CN112028866A - Hydrazone compound, preparation method thereof, ion recognition receptor and application - Google Patents
Hydrazone compound, preparation method thereof, ion recognition receptor and application Download PDFInfo
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- -1 Hydrazone compound Chemical class 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 150000001450 anions Chemical class 0.000 claims abstract description 31
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- 239000001257 hydrogen Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 21
- 150000002500 ions Chemical class 0.000 claims abstract description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 4
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- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 229940067157 phenylhydrazine Drugs 0.000 claims description 16
- 238000001514 detection method Methods 0.000 claims description 12
- 229910052731 fluorine Inorganic materials 0.000 claims description 12
- 239000011737 fluorine Substances 0.000 claims description 12
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 6
- NTCCNERMXRIPTR-UHFFFAOYSA-N 2-hydroxy-1-naphthaldehyde Chemical compound C1=CC=CC2=C(C=O)C(O)=CC=C21 NTCCNERMXRIPTR-UHFFFAOYSA-N 0.000 claims description 5
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 claims description 5
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- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 5
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
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- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
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- 239000000203 mixture Substances 0.000 description 3
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- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 239000000370 acceptor Substances 0.000 description 2
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- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
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- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical class CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 2
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 2
- HORQAOAYAYGIBM-UHFFFAOYSA-N 2,4-dinitrophenylhydrazine Chemical compound NNC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O HORQAOAYAYGIBM-UHFFFAOYSA-N 0.000 description 1
- KMVPXBDOWDXXEN-UHFFFAOYSA-N 4-nitrophenylhydrazine Chemical compound NNC1=CC=C([N+]([O-])=O)C=C1 KMVPXBDOWDXXEN-UHFFFAOYSA-N 0.000 description 1
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
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- LPVWZQYOCIAYQJ-UHFFFAOYSA-N butyl 9-(dicyanomethylidene)-2,7-dinitrofluorene-4-carboxylate Chemical compound N#CC(C#N)=C1C2=CC([N+]([O-])=O)=CC=C2C2=C1C=C([N+]([O-])=O)C=C2C(=O)OCCCC LPVWZQYOCIAYQJ-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/78—Ring systems having three or more relevant rings
- C07D311/92—Naphthopyrans; Hydrogenated naphthopyrans
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- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- 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
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Abstract
The invention relates to the field of chemistry, and particularly discloses a hydrazone compound, a preparation method thereof, an ion recognition receptor and application, wherein the hydrazone compound has the following structure:
wherein R is selected from hydrogen, 2, 4-dinitro or 4-nitro; the hydrazone compound can be used for detecting common anions, the hydrazone compound is synthesized by a simple method, the hydrazone group is introduced to serve as a binding site of a hydrogen bond effect of the anions, and the benzocoumarin is used as a signal reporting group, so that the anions with weaker binding capacity can be identified, and the problems that the existing synthesis method of an anion recognition receptor is complex and the synthesis cost is high are solved; to provideThe preparation method is simple and suitable for industrial production.
Description
Technical Field
The invention relates to the field of chemistry, in particular to a hydrazone compound, a preparation method thereof, an ion recognition receptor and application.
Background
The molecular recognition is a process of combining and interacting two or more molecules through non-covalent bonds, and can be used in a sensor recognition system to further realize the detection of the species and the content of substances.
Among them, the anion recognition receptor is a common means for detecting anions, and among various developed anion receptors, particularly the fluorine ion recognition receptor, the receptors based on hydrogen bonding and deprotonation are receiving wide attention from scientists. The acceptors comprise compounds containing phenolic hydroxyl, heterocyclic compounds, hydrazone, acylhydrazone, urea, thiourea and the like which can provide active H protons, fluorine ions and the active H can form hydrogen bonds or generate deprotonation to cause the color change of the solution, and proper fluorescent groups are introduced to possibly realize colorimetric fluorescence double-channel identification.
However, the above technical solutions have the following disadvantages: the existing synthesis method of the anion recognition receptor is complex and has the problem of high synthesis cost. Therefore, it is an urgent problem to design an anion recognition receptor that can be obtained by a simple method at low cost.
Disclosure of Invention
The embodiment of the invention aims to provide a hydrazone compound to solve the problems that the existing synthesis method of an anion recognition receptor in the background art is complex and has high synthesis cost.
In order to achieve the above purpose, the embodiments of the present invention provide the following technical solutions:
a hydrazone compound has a structure shown in formula 1:
wherein R is selected from hydrogen, 2, 4-dinitro or 4-nitro.
As a further scheme of the invention: the hydrazone compound is prepared from 3-acetyl benzocoumarin and phenylhydrazine compounds serving as raw materials in an organic solvent.
As a still further scheme of the invention: the dosage of the 3-acetyl benzo coumarin and the phenylhydrazine compound is 0.9-1.1: 0.9-1.1.
As a still further scheme of the invention: the organic solvent is absolute ethyl alcohol (EtOH) and/or piperidine.
Preferably, the 3-acetyl benzo coumarin and the phenylhydrazine compound are used in a molar ratio of 1: 1. for example, 2 mmol (0.48 g) of 3-acetyl benzocoumarin and 2 mmol (0.216 g) of phenylhydrazine are added, the mixture is placed in 20mL of absolute ethanol (EtOH) and 0.5mL of piperidine, and the hydrazone compound is obtained by heating, stirring and refluxing at 80 ℃.
As a still further scheme of the invention: the structure of the phenylhydrazine compound is shown as formula 2:
wherein R is selected from hydrogen, 2, 4-dinitro or 4-nitro.
Another object of an embodiment of the present invention is to provide a method for preparing a hydrazone compound, comprising the steps of:
and (2) putting the 3-acetyl benzocoumarin and the phenylhydrazine compound into an organic solvent, uniformly mixing, then reacting for 3-5h at 70-90 ℃ (TCL tracking reaction, namely thin layer plate tracking reaction), cooling, filtering, washing a product, drying, and recrystallizing to obtain a target compound, namely the hydrazone compound.
Preferably, the preparation method of the hydrazone compound comprises the following steps:
adding 2 mmol (0.48 g) of 3-acetyl benzocoumarin and 2 mmol (0.216 g) of phenylhydrazine compound, placing the mixture into 20mL of absolute ethyl alcohol (EtOH) and 0.5mL of piperidine, heating, stirring and refluxing for reaction for 3-5h at 80 ℃ (TCL tracking reaction, namely thin layer plate tracking reaction), naturally cooling after a small amount of solvent is evaporated, leaching after a product is separated out, washing the product with 95wt% of cold ethanol, drying, and recrystallizing with EtOH-DMF (dimethylformamide) to obtain a target compound, namely the hydrazone compound.
As a still further scheme of the invention: in the preparation method of the hydrazone compound, the step of synthesizing 3-acetyl benzocoumarin is further included, and specifically, the step of synthesizing 3-acetyl benzocoumarin includes:
adding 2-hydroxy-1 naphthaldehyde and ethyl acetoacetate in equimolar amount, uniformly mixing in absolute ethyl alcohol and piperidine, heating at 70-90 ℃, stirring, refluxing, standing, performing suction filtration on precipitated solid substances, washing with ethanol, drying, and recrystallizing with EtOH-DMF to obtain the target compound 3-acetyl benzocoumarin.
Preferably, the step of synthesizing 3-acetylbenzocoumarin comprises: adding 20 mmol (3.44 g) of 2-hydroxy-1-naphthaldehyde, 20 mmol (2.6 g) of ethyl acetoacetate, 25 mL of absolute ethyl alcohol and 5 drops of piperidine into a 100 mL round-bottom flask, heating, stirring, refluxing and reacting for 5 hours at 80 ℃, standing reaction liquid overnight, filtering precipitated solid substances, washing for 3 times with ethanol, drying, and recrystallizing with EtOH-DMF to obtain the target compound 3-acetyl benzocoumarin.
As a still further scheme of the invention: the synthetic route of the preparation method of the hydrazone compound is as follows:
wherein R is selected from hydrogen, 2, 4-dinitro or 4-nitro, and correspondingly, hydrazone compounds obtained by respectively using R as hydrogen, 2, 4-dinitro and 4-nitro are respectively marked as Z1, Z2 and Z3.
Another object of the embodiments of the present invention is to provide a hydrazone compound prepared by the above method for preparing a hydrazone compound.
Another object of the present invention is to provide an ion recognition receptor, which comprises a hydrazone compound as described above partially or completely.
As a still further scheme of the invention: the ion recognition receptor can be the hydrazone compound singly, or can be a substance which can provide active H protons with a compound containing phenolic hydroxyl, a heterocyclic compound, acylhydrazone, urea, thiourea and the like, and colorimetric fluorescence dual-channel recognition can be realized by introducing a proper fluorescent group.
Another object of the embodiments of the present invention is to provide an application of the above-mentioned ion recognition receptor in anion recognition and/or anion content detection.
As a self-service hairIn yet a further embodiment: the anion may be F-，Cl-，Br-，I-，AcO-，H2PO4 -，CN-，HSO4 -，SCN- And ClO4 -And (4) plasma.
The embodiment of the invention also aims to provide an application of the preparation method of the hydrazone compound in preparation of a fluorine sensor. By introducing hydrazone groups as (F)-) A binding site for hydrogen bonding of fluoride ions; secondly, adopting benzocoumarin (preferably 3-acetyl benzocoumarin) as a signal reporter group; the benzocoumarin group has a larger conjugated system, so that the benzocoumarin group also has better color change on an ultraviolet-visible absorption spectrum, and can be used for preparing a fluorine sensor for fluorine content detection.
Compared with the prior art, the invention has the beneficial effects that:
the hydrazone compound provided by the invention can be used for detecting common anions, the hydrazone compound is synthesized by a simple method, the hydrazone group is introduced to serve as a binding site for a hydrogen bond effect of the anions, and the benzocoumarin is used as a signal reporting group; the provided preparation method is simple, and the obtained hydrazone compound has a plurality of hydrogen bond binding sites, so that the hydrazone compound has stronger hydrogen bond forming capability, can identify anions with weaker binding capability, and has wide market prospect.
Drawings
FIG. 1 is a UV-Vis spectrum diagram of a hydrazone compound added with different anions in a DMSO solution according to an embodiment of the present invention.
FIG. 2 is a fluorescence spectrum of a hydrazone compound in DMSO (dimethylsulfoxide) when different anions are added to the solution to interact with each other.
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
The reagents and solvents used in the following examples are as follows:
2-hydroxy-1-naphthaldehyde, ethyl acetoacetate, piperidine, absolute ethyl alcohol, DMF, phenylhydrazine, 4-nitrophenylhydrazine and 2, 4-dinitrophenylhydrazine, and all the reagents are domestic analytical purifications. DMSO (dimethyl sulfoxide, available from Beijing chemical industry, analytically pure). Tetrabutylammonium salts (available from Alfa Aesar chemical ltd, all analytically pure).
The test and analytical equipment was as follows:
1h NMR spectrum (hydrogen nuclear magnetic resonance spectrum) and13c NMR spectrum (carbon nuclear magnetic resonance spectrum) was measured using a nuclear magnetic resonance apparatus model Mercury-400BB, TMS (tetramethylsilane) as an internal standard. IR (Fourier Infrared Spectroscopy) was determined using a Digilab FTS-3000 FT-IR Fourier Infrared spectrometer (KBr pellet); melting points were determined using an X-4 digital display micro melting point apparatus (thermometer uncorrected); ESI-MS (electrospray mass spectrometry) was determined using a ZAB-HS type mass spectrometer. Ultraviolet-visible spectra (UV-Vis) were determined using a Japan Shimadzu UV-2550 ultraviolet-visible spectrophotometer (1 cm quartz cell). The fluorescence spectrum was measured using Shimadzu RF-5301 fluorescence photometer, Japan.
Example 1
A hydrazone compound has a structure shown in formula 1:
wherein R is selected from hydrogen, and is Z3 correspondingly, the specific preparation method comprises the following steps:
synthesis of 3-acetylbenzocoumarin: adding 20 mmol (3.44 g) of 2-hydroxy-1-naphthaldehyde, 20 mmol (2.6 g) of ethyl acetoacetate, 25 mL of absolute ethyl alcohol and 5 drops of piperidine into a 100 mL round-bottom flask, heating, stirring, refluxing and reacting for 5 hours at 80 ℃, standing reaction liquid overnight, performing suction filtration on precipitated solid substances, washing for 3 times with ethanol, drying, and recrystallizing with EtOH-DMF to obtain a target compound, namely 3-acetyl benzocoumarin;
synthesis of hydrazone Compounds: adding 2 mmol (0.48 g) of 3-acetyl benzocoumarin and 2 mmol (0.216 g) of phenylhydrazine compound, placing the mixture into 20mL of absolute ethanol and 0.5mL of piperidine, heating, stirring and refluxing for 3-5h (TCL tracking reaction, namely thin layer plate tracking reaction) at 80 ℃, naturally cooling after evaporating a small amount of solvent, leaching after precipitating a product, washing the product with 95wt% cold ethanol, drying, and recrystallizing with EtOH-DMF (dimethylformamide) to obtain a target compound, namely the hydrazone compound, which is recorded as Z3.
In this embodiment, the structure of the phenylhydrazine compound is shown as formula 2.
Wherein R is selected from hydrogen.
Example 2
A hydrazone compound has a structure shown in formula 1:
wherein R is selected from 2, 4-dinitro, and the corresponding is Z1, and the specific synthetic steps refer to example 1.
Example 3
A hydrazone compound has a structure shown in formula 1:
wherein R is selected from 4-nitro, and is Z2 correspondingly, and the specific synthesis steps refer to the preparation method in example 1.
Example 4
Compound Z1 obtained using the method in example 2, bright red solid powder, yield: 87 percent. And (3) carrying out performance detection on the Z1, wherein the corresponding performance detection results are as follows:
mp (melting point) > 300 ℃.
IR（KBr, cm-1）ν: 3431, 2970, 1720, 1604, 1330, 1101, 664。
1H NMR (DMSO-d 6 , 600 MHz): 5.02 (s, 3H, -CH3), 7.65-7.66 (d, 1H, ArH), 7.76-7.79 (t, 2H, ArH), 8.07-8.09 (d, 2H, ArH), 8.31-8.33 (d, 2H, ArH), 8.62-8.63 (d, 2H, ArH), 9.28 (s, 2H, ArH), 9.97 (s, 1H, NH)。
13C NMR (DMSO-d 6 , 100 MHz): 195.49, 158.84, 155.75, 149.59, 142.85, 136.62, 130.29, 129.97, 129.80, 129.52, 126.94, 123.89, 123.46, 122.77, 116.85, 115.98, 112.77。
ESI-MS: m/z calcd for C21H14N4O6, [M-H]+ = 418.09, found [M-H]+ = 417.1348。
Example 5
Compound Z2 obtained using the procedure in example 3, dark red solid powder, yield: 80 percent. And (3) carrying out performance detection on the Z2, wherein the corresponding performance detection results are as follows:
mp (melting point) > 300 ℃.
IR（KBr, cm-1）ν: 3431, 2340, 1690, 1582, 1497, 1352, 809, 679。
1H NMR (DMSO-d 6 , 600 MHz): 3.31 (s, 3H, -CH3), 7.39-7.64 (m, 4H, ArH), 7.73-7.76 (t, 1H, ArH), 8.14-8.15 (d, 2H, ArH), 8.19 (s, 1H, ArH), 8.63-8.64 (d, 1H, ArH), 8.95 (s, 1H, ArH), 10.37 (s, 1H, NH)。
ESI-MS: m/z calcd for C21H15N3O4, [M-H]+ = 373.11, found [M-H]+ = 372.1471。
Example 6
Compound Z3 obtained using the method in example 1, light red solid powder, yield: 71 percent. And (3) carrying out performance detection on the Z3, wherein the corresponding performance detection results are as follows:
mp (melting point) > 300 ℃.
IR（KBr, cm-1）ν: 3429, 1705, 1577, 1384, 1234, 743, 679。
1H NMR (DMSO-d 6 , 400 MHz): 2.30 (s, 3H, -CH3), 6.79-7.31 (m, 5H, ArH), 7.74-8.89 (m, 7H, ArH), 9.50 (s, 1H, NH)。
13C NMR (DMSO-d 6 , 100 MHz): 159.88, 153.08, 146.03, 142.81, 139.27, 136.58, 135.20, 133.19, 130.37, 129.50, 129.48, 129.33, 129.28, 129.24, 128.73, 126.96, 126.90, 126.49, 122.78, 122.72, 119.83, 116.81, 116.77, 113.66。
ESI-MS: m/z calcd for C21H16N2O2, [M-H]+ = 328.12, found [M-H]+ = 327.1561。
Example 7
The detection of the identification performance of anions is carried out on the Z3 prepared in the example 1, and the detection specifically comprises a selective identification experiment of an absorption spectrum and a selective identification experiment of a fluorescence spectrum.
In order to examine the selectivity of the receptor molecule Z3 for anion recognition, F was added to a DMSO solution of the receptor molecule Z3 in each case-，Cl-，Br-，I-，AcO-，H2PO4 -，CN-，SCN-，HSO4 - And ClO4 -Total 10 anions in DMSO, and their absorption spectra were determined in turn, when the 10 anions were added to the receptor molecule Z3, only F was present-Can cause obvious changes in the UV-visible spectrum and the color of the solution, as shown in FIG. 1, in which FIG. 1 is the addition of various anions to a DMSO solution of Z3UV-Vis spectra of ions, it can be seen that only for F-Can cause sensitive detection due to electron-withdrawing group-NO2The acidity of the-NH proton on the hydrazone is increased, resulting in an increased binding capacity with basic anions.
To examine the receptor molecules Z3 for F- For selectivity of fluorescence spectrum discrimination, F was added to a DMSO solution of Z3-，Cl-，Br-，I-，AcO-，H2PO4 -，CN-，SCN-，HSO4 - And ClO4 -The fluorescence spectrum properties of 10 anions in DMSO (tetrabutylammonium) salt are sequentially measured, and particularly, as shown in figure 2, figure 2 is the fluorescence spectrum when various anions interact in Z3 in DMSO solution, and the result shows that the compound Z3 can specifically identify F-Adding 50 times of F-When the fluorescent material is used, a blue shift of about 50 nm appears on the fluorescence spectrum, and the result is consistent with the ultraviolet spectrum property.
Example 8
Compared with example 1, except that the 3-acetyl benzocoumarin and the phenylhydrazine compound are used according to a molar ratio of 0.9: the procedure of example 1 was repeated except for 1.
Example 9
Compared with example 1, except that the 3-acetyl benzo coumarin and the phenylhydrazine compound are used according to a molar ratio of 1.1: the procedure was repeated except for 0.9 in the same manner as in example 1.
Example 10
Compared with example 1, except that the 3-acetyl benzocoumarin and the phenylhydrazine compound are used according to a molar ratio of 1: the procedure was repeated except for 0.9 in the same manner as in example 1.
Example 11
Compared with example 1, except that the 3-acetyl benzocoumarin and the phenylhydrazine compound are used according to a molar ratio of 1: 1.1 the same as example 1.
Example 12
The procedure of example 1 was repeated, except that the solution was replaced with 20.5mL of absolute ethanol and 0.5mL of piperidine, as compared with example 1.
Example 13
The procedure of example 1 was repeated, except that the solution was replaced with 20mL of piperidine instead of 20mL of absolute ethanol and 0.5mL of piperidine, as compared with example 1.
Example 14
The same procedure as in example 1 was repeated, except that the reaction was carried out in the presence of heat and stirring at 80 ℃ for 3 to 5 hours and in the presence of 70 ℃ for 5 hours, in comparison with example 1.
Example 15
The same procedure as in example 1 was repeated, except that the reaction was carried out in the presence of heat and stirring at 80 ℃ for 3 to 5 hours and in the presence of 90 ℃ for 3 hours, as compared with example 1.
Example 16
The reaction was carried out in the same manner as in example 1 except that the reaction was carried out in the presence of heat under stirring at 80 ℃ for 5 hours and in the presence of heat under stirring at 70 ℃ for 5 hours, as compared with example 1.
Example 17
The reaction was carried out in the same manner as in example 1 except that the reaction was carried out in the presence of heat under stirring and refluxing at 80 ℃ for 5 hours and was replaced with the reaction was carried out in the presence of heat under stirring and refluxing at 90 ℃ for 3 hours, as compared with example 1.
Example 18
The reaction was carried out in the same manner as in example 1 except that the reaction was carried out under heating and stirring at 80 ℃ for 5 hours and the reaction was carried out under heating and stirring at 85 ℃ for 5 hours, as compared with example 1.
The hydrazone compound is synthesized by a simple method, the hydrazone group is introduced to serve as a binding site for hydrogen bond action of anions, and the benzocoumarin is used as a signal reporting group, so that the benzocoumarin group has a large conjugated system, and therefore, the color change is good on an ultraviolet-visible absorption spectrum, and the problems that the existing synthesis method of an anion recognition receptor is complex and the synthesis cost is high are solved; the provided preparation method is simple, and the obtained hydrazone compound has a plurality of hydrogen bond binding sites, so that the hydrazone compound has stronger hydrogen bond forming capability, can identify anions with weaker binding capability, and has wide market prospect.
It should be noted that fluorine is an element widely existing in nature, and in recent years, the use of fluorine ions in biology and medicine has become more and more important. However, fluorine compounds are harmful to human bodies, a small amount of fluorine (within 150 mg) can cause a series of pains, and a large amount of fluoride entering the body can cause acute poisoning. Various disorders such as anorexia, nausea, abdominal pain, gastric ulcer, cramped bleeding and even death can occur due to the varying inhaled amount of fluorine. The common contact with fluoride can easily cause the symptoms of bone hardening, embrittlement, tooth brittle fracture, fracture and the like, the fluorine content in drinking water in part of areas exceeds the standard, and the common drinking can also easily cause fluorine poisoning. Therefore, the design, synthesis and performance studies of fluorine sensors have become the focus of general attention of host-guest supramolecular chemists. In view of this, the examples of the present invention synthesized the acceptor molecule Z1-Z3 by a simple method, specifically by introducing a hydrazone group as F-The binding site of hydrogen bond function, and the signal reporting group is benzocoumarin; the benzocoumarin group has a larger conjugated system, so that the benzocoumarin group also has better color change on an ultraviolet-visible absorption spectrum. The experimental result shows that only Z3 can singly and selectively recognize F through hydrogen bonding for the recognition capability of common 10 anions-There was a significant change in both the uv-vis spectrum and the fluorescence spectrum. The hydrazone compound is designed and synthesized in the application, and has a plurality of hydrogen bond binding sites, so that the hydrazone compound is stronger in hydrogen bond forming capability and can be identified aiming at anions with weaker binding capability, and the identification performance research of the hydrazone compound is not reported in documents.
While the preferred embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the scope of the invention.
Claims (10)
1. A hydrazone compound has a structure shown in formula 1:
R is selected from hydrogen, 2, 4-dinitro or 4-nitro.
2. The hydrazone compound of claim 1, wherein the hydrazone compound is prepared from a 3-acetylbenzocoumarin and a phenylhydrazine compound as raw materials in an organic solvent.
3. The hydrazone compound according to claim 1, wherein the organic solvent is absolute ethanol (EtOH) and/or piperidine.
4. The hydrazone compound according to claim 1, wherein the phenylhydrazine compound has a structure represented by formula 2:
5. A process for the preparation of a hydrazone compound according to any one of claims 1 to 4, comprising the steps of: and (2) putting the 3-acetyl benzocoumarin and the phenylhydrazine compound into an organic solvent, uniformly mixing, then reacting for 3-5h at 70-90 ℃, cooling, filtering, washing a product, drying, and recrystallizing to obtain the hydrazone compound.
6. The method of claim 5, further comprising a step of synthesizing 3-acetyl benzocoumarin, wherein the step of synthesizing 3-acetyl benzocoumarin comprises: putting equal molar amounts of 2-hydroxy-1 naphthaldehyde and ethyl acetoacetate into absolute ethyl alcohol and piperidine, uniformly mixing, heating at 70-90 ℃ for reaction, standing, filtering, washing a product, drying, and recrystallizing to obtain the 3-acetyl benzocoumarin.
7. A hydrazone compound prepared by the method of claim 5 or 6.
8. An ion recognition receptor comprising, in part or in whole, the hydrazone compound of claim 1 or 2 or 3 or 4 or 7.
9. Use of an ion recognition receptor according to claim 8 for anion recognition and/or anion content detection.
10. Use of a hydrazone compound according to claim 5 or 6, in the preparation of a fluorine sensor.
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