, 1, 3-benzothiadiazole, 4- (triphenylphosphine) palladium and potassium carbonate in a three-necked flask, and adding Tetrahydrofuran (THF), toluene and distilled water (H) to the mixture2O, dropwise adding methyl trioctyl ammonium chloride; adding magnetite, fully stirring, and reacting under nitrogen atmosphere; after the reaction is finished, adding distilled water into the reactant, extracting with dichloromethane to obtain an organic phase, carrying out vacuum distillation on the organic phase obtained by extraction to obtain a concentrate, and carrying out column chromatography separation, concentration and drying on the concentrate to obtain an intermediate TPA-BTD-Br; the eluent for column chromatography separation is a mixture of dichloromethane and petroleum ether;
(2) synthesizing an intermediate TPA-BTD-CHO from the intermediate TPA-BTD-Br, wherein the intermediate TPA-BTD-CHO is represented by the formula (III):
Figure FDA0002449301290000013
placing intermediate TPA-BTD-Br, 4-formylphenylboronic acid, 4- (triphenylphosphine) palladium and potassium carbonate into a three-neck flask, dropwise adding methyl trioctyl ammonium chloride, and adding tetrahydrofuran THF, toluene and distilled water H into the mixture2O; adding magnetite, fully stirring and dissolving, and carrying out reflux reaction under nitrogen atmosphere; after the reaction is finished, extracting with an extracting agent dichloromethane to obtain an organic phase, and performing rotary evaporation on the organic phase obtained by extraction to obtain a dry solid; separating, concentrating and drying the dried solid by column chromatography to obtain an intermediate TPA-BTD-CHO, wherein the eluent of the column chromatography separation is a mixture of dichloromethane and petroleum ether;
(3) the synthesis of benzothiadiazole malononitrile TPA-BTD-BT, which is represented by formula (I):
Figure FDA0002449301290000021
putting intermediate TPA-BTD-CHO, malononitrile and ammonium acetate into a three-neck flask, adding glacial acetic acid into the mixture, adding a magnet, fully stirring, and reacting under nitrogen atmosphere; after the reaction is finished, extracting with an extracting agent dichloromethane to obtain an organic phase, performing rotary evaporation on the organic phase obtained by extraction to obtain a concentrate, performing column chromatography separation, concentration and drying on the concentrate to obtain benzothiadiazole malononitrile TPA-BTD-BT, wherein an eluent obtained by the column chromatography separation is a mixture of dichloromethane and petroleum ether.
3. The method for synthesizing diazosulfide malononitrile according to claim 2, wherein in the step (1), 2.7568g of 4-dianilinophenylboronic acid, 2.3576g of 4, 7-dibromo-2, 1, 3-benzothiadiazole, 0.1342g of 4- (triphenylphosphine) palladium and 1.7880g of potassium carbonate are put in a 250mL three-necked bottle, and the mixture is added60mL of tetrahydrofuran THF, 45mL of toluene and 22mL of distilled water H2O, then 0.1mL of methyl trioctyl ammonium chloride is added dropwise; adding a magnet, fully stirring, and carrying out reflux reaction for 16 hours under a nitrogen atmosphere, wherein the temperature of the reflux reaction is 85 ℃; after the reaction is finished, adding 200mL of distilled water into the reactant, extracting with dichloromethane to obtain an organic phase, carrying out vacuum distillation on the organic phase obtained by extraction to obtain a concentrate, and carrying out column chromatography separation, concentration and drying on the concentrate to obtain an intermediate TPA-BTD-Br; the eluent for column chromatography separation is a mixture of dichloromethane and petroleum ether, and the volume ratio of the dichloromethane to the petroleum ether is 1: 3.5.
4. The method for synthesizing diazosulfide malononitrile according to claim 2, wherein in the step (2), the intermediate TPA-BTD-Br2.2737g, 1.1100g of 4-formylphenylboronic acid, 0.2588g of 4- (triphenylphosphine) palladium and 1.5525g of potassium carbonate are put in a 250mL three-necked flask, 0.1mL of methyltrioctylammonium chloride is added dropwise, and then 40mL of tetrahydrofuran THF, 60mL of toluene and 25mL of distilled water H are added to the mixture2O; adding a magnet, fully stirring and dissolving, and carrying out reflux reaction for 16 hours under a nitrogen atmosphere, wherein the temperature of the reflux reaction is 85 ℃; after the reaction is finished, extracting with an extracting agent dichloromethane to obtain an organic phase, and performing rotary evaporation on the organic phase obtained by extraction to obtain a dry solid; and (3) carrying out column chromatography separation, concentration and drying on the dried solid to obtain an intermediate TPA-BTD-CHO, wherein an eluent for column chromatography separation is a mixture of dichloromethane and petroleum ether, and the volume ratio of the dichloromethane to the petroleum ether is 1: 3.5.
5. The method for synthesizing diazosulfide malononitrile according to claim 2, wherein in the step (3), the intermediate TPA-BTD-CHO1.5045g, malononitrile 2.5219g and ammonium acetate 4.7811g are placed in a 500mL three-neck flask, 200mL glacial acetic acid is added into the mixture, and then the magnetite is added into the mixture to be fully stirred, and then the mixture is reacted for 8 hours under nitrogen atmosphere, wherein the reaction temperature is 117 ℃; after the reaction is finished, extracting an upper layer of organic matter by using an extracting agent dichloromethane, carrying out rotary evaporation on the upper layer of organic matter to obtain a concentrate, carrying out column chromatography separation, concentration and drying on the concentrate to obtain the benzothiadiazole malononitrile TPA-BTD-BT, wherein an eluent for the column chromatography separation is a mixture of dichloromethane and petroleum ether, and the volume ratio of the dichloromethane to the petroleum ether is 1: 1.
6. Diazosulfide malononitrile fluorescence detection CN-The method is characterized by comprising the following steps:
(1) adding benzothiadiazole malononitrile TPA-BTD-BT into tetrahydrofuran THF (tetrahydrofuran) serving as a solvent to prepare a tetrahydrofuran THF solution of the benzothiadiazole malononitrile TPA-BTD-BT; the benzothiadiazole malononitrile TPA-BTD-BT is shown below:
Figure FDA0002449301290000031
(2) adding a sample to be detected into a tetrahydrofuran THF solution of benzothiadiazole malononitrile TPA-BTD-BT; (3) identifying whether CN exists in the sample to be detected through naked eye observation, ultraviolet-visible absorption spectrum or fluorescence spectrum-(ii) a The visual observation and identification method comprises the following steps: the color of the solution changes from orange to yellow, which indicates that CN exists in the sample to be detected-(ii) a The identification method of the ultraviolet-visible absorption spectrum comprises the following steps: performing UV-vis spectrum test at 660nm of 200--(ii) a The fluorescence spectrum identification method comprises the following steps: generating an emission peak at 600nm under the excitation of 465nm, and showing that CN exists in the sample to be detected-Or under the irradiation of 365nm ultraviolet lamp, the solution shows bright orange fluorescence, which indicates CN in the sample to be detected-。
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